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Sample records for metal chelates final

  1. Chelation in Metal Intoxication

    PubMed Central

    Flora, Swaran J.S.; Pachauri, Vidhu

    2010-01-01

    Chelation therapy is the preferred medical treatment for reducing the toxic effects of metals. Chelating agents are capable of binding to toxic metal ions to form complex structures which are easily excreted from the body removing them from intracellular or extracellular spaces. 2,3-Dimercaprol has long been the mainstay of chelation therapy for lead or arsenic poisoning, however its serious side effects have led researchers to develop less toxic analogues. Hydrophilic chelators like meso-2,3-dimercaptosuccinic acid effectively promote renal metal excretion, but their ability to access intracellular metals is weak. Newer strategies to address these drawbacks like combination therapy (use of structurally different chelating agents) or co-administration of antioxidants have been reported recently. In this review we provide an update of the existing chelating agents and the various strategies available for the treatment of heavy metals and metalloid intoxications. PMID:20717537

  2. Enhanced NO{sub x} removal in wet scrubbers using metal chelates. Final report, Volume 1

    SciTech Connect

    Smith, K.; Lani, B.; Berisko, D.; Schultz, C.; Carlson, W.; Benson, L.B.

    1992-12-01

    Successful pilot plant tests of simultaneous removal of S0{sub 2} and NO{sub x} in a wet lime flue gas desulfurization system were concluded in December. The tests, at up to 1.5 MW(e) capacity, were conducted by the Cincinnati Gas and Electric Company and Dravo Lime Company for the US Department of Energy at a pilot facility at the Miami Fort station of CG&E near Cincinnati, Ohio. The pilot plant scrubbed a slipstream of flue gas from Unit 7, a 530 MW coal-fired electric generating unit. Tests were conducted in three phases between April and December. The technology tested was wet scrubbing with Thiosorbic{reg_sign} magnesium-enhanced lime for S0{sub 2} removal and simultaneous NO scrubbing with ferrous EDTA, a metal chelate. Magnesium-enhanced lime-based wet scrubbing is used at 20 full-scale high-sulfur coal-fired electric generating units with a combined capacity of 8500 NW. Ferrous EDTA reacts with nitric oxide, NO, which comprises about 95% of NO{sub x} from coal-fired boilers. In this report, although not precise, NO and NO{sub x} are used interchangably. A major objective of the tests was to combine NO{sub x} removal using ferrous EDTA, a developing technology, with SO{sub 2} removal using wet lime FGD, already in wide commercial use. If successful, this could allow wide application of this NO{sub x} removal technology.

  3. Enhanced NO{sub x} removal in wet scrubbers using metal chelates. Final report, Volume 2

    SciTech Connect

    1992-12-01

    Successful pilot plant tests of simultaneous removal of SO{sub 2} and NO{sub x} in a wet lime flue gas desulfurization system were concluded in December. The test, at up to 1.5 MW(e) capacity, were conducted by the Cincinnati Gas and Electric Company and Dravo Lime Company for the US Department of Energy at a pilot plant facility at the Miami Fort station of CG&E near Cincinnati, Ohio. The pilot plant scrubbed a slipstream of flue gas from Unit 7 a 530 MW coal-fired electric generating unit. Tests were conducted in three phases between April and December. The technology tested was wet scrubbing with Thiosorbic{reg_sign} magnesium-enhanced lime for SO{sub 2} removal and simultaneous NO scrubbing with ferrous EDTA, a metal chelate. Magnesium-enhanced lime-based wet scrubbing is used at 20 full-scale high-sulfur coal-fired electric generating units with a combined capacity of 8500 MW. Ferrous EDTA reacts with nitric oxide, NO, which comprises about 96% of NO{sub x} from coal-fired boilers. In this report, although not precise, NO and NO{sub x} are used interchangeably. A major objective of the tests was to combine NO{sub x} removal using ferrous EDTA, a developing technology, with SO{sub 2} removal using wet lime FGD, already in wide commercial use. If successful, this could allow wide application of this NO{sub x} removal technology. Volume 2 covers: description and results of NO{sub x} removal tests; and description and results of waste characterization studies.

  4. Modern Chemistry Techniques Applied to Metal Behavior and Chelation in Medical and Environmental Systems ? Final Report

    SciTech Connect

    Sutton, M; Andresen, B; Burastero, S R; Chiarappa-Zucca, M L; Chinn, S C; Coronado, P R; Gash, A E; Perkins, J; Sawvel, A M; Szechenyi, S C

    2005-02-03

    This report details the research and findings generated over the course of a 3-year research project funded by Lawrence Livermore National Laboratory (LLNL) Laboratory Directed Research and Development (LDRD). Originally tasked with studying beryllium chemistry and chelation for the treatment of Chronic Beryllium Disease and environmental remediation of beryllium-contaminated environments, this work has yielded results in beryllium and uranium solubility and speciation associated with toxicology; specific and effective chelation agents for beryllium, capable of lowering beryllium tissue burden and increasing urinary excretion in mice, and dissolution of beryllium contamination at LLNL Site 300; {sup 9}Be NMR studies previously unstudied at LLNL; secondary ionization mass spec (SIMS) imaging of beryllium in spleen and lung tissue; beryllium interactions with aerogel/GAC material for environmental cleanup. The results show that chelator development using modern chemical techniques such as chemical thermodynamic modeling, was successful in identifying and utilizing tried and tested beryllium chelators for use in medical and environmental scenarios. Additionally, a study of uranium speciation in simulated biological fluids identified uranium species present in urine, gastric juice, pancreatic fluid, airway surface fluid, simulated lung fluid, bile, saliva, plasma, interstitial fluid and intracellular fluid.

  5. Metal Chelating Crosslinkers Form Nanogels with High Chelation Stability.

    PubMed

    Lux, Jacques; Chan, Minnie; Elst, Luce Vander; Schopf, Eric; Mahmoud, Enas; Laurent, Sophie; Almutairi, Adah

    2013-12-14

    We present a series of hydrogel nanoparticles (nanogels) incorporating either acyclic or cyclic metal chelates as crosslinkers. These crosslinkers are used to formulate polyacrylamide-based nanogels (diameter 50 to 85 nm) yielding contrast agents with enhanced relaxivities (up to 6-fold greater than Dotarem®), because this nanogel structure slows the chelator's tumbling frequency and allows fast water exchange. Importantly, these nanogels also stabilize Gd(3+) within the chelator thermodynamically and kinetically against metal displacement through transmetallation, which should reduce toxicity associated with release of free Gd(3+). This chelation stability suggests that the chelate crosslinker strategy may prove useful for other applications of metal-chelating nanoparticles in medicine, including other imaging modalities and radiotherapy.

  6. Metal Chelating Crosslinkers Form Nanogels with High Chelation Stability

    PubMed Central

    Elst, Luce Vander; Schopf, Eric; Mahmoud, Enas; Laurent, Sophie; Almutairi, Adah

    2013-01-01

    We present a series of hydrogel nanoparticles (nanogels) incorporating either acyclic or cyclic metal chelates as crosslinkers. These crosslinkers are used to formulate polyacrylamide-based nanogels (diameter 50 to 85 nm) yielding contrast agents with enhanced relaxivities (up to 6-fold greater than Dotarem®), because this nanogel structure slows the chelator's tumbling frequency and allows fast water exchange. Importantly, these nanogels also stabilize Gd3+ within the chelator thermodynamically and kinetically against metal displacement through transmetallation, which should reduce toxicity associated with release of free Gd3+. This chelation stability suggests that the chelate crosslinker strategy may prove useful for other applications of metal-chelating nanoparticles in medicine, including other imaging modalities and radiotherapy. PMID:24505553

  7. Metal Chelating Crosslinkers Form Nanogels with High Chelation Stability.

    PubMed

    Lux, Jacques; Chan, Minnie; Elst, Luce Vander; Schopf, Eric; Mahmoud, Enas; Laurent, Sophie; Almutairi, Adah

    2013-12-14

    We present a series of hydrogel nanoparticles (nanogels) incorporating either acyclic or cyclic metal chelates as crosslinkers. These crosslinkers are used to formulate polyacrylamide-based nanogels (diameter 50 to 85 nm) yielding contrast agents with enhanced relaxivities (up to 6-fold greater than Dotarem®), because this nanogel structure slows the chelator's tumbling frequency and allows fast water exchange. Importantly, these nanogels also stabilize Gd(3+) within the chelator thermodynamically and kinetically against metal displacement through transmetallation, which should reduce toxicity associated with release of free Gd(3+). This chelation stability suggests that the chelate crosslinker strategy may prove useful for other applications of metal-chelating nanoparticles in medicine, including other imaging modalities and radiotherapy. PMID:24505553

  8. Permselective, metal chelate containing, plasma polymers

    SciTech Connect

    Morosoff, N.C.; Clymer, S.D.; Stannett, V.T.; Skelly, J.M.; Crumbliss, A.L.

    1993-12-31

    Metal chelates, including cobalt Schiff bases and a cobalt porphyrin complex, have been codeposited with hydrocarbon plasma polymers to form thin films. The hydrocarbon monomers used were trans-2-butene and cyclooctene. The sorption of O{sub 2} by such membranes before and after reaction with pyridine (Pyr) or 1-methylimidazole (1-MeIm) was measured and the association FTIR and uv/visible absorption spectra were obtained. In addition permeability to O{sub 2} and N{sub 2} was determined. It was found that the structure of the metal chelates, which were sublimed into the plasma, was preserved. When bound to an axial base (Pyr or 1-MeIm), the plasma polymer occluded chelates bound O{sub 2} reversibly. O{sub 2} diffusion coefficients varied with the nature of the plasma polymer matrix. The ideal separation factor (O{sub 2}/N{sub 2}) increased for metal chelate containing plasma polymers vis-a-vis that for the plasma polymer matrix (without metal chelate). The ideal separation factor was at a maximum for low metal chelate loading and at a {open_quotes}mass thickness{close_quotes} of {approximately} 10 {mu}g/(cm{sup 2}min).

  9. Heavy metal chelation in neurotoxic exposures.

    PubMed

    Jang, David H; Hoffman, Robert S

    2011-08-01

    Metals such as iron and copper are critical to living organisms, whereas other metals such as lead and arsenic have no known biologic role. Any metals in large amounts may cause toxicity. Many metals cause pervasive systemic effects involving the nervous system, which can be subtle in some cases. Although challenging, the diagnosis and treatment of metal poisoning can be made based on history, physical examination, and the proper use of metal testing. This article focuses on the use, and misuse, of chelation in the diagnosis and management of metal intoxication. PMID:21803213

  10. Method and apparatus for back-extracting metal chelates

    DOEpatents

    Wai, Chien M.; Smart, Neil G.; Lin, Yuehe

    1998-01-01

    A method of extracting metal and metalloid species from a solid or liquid substrate using a supercritical fluid solvent containing one or more chelating agents followed by back-extracting the metal and metalloid species from the metal and metalloid chelates formed thereby. The back-extraction acidic solution is performed utilizing an acidic solution. Upon sufficient exposure of the metal and metalloid chelates to the acidic solution, the metal and metalloid species are released from the chelates into the acid solution, while the chelating agent remains in the supercritical fluid solvent. The chelating agent is thereby regenerated and the metal and metalloid species recovered.

  11. Method and apparatus for back-extracting metal chelates

    DOEpatents

    Wai, C.M.; Smart, N.G.; Lin, Y.

    1998-08-11

    A method is described for extracting metal and metalloid species from a solid or liquid substrate using a supercritical fluid solvent containing one or more chelating agents followed by back-extracting the metal and metalloid species from the metal and metalloid chelates formed thereby. The back-extraction acidic solution is performed utilizing an acidic solution. Upon sufficient exposure of the metal and metalloid chelates to the acidic solution, the metal and metalloid species are released from the chelates into the acid solution, while the chelating agent remains in the supercritical fluid solvent. The chelating agent is thereby regenerated and the metal and metalloid species recovered. 3 figs.

  12. 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.

  13. Clawing Back: Broadening the Notion of Metal Chelators in Medicine

    PubMed Central

    Franz, Katherine J.

    2013-01-01

    The traditional notion of chelation therapy is the administration of a chemical agent to remove metals from the body. But formation of a metal-chelate can have biological ramifications that are much broader than metal elimination. Exploring these other possibilities could lead to pharmacological interventions that alter the concentration, distribution, or reactivity of metals in targeted ways for therapeutic benefit. This review highlights recent examples that showcase four general strategies of using principles of metal chelation in medicinal contexts beyond the traditional notion of chelation therapy. These strategies include altering metal biodistribution, inhibiting specific metalloenzymes associated with disease, enhancing the reactivity of a metal complex to promote cytotoxicity, and conversely, passivating the reactivity of metals by site-activated chelation to prevent cytotoxicity. PMID:23332666

  14. Metal regeneration of iron chelates in nitric oxide scrubbing

    DOEpatents

    Chang, Shih-Ger; Littlejohn, David; Shi, Yao

    1997-08-19

    The present invention relates to a process of using metal particles to reduce NO to NH.sub.3. More specifically, the invention concerns an improved process to regenerate iron (II) (CHELATE) by reduction of iron (II) (CHELATE) (NO) complex, which process comprises: a) contacting an aqueous solution containing iron (II) (CHELATE) (NO) with metal particles at between about 20.degree. and 90.degree. C. to reduce NO present, produce ammonia or an ammonium ion, and produce free iron (II) (CHELATE) at a pH of between about 3 and 8. The process is useful to remove NO from flue gas and reduce pollution.

  15. Metal regeneration of iron chelates in nitric oxide scrubbing

    DOEpatents

    Chang, S.G.; Littlejohn, D.; Shi, Y.

    1997-08-19

    The present invention relates to a process of using metal particles to reduce NO to NH{sub 3}. More specifically, the invention concerns an improved process to regenerate iron (II) (CHELATE) by reduction of iron (II) (CHELATE) (NO) complex, which process comprises: (a) contacting an aqueous solution containing iron (II) (CHELATE) (NO) with metal particles at between about 20 and 90 C to reduce NO present, produce ammonia or an ammonium ion, and produce free iron (II) (CHELATE) at a pH of between about 3 and 8. The process is useful to remove NO from flue gas and reduce pollution. 34 figs.

  16. Chelation therapy for metal intoxication: comments from a thermodynamic viewpoint.

    PubMed

    Nurchi, Valeria Marina; Alonso, Miriam Crespo; Toso, Leonardo; Lachowicz, Joanna Izabela; Crisponi, Guido

    2013-10-01

    Chelation therapy plays a prominent role in the clinical treatment of metal intoxication. In this paper the principal causes of metal toxicity are exposed, and the chemical and biomedical requisites of a chelating agent are sketched. The chelating agents currently in use for scavenging toxic metal ions from humans belong to few categories: those characterized by coordinating mercapto groups, by oxygen groups, poliaminocarboxylic acids, and dithiocarbamates. Considering that the complex formation equilibria have been studied for less than 50% of chelators in use, some reflections on the utility of stability constants are presented, together with an evaluation of ligands under the stability profile. The competition between endogenous and toxic target metal ions for the same chelating agent is furthermore examined. A thorough examination of stability constant databases has allowed to select, for each toxic metal, the ligands distinguished by the best pMe values. Even though this selection does not consider the biomedical requisites of a chelating agent, it gives a clear picture both of the pMe values that can be attained, and of the most appropriate chelators for each metal ion.

  17. Chelation therapy for metal intoxication: comments from a thermodynamic viewpoint.

    PubMed

    Nurchi, Valeria Marina; Alonso, Miriam Crespo; Toso, Leonardo; Lachowicz, Joanna Izabela; Crisponi, Guido

    2013-10-01

    Chelation therapy plays a prominent role in the clinical treatment of metal intoxication. In this paper the principal causes of metal toxicity are exposed, and the chemical and biomedical requisites of a chelating agent are sketched. The chelating agents currently in use for scavenging toxic metal ions from humans belong to few categories: those characterized by coordinating mercapto groups, by oxygen groups, poliaminocarboxylic acids, and dithiocarbamates. Considering that the complex formation equilibria have been studied for less than 50% of chelators in use, some reflections on the utility of stability constants are presented, together with an evaluation of ligands under the stability profile. The competition between endogenous and toxic target metal ions for the same chelating agent is furthermore examined. A thorough examination of stability constant databases has allowed to select, for each toxic metal, the ligands distinguished by the best pMe values. Even though this selection does not consider the biomedical requisites of a chelating agent, it gives a clear picture both of the pMe values that can be attained, and of the most appropriate chelators for each metal ion. PMID:23895193

  18. Chelation: harnessing and enhancing heavy metal detoxification--a review.

    PubMed

    Sears, Margaret E

    2013-01-01

    Toxic metals such as arsenic, cadmium, lead, and mercury are ubiquitous, have no beneficial role in human homeostasis, and contribute to noncommunicable chronic diseases. While novel drug targets for chronic disease are eagerly sought, potentially helpful agents that aid in detoxification of toxic elements, chelators, have largely been restricted to overt acute poisoning. Chelation, that is multiple coordination bonds between organic molecules and metals, is very common in the body and at the heart of enzymes with a metal cofactor such as copper or zinc. Peptides glutathione and metallothionein chelate both essential and toxic elements as they are sequestered, transported, and excreted. Enhancing natural chelation detoxification pathways, as well as use of pharmaceutical chelators against heavy metals are reviewed. Historical adverse outcomes with chelators, lessons learned in the art of using them, and successes using chelation to ameliorate renal, cardiovascular, and neurological conditions highlight the need for renewed attention to simple, safe, inexpensive interventions that offer potential to stem the tide of debilitating, expensive chronic disease.

  19. Heavy metal displacement in chelate-irrigated soil during phytoremediation

    NASA Astrophysics Data System (ADS)

    Madrid, F.; Liphadzi, M. S.; Kirkham, M. B.

    2003-03-01

    Heavy metals in wastewater sewage sludge (biosolids), applied to land, contaminate soils. Phytoremediation, the use of plants to clean up toxic heavy metals, might remove them. Chelating agents are added to soil to solubilize the metals for enhanced phytoextraction. Yet no studies follow the displacement and leaching of heavy metals in soil with and without roots following solubilization with chelates. The objective of this work was to determine the mobility of heavy metals in biosolids applied to the surface of soil columns (76 cm long; 17 cm diam.) with or without plants (barley; Hordeum vulgare L.). Three weeks after barley was planted, all columns were irrigated with the disodium salt of the chelating agent, EDTA (ethylenediamine tetraacetic acid) (0.5 g/kg soil). Drainage water, soil, and plants were analyzed for heavy metals (Cd, Cu, Fe, Mn, Ni, Pb, Zn). Total concentrations of the heavy metals in all columns at the end of the experiment generally were lower in the top 30 cm of soil with EDTA than without EDTA. The chelate increased concentrations of heavy metals in shoots. With or without plants, the EDTA mobilized Cd, Fe, Mn, Ni, Pb, and Zn, which leached to drainage water. Drainage water from columns without EDTA had concentrations of these heavy metals below detection limits. Only Cu did not leach in the presence of EDTA. Even though roots retarded the movement of Cd, Fe, Mn, Ni, Pb, and Zn through the EDTA-treated soil from 1 d (Cd) to 5 d (Fe), the drainage water from columns with EDTA had concentrations of Cd, Fe, Mn, and Pb that exceeded drinking water standards by 1.3, 500, 620, and 8.6 times, respectively. Because the chelate rendered Cd, Fe, Mn, Ni, Pb, and Zn mobile, it is suggested that the theory for leaching of soluble salts, put forward by Nielsen and associates in 1965, could be applied to control movement of the heavy metals for maximum uptake during chelate-assisted phytoremediation.

  20. Metal chelate process to remove pollutants from fluids

    DOEpatents

    Chang, Shih-Ger T.

    1994-01-01

    The present invention relates to improved methods using an organic iron chelate to remove pollutants from fluids, such as flue gas. Specifically, the present invention relates to a process to remove NO.sub.x and optionally SO.sub.2 from a fluid using a metal ion (Fe.sup.2+) chelate wherein the ligand is a dimercapto compound wherein the --SH groups are attached to adjacent carbon atoms (HS--C--C--SH) or (SH--C--CCSH) and contain a polar functional group so that the ligand of DMC chelate is water soluble. Alternatively, the DMC' is covalently attached to a water insoluble substrate such as a polymer or resin, e.g., polystyrene. The chelate is regenerated using electroreduction or a chemical additive. The dimercapto compound bonded to a water insoluble substrate is also useful to lower the concentration or remove hazardous metal ions from an aqueous solution.

  1. Metal chelate process to remove pollutants from fluids

    DOEpatents

    Chang, S.G.T.

    1994-12-06

    The present invention relates to improved methods using an organic iron chelate to remove pollutants from fluids, such as flue gas. Specifically, the present invention relates to a process to remove NO[sub x] and optionally SO[sub 2] from a fluid using a metal ion (Fe[sup 2+]) chelate wherein the ligand is a dimercapto compound wherein the --SH groups are attached to adjacent carbon atoms (HS--C--C--SH) or (SH--C--CCSH) and contain a polar functional group so that the ligand of DMC chelate is water soluble. Alternatively, the DMC is covalently attached to a water insoluble substrate such as a polymer or resin, e.g., polystyrene. The chelate is regenerated using electroreduction or a chemical additive. The dimercapto compound bonded to a water insoluble substrate is also useful to lower the concentration or remove hazardous metal ions from an aqueous solution. 26 figures.

  2. Direct measurement of metal ion chelation in the active site of human ferrochelatase.

    PubMed

    Hoggins, M; Dailey, H A; Hunter, C N; Reid, J D

    2007-07-10

    The final step in heme biosynthesis, insertion of ferrous iron into protoporphyrin IX, is catalyzed by protoporphyrin IX ferrochelatase (EC 4.99.1.1). We demonstrate that pre-steady state human ferrochelatase (R115L) exhibits a stoichiometric burst of product formation and substrate consumption, consistent with a rate-determining step following metal ion chelation. Detailed analysis shows that chelation requires at least two steps, rapid binding followed by a slower (k approximately 1 s-1) irreversible step, provisionally assigned to metal ion chelation. Comparison with steady state data reveals that the rate-determining step in the overall reaction, conversion of free porphyrin to free metalloporphyrin, occurs after chelation and is most probably product release. We have measured rate constants for significant steps on the enzyme and demonstrate that metal ion chelation, with a rate constant of 0.96 s-1, is approximately 10 times faster than the rate-determining step in the steady state (kcat = 0.1 s-1). The effect of an additional E343D mutation is apparent at multiple stages in the reaction cycle with a 7-fold decrease in kcat and a 3-fold decrease in kchel. This conservative mutation primarily affects events occurring after metal ion chelation. Further evaluation of structure-function data on site-directed mutants will therefore require both steady state and pre-steady state approaches.

  3. Chelation And Extraction Of Metals For GC-MS Analysis

    NASA Technical Reports Server (NTRS)

    Sinha, Mahadeva P.

    1995-01-01

    Chelation followed by supercritical-fluid extraction enables mass-spectrometric analysis. When fully developed, method implemented in field-portable apparatus for detection and quantification of metals in various matrices without need for elaborate preparation of samples. Used to analyze soil samples for toxic metals.

  4. Molecular nanotechnologies of gelatin-immobilization using macrocyclic metal chelates

    PubMed Central

    Mikhailov, Oleg V.

    2014-01-01

    This article is a review of recent developments in the self-assembled nanostructures based on chelate coordination compounds. Molecular nanotechnologies of self-assembly of 3d-element aza- and thiazametalmacrocyclic complexes that happen in nanoreactors on the basis of metal hexacyanoferrate(II) gelatin-immobilized matrix under their contact with water solutions containing various (N,O,S)-donor atomic ligands and organic compounds having one or two carbonyl groups have been considered in this review. It has been noted that the assortment of macrocyclic metal chelates obtained as a result of using molecular nanotechnologies in such specific conditions considerably differs from the assortment of metal chelates formed at the conditions traditional for chemical synthesis. PMID:24516711

  5. Chelation and foam separation of metal ions from solutions

    SciTech Connect

    Carleson, T.E.; Moussavi, M.

    1988-08-01

    An experimental study was conducted on the chelation and foam separation of trace amounts of cadmium, zinc, and lead from their water solutions. The chelation agents ethylenediaminetetraacetate (sodium salt), sodium diethyldithiocarbamate, and citric acid were used with sodium dodecylsulfate (SDS) as a foam-producing agent. The chelation agents did not produce metal complexes that were very surface active. The foam-producing agent produced metal ion complexes that were surface active and resulted in appreciable separation of the metal ions. The use of 100 ppm SDS resulted in separation of 90% of the zinc ions from solution containing 2 to 20 ppm zinc. At concentrations below and above this, the removal efficiency dropped significantly.

  6. Chelation in metal intoxication--Principles and paradigms.

    PubMed

    Aaseth, Jan; Skaug, Marit Aralt; Cao, Yang; Andersen, Ole

    2015-01-01

    The present review provides an update of the general principles for the investigation and use of chelating agents in the treatment of intoxications by metals. The clinical use of the old chelators EDTA (ethylenediamine tetraacetate) and BAL (2,3-dimercaptopropanol) is now limited due to the inconvenience of parenteral administration, their own toxicity and tendency to increase the neurotoxicity of several metals. The hydrophilic dithiol chelators DMSA (meso-2,3-dimercaptosuccinic acid) and DMPS (2,3-dimercapto-propanesulphonate) are less toxic and more efficient than BAL in the clinical treatment of heavy metal poisoning, and available as capsules for oral use. In copper overload, DMSA appears to be a potent antidote, although d-penicillamine is still widely used. In the chelation of iron, the thiols are inefficient, since iron has higher affinity for ligands with nitrogen and oxygen, but the new oral iron antidotes deferiprone and desferasirox have entered into the clinical arena. Comparisons of these agents and deferoxamine infusions are in progress. General principles for research and development of new chelators are briefly outlined in this review.

  7. Chelation in metal intoxication--Principles and paradigms.

    PubMed

    Aaseth, Jan; Skaug, Marit Aralt; Cao, Yang; Andersen, Ole

    2015-01-01

    The present review provides an update of the general principles for the investigation and use of chelating agents in the treatment of intoxications by metals. The clinical use of the old chelators EDTA (ethylenediamine tetraacetate) and BAL (2,3-dimercaptopropanol) is now limited due to the inconvenience of parenteral administration, their own toxicity and tendency to increase the neurotoxicity of several metals. The hydrophilic dithiol chelators DMSA (meso-2,3-dimercaptosuccinic acid) and DMPS (2,3-dimercapto-propanesulphonate) are less toxic and more efficient than BAL in the clinical treatment of heavy metal poisoning, and available as capsules for oral use. In copper overload, DMSA appears to be a potent antidote, although d-penicillamine is still widely used. In the chelation of iron, the thiols are inefficient, since iron has higher affinity for ligands with nitrogen and oxygen, but the new oral iron antidotes deferiprone and desferasirox have entered into the clinical arena. Comparisons of these agents and deferoxamine infusions are in progress. General principles for research and development of new chelators are briefly outlined in this review. PMID:25457281

  8. Extraction of metals using supercritical fluid and chelate forming ligand

    DOEpatents

    Wai, C.M.; Laintz, K.E.

    1998-03-24

    A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated {beta}-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated {beta}-diketone and a trialkyl phosphate, or a fluorinated {beta}-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated {beta}-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process. 7 figs.

  9. Extraction of metals using supercritical fluid and chelate forming legand

    DOEpatents

    Wai, Chien M.; Laintz, Kenneth E.

    1998-01-01

    A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated .beta.-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated .beta.-diketone and a trialkyl phosphate, or a fluorinated .beta.-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated .beta.-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

  10. Challenges Associated with Metal Chelation Therapy in Alzheimer's Disease

    PubMed Central

    Hegde, Muralidhar L.; Bharathi, P.; Suram, Anitha; Venugopal, Chitra; Jagannathan, Ramya; Poddar, Pankaj; Srinivas, Pullabhatla; Sambamurti, Kumar; Rao, Kosagisharaf Jagannatha; Scancar, Janez; Messori, Luigi; Zecca, Luigi; Zatta, Paolo

    2010-01-01

    A close association between brain metal dishomeostasis and the onset and/or progression of Alzheimer's disease (AD) has been clearly established in a number of studies, although the underlying biochemical mechanisms remain obscure. This observation renders chelation therapy an attractive pharmacological option for the treatment of this disease. However, a number of requirements must be fulfilled in order to adapt chelation therapy to AD so that the term “metal targeted strategies” seems now more appropriate. Indeed, brain metal redistribution rather than brain metal scavenging and removal is the major goal of this type of intervention. The most recent developments in metal targeted strategies for AD will be discussed using, as useful examples, clioquinol, curcumin, and epigallocatechin, and the future perspectives will also be outlined. PMID:19363258

  11. mer and fac isomerism in tris chelate diimine metal complexes.

    PubMed

    Dabb, Serin L; Fletcher, Nicholas C

    2015-03-14

    In this perspective, we highlight the issue of meridional (mer) and facial (fac) orientation of asymmetrical diimines in tris-chelate transition metal complexes. Diimine ligands have long been the workhorse of coordination chemistry, and whilst there are now good strategies to isolate materials where the inherent metal centered chirality is under almost complete control, and systematic methodologies to isolate heteroleptic complexes, the conceptually simple geometrical isomerism has not been widely investigated. In systems where the two donor atoms are significantly different in terms of the σ-donor and π-accepting ability, the fac isomer is likely to be the thermodynamic product. For the diimine complexes with two trigonal planar nitrogen atoms there is much more subtlety to the system, and external factors such as the solvent, lattice packing and the various steric considerations play a delicate role in determining the observed and isolable product. In this article we discuss the possibilities to control the isomeric ratio in labile systems, consider the opportunities to separate inert complexes and discuss the observed differences in their spectroscopic properties. Finally we report on the ligand orientation in supramolecular systems where facial coordination leads to simple regular structures such as helicates and tetrahedra, but the ability of the ligand system to adopt a mer orientation enables self-assembled structures of considerable beauty and complexity.

  12. mer and fac isomerism in tris chelate diimine metal complexes.

    PubMed

    Dabb, Serin L; Fletcher, Nicholas C

    2015-03-14

    In this perspective, we highlight the issue of meridional (mer) and facial (fac) orientation of asymmetrical diimines in tris-chelate transition metal complexes. Diimine ligands have long been the workhorse of coordination chemistry, and whilst there are now good strategies to isolate materials where the inherent metal centered chirality is under almost complete control, and systematic methodologies to isolate heteroleptic complexes, the conceptually simple geometrical isomerism has not been widely investigated. In systems where the two donor atoms are significantly different in terms of the σ-donor and π-accepting ability, the fac isomer is likely to be the thermodynamic product. For the diimine complexes with two trigonal planar nitrogen atoms there is much more subtlety to the system, and external factors such as the solvent, lattice packing and the various steric considerations play a delicate role in determining the observed and isolable product. In this article we discuss the possibilities to control the isomeric ratio in labile systems, consider the opportunities to separate inert complexes and discuss the observed differences in their spectroscopic properties. Finally we report on the ligand orientation in supramolecular systems where facial coordination leads to simple regular structures such as helicates and tetrahedra, but the ability of the ligand system to adopt a mer orientation enables self-assembled structures of considerable beauty and complexity. PMID:25600485

  13. Chelation in metal intoxication XXI: chelation in lead intoxication during vitamin B complex deficiency

    SciTech Connect

    Not Available

    1986-09-01

    The vitamin B-complex deficiency increases the vulnerability to neuro- and systemic toxicity of Pb in young rats. Thus, the nutritional status of vitamins like that of protein or minerals seems to influence the etiology of Pb toxicity and may be expected to affect the response toward Pb chelators. 2,3 dimercaptosuccinic acid (DMSA) and N-(2-hydroxyethyl) ethylene-diamine triacetic acid (HEDTA) have been found to be effective antidotes to Pb intoxication. In the present study, these selective metal chelating agents were compared for their ability to reduce the body burden of Pb and restore the altered biochemical parameters in young developing Pb intoxicated rats maintained on normal or vitamin B-complex deficient diet. The investigation was aimed to suggest suitable prophylaxis of Pb poisoning prevalent among children who may also be suffering from vitamin deficiency in developing and poor countries.

  14. Flue gas desulfurization/denitrification using metal-chelate additives

    DOEpatents

    Harkness, John B. L.; Doctor, Richard D.; Wingender, Ronald J.

    1986-01-01

    A method of simultaneously removing SO.sub.2 and NO from oxygen-containing flue gases resulting from the combustion of carbonaceous material by contacting the flue gas with an aqueous scrubber solution containing an aqueous sulfur dioxide sorbent and an active metal chelating agent which promotes a reaction between dissolved SO.sub.2 and dissolved NO to form hydroxylamine N-sulfonates. The hydroxylamine sulfonates are then separated from the scrubber solution which is recycled.

  15. Flue gas desulfurization/denitrification using metal-chelate additives

    DOEpatents

    Harkness, J.B.L.; Doctor, R.D.; Wingender, R.J.

    1985-08-05

    A method of simultaneously removing SO/sub 2/ and NO from oxygen-containing flue gases resulting from the combustion of carbonaceous material by contacting the flue gas with an aqueous scrubber solution containing an aqueous sulfur dioxide sorbent and an active metal chelating agent which promotes a reaction between dissolved SO/sub 2/ and dissolved NO to form hydroxylamine N-sulfonates. The hydroxylamine sulfonates are then separated from the scrubber solution which is recycled. 3 figs.

  16. Prevention by chelating agents of metal-induced developmental toxicity.

    PubMed

    Domingo, J L

    1995-01-01

    Chelating agents such as calcium disodium ethylenediaminetetraacetate (EDTA), 2,3-dimercaptopropanol (BAL), or D-penicillamine (D-PA) have been widely used for the past 4 decades as antidotes for the treatment of acute and chronic metal poisoning. In recent years, meso-2,3-dimercaptosuccinic acid (DMSA), sodium 2,3-dimercapto-1-propanesulfonate (DMPS) and sodium 4,5-dihydroxybenzene-1,3-disulfonate (Tiron) have also shown to be effective to prevent against toxicity induced by a number of heavy metals. The purpose of the present article was to review the protective activity of various chelating agents against the embryotoxic and teratogenic effects of well-known developmental toxicants (arsenic, cadmium, lead, mercury, uranium, and vanadium). DMSA and DMPS were found to be effective in alleviating arsenate- and arsenite-induced teratogenesis, whereas BAL afforded only some protection against arsenic-induced embryo/fetal toxicity. Also, DMSA, DMPS, and Tiopronin were effective in ameliorating methyl mercury-induced developmental toxicity. Although the embryotoxic and teratogenic effects of vanadate were significantly reduced by Tiron, no significant amelioration of uranium-induced embryotoxicity was observed after treatment with this chelator.

  17. The role of chelation in the treatment of other metal poisonings.

    PubMed

    Smith, Silas W

    2013-12-01

    These proceedings will review the role of chelation in five metals-aluminum, cadmium, chromium, cobalt, and uranium-in order to illustrate various chelation concepts. The process of "chelation" can often be oversimplified, leading to incorrect assumptions and risking patient harm. For chelation to be effective, two critical assumptions must be fulfilled: the presumed "metal toxicity" must correlate with a given body or a particular compartment burden, and reducing this compartmental or the body burden (through chelation) attenuates toxicity. Fulfilling these assumptions requires an established dose-response relationship, a validated, reproducible means of toxicity assessment (clinical, biochemical, or radiographical), and an appropriate assessment mechanisms of body or compartment burden. While a metal might "technically" be capable of chelation (and readily demonstrable in urine or feces), this is an insufficient endpoint. Clinical relevance must be affirmed. Deferoxamine is an accepted chelator for appropriately documented aluminum toxicity. There is a very minimal treatment window in order to address chelation in cadmium toxicity. In acute toxicity, while no definitive chelation benefit is described, succimer (DMSA), diethylenetriaminepentaacetate (DTPA), and potentially ethylenediaminetetraacetic acid (EDTA) have been considered. In chronic toxicity, chelation is unsupported. There is little evidence to suggest that currently available chromium chelators are efficacious. Similarly, scant human evidence exists with which to provide recommendation for cobalt chelation. DTPA has been recommended for cobalt radionuclide chelation, although DMSA, EDTA, and N-acetylcysteine have also been suggested. DTPA is unsupported for uranium chelation. Sodium bicarbonate is currently recommended, although animal evidence is conflicting.

  18. Metal chelation therapy in rheumathoid arthritis: a case report. Successful management of rheumathoid arthritis by metal chelation therapy.

    PubMed

    Bamonti, Fabrizia; Fulgenzi, Alessandro; Novembrino, Cristina; Ferrero, Maria Elena

    2011-12-01

    Toxic metals are involved in the pathogenesis of some neurodegenerative and vascular diseases and are known to impair the immune system functions. We report here the case of a patient affected by heavy metal intoxication, who had developed an autoimmune disease. There was evidence of aluminium, cadmium and lead intoxication in a 63-year old Italian woman affected by rheumatoid arthritis (RA). We treated the patient with calcium disodium edetate (EDTA) once a week for a year in order to remove traces of heavy metal intoxication. Oxidative status profile was carried out at the beginning and after 6 months' EDTA chelation. At the end of the treatment, the patient did not show any signs of metal intoxication, RA symptoms and oxidative status improved.

  19. 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.

  20. Metal ion coordination, conditional stability constants, and solution behavior of chelating surfactant metal complexes.

    PubMed

    Svanedal, Ida; Boija, Susanne; Almesåker, Ann; Persson, Gerd; Andersson, Fredrik; Hedenström, Erik; Bylund, Dan; Norgren, Magnus; Edlund, Håkan

    2014-04-29

    Coordination complexes of some divalent metal ions with the DTPA (diethylenetriaminepentaacetic acid)-based chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) have been examined in terms of chelation and solution behavior. The headgroup of 4-C12-DTPA contains eight donor atoms that can participate in the coordination of a metal ion. Conditional stability constants for five transition metal complexes with 4-C12-DTPA were determined by competition measurements between 4-C12-DTPA and DTPA, using electrospray ionization mass spectrometry (ESI-MS). Small differences in the relative strength between the coordination complexes of DTPA and 4-C12-DTPA indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. The coordination of Cu(2+) ions was investigated in particular, using UV-visible spectroscopy. By constructing Job's plots, it was found that 4-C12-DTPA could coordinate up to two Cu(2+) ions. Surface tension measurements and NMR diffusometry showed that the coordination of metal ions affected the solution behavior of 4-C12-DTPA, but there were no specific trends between the studied divalent metal complexes. Generally, the effects of the metal ion coordination could be linked to the neutralization of the headgroup charge of 4-C12-DTPA, and the resulting reduced electrostatic repulsions between adjacent surfactants in micelles and monolayers. The pH vs concentration plots, on the other hand, showed a distinct difference between 4-C12-DTPA complexes of the alkaline earth metals and the transition metals. This was explained by the difference in coordination between the two groups of metal ions, as predicted by the hard and soft acid and base (HSAB) theory.

  1. Metal ion coordination, conditional stability constants, and solution behavior of chelating surfactant metal complexes.

    PubMed

    Svanedal, Ida; Boija, Susanne; Almesåker, Ann; Persson, Gerd; Andersson, Fredrik; Hedenström, Erik; Bylund, Dan; Norgren, Magnus; Edlund, Håkan

    2014-04-29

    Coordination complexes of some divalent metal ions with the DTPA (diethylenetriaminepentaacetic acid)-based chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) have been examined in terms of chelation and solution behavior. The headgroup of 4-C12-DTPA contains eight donor atoms that can participate in the coordination of a metal ion. Conditional stability constants for five transition metal complexes with 4-C12-DTPA were determined by competition measurements between 4-C12-DTPA and DTPA, using electrospray ionization mass spectrometry (ESI-MS). Small differences in the relative strength between the coordination complexes of DTPA and 4-C12-DTPA indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. The coordination of Cu(2+) ions was investigated in particular, using UV-visible spectroscopy. By constructing Job's plots, it was found that 4-C12-DTPA could coordinate up to two Cu(2+) ions. Surface tension measurements and NMR diffusometry showed that the coordination of metal ions affected the solution behavior of 4-C12-DTPA, but there were no specific trends between the studied divalent metal complexes. Generally, the effects of the metal ion coordination could be linked to the neutralization of the headgroup charge of 4-C12-DTPA, and the resulting reduced electrostatic repulsions between adjacent surfactants in micelles and monolayers. The pH vs concentration plots, on the other hand, showed a distinct difference between 4-C12-DTPA complexes of the alkaline earth metals and the transition metals. This was explained by the difference in coordination between the two groups of metal ions, as predicted by the hard and soft acid and base (HSAB) theory. PMID:24702119

  2. Analysis of Supercritical-Extracted Chelated Metal Ions From Mixed Organic-Inorganic Samples

    NASA Technical Reports Server (NTRS)

    Sinha, Mahadeva P. (Inventor)

    1996-01-01

    Organic and inorganic contaminants of an environmental sample are analyzed by the same GC-MS instrument by adding an oxidizing agent to the sample to oxidize metal or metal compounds to form metal ions. The metal ions are converted to chelate complexes and the chelate complexes are extracted into a supercritical fluid such as CO2. The metal chelate extract after flowing through a restrictor tube is directly injected into the ionization chamber of a mass spectrometer, preferably containing a refractory metal filament such as rhenium to fragment the complex to release metal ions which are detected. This provides a fast, economical method for the analysis of metal contaminants in a sample and can be automated. An organic extract of the sample in conventional or supercritical fluid solvents can be detected in the same mass spectrometer, preferably after separation in a supercritical fluid chromatograph.

  3. Method for separating metal chelates from other materials based on solubilities in supercritical fluids

    DOEpatents

    Wai, Chien M.; Smart, Neil G.; Phelps, Cindy

    2001-01-01

    A method for separating a desired metal or metalloi from impurities using a supercritical extraction process based on solubility differences between the components, as well as the ability to vary the solvent power of the supercritical fluid, is described. The use of adduct-forming agents, such as phosphorous-containing ligands, to separate metal or metalloid chelates in such processes is further disclosed. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones; phosphine oxides, such as trialkylphosphine oxides, triarylphosphine oxides and alkylarylphosphine oxides; phosphinic acids; carboxylic acids; phosphates, such as trialkylphosphates, triarylphosphates and alkylarylphosphates; crown ethers; dithiocarbamates; phosphine sulfides; phosphorothioic acids; thiophosphinic acids; halogenated analogs of these chelating agents; and mixtures of these chelating agents. In especially preferred embodiments, at least one of the chelating agents is fluorinated.

  4. Chemical and biological properties of toxic metals and use of chelating agents for the pharmacological treatment of metal poisoning.

    PubMed

    Sinicropi, Maria Stefania; Amantea, Diana; Caruso, Anna; Saturnino, Carmela

    2010-07-01

    Exposure to toxic metals is a well-known problem in industrialized countries. Metals interfere with a number of physiological processes, including central nervous system (CNS), haematopoietic, hepatic and renal functions. In the evaluation of the toxicity of a particular metal it is crucial to consider many parameters: chemical forms (elemental, organic or inorganic), binding capability, presence of specific proteins that selectively bind metals, etc. Medical treatment of acute and chronic metal toxicity is provided by chelating agents, namely organic compounds capable of interacting with metal ions to form structures called chelates. The present review attempts to provide updated information about the mechanisms, the cellular targets and the effects of toxic metals.

  5. Chromium uptake by Spirodela polyrrhiza (L. ) Schleiden in relation to metal chelators and pH

    SciTech Connect

    Tripathi, R.D.; Chandra, P. )

    1991-11-01

    This paper reports the influence of metal chelators, ethylenediaminetetraacetic acid (EDTA) and salicylic acid, and pH on the accumulation of Cr by S. polyrrhiza under the laboratory conditions. This also includes the results of K.D. pond water treatment study by cultured fronds of S. polyrrhiza. In view of the occurrence of metal chelators in natural waters and pH variation the present study would enable to assess the performance of this species under the influence of these factors.

  6. Chelating capture and magnetic removal of non-magnetic heavy metal substances from soil

    PubMed Central

    Fan, Liren; Song, Jiqing; Bai, Wenbo; Wang, Shengping; Zeng, Ming; Li, Xiaoming; Zhou, Yang; Li, Haifeng; Lu, Haiwei

    2016-01-01

    A soil remediation method based on magnetic beneficiation is reported. A new magnetic solid chelator powder, FS@IDA (core-shell Fe3O4@SiO2 nanoparticles coated with iminodiacetic acid chelators), was used as a reactive magnetic carrier to selectively capture non-magnetic heavy metals in soil by chelation and removal by magnetic separation. FS@IDA was prepared via inorganic-organic and organic synthesis reactions that generated chelating groups on the surface of magnetic, multi-core, core-shell Fe3O4@SiO2 (FS) nanoparticles. These reactions used a silane coupling agent and sodium chloroacetate. The results show that FS@IDA could chelate the heavy metal component of Cd, Zn, Pb, Cu and Ni carbonates, lead sulfate and lead chloride in water-insoluble salt systems. The resulting FS@IDA-Cd and FS@IDA-Pb chelates could be magnetically separated, resulting in removal rates of approximately 84.9% and 72.2% for Cd and Pb, respectively. FS@IDA could not remove the residual heavy metals and those bound to organic matter in the soil. FS@IDA did not significantly alter the chemical composition of the soil, and it allowed for fast chelating capture, simple magnetic separation and facilitated heavy metal elution. FS@IDA could also be easily prepared and reprocessed. PMID:26878770

  7. Chelating capture and magnetic removal of non-magnetic heavy metal substances from soil.

    PubMed

    Fan, Liren; Song, Jiqing; Bai, Wenbo; Wang, Shengping; Zeng, Ming; Li, Xiaoming; Zhou, Yang; Li, Haifeng; Lu, Haiwei

    2016-02-16

    A soil remediation method based on magnetic beneficiation is reported. A new magnetic solid chelator powder, FS@IDA (core-shell Fe3O4@SiO2 nanoparticles coated with iminodiacetic acid chelators), was used as a reactive magnetic carrier to selectively capture non-magnetic heavy metals in soil by chelation and removal by magnetic separation. FS@IDA was prepared via inorganic-organic and organic synthesis reactions that generated chelating groups on the surface of magnetic, multi-core, core-shell Fe3O4@SiO2 (FS) nanoparticles. These reactions used a silane coupling agent and sodium chloroacetate. The results show that FS@IDA could chelate the heavy metal component of Cd, Zn, Pb, Cu and Ni carbonates, lead sulfate and lead chloride in water-insoluble salt systems. The resulting FS@IDA-Cd and FS@IDA-Pb chelates could be magnetically separated, resulting in removal rates of approximately 84.9% and 72.2% for Cd and Pb, respectively. FS@IDA could not remove the residual heavy metals and those bound to organic matter in the soil. FS@IDA did not significantly alter the chemical composition of the soil, and it allowed for fast chelating capture, simple magnetic separation and facilitated heavy metal elution. FS@IDA could also be easily prepared and reprocessed.

  8. Chelating capture and magnetic removal of non-magnetic heavy metal substances from soil

    NASA Astrophysics Data System (ADS)

    Fan, Liren; Song, Jiqing; Bai, Wenbo; Wang, Shengping; Zeng, Ming; Li, Xiaoming; Zhou, Yang; Li, Haifeng; Lu, Haiwei

    2016-02-01

    A soil remediation method based on magnetic beneficiation is reported. A new magnetic solid chelator powder, FS@IDA (core-shell Fe3O4@SiO2 nanoparticles coated with iminodiacetic acid chelators), was used as a reactive magnetic carrier to selectively capture non-magnetic heavy metals in soil by chelation and removal by magnetic separation. FS@IDA was prepared via inorganic-organic and organic synthesis reactions that generated chelating groups on the surface of magnetic, multi-core, core-shell Fe3O4@SiO2 (FS) nanoparticles. These reactions used a silane coupling agent and sodium chloroacetate. The results show that FS@IDA could chelate the heavy metal component of Cd, Zn, Pb, Cu and Ni carbonates, lead sulfate and lead chloride in water-insoluble salt systems. The resulting FS@IDA-Cd and FS@IDA-Pb chelates could be magnetically separated, resulting in removal rates of approximately 84.9% and 72.2% for Cd and Pb, respectively. FS@IDA could not remove the residual heavy metals and those bound to organic matter in the soil. FS@IDA did not significantly alter the chemical composition of the soil, and it allowed for fast chelating capture, simple magnetic separation and facilitated heavy metal elution. FS@IDA could also be easily prepared and reprocessed.

  9. Targeted cleavage of HIV RRE RNA by Rev-coupled transition metal chelates.

    PubMed

    Joyner, Jeff C; Cowan, J A

    2011-06-29

    A series of compounds that target reactive metal chelates to the HIV-1 Rev response element (RRE) mRNA have been synthesized. Dissociation constants and chemical reactivity toward HIV RRE RNA have been determined and evaluated in terms of reduction potential, coordination unsaturation, and overall charge associated with the metal-chelate-Rev complex. Ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) were linked to a lysine side chain of a Rev-derived peptide by either EDC/NHS or isothiocyanate coupling. The resulting chelate-Rev (EDTA-Rev, DTPA-Rev, NTA-Rev, and DOTA-Rev) conjugates were used to form coordination complexes with Fe(2+), Co(2+), Ni(2+), and Cu(2+) such that the arginine-rich Rev peptide could mediate localization of the metal chelates to the Rev peptide's high-affinity mRNA binding partner, RRE stem loop IIB. Metal complexes of the extended peptides GGH-Rev and KGHK-Rev, which also contain N-terminal peptidic chelators (ATCUN motifs), were studied for comparison. A fluorescence titration assay revealed high-affinity RRE RNA binding by all 22 metal-chelate-Rev species, with K(D) values ranging from ~0.2 to 16 nM, indicating little to no loss of RNA affinity due to the coupling of the metal chelates to the Rev peptide. Dissociation constants for binding at a previously unobserved low-affinity site are also reported. Rates of RNA modification by each metal-chelate-Rev species were determined and varied from ~0.28 to 4.9 nM/min but were optimal for Cu(2+)-NTA-Rev. Metal-chelate reduction potentials were determined and varied from -228 to +1111 mV vs NHE under similar solution conditions, allowing direct comparison of reactivity with redox thermodynamics. Optimal activity was observed when the reduction potential for the metal center was poised between those of the two principal co-reagents for metal-promoted formation of

  10. Stable bifunctional chelates of metals used in radiotherapy.

    PubMed

    Moi, M K; DeNardo, S J; Meares, C F

    1990-02-01

    Monoclonal antibody technology allows the specificity of an antibody for its antigen to be used in targeting cancer cells. The conjugation of metals, particularly radionuclides such as 90Y or 67Cu, to monoclonal antibodies results in agents for radioimmunotherapy and other medical applications. Chelators that can hold radiometals with high stability under physiological conditions are essential to avoid excessive radiation damage to nontarget cells. Derivatives of polyazamacrocycles (bearing a C-substituted functional group for antibody attachment) can exhibit remarkable kinetic inertness; for example, the copper complex of the 14-membered 6-(p-nitrobenzyl)-1,4,8,11-tetraazacyclotetradecane-N,N',N'',N'''- tetraacetic acid is very stable in human serum under physiological conditions, and a conjugate of this complex with a monoclonal antibody has tested well in tumor-bearing mice. Desreux and coworkers [Loncin, M. F., Desreux, J. F., and Merciny, E. Inorg. Chem., 25: 2646-2648, 1986] have shown that complexes of lanthanides with 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid have formation constants that are several orders of magnitude higher than that of 1,4,8,11-tetraazacyclotetradecane-N,N',N'',N'''-tetraacetic acid; thus the 12-membered macrocycle is the favored target for binding trivalent yttrium. We have developed a new synthetic route to these macrocycles via peptide synthesis and intramolecular tosylamide ring closure. Incubation of the 88Y-(III) complex of 2-p-nitrobenzyl-1,4,7,10-tetraazacyclododecane-N,N',N'',N'''- tetraacetic acid for 18 days in serum results in loss of so little Y(III) from the complex (less than 0.5%) that the rate of loss cannot be measured under these conditions.

  11. Chelation in metal intoxication XVI. Influence of chelating agents on chromate poisoned rats

    SciTech Connect

    Tandon, S.K.; Srivastava, L.

    1985-01-01

    The ability of selective polyaminocarboxylic acids and common drugs to reduce the body burden of chromium and restore Cr induced biochemical alterations in chromate intoxicated rats was investigated. 1,2 Cychlohexylene dinitrilotetraacetic acid (CDTA) and triethylenetetramine hexacetic acid (TTHA) were more effective than p-aminosalicylic acid (PAS) and isoniazid (INH) in enhancing urinary excretion of Cr, lowering hepatic and blood levels of Cr and restoring inhibited activity of hepatic aldolase. The chromate antidotal property of chelators seem to be related to the combination of nitrogen and oxygen as the electron donating centres.

  12. Fluorous-assisted metal chelate affinity extraction technique for analysis of protein kinase activity.

    PubMed

    Hayama, Tadashi; Kiyokawa, Ena; Yoshida, Hideyuki; Imakyure, Osamu; Yamaguchi, Masatoshi; Nohta, Hitoshi

    2016-08-15

    We have developed a fluorous affinity-based extraction method for measurement of protein kinase activity. In this method, a fluorescent peptide substrate was phosphorylated by a protein kinase, and the obtained phosphopeptide was selectively captured with Fe(III)-immobilized perfluoroalkyliminodiacetic acid reagent via a metal chelate affinity technique. Next, the captured phosphopeptide was selectively extracted into a fluorous solvent mixture, tetradecafluorohexane and 1H,1H,2H,2H-tridecafluoro-1-n-octanol (3:1, v/v), using the specificity of fluorous affinity (fluorophilicity). In contrast, the remained substrate peptide in the aqueous (non-fluorous) phase was easily measured fluorimetrically. Finally, the enzyme activity could be assayed by measuring the decrease in fluorescence. The feasibility of this method was demonstrated by applying the method for measurement of the activity of cAMP-dependent protein kinase (PKA) using its substrate peptide (kemptide) pre-labeled with carboxytetramethylrhodamine (TAMRA).

  13. (Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents)

    SciTech Connect

    Not Available

    1991-01-01

    Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

  14. [Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents

    SciTech Connect

    Not Available

    1991-12-31

    Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

  15. [Extraction of Heavy Metals from Sludge Using Biodegradable Chelating Agent N,N-bis(carboxymethyl) Glutamic Acid Tetrasodium].

    PubMed

    Wu, Qing; Cui, Yan-rui; Tang, Xiao-xiao; Yang, Hui-juan; Sun, Jian-hui

    2015-05-01

    N, N-bis (carboxymethyl) glutamic acid tetrasodium (GLDA), a novel biodegradable and green chelating agent, has excellent metal chelating ability. Batch experiment was conducted to study the extraction process of Cd, Ni, Cu and Zn in industrial sludge using GLDA. The effects of contact time, pH of the system, content of chelating agent were investigated, and the forms of heavy metals in sludge pre- and post-extraction using the modified BCR sequential extraction procedure were studied. The results showed that GLDA was effective for cadmium extraction in sludge. Several heavy metals could be effectively extracted under the condition of pH 4 and molar ratio of chelating agent to total heavy metal 3:1. Residual fraction took the largest fraction in Zn, which caused the low extraction efficiency of this metal. Chelating properties were related not only to contact time, pH, chelating agent's concentration, and stability constant but also to species distribution of metals.

  16. Effect of metal chelators on excretion and tissue levels of essential trace elements

    SciTech Connect

    Tandon, S.K.; Jain, V.K.; Mathur, A.K.

    1984-10-01

    The influence of one, three, and six doses of ethylenediaminetetraacetic acid (EDTA) diethylenetriaminepentaacetic acid (DTPA), and triethylenetetramine (TETA) on the urinary excretion of Ca, Cu, Fe, and Zn, and on their levels in liver, kidneys, heart, and serum in rats, was investigated to ascertain their suitability in amelioration of metal intoxication. While excretion of all the essential trace metals examined was enhanced significantly, the tissue and serum levels of some of them either increased or decreased after administration of the chelators. The results suggest depletion of some of the endogenous trace metals from the body and their intertissue redistribution following treatment with these chelating agents.

  17. A Speciation Study on the Perturbing Effects of Iron Chelators on the Homeostasis of Essential Metal Ions.

    PubMed

    Crisponi, Guido; Nurchi, Valeria Marina; Crespo-Alonso, Miriam; Sanna, Gavino; Zoroddu, Maria Antonietta; Alberti, Giancarla; Biesuz, Raffaela

    2015-01-01

    A number of reports have appeared in literature calling attention to the depletion of essential metal ions during chelation therapy on β-thalassaemia patients. We present a speciation study to determine how the iron chelators used in therapy interfere with the homeostatic equilibria of essential metal ions. This work includes a thorough analysis of the pharmacokinetic properties of the chelating agents currently in clinical use, of the amounts of iron, copper and zinc available in plasma for chelation, and of all the implied complex formation constants. The results of the study show that a significant amount of essential metal ions is complexed whenever the chelating agent concentration exceeds the amount necessary to coordinate all disposable iron--a frequently occurring situation during chelation therapy. On the contrary, copper and zinc do not interfere with iron chelation, except for a possible influence of copper on iron speciation during deferiprone treatment.

  18. Modifications of boronic ester pro-chelators triggered by hydrogen peroxide tune reactivity to inhibit metal-promoted oxidative stress.

    PubMed

    Charkoudian, Louise K; Pham, David M; Kwon, Ashley M; Vangeloff, Abbey D; Franz, Katherine J

    2007-11-21

    Several new analogs of salicylaldehyde isonicotinoyl hydrazone (SIH) and salicylaldehyde benzoyl hydrazone (SBH) that contain an aryl boronic ester (BSIH, BSBH) or acid (BASIH) in place of an aryl hydroxide have been synthesized and characterized as masked metal ion chelators. These pro-chelators show negligible interaction with iron(III), although the boronic acid versions exhibit some interaction with copper(II), zinc(II) and nickel(II). Hydrogen peroxide oxidizes the aryl boronate to phenol, thus converting the pro-chelators to tridentate ligands with high affinity metal binding properties. An X-ray crystal structure of a bis-ligated iron(III) complex, [Fe(SBH(m-OMe)(3))(2)]NO(3), confirms the meridonal binding mode of these ligands. Modifications of the aroyl ring of the chelators tune their iron affinity, whereas modifications on the boron-containing ring of the pro-chelators attenuate their reaction rates with hydrogen peroxide. Thus, the methoxy derivative pro-chelator (p-OMe)BASIH reacts with hydrogen peroxide nearly 5 times faster than the chloro derivative (m-Cl)BASIH. Both the rate of pro-chelator to chelator conversion as well as the metal binding affinity of the chelator influence the overall ability of these molecules to inhibit hydroxyl radical formation catalyzed by iron or copper in the presence of hydrogen peroxide and ascorbic acid. This pro-chelator strategy has the potential to improve the efficacy of medicinal chelators for inhibiting metal-promoted oxidative stress. PMID:17992288

  19. Spectroscopy, modeling and computation of metal chelate solubility in supercritical CO{sub 2}

    SciTech Connect

    J. F. Brennecke; M. A. Stadtherr

    1999-12-10

    The overall objectives of this project were to gain a fundamental understanding of the solubility and phase behavior of metal chelates in supercritical CO{sub 2}. Extraction with CO{sub 2} is an excellent way to remove organic compounds from soils, sludges and aqueous solutions, and recent research has demonstrated that, together with chelating agents, it is a viable way to remove metals, as well. In this project the authors sought to gain fundamental knowledge that is vital to computing phase behavior, and modeling and designing processes using CO{sub 2} to separate organics and metal compounds from DOE mixed wastes. The overall program was a comprehensive one to measure, model and compute the solubility of metal chelate complexes in supercritical CO{sub 2} and CO{sub 2}/cosolvent mixtures. Through a combination of phase behavior measurements, spectroscopy and the development of a new computational technique, the authors have achieved a completely reliable way to model metal chelate solubility in supercritical CO{sub 2} and CO{sub 2}/co-contaminant mixtures. Thus, they can now design and optimize processes to extract metals from solid matrices using supercritical CO{sub 2}, as an alternative to hazardous organic solvents that create their own environmental problems, even while helping in metals decontamination.

  20. Investigating the role of metal chelation in HIV-1 integrase strand transfer inhibitors.

    PubMed

    Bacchi, Alessia; Carcelli, Mauro; Compari, Carlotta; Fisicaro, Emilia; Pala, Nicolino; Rispoli, Gabriele; Rogolino, Dominga; Sanchez, Tino W; Sechi, Mario; Sinisi, Valentina; Neamati, Nouri

    2011-12-22

    HIV-1 integrase (IN) has been validated as an attractive target for the treatment of HIV/AIDS. Several studies have confirmed that the metal binding function is a crucial feature in many of the reported IN inhibitors. To provide new insights on the metal chelating mechanism of IN inhibitors, we prepared a series of metal complexes of two ligands (HL1 and HL2), designed as representative models of the clinically used compounds raltegravir and elvitegravir. Potentiometric measurements were conducted for HL2 in the presence of Mg(II), Mn(II), Co(II), and Zn(II) in order to delineate a metal speciation model. We also determined the X-ray structures of both of the ligands and of three representative metal complexes. Our results support the hypothesis that several selective strand transfer inhibitors preferentially chelate one cation in solution and that the metal complexes can interact with the active site of the enzyme.

  1. Effect of the chelation of metal cation on the antioxidant activity of chondroitin sulfates.

    PubMed

    Ajisaka, Katsumi; Oyanagi, Yutaka; Miyazaki, Tatsuo; Suzuki, Yasuhiro

    2016-06-01

    The antioxidant potencies of chondroitin sulfates (CSs) from shark cartilage, salmon cartilage, bovine trachea, and porcine intestinal mucosa were compared by three representative methods for the measurement of the antioxidant activity; DPPH radical scavenging activity, superoxide radical scavenging activity, and hydroxyl radical scavenging activity. CSs from salmon cartilage and bovine trachea showed higher potency in comparison with CSs from shark cartilage and porcine intestinal mucosa. Next, CS from salmon cartilage chelating with Ca(2+), Mg(2+), Mn(2+), or Zn(2+) were prepared, and their antioxidant potencies were compared. CS chelating with Ca(2+) or Mg(2+) ions showed rather decreased DPPH radical scavenging activity in comparison with CS of H(+) form. In contrast, CS chelating with Ca(2+) or Mg(2+) ion showed remarkably enhanced superoxide radical scavenging activity than CS of H(+) or Na(+) form. Moreover, CS chelating with divalent metal ions, Ca(2+), Mg(2+), Mn(2+), or Zn(2+), showed noticeably higher hydroxyl radical scavenging activity than CS of H(+) or Na(+) form. The present results revealed that the scavenging activities of, at least, superoxide radical and hydroxyl radical were enhanced by the chelation with divalent metal ions.

  2. Effect of the chelation of metal cation on the antioxidant activity of chondroitin sulfates.

    PubMed

    Ajisaka, Katsumi; Oyanagi, Yutaka; Miyazaki, Tatsuo; Suzuki, Yasuhiro

    2016-06-01

    The antioxidant potencies of chondroitin sulfates (CSs) from shark cartilage, salmon cartilage, bovine trachea, and porcine intestinal mucosa were compared by three representative methods for the measurement of the antioxidant activity; DPPH radical scavenging activity, superoxide radical scavenging activity, and hydroxyl radical scavenging activity. CSs from salmon cartilage and bovine trachea showed higher potency in comparison with CSs from shark cartilage and porcine intestinal mucosa. Next, CS from salmon cartilage chelating with Ca(2+), Mg(2+), Mn(2+), or Zn(2+) were prepared, and their antioxidant potencies were compared. CS chelating with Ca(2+) or Mg(2+) ions showed rather decreased DPPH radical scavenging activity in comparison with CS of H(+) form. In contrast, CS chelating with Ca(2+) or Mg(2+) ion showed remarkably enhanced superoxide radical scavenging activity than CS of H(+) or Na(+) form. Moreover, CS chelating with divalent metal ions, Ca(2+), Mg(2+), Mn(2+), or Zn(2+), showed noticeably higher hydroxyl radical scavenging activity than CS of H(+) or Na(+) form. The present results revealed that the scavenging activities of, at least, superoxide radical and hydroxyl radical were enhanced by the chelation with divalent metal ions. PMID:26856546

  3. Regulation of copper and iron homeostasis by metal chelators: a possible chemotherapy for Alzheimer's disease.

    PubMed

    Robert, Anne; Liu, Yan; Nguyen, Michel; Meunier, Bernard

    2015-05-19

    With the increase of life expectancy of humans in more than two-thirds of the countries in the World, aging diseases are becoming the frontline health problems. Alzheimer's disease (AD) is now one of the major challenges in drug discovery, since, with the exception of memantine in 2003, all clinical trials with drug candidates failed over the past decade. If we consider that the loss of neurons is due to a high level of oxidative stress produced by nonregulated redox active metal ions like copper linked to amyloids of different sizes, regulation of metal homeostasis is a key target. The difficulty for large copper-carrier proteins to directly extract copper ions from metalated amyloids might be considered as being at the origin of the rupture of the copper homeostasis regulation in AD brains. So, there is an urgent need for new specific metal chelators that should be able to regulate the homeostasis of metal ions, specially copper and iron, in AD brains. As a consequence of that concept, chelators promoting metal excretion from brain are not desired. One should favor ligands able to extract copper ions from sinks (amyloids being the major one) and to transfer these redox-active metal ions to copper-carrier proteins or copper-containing enzymes. Obviously, the affinity of these chelators for the metal ion should not be a sufficient criterion, but the metal specificity and the ability of the chelators to release the metal under specific biological conditions should be considered. Such an approach is still largely unexplored. The requirements for the chelators are very high (ability to cross the brain-blood barrier, lack of toxicity, etc.), few chemical series were proposed, and, among them, biochemical or biological data are scarce. As a matter of fact, the bioinorganic pharmacology of AD represents less than 1% of all articles dedicated to AD drug research. The major part of these articles deals with an old and rather toxic drug, clioquinol and related analogs, that

  4. Transition-metal-catalyzed Chelation-assisted C-H Functionalization of Aromatic Substrates.

    PubMed

    Zhao, Binlin; Shi, Zhuangzhi; Yuan, Yu

    2016-04-01

    In the past decade, transition-metal-catalyzed C-H activations have been very popular in the research field of organometallic chemistry, and have been considered as efficient and convenient strategies to afford complex natural products, functional advanced materials, fluorescent compounds, and pharmaceutical compounds. In this account, we begin with a brief introduction to the development of transition-metal-catalyzed C-H activation, especially the development of transition-metal-catalyzed chelation-assisted C-H activation. Then, a more detailed discussion is directed towards our recent studies on the transition-metal-catalyzed chelation-assisted oxidative C-H/C-H functionalization of aromatic substrates bearing directing functional groups.

  5. Transition-metal-catalyzed Chelation-assisted C-H Functionalization of Aromatic Substrates.

    PubMed

    Zhao, Binlin; Shi, Zhuangzhi; Yuan, Yu

    2016-04-01

    In the past decade, transition-metal-catalyzed C-H activations have been very popular in the research field of organometallic chemistry, and have been considered as efficient and convenient strategies to afford complex natural products, functional advanced materials, fluorescent compounds, and pharmaceutical compounds. In this account, we begin with a brief introduction to the development of transition-metal-catalyzed C-H activation, especially the development of transition-metal-catalyzed chelation-assisted C-H activation. Then, a more detailed discussion is directed towards our recent studies on the transition-metal-catalyzed chelation-assisted oxidative C-H/C-H functionalization of aromatic substrates bearing directing functional groups. PMID:26968749

  6. Jacks of metal/metalloid chelation trade in plants-an overview.

    PubMed

    Anjum, Naser A; Hasanuzzaman, Mirza; Hossain, Mohammad A; Thangavel, Palaniswamy; Roychoudhury, Aryadeep; Gill, Sarvajeet S; Rodrigo, Miguel A Merlos; Adam, Vojtěch; Fujita, Masayuki; Kizek, Rene; Duarte, Armando C; Pereira, Eduarda; Ahmad, Iqbal

    2015-01-01

    Varied environmental compartments including soils are being contaminated by a myriad toxic metal(loid)s (hereafter termed as "metal/s") mainly through anthropogenic activities. These metals may contaminate food chain and bring irreparable consequences in human. Plant-based approach (phytoremediation) stands second to none among bioremediation technologies meant for sustainable cleanup of soils/sites with metal-contamination. In turn, the capacity of plants to tolerate potential consequences caused by the extracted/accumulated metals decides the effectiveness and success of phytoremediation system. Chelation is among the potential mechanisms that largely govern metal-tolerance in plant cells by maintaining low concentrations of free metals in cytoplasm. Metal-chelation can be performed by compounds of both thiol origin (such as GSH, glutathione; PCs, phytochelatins; MTs, metallothioneins) and non-thiol origin (such as histidine, nicotianamine, organic acids). This paper presents an appraisal of recent reports on both thiol and non-thiol compounds in an effort to shed light on the significance of these compounds in plant-metal tolerance, as well as to provide scientific clues for the advancement of metal-phytoextraction strategies.

  7. Jacks of metal/metalloid chelation trade in plants-an overview.

    PubMed

    Anjum, Naser A; Hasanuzzaman, Mirza; Hossain, Mohammad A; Thangavel, Palaniswamy; Roychoudhury, Aryadeep; Gill, Sarvajeet S; Rodrigo, Miguel A Merlos; Adam, Vojtěch; Fujita, Masayuki; Kizek, Rene; Duarte, Armando C; Pereira, Eduarda; Ahmad, Iqbal

    2015-01-01

    Varied environmental compartments including soils are being contaminated by a myriad toxic metal(loid)s (hereafter termed as "metal/s") mainly through anthropogenic activities. These metals may contaminate food chain and bring irreparable consequences in human. Plant-based approach (phytoremediation) stands second to none among bioremediation technologies meant for sustainable cleanup of soils/sites with metal-contamination. In turn, the capacity of plants to tolerate potential consequences caused by the extracted/accumulated metals decides the effectiveness and success of phytoremediation system. Chelation is among the potential mechanisms that largely govern metal-tolerance in plant cells by maintaining low concentrations of free metals in cytoplasm. Metal-chelation can be performed by compounds of both thiol origin (such as GSH, glutathione; PCs, phytochelatins; MTs, metallothioneins) and non-thiol origin (such as histidine, nicotianamine, organic acids). This paper presents an appraisal of recent reports on both thiol and non-thiol compounds in an effort to shed light on the significance of these compounds in plant-metal tolerance, as well as to provide scientific clues for the advancement of metal-phytoextraction strategies. PMID:25883598

  8. A comparison of chelator-facilitated metal uptake by a halophyte and a glycophyte.

    PubMed

    Jordan, Fiona L; Robin-Abbott, Molly; Maier, Raina M; Glenn, Edward P

    2002-12-01

    Phytoextraction is the use of plants to remove contaminants, in particular metals, from soil via root uptake and translocation to the shoots. Efficient phytoextraction requires high-biomass plants with efficient translocating properties. Halophytes characteristically accumulate large quantities of salts in above ground tissue material and can have high biomass production. It has been speculated that salt-tolerant plants may also be heavy metal tolerant and, further, may be able to accumulate metals. This study compared growth and metal uptake by a halophyte, Atriplex nummularia, and a common glycophyte, Zea mays, in a mine-tailing contaminated soil:mulch mixture. Two chelators, ethylenediaminetetraacetic acid (EDTA) and rhamnolipid, were used to facilitate plant metal uptake. Despite a lower growth rate (2% growth/d) in the contaminated soil, the halophyte accumulated roughly the same amount of metals as the glycophyte on a mass basis (30-40 mg/kg dry wt). Neither plant, however, hyperaccumulated any of the metals tested. When treated with EDTA, specific differences in patterns of metal uptake between the two plants emerged. The halophyte accumulated significantly more Cu (2x) and Pb (1x) in the shoots than the glycophyte, but root metal concentrations were generally higher for the glycophyte, indicating that the halophyte translocated more metal from the root to the shoot than the glycophyte. For example, Zn shoot-to-root ratios ranged from 1.4 to 2.1 for Atriplex and from 0.5 to 0.6 for Z. mays. The biodegradable chelator rhamnolipid was not effective at enhancing shoot metal concentrations, even though radiolabeled chelator was found in the shoot material of both plants. Our results suggest that halophytes, despite their slower growth rates, may have greater potential to selectively phytoextract metals from contaminated soils than glycophytes. PMID:12463567

  9. Heavy Metal Displacement in Chelate-Assisted Phytoremediation of Biosolids Soil

    NASA Astrophysics Data System (ADS)

    Kirkham, M. B.; Liphadzi, M. S.

    2005-05-01

    Heavy metals in biosolids (sewage sludge) applied to land contaminate the soil. Phytoremediation, the use of plants to clean up toxic heavy metals, might remove them. Chelating agents are added to soil to solubilize the metals for enhanced phytoextraction. Yet no studies follow the displacement and leaching of heavy metals in soil with biosolids following solubilization with chelates. The objective of this work was to determine the mobility of heavy metals, as affected by a chelate, in soil (Haynie very fine sandy loam) from a 25-year old sludge farm. Soil columns (105 cm long; 39 cm in diameter) either had a plant (hybrid poplar; Populus deltoides Marsh. x P. nigra L.) or no plant. When the poplars were 144 days old, the tetrasodium salt of the chelating agent EDTA (ethylenediamine-tetraacetic acid) was irrigated onto the soil at a rate of 1 g per kg of soil. Drainage water, soil, and plants were analyzed for three toxic heavy metals (Cd, Ni, Pb) and four essential heavy metals (Cu, Fe, Mn, Zn). Without EDTA, concentrations of the seven heavy metals in the leachate from columns with or without plants were low or below detection limits. With or without plants, the EDTA mobilized all heavy metals and increased their concentration in drainage water. Without plants, the concentrations of Cd, Cu, Fe, Pb, and Zn in the leachate from columns with EDTA were above drinking-water standards. (There is no drinking-water standard for Ni.) The presence of poplar plants in the soil reduced the concentrations of Cu, Fe, and Zn in the leachate so it fell within drinking-water standards. Concentrations of Cd and Pb in the leachate remained above drinking-water standards with or without plants. At harvest (124 days after the EDTA application), total concentration of each heavy metal in the soil at different depths in the columns with EDTA was similar to that in the columns without EDTA. The chelate did not affect the concentration of heavy metals in the roots, stems, or leaves

  10. Pressure assisted chelating extraction: a novel technique for digesting metals in solid matrices.

    PubMed

    Wanekaya, Adam K; Myung, Sunnie; Sadik, Omowunmi A

    2002-09-01

    This work describes a novel technique for the digestion of metals in solid matrices. The technique is called pressure assisted chelating extraction (PACE). In a typical procedure, a solid sample is placed in a stainless steel cell and is mixed with appropriate chelating agents. Using a programmed sequence of temperature, static time, pressure and thermal equilibration available in ASE 200, the metal is removed under moderate temperature (up to 200 degrees C) and pressure (up to 3000 psi). PACE achieves metal recovery that is equivalent to that of wet digestion techniques and also provides for a clean and safe operation by substituting the strong acids commonly used during wet digestion with chelating agents. It uses less solvents and significantly less time (minutes vs. hours) for metal digestion. PACE has been validated using certified standard reference materials (SRMs) including industrial sludge, buffalo river sediments and coal fly ash. The total time required to remove metals was approximately 20 min. Results show that the PACE system provides an ideal platform for efficient, rapid, and safe metal digestion. Good agreement between measured and reference values for Pb, Mn, and Cu were found with recoveries averaging between 80 and 101% and a relative standard deviation of less than 5%. This approach may provide an alternative digestion technique for environmental samples, alloys, biological materials and samples of geological importance. The potential advantage offered lies in non-destruction of the sample, automation and the exclusion of concentrated mineral acids during the digestion procedure.

  11. 8-Hydroxyquinolines: a review of their metal chelating properties and medicinal applications

    PubMed Central

    Prachayasittikul, Veda; Prachayasittikul, Supaluk; Ruchirawat, Somsak; Prachayasittikul, Virapong

    2013-01-01

    Metal ions play an important role in biological processes and in metal homeostasis. Metal imbalance is the leading cause for many neurodegenerative diseases such as Alzheimer’s disease, Parkinson’s disease, and multiple sclerosis. 8-Hydroxyquinoline (8HQ) is a small planar molecule with a lipophilic effect and a metal chelating ability. As a result, 8HQ and its derivatives hold medicinal properties such as antineurodegenerative, anticancer, antioxidant, antimicrobial, anti-inflammatory, and antidiabetic activities. Herein, diverse bioactivities of 8HQ and newly synthesized 8HQ-based compounds are discussed together with their mechanisms of actions and structure–activity relationships. PMID:24115839

  12. 8-Hydroxyquinolines: a review of their metal chelating properties and medicinal applications.

    PubMed

    Prachayasittikul, Veda; Prachayasittikul, Supaluk; Ruchirawat, Somsak; Prachayasittikul, Virapong

    2013-01-01

    Metal ions play an important role in biological processes and in metal homeostasis. Metal imbalance is the leading cause for many neurodegenerative diseases such as Alzheimer's disease, Parkinson's disease, and multiple sclerosis. 8-Hydroxyquinoline (8HQ) is a small planar molecule with a lipophilic effect and a metal chelating ability. As a result, 8HQ and its derivatives hold medicinal properties such as antineurodegenerative, anticancer, antioxidant, antimicrobial, anti-inflammatory, and antidiabetic activities. Herein, diverse bioactivities of 8HQ and newly synthesized 8HQ-based compounds are discussed together with their mechanisms of actions and structure-activity relationships.

  13. Jacks of metal/metalloid chelation trade in plants—an overview

    PubMed Central

    Anjum, Naser A.; Hasanuzzaman, Mirza; Hossain, Mohammad A.; Thangavel, Palaniswamy; Roychoudhury, Aryadeep; Gill, Sarvajeet S.; Rodrigo, Miguel A. Merlos; Adam, Vojtěch; Fujita, Masayuki; Kizek, Rene; Duarte, Armando C.; Pereira, Eduarda; Ahmad, Iqbal

    2015-01-01

    Varied environmental compartments including soils are being contaminated by a myriad toxic metal(loid)s (hereafter termed as “metal/s”) mainly through anthropogenic activities. These metals may contaminate food chain and bring irreparable consequences in human. Plant-based approach (phytoremediation) stands second to none among bioremediation technologies meant for sustainable cleanup of soils/sites with metal-contamination. In turn, the capacity of plants to tolerate potential consequences caused by the extracted/accumulated metals decides the effectiveness and success of phytoremediation system. Chelation is among the potential mechanisms that largely govern metal-tolerance in plant cells by maintaining low concentrations of free metals in cytoplasm. Metal-chelation can be performed by compounds of both thiol origin (such as GSH, glutathione; PCs, phytochelatins; MTs, metallothioneins) and non-thiol origin (such as histidine, nicotianamine, organic acids). This paper presents an appraisal of recent reports on both thiol and non-thiol compounds in an effort to shed light on the significance of these compounds in plant-metal tolerance, as well as to provide scientific clues for the advancement of metal-phytoextraction strategies. PMID:25883598

  14. Product Release Rather than Chelation Determines Metal Specificity for Ferrochelatase

    SciTech Connect

    Medlocka, Amy E.; Cartera, Michael; Daileya, Tamara A.; Daileya, Harry A.; Lanzilotta, William N.

    2009-11-16

    Ferrochelatase (protoheme ferrolyase, E.C. 4.99.1.1) is the terminal enzyme in heme biosynthesis and catalyzes the insertion of ferrous iron into protoporphyrin IX to form protoheme IX (heme). Within the past two years, X-ray crystallographic data obtained with human ferrochelatase have clearly shown that significant structural changes occur during catalysis that are predicted to facilitate metal insertion and product release. One unanswered question about ferrochelatase involves defining the mechanism whereby some metals, such as divalent Fe, Co, Ni, and Zn, can be used by the enzyme in vitro to produce the corresponding metalloporphyrins, while other metals, such as divalent Mn, Hg, Cd, or Pb, are inhibitors of the enzyme. Through the use of high-resolution X-ray crystallography along with characterization of metal species via their anomalous diffraction, the identity and position of Hg, Cd, Ni, or Mn in the center of enzyme-bound porphyrin macrocycle were determined. When Pb, Hg, Cd, or Ni was present in the macrocycle, the conserved {pi} helix was in the extended, partially unwound 'product release' state. Interestingly, in the structure of ferrochelatase with Mn-porphyrin bound, the {pi} helix is not extended or unwound and is in the 'substrate-bound' conformation. These findings show that at least in the cases of Mn, Pb, Cd, and Hg, metal 'inhibition' of ferrochelatase is not due to the inability of the enzyme to insert the metal into the macrocycle or by binding to a second metal binding site as has been previously proposed. Rather, inhibition occurs after metal insertion and results from poor or diminished product release. Possible explanations for the lack of product release are proposed herein.

  15. Synthesis, Characterization, and Application of Metal-Chelating Polymers for Mass Cytometric Bioassays

    NASA Astrophysics Data System (ADS)

    Majonis, Daniel

    This thesis describes the synthesis, characterization, and application of metal-chelating polymers for mass-cytometric bioassays. Mass cytometry is a cell characterization technique in which cells are injected individually into an ICP-MS detector. Signal is provided by staining cell-surface or intracellular antigens with metal-labeled antibodies (Abs). These Abs are labeled through the covalent attachment of metal-chelating polymers which carry multiple copies of a lanthanide isotope. In this work, my first goal was to develop a facile, straightforward synthesis of a new generation of metal-chelating polymers. The synthesis began with reversible addition-fragmentation chain transfer polymerization, and was followed by numerous post-polymerization pendant group transformations to introduce DTPA lanthanide chelators to every repeat unit, and a maleimide at the end of the chain. The second goal was to apply these metal-chelating polymers in bioassay experiments. The DTPA groups were loaded with lanthanide ions, and the maleimide group was used to covalently attach the polymer to an Ab. This goat anti-mouse conjugate was found to carry an average of 2.4 +/- 0.3 polymer chains. Then, primary Ab conjugates were prepared and used in an 11-plex mass cytometry assay in the characterization of umbilical cord blood cells. The third goal was to expand the multiplexity of the assay. In current technology, the number of Abs that can be monitored simultaneously is limited to the 31 commercially available, stable lanthanide isotopes. Thus, I had an interest in preparing metal-chelating polymers that could carry other metals in the 100-220 amu range. I synthesized polymers with four different polyaminocarboxylate ligands, and investigated the loading of palladium and platinum ions into these polymers. Polymer-Ab conjugates prepared with palladium- and platinum-loaded polymers gave curious results, in that only dead cells were recognized. The fourth goal was to create dual

  16. Heavy Metals, Cardiovascular Disease, and the Unexpected Benefits of Chelation Therapy.

    PubMed

    Lamas, Gervasio A; Navas-Acien, Ana; Mark, Daniel B; Lee, Kerry L

    2016-05-24

    This review summarizes evidence from 2 lines of research previously thought to be unrelated: the unexpectedly positive results of TACT (Trial to Assess Chelation Therapy), and a body of epidemiological data showing that accumulation of biologically active metals, such as lead and cadmium, is an important risk factor for cardiovascular disease. Considering these 2 areas of work together may lead to the identification of new, modifiable risk factors for atherosclerotic cardiovascular disease. We examine the history of chelation up through the report of TACT. We then describe work connecting higher metal levels in the body with the future risk of cardiovascular disease. We conclude by presenting a brief overview of a newly planned National Institutes of Health trial, TACT2, in which we will attempt to replicate the findings of TACT and to establish that removal of toxic metal stores from the body is a plausible mechanistic explanation for the benefits of edetate disodium treatment.

  17. Actinide chelation: biodistribution and in vivo complex stability of the targeted metal ions.

    PubMed

    Kullgren, Birgitta; Jarvis, Erin E; An, Dahlia D; Abergel, Rebecca J

    2013-01-01

    Because of the continuing use of nuclear fuel sources and heightened threats of nuclear weapon use, the amount of produced and released radionuclides is increasing daily, as is the risk of larger human exposure to fission product actinides. A rodent model was used to follow the in vivo distribution of representative actinides, administered as free metal ions or complexed with chelating agents including diethylenetriamine pentaacetic acid (DTPA) and the hydroxypyridinonate ligands 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO). Different metabolic pathways for the different metal ions were evidenced, resulting in intricate ligand- and metal-dependent decorporation mechanisms. While the three studied chelators are known for their unrivaled actinide decorporation efficiency, the corresponding metal complexes may undergo in vivo decomposition and release metal ions in various biological pools. This study sets the basis to further explore the metabolism and in vivo coordination properties of internalized actinides for the future development of viable therapeutic chelating agents. PMID:22957518

  18. Actinide chelation: biodistribution and in vivo complex stability of the targeted metal ions.

    PubMed

    Kullgren, Birgitta; Jarvis, Erin E; An, Dahlia D; Abergel, Rebecca J

    2013-01-01

    Because of the continuing use of nuclear fuel sources and heightened threats of nuclear weapon use, the amount of produced and released radionuclides is increasing daily, as is the risk of larger human exposure to fission product actinides. A rodent model was used to follow the in vivo distribution of representative actinides, administered as free metal ions or complexed with chelating agents including diethylenetriamine pentaacetic acid (DTPA) and the hydroxypyridinonate ligands 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO). Different metabolic pathways for the different metal ions were evidenced, resulting in intricate ligand- and metal-dependent decorporation mechanisms. While the three studied chelators are known for their unrivaled actinide decorporation efficiency, the corresponding metal complexes may undergo in vivo decomposition and release metal ions in various biological pools. This study sets the basis to further explore the metabolism and in vivo coordination properties of internalized actinides for the future development of viable therapeutic chelating agents.

  19. Solid-phase materials for chelating metal ions and methods of making and using same

    DOEpatents

    Harrup, Mason K.; Wey, John E.; Peterson, Eric S.

    2003-06-10

    A solid material for recovering metal ions from aqueous streams, and methods of making and using the solid material, are disclosed. The solid material is made by covalently bonding a chelating agent to a silica-based solid, or in-situ condensing ceramic precursors along with the chelating agent to accomplish the covalent bonding. The chelating agent preferably comprises a oxime type chelating head, preferably a salicylaldoxime-type molecule, with an organic tail covalently bonded to the head. The hydrocarbon tail includes a carbon-carbon double bond, which is instrumental in the step of covalently bonding the tail to the silica-based solid or the in-situ condensation. The invented solid material may be contacted directly with aqueous streams containing metal ions, and is selective to ions such as copper (II) even in the presence of such ions as iron (III) and other materials that are present in earthen materials. The solid material with high selectivity to copper may be used to recover copper from mining and plating industry streams, to replace the costly and toxic solvent extraction steps of conventional copper processing.

  20. Essential trace metal excretion from rats with lead exposure and during chelation therapy.

    PubMed

    Victery, W; Miller, C R; Goyer, R A

    1986-02-01

    Urinary excretion of lead, zinc, calcium, magnesium, iron, copper, sodium, and potassium was measured in rats daily for 1 week after a 6-week exposure to 10,000 micrograms/ml lead in drinking water. Beginning on the third day, half of the lead-exposed and control rats were injected intraperitoneally with calcium disodium ethylenediaminetetraacetate (EDTA) daily for 3 days. Whole blood, plasma, and kidney metal concentrations were determined from samples obtained at the end of the experiment. Exposure to lead increased urinary excretion, not only of lead, but also of calcium, magnesium, zinc, copper, and iron. Excretion of sodium and potassium was not altered. Chelation therapy further increased excretion of lead, zinc, copper, and iron, but not magnesium. The increase in calcium excretion during chelation treatment (beyond that resulting from lead exposure per se) was accounted for by the Ca content of CaNa2-EDTA. EDTA treatment increased renal concentration of zinc but lowered renal concentration of lead, copper, and iron. These multimetal alterations may have implications for essential metal supplementation, particularly zinc, in persons being given chelation agents for excess lead exposure and in infants and children with low-level lead exposure not necessarily requiring chelation therapy.

  1. Immobilized triazacyclononane derivatives as selective oxidation catalysts. Final technical report of DOE Award No. DE-FG02-99ER14968 with the University of Munich [Encapsulation of metal chelate and oxocatalysts in nanoporous hosts

    SciTech Connect

    Bein, Thomas

    2002-10-28

    This project deals with the covalent anchoring of various derivatives of triazacyclononane (TACN)ligands in the channels of period mesoporous materials and the catalytic activity of the corresponding metal complexes. Catalyst preparation, ligand immobilization, catalyst characterization, and catalyst performance in selective oxidation are discussed. A wide range of pendant variations on the TACN ligand can be synthesized, and ligands can be covalently bound to high surface area, pseudo-crystalline, silicate solids, before or after pendant addition.

  2. The cation-chelation mechanism of metal-ion sorption by polyurethanes.

    PubMed

    Hamon, R F; Khan, A S; Chow, A

    1982-04-01

    The mechanism of sorption of ions by polyurethanes has been investigated through detailed studies of the extraction of cobalt(II) thiocyanate and the salts of several organic acids. Polyether-based polyurethanes. particularly those containing poly(ethylene oxide), were found to be distinctly superior to polyesters in the sorption of salts and performed much better than might be expected by analogy with monomeric liquid solvents. The results were judged to be inconsistent with several possible mechanisms, including adsorption, solvent extraction, weak or strong base anion-exchange, and complexation of metal anions by the polymer. A new proposal, termed the cation chelation mechanism (CCM), was advanced to account for the observations. In this view, a number of cations (including those of the alkali metals, alkaline earth metals, some transition metals, NH(+)(4), RNH(+)(3) and perhaps H(3)O(+)) may be multiply complexed (chelated) by portions of the polymer, thus facilitating the sorption of accompanying anions. As predicted by the mechanism, moderately strong and selective complexation of several cations was observed to occur with the following order of selectivity: Li(+) < Na(+) < Cs(+) < Rb(+) < K(+) approximately NH(+)(4) < Ag(+) approximately Tl(+) < Ba(2+) < Hg(2+) < Pb(2+). Such behaviour parallels that known for many crown and non-cyclic polyethers and is therefore identified with the polyether portions of the polymer, which are thought to adopt helical conformations surrounding the complexed cations. The cation-chelation mechanism may be widely applicable to the sorption of ions of several types by polyether-based polyurethanes, particularly when large, hydrophobic anions (such as anionic metal complexes) are accompanied by an excess of chelatable cations. PMID:18963133

  3. Mobilization of metals during treatment of contaminated soils by modified Fenton's reagent using different chelating agents.

    PubMed

    Bennedsen, Lars R; Krischker, Anne; Jørgensen, Torben H; Søgaard, Erik G

    2012-01-15

    Changes in pH and redox conditions and the application of chelating agents when applying in situ chemical oxidation (ISCO) for remediation of contaminated sites can cause mobilization of metals to the groundwater above threshold limit values. The mechanisms causing the mobilization are not fully understood and have only been investigated in few studies. The present work investigated the mobilization of 9 metals from two very different contaminated soils in bench and pilot tests during treatment with modified Fenton's reagent (MFR) and found significant mobilization of Cu and Pb to the water in mg/l levels. Also Fe, As, Mn, Ni, Zn, Mg, and Ca mobilization was observed. These findings were confirmed in a pilot test where concentrations of Cu and Pb up to 52.2 and 33.7 mg/l were observed, respectively. Overall, the chelating agents tested (EDTA, citrate and pyrophosphate) did not seem to increase mobilization of metals compared to treatment with only hydrogen peroxide and iron. The results strongly indicate that the mobilization is caused by hydrogen peroxide and reactive species including oxidants and reductants formed with MFR. Based on these results, the use of chelating agents for ISCO will not cause an increase in metal mobilization.

  4. Fluorescent chelates for monitoring metal binding with macromolecules.

    PubMed

    Islam, M; Khanin, M; Sadik, O A

    2003-01-01

    Metals and radionuclides are usually coupled with proteins together with suitable ligands for therapeutic, tumor-imaging, pharmaceuticals, and biocompatibility applications. Several ligands that can strongly coordinate a given nuclide in a specific valency are already known. However, the demand for bifunctionality has limited the applications of these ligands. We hereby report the molecular design of a receptor system based on the linkage of protein to monoazo ligands. By use of basic coordination chemistry, 4-(3-quinolinoazo)hydroxybenzoic acid (QABA) and derivatives were successfully conjugated to ovalbumin, bovine serum albumin, and alkaline phosphatase at a site that was distinct from the metal binding site. The presence of carboxylic acid linkage in the QABA served as a convenient bridge for protein conjugation and may allow the generic application of these ligands for bioconjugate synthesis while ensuring a high in vivo stability. The ligand-protein conjugates were characterized using UV-vis spectroscopy, Fourier transform infrared spectroscopy, thin layer chromatography, NMR, and surface-enhanced laser desorption ionization time-of-flight mass spectrometry. The conjugate was tested for the ability to recognize nonradioactive Ga(3+) at a physiological pH, and a binding constant of 1 x 10(20) was recorded. Also, the in vitro testing results indicated that the fluorescent conjugates exhibited significant selectivity for gallium compared to Pb(2+), Hg(2+), Zn(2+), Cu(2+), Fe(3+), and Co(2+) while no responses were obtained for alkaline and alkaline earth metals. These attributes could allow these conjugates to be used as a model for imaging sensors and for metal detection. PMID:12523855

  5. Spectroscopy, modeling and computation of metal chelate solubility in supercritical CO{sub 2}. Annual progress report, September 15, 1996--September 14, 1997

    SciTech Connect

    Brennecke, J.F.; Stadtherr, M.A.; Chateauneuf, J.E.

    1997-01-01

    'This progress report contains (1) a statement of the objectives of the overall project, (2) a discussion of the results obtained during the first year of the three year grant period, (3) a summary, (4) a description of the future work that will be pursued during the next year, and (5) accounting information. This is followed by the literature cited and the pertinent tables and figures. The overall objectives of this project are to gain a fundamental understanding of the solubility and stability of metal chelates in supercritical CO{sub 2}. Extraction with CO{sub 2} is a excellent way to remove organic compounds from soils, sludges and aqueous solutions and recent research has demonstrated that together with chelating agents it is a viable way to remove metals, as well. The authors seek to gain fundamental knowledge that is vital to computing phase behavior, and modeling and designing processes using CO{sub 2} to separate organics and metal compounds from DOE mixed wastes. The overall program is a comprehensive one to measure local solvation of metal chelates and to determine metal chelate stability in supercritical fluid mixtures using UV-vis and FTIR spectroscopy. The spectroscopic studies provide information on the solution microstructure, which they are using in concert with their own and published solubility data to evaluate and develop thermodynamic models of the solubility behavior. Finally, they are implementing a more reliable computational technique, based on interval mathematics, to compute the phase equilibria using the thermodynamic modeIs. This fundamental information about metal chelate stability and solubility in supercritical CO{sub 2} is important in the design of processes using CO{sub 2} to extract components from mixed wastes and in determining the optimum operating conditions.'

  6. Preparation, spectral, X-ray powder diffraction and computational studies and genotoxic properties of new azo-azomethine metal chelates

    NASA Astrophysics Data System (ADS)

    Bitmez, Şirin; Sayin, Koray; Avar, Bariş; Köse, Muhammet; Kayraldız, Ahmet; Kurtoğlu, Mükerrem

    2014-11-01

    A new tridentate azo-azomethine ligand, N‧-[{2-hydroxy-5-[(4-nitrophenyl)diazenyl]phenyl}methylidene]benzohydrazidemonohydrate, (sbH·H2O) (1), is prepared by condensation of benzohydrazide and 2-hydroxy-5-[(4-nitrophenyl)diazenyl]benzaldehyde (a) with treatment of a solution of diazonium salt of p-nitroaniline and 2-hydroxybenzaldehyde in EtOH. The five coordination compounds, [Co(sb)2]·4H2O (2), [Ni(sb)2]·H2O (3), [Cu(sb)2]·4H2O (4), [Zn(sb)2]·H2O (5) and [Cd(sb)2]·H2O (6) are prepared by reacting the Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with the ligand. The structures of the compounds are elucidated from the elemental analyses data and spectroscopic studies. It is found the ligand acts as a tridentate bending through phenolic and carbonyl oxygens and nitrogen atom of the Cdbnd Nsbnd group similar to the most of salicylaldimines. Comparison of the infrared spectra of the ligand and its metal complexes confirm that azo-Schiff base behaves as a monobasic tridentate ligand towards the central metal ion with an ONO donor sequence. Upon complexation with the ligand, the Cd(II), and Zn(II) ions form monoclinic structures, while Co(II), Cu(II) and Ni(II) ions form orthorhombic structures. Quantum chemical calculations are performed on tautomers and its metal chelates by using DFT/B3LYP method. Most stable tautomer is determined as tautomer (1a). The geometrical parameters of its metal chelates are obtained as theoretically. The NLO properties of tautomer (1a) and its metal complexes are investigated. Finally, the ligand and its metal complexes are assessed for their genotoxicity.

  7. Chelation gradients for investigation of metal ion binding at silica surfaces.

    PubMed

    Kannan, Balamurali; Higgins, Daniel A; Collinson, Maryanne M

    2014-08-26

    Centimeter-long surface gradients in bi- and tridentate chelating agents have been formed via controlled rate infusion, and the coordination of Cu(2+) and Zn(2+) to these surfaces has been examined as a function of distance by X-ray photoelectron spectroscopy (XPS). 3-(Trimethoxysilylpropyl)ethylenediamine and 3-(trimethoxysilylpropyl)diethylenetriamine were used as precursor silanes to form the chelation gradients. When the gradients were exposed to a metal ion solution, a series of coordination complexes formed along the length of the substrate. For both chelating agents at the three different concentrations studied, the amine content gradually increased from top to bottom as expected for a surface chemical gradient. While the Cu 2p peak area had nearly the same profile as nitrogen, the Zn 2p peak area did not and exhibited a plateau along much of the gradient. The normalized nitrogen-to-metal peak area ratio (N/M) was found to be highly dependent on the type of ligand, its surface concentration, and the type of metal ion. For Cu(2+), the N/M ratio ranged from 8 to 11 on the diamine gradient and was ∼4 on the triamine gradient, while for Zn(2+), the N/M ratio was 4-8 on diamine and 5-7 on triamine gradients. The extent of protonation of amine groups was higher for the diamine gradients, which could lead to an increased N/M ratio. Both 1:1 and 1:2 ligand/metal complexes along with dinuclear complexes are proposed to form, with their relative amounts dependent on the ligand, ligand density, and metal ion. Collectively, the methods and results described herein represent a new approach to study metal ion binding and coordination on surfaces, which is especially important to the extraction, preconcentration, and separation of metal ions.

  8. [Enhanced Phytoextraction of Heavy Metals from Contaminated Soils Using Sedum alfredii Hance with Biodegradable Chelate GLDA].

    PubMed

    Wei, Ze-bin; Chen, Xiao-hong; Wu, Qi-tang; Tan, Meng

    2015-05-01

    Chemically enhanced phytoextraction by hyperaccumulator has been proposed as an effective approach to remove heavy metals from contaminated soil. Pot experiment was conducted to investigate the effect of application of the biodegradable chelate GLDA (L glutamic acid N,N-diacetic acid) at different doses or the combination of GLDA with EDTA (ethylenediamine tetraacetic acid) or CIT (citric acid) on the uptake of Cd, Zn and Pb by Sedum alfredii Hance (a Zn and Cd hyperaccumulator). Experimental results showed that GLDA addition to soil significantly increased the concentrations of Cd and Zn in Sedum alfredii Hance and its Cd and Zn phytoextraction compared to the control. Additionally, GLDA at 2.5 mmol · kg(-1) resulted in the highest phytoextraction, being 2.5 and 2.6 folds of the control for Cd and Zn, respectively. However, the combined application of GLDA + EDTA (1:1) and GLDA + CIT (1 :1 and 1:3) at a total dose of 5 mmol · kg(-1) did not increase the phytoextraction of Zn and Cd, compared to the GLDA only treatment. Therefore, the biodegradable chelate GLDA could be regarded as a good chelate candidate for the phytoextraction of heavy metals of heavy metals from contaminated soils, particularly for Cd and Zn contaminated soils.

  9. Potentiometric responses of polymeric liquid membranes based on hydrophobic chelating agents to metal ions.

    PubMed

    Itoh, Y; Ueda, Y; Hirano, A; Sugawara, M; Tohda, K; Akaiwa, H; Umezawa, Y

    2001-05-01

    The effect of hydrophobicity of acidic chelating agents as sensing materials on the potentiometric responses of polymeric liquid membranes was investigated. The chelating agents tested were 8-quinolinol (HOx), dithizone (HDz), 1-(2-pyridylazo)-2-naphthol (PAN) and their alkylated analogues, 5-octyloxymethyl-8-quinolinol (HO8Q), di(phexylphenyl)thiocarbazone (C6HDz), 7-pentadecyloxy-1-(2-pyridylazo)-2-naphthol (C15PAN) and a series of N-alkylcarbonyl-N-phenylhydroxylamines (CnPHA, n = 3, 6, 9, 12). The distribution coefficients between membrane solvent and water were determined to evaluate the hydrophobicity of the agents. The potential-pH profiles of the membranes containing hydrophobic chelating agents demonstrated the generation of potentiometric responses, while less hydrophobic agents gave no response. A possible model for the generation of membrane potential is proposed. The charge separation is attained by the permselective uptake of metal cations by the chelating agent anion at membrane/solution interface, where the high hydrophobicity of the agent enables the anionic or deprotonated form of the agents to remain at the membrane/solution interface.

  10. Investigation of biologically-designed metal-specific chelators for potential metal recovery and waste remediation applications.

    SciTech Connect

    Criscenti, Louise Jacqueline; Ockwig, Nathan W.

    2009-01-01

    Bacteria, algae and plants produce metal-specific chelators to capture required nutrient or toxic trace metals. Biological systems are thought to be very efficient, honed by evolutionary forces over time. Understanding the approaches used by living organisms to select for specific metals in the environment may lead to design of cheaper and more effective approaches for metal recovery and contaminant-metal remediation. In this study, the binding of a common siderophore, desferrioxamine B (DFO-B), to three aqueous metal cations, Fe(II), Fe(III), and UO{sub 2}(VI) was investigated using classical molecular dynamics. DFO-B has three acetohydroxamate groups and a terminal amine group that all deprotonate with increasing pH. For all three metals, complexes with DFO-B (-2) are the most stable and favored under alkaline conditions. Under more acidic conditions, the metal-DFO complexes involve chelation with both acetohydroxamate and acetylamine groups. The approach taken here allows for detailed investigation of metal binding to biologically-designed organic ligands.

  11. Isothermal titration calorimetric procedure to determine protein-metal ion binding parameters in the presence of excess metal ion or chelator.

    PubMed

    Nielsen, Anders D; Fuglsang, Claus C; Westh, Peter

    2003-03-15

    Determination of binding parameters for metal ion binding to proteins usually requires preceding steps to remove protein-bound metal ions. Removal of bound metal ions from protein is often associated with decreased stability and inactivation. We present two simple isothermal titration calorimetric procedures that eliminate separate metal ion removal steps and directly monitor the exchange of metal ions between buffer, protein, and chelator. The concept is to add either excess chelator or metal ion to the protein under investigation and subsequently titrate with metal ion or chelator, respectively. It is thereby possible in the same experimental trial to obtain both chelator-metal ion and protein-metal ion binding parameters due to the different thermodynamic "fingerprints" of chelator and protein. The binding models and regression routines necessary to analyze the corresponding binding isotherms have been constructed. Verifications of the models have been done by titrations of mixtures of calcium chelators (BAPTA, HEDTA, and EGTA) and calcium ions and they were both able to account satisfactorily for the observed binding isotherms. Therefore, it was possible to determine stoichiometric and thermodynamic binding parameters. In addition, the concept has been tested on a recombinant alpha-amylase from Bacillus halmapalus where it proved to be a consistent procedure to obtain calcium binding parameters.

  12. Cellular Zn depletion by metal ion chelators (TPEN, DTPA and chelex resin) and its application to osteoblastic MC3T3-E1 cells

    PubMed Central

    Cho, Young-Eun; Lomeda, Ria-Ann R.; Ryu, Sang-Hoon; Lee, Jong-Hwa; Beattie, John H.

    2007-01-01

    Trace mineral studies involving metal ion chelators have been conducted in investigating the response of gene and protein expressions of certain cell lines but a few had really focused on how these metal ion chelators could affect the availability of important trace minerals such as Zn, Mn, Fe and Cu. The aim of the present study was to investigate the availability of Zn for the treatment of MC3T3-E1 osteoblast-like cells and the availability of some trace minerals in the cell culture media components after using chelexing resin in the FBS and the addition of N,N,N',N'-tetrakis-(2-pyridylmethyl)ethylenediamine (TPEN, membrane-permeable chelator) and diethylenetriaminepentaacetic acid (DTPA, membrane-impermeable chelator) in the treatment medium. Components for the preparation of cell culture medium and Zn-treated medium have been tested for Zn, Mn, Fe and Cu contents by atomic absorption spectrophotometer or inductively coupled plasma spectrophotometer. Also, the expression of bone-related genes (ALP, Runx2, PTH-R, ProCOL I, OPN and OC) was measured on the cellular Zn depletion such as chelexing or TPEN treatment. Results have shown that using the chelexing resin in FBS would significantly decrease the available Zn (p<0.05) (39.4 ± 1.5 µM vs 0.61 ± 10.15 µM) and Mn (p<0.05) (0.74 ± 0.01 µM vs 0.12 ± 0.04 µM). However, levels of Fe and Cu in FBS were not changed by chelexing FBS. The use of TPEN and DTPA as Zn-chelators did not show significant difference on the final concentration of Zn in the treatment medium (0, 3, 6, 9, 12 µM) except for in the addition of higher 15 µM ZnCl2 which showed a significant increase of Zn level in DTPA-chelated treatment medium. Results have shown that both chelators gave the same pattern for the expression of the five bone-related genes between Zn- and Zn+, and TPEN-treated experiments, compared to chelex-treated experiment, showed lower bone-related gene expression, which may imply that TPEN would be a stronger chelator

  13. Metal chelate affinity precipitation of RNA and purification of plasmid DNA

    NASA Technical Reports Server (NTRS)

    Balan, Sindhu; Murphy, Jason; Galaev, Igor; Kumar, Ashok; Fox, George E.; Mattiasson, Bo; Willson, Richard C.

    2003-01-01

    The affinity of metal chelates for amino acids, such as histidine, is widely used in purifying proteins, most notably through six-histidine 'tails'. We have found that metal affinity interactions can also be applied to separation of single-stranded nucleic acids through interactions involving exposed purines. Here we describe a metal affinity precipitation method to resolve RNA from linear and plasmid DNA. A copper-charged copolymer of N-isopropyl acrylamide (NIPAM) and vinyl imidazole (VI) is used to purify plasmid from an alkaline lysate of E. coli. The NIPAM units confer reversible solubility on the copolymer while the imidazole chelates metal ions in a manner accessible to interaction with soluble ligands. RNA was separated from the plasmid by precipitation along with the polymer in the presence of 800 mM NaCl. Bound RNA could be recovered by elution with imidazole and separated from copolymer by a second precipitation step. RNA binding showed a strong dependence on temperature and on the type of buffer used.

  14. Leaching heavy metals in municipal solid waste incinerator fly ash with chelator/biosurfactant mixed solution.

    PubMed

    Xu, Ying; Chen, Yu

    2015-07-01

    The chelator [S,S]-ethylene diamine disuccinic acid, citric acid, and biosurfactant saponin are selected as leaching agents. In this study, the leaching effect of saponin mixed with either ethylene diamine disuccinic acid or citric acid on the levels of copper, zinc, lead, and cadmium in municipal solid waste incinerator fly ash is investigated. Results indicate that saponin separately mixed with ethylene diamine disuccinic acid and citric acid exhibits a synergistic solubilisation effect on copper, zinc, lead, and cadmium leaching from fly ash. However, saponin and ethylene diamine disuccinic acid mixed solution exhibits a synergistic solubilisation effect that is superior to that of a saponin and citric acid mixed solution. The extraction rate of heavy metal in fly ash leached with a saponin and chelator mixed solution is related to the pH of the leaching solution, and the optimal range of the pH is suggested to be approximately neutral. After leaching with a saponin and chelator mixed solution, copper, zinc, lead, and cadmium contents significantly decreased (p < 0.05) in the extractable or acid-soluble and reducible fractions. By adopting the proposed approach, the leaching concentrations of copper, zinc, lead, and cadmium in treated fly ash are in accordance with Standard for Pollution Control on the Security Landfill Site for Hazardous Wastes GB18598-2001. PMID:26185165

  15. Spectral, biological screening of metal chelates of chalcone based Schiff bases of N-(3-aminopropyl) imidazole

    NASA Astrophysics Data System (ADS)

    Kalanithi, M.; Rajarajan, M.; Tharmaraj, P.; Sheela, C. D.

    2012-02-01

    Tridentate chelate complexes of Co(II), Ni(II), Cu(II) and Zn(II) have been synthesized from the chalcone based ligands 2-[1-(3-(1H-imidazol-1-yl)propylimino)-3-(phenylallyl)]phenol( HL1), 2-[1-(3-(1H-imidazol-1-yl)propylimino)-3-p-tolylallyl]phenol( HL2), 2-[1-(3-(1H-imidazol-1-yl)propylimino)-3-4-nitrophenylallyl]phenol( HL3). Microanalytical data, UV-vis spectrophotometric method, magnetic susceptibility measurements, IR, 1H NMR, Mass, and EPR techniques were used to characterize the structure of chelates. The electronic absorption spectra and magnetic susceptibility measurements suggest a distorted square planar geometry for the copper(II) ion. The other metal complexes show distorted tetrahedral geometry. The coordination of the ligands with metal(II) ions was further confirmed by solution fluorescence spectrum. The antimicrobial activity of the ligands and metal(II) complexes against the species Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Candida albigans and Aspergillus niger has been carried out and compared. The electrochemical behavior of copper(II) complex is studied by cyclic voltammetry.

  16. Curcumin derivatives as metal-chelating agents with potential multifunctional activity for pharmaceutical applications.

    PubMed

    Ferrari, Erika; Benassi, Rois; Sacchi, Stefania; Pignedoli, Francesca; Asti, Mattia; Saladini, Monica

    2014-10-01

    Curcuminoids represent new perspectives for the development of novel therapeutics for Alzheimer's disease (AD), one probable mechanism of action is related to their metal complexing ability. In this work we examined the metal complexing ability of substituted curcuminoids to propose new chelating molecules with biological properties comparable with curcumin but with improved stability as new potential AD therapeutic agents. The K2T derivatives originate from the insertion of a -CH2COOC(CH3)3 group on the central atom of the diketonic moiety of curcumin. They retain the diketo-ketoenol tautomerism which is solvent dependent. In aqueous solution the prevalent form is the diketo one but the addition of metal ion (Ga(3+), Cu(2+)) causes the dissociation of the enolic proton creating chelate complexes and shifting the tautomeric equilibrium towards the keto-enol form. The formation of metal complexes is followed by both NMR and UV-vis spectroscopy. The density functional theory (DFT) calculations on K2T21 complexes with Ga(3+) and Cu(2+) are performed and compared with those on curcumin complexes. [Ga(K2T21)2(H2O)2](+) was found more stable than curcumin one. Good agreement is detected between calculated and experimental (1)H and (13)C NMR data. The calculated OH bond dissociation energy (BDE) and the OH proton dissociation enthalpy (PDE), allowed to predict the radical scavenging ability of the metal ion complexed with K2T21, while the calculated electronic affinity (EA) and ionization potential (IP) represent yardsticks of antioxidant properties. Eventually theoretical calculations suggest that the proton-transfer-associated superoxide-scavenging activity is enhanced after binding metal ions, and that Ga(3+) complexes display possible superoxide dismutase (SOD)-like activity.

  17. Metal distribution and spectroscopic analysis after soil washing with chelating agents and humic substances.

    PubMed

    Tsang, Daniel C W; Hartley, Neil R

    2014-03-01

    Biodegradable chelating agents ([S,S]-ethylenediamine-N,N-disuccinic acid (EDDS) and glutamic-N,N-diacetic acid (GLDA)) and natural humic substances (lignite-derived, standard, and commercially available humic acids) are potentially useful for enhancing soil remediation of timber treatment sites. This study integrated macroscopic and spectroscopic analyses to assess their influence on the distribution and chemical speciation of the remaining metals as well as their interaction with the soil surface after 48-h washing of a field-contaminated soil. The results demonstrated that EDDS and GLDA were an appealing alternative to non-biodegradable ethylenediamine-tetraacetic acid, but the three humic substances were less effective. As shown by sequential extractions, Cu was primarily extracted from the carbonate fraction while Cr and As extraction resulted from (co-)dissolution of the oxide fraction. As a result, the relative proportion of strongly bound organic matter and residual fractions increased by 7-16 %. However, it was noteworthy that the exchangeable fraction also increased by 5-11 %, signifying that a portion of the remaining metals was destabilized by chelating agents and transformed to be more labile in the treated soil. The X-ray photoelectron spectroscopy spectra confirmed the substantial removal of readily accessible Cu from the soil surface, but Cr maintained its original chemical forms of trivalent chromium oxides and iron-chromium coprecipitates, whereas As remained as arsenic trioxide/pentoxide and copper arsenate precipitates. On the other hand, the absence of characteristic peaks of adsorbed carboxylate groups in the Fourier-transform infrared (FTIR) spectra inferred that the extent of adsorption of chelating agents and humic substances on the bulk soil was insufficient to be characterized by FTIR analysis. These results suggested that attention should be paid to the exchangeable fraction of Cu and oxides/coprecipitates of As prior to possible on

  18. Metal Chelation as a Powerful Strategy to Probe Cellular Circuitry Governing Fungal Drug Resistance and Morphogenesis

    PubMed Central

    Averette, Anna F.; Lee, Soo Chan; Kim, Taeyup; Bahn, Yong-Sun; Robbins, Nicole; Heitman, Joseph; Cowen, Leah E.

    2016-01-01

    Fungal pathogens have evolved diverse strategies to sense host-relevant cues and coordinate cellular responses, which enable virulence and drug resistance. Defining circuitry controlling these traits opens new opportunities for chemical diversity in therapeutics, as the cognate inhibitors are rarely explored by conventional screening approaches. This has great potential to address the pressing need for new therapeutic strategies for invasive fungal infections, which have a staggering impact on human health. To explore this approach, we focused on a leading human fungal pathogen, Candida albicans, and screened 1,280 pharmacologically active compounds to identify those that potentiate the activity of echinocandins, which are front-line therapeutics that target fungal cell wall synthesis. We identified 19 compounds that enhance activity of the echinocandin caspofungin against an echinocandin-resistant clinical isolate, with the broad-spectrum chelator DTPA demonstrating the greatest synergistic activity. We found that DTPA increases susceptibility to echinocandins via chelation of magnesium. Whole genome sequencing of mutants resistant to the combination of DTPA and caspofungin identified mutations in the histidine kinase gene NIK1 that confer resistance to the combination. Functional analyses demonstrated that DTPA activates the mitogen-activated protein kinase Hog1, and that NIK1 mutations block Hog1 activation in response to both caspofungin and DTPA. The combination has therapeutic relevance as DTPA enhanced the efficacy of caspofungin in a mouse model of echinocandin-resistant candidiasis. We found that DTPA not only reduces drug resistance but also modulates morphogenesis, a key virulence trait that is normally regulated by environmental cues. DTPA induced filamentation via depletion of zinc, in a manner that is contingent upon Ras1-PKA signaling, as well as the transcription factors Brg1 and Rob1. Thus, we establish a new mechanism by which metal chelation

  19. [Continuous remediation of heavy metal contaminated soil by co-cropping system enhanced with chelator].

    PubMed

    Wei, Ze-Bin; Guo, Xiao-Fang; Wu, Qi-Tang; Long, Xin-Xian

    2014-11-01

    In order to elucidate the continuous effectiveness of co-cropping system coupling with chelator enhancement in remediating heavy metal contaminated soils and its environmental risk towards underground water, soil lysimeter (0.9 m x 0.9 m x 0.9 m) experiments were conducted using a paddy soil affected by Pb and Zn mining in Lechang district of Guangdong Province, 7 successive crops were conducted for about 2.5 years. The treatments included mono-crop of Sedum alfredii Hance (Zn and Cd hyperaccumulator), mono-crop of corn (Zea mays, cv. Yunshi-5, a low-accumulating cultivar), co-crop of S. alfredii and corn, and co-crop + MC (Mixture of Chelators, comprised of citric acid, monosodium glutamate waste liquid, EDTA and KCI with molar ratio of 10: 1:2:3 at the concentration of 5 mmol x kg(-1) soil). The changes of heavy metal concentrations in plants, soil and underground water were monitored. Results showed that the co-cropping system was suitable only in spring-summer seasons and significantly increased Zn and Cd phytoextraction. In autumn-winter seasons, the growth of S. alfredii and its phytoextraction of Zn and Cd were reduced by co-cropping and MC application. In total, the mono-crops of S. alfredii recorded a highest phytoextraction of Zn and Cd. However, the greatest reduction of soil Zn, Cd and Pb was observed with the co-crop + MC treatment, the reduction rates were 28%, 50%, and 22%, respectively, relative to the initial soil metal content. The reduction of this treatment was mainly attributed to the downwards leaching of metals to the subsoil caused by MC application. The continuous monitoring of leachates during 2. 5 year's experiment also revealed that the addition of MC increased heavy metal concentrations in the leaching water, but they did not significantly exceed the III grade limits of the underground water standard of China.

  20. Adsorption of metal ions on polyaminated highly porous chitosan chelating resin

    SciTech Connect

    Kawamura, Yoshihide; Mitsuhashi, Masaki; Tanibe, Hiroaki ); Yoshida, Hiroyuki )

    1993-02-01

    Highly porous chelating resin was fabricated from the natural polysaccharide chitosan. The adsorption capacity was increased by polyamination with poly(ethylene imine) (MW = 10,000). The capacity was about 1-2 times larger than that of commercial chelate resins. The selectivity for adsorption of metal ions on the resin, which was determined for a single solute at pH [approx equal] 7, was Hg(II) > UO[sub 2](II) > Cd(II) > Zn(II) > Cu(II) > Ni(II). Mg(II), Ca(II), Ga(III), As(III), and Sr(II) were not adsorbed on the resin at all. The selectivity depended on the pH of each metal solution. The equilibrium isotherms for adsorption of HgCl[sub 2] were correlated by the Langmuir equation. The saturation capacities were close to the concentration of amino group fixed on the resin. When HCl or NaCl coexisted in HgCl[sub 2] solution and their concentrations were lower than 100 mol/m[sup 3], the saturation capacity of HgCl[sub 2] was little affected by them. When 500 mol/m[sup 3] H[sub 2]SO[sub 4] coexisted in HgCl[sub 2] solution, extremely low pH inhibited the adsorption of Hg(II) at all.

  1. Antioxidant, Metal Chelating, Anti-glucosidase Activities and Phytochemical Analysis of Selected Tropical Medicinal Plants

    PubMed Central

    Wong, Fai-Chu; Yong, Ann-Li; Ting, Evon Peir-Shan; Khoo, Sim-Chyi; Ong, Hean-Chooi; Chai, Tsun-Thai

    2014-01-01

    The purpose of this investigation was to determine the antioxidant potentials and anti-glucosidase activities of six tropical medicinal plants. The levels of phenolic constituents in these medicinal plants were also quantified and compared. Antioxidation potentials were determined colorimetrically for scavenging activities against DPPH and NO radicals. Metal chelating assay was based on the measurement of iron-ferrozine absorbance at 562 nm. Anti-diabetic potentials were measured by using α-glucosidase as target enzyme. Medicinal plants’ total phenolic, total flavonoid and hydroxycinnamic acid contents were determined using spectrophotometric methods, by comparison to standard plots prepared using gallic acid, quercetin and caffeic acid standards, respectively. Radical scavenging and metal chelating activities were detected in all medicinal plants, in concentration-dependent manners. Among the six plants tested, C. nutans, C. formosana and H. diffusa were found to possess α-glucosidase inhibitory activities. Spectrophotometric analysis indicated that the total phenolic, total flavonoid and hydroxycinnamic acid contents ranged from 12.13-21.39 mg GAE per g of dry sample, 1.83-9.86 mg QE per g of dry sample, and 0.91-2.74 mg CAE per g of dry sample, respectively. Our results suggested that C. nutans and C. formosana could potentially be used for the isolation of potent antioxidants and anti-diabetic compounds. To the best of our knowledge, this study represents the first time that C. nutans (Acanthaceae family) was reported in literature with glucosidase inhibition activity. PMID:25587331

  2. Free radical scavenging activity, metal chelation and antioxidant power of some of the Indian spices.

    PubMed

    Yadav, Amit Singh; Bhatnagar, Deepak

    2007-01-01

    Food constituents are the major source of various phytochemicals and micronutrients. The importance of these dietary constituents has been stressed in recent years due to their antioxidant and anticarcinogenic potential. Spices used in Indian foods such as cloves (Syzygium aromaticum), licorice (Glycyrrhiza glabra), mace (aril of Myristica fragans), and greater cardamom (Amomum subulatum) were tested for their antioxidant properties in vitro. The metal chelating activity, bleomycin dependent DNA oxidation, diphenyl-p-picryl hydrazyl (DPPH) radical scavenging activity and the ferric reducing /antioxidant power (FRAP) were measured in rat liver homogenate in presence of spices. Metal chelating activity was significantly high with all the spice extracts except mace. The spices due to higher reducing potential (in presence of bleomycin-FeCl_{3}) showed increased DNA oxidation. Cloves showed the highest DPPH radical scavenging activity, followed by licorice, mace and cardamom. FRAP values for cloves were also the highest, while other spices showed comparatively lesser FRAP values. The results show that the spices tested are strong antioxidants and may have beneficial effects on human health.

  3. A new morphological approach for removing acid dye from leather waste water: preparation and characterization of metal-chelated spherical particulated membranes (SPMs).

    PubMed

    Şenay, Raziye Hilal; Gökalp, Safiye Meriç; Türker, Evren; Feyzioğlu, Esra; Aslan, Ahmet; Akgöl, Sinan

    2015-03-15

    In this study, p(HEMA-GMA) poly(hydroxyethyl methacrylate-co-glycidyl methacrylate) spherical particulated membranes (SPMs) were produced by UV-photopolymerization and the synthesized SPMs were coupled with iminodiacetic acid (IDA). Finally the novel SPMs were chelated with Cr(III) ions as ligand and used for removing acid black 210 dye. Characterizations of the metal-chelated SPMs were made by SEM, FTIR and swelling test. The water absorption capacities and acid dye adsorption properties of the SPMs were investigated and the results were 245.0, 50.0, 55.0 and 51.9% for p(HEMA), p(HEMA-GMA), p(HEMA-GMA)-IDA and p(HEMA-GMA)-IDA-Cr(III) SPMs respectively. Adsorption properties of the p(HEMA-GMA)-IDA-Cr(III) SPMs were investigated under different conditions such as different initial dye concentrations and pH. The optimum pH was observed at 4.3 and the maximum adsorption capacity was determined as 885.14 mg/g at about 8000 ppm initial dye concentration. The concentrations of the dyes were determined using a UV/Vis Spectrophotometer at a wavelength of 435 nm. Reusability of p(HEMA-GMA)-IDA-Cr(III) SPMs was also shown for five adsorption-desorption cycles without considerable decrease in its adsorption capacity. Finally, the results showed that the metal-chelated p(HEMA-GMA)-IDA SPMs were effective sorbent systems removing acid dye from leather waste water.

  4. Nanogels from metal-chelating crosslinkers as versatile platforms applied to copper-64 PET imaging of tumors and metastases.

    PubMed

    Lux, Jacques; White, Alexander G; Chan, Minnie; Anderson, Carolyn J; Almutairi, Adah

    2015-01-01

    Metals are essential in medicine for both therapy and diagnosis. We recently created the first metal-chelating nanogel imaging agent, which employed versatile, reproducible chemistry that maximizes chelation stability. Here we demonstrate that our metal chelating crosslinked nanogel technology is a powerful platform by incorporating (64)Cu to obtain PET radiotracers. Polyacrylamide-based nanogels were crosslinked with three different polydentate ligands (DTPA, DOTA, NOTA). NOTA-based nanogels stably retained (64)Cu in mouse serum and accumulated in tumors in vivo as detected by PET/CT imaging. Measurement of radioactivity in major organs ex vivo confirmed this pattern, revealing a high accumulation (12.3% ID/g and 16.6% ID/g) in tumors at 24 and 48 h following administration, with lower accumulation in the liver (8.5% ID/g at 24 h) and spleen (5.5% ID/g). Nanogels accumulated even more efficiently in metastases (29.9% and 30.4% ID/g at 24 and 48 h). These metal-chelating nanogels hold great promise for future application as bimodal PET/MRI agents; chelation of β-emitting radionuclides could enable radiation therapy.

  5. Nanogels from Metal-Chelating Crosslinkers as Versatile Platforms Applied to Copper-64 PET Imaging of Tumors and Metastases

    PubMed Central

    Lux, Jacques; White, Alexander G.; Chan, Minnie; Anderson, Carolyn J.; Almutairi, Adah

    2015-01-01

    Metals are essential in medicine for both therapy and diagnosis. We recently created the first metal-chelating nanogel imaging agent, which employed versatile, reproducible chemistry that maximizes chelation stability. Here we demonstrate that our metal chelating crosslinked nanogel technology is a powerful platform by incorporating 64Cu to obtain PET radiotracers. Polyacrylamide-based nanogels were crosslinked with three different polydentate ligands (DTPA, DOTA, NOTA). NOTA-based nanogels stably retained 64Cu in mouse serum and accumulated in tumors in vivo as detected by PET/CT imaging. Measurement of radioactivity in major organs ex vivo confirmed this pattern, revealing a high accumulation (12.3% ID/g and 16.6% ID/g) in tumors at 24 and 48 h following administration, with lower accumulation in the liver (8.5% ID/g at 24 h) and spleen (5.5% ID/g). Nanogels accumulated even more efficiently in metastases (29.9% and 30.4% ID/g at 24 and 48 h). These metal-chelating nanogels hold great promise for future application as bimodal PET/MRI agents; chelation of β-emitting radionuclides could enable radiation therapy. PMID:25553115

  6. Nanogels from metal-chelating crosslinkers as versatile platforms applied to copper-64 PET imaging of tumors and metastases.

    PubMed

    Lux, Jacques; White, Alexander G; Chan, Minnie; Anderson, Carolyn J; Almutairi, Adah

    2015-01-01

    Metals are essential in medicine for both therapy and diagnosis. We recently created the first metal-chelating nanogel imaging agent, which employed versatile, reproducible chemistry that maximizes chelation stability. Here we demonstrate that our metal chelating crosslinked nanogel technology is a powerful platform by incorporating (64)Cu to obtain PET radiotracers. Polyacrylamide-based nanogels were crosslinked with three different polydentate ligands (DTPA, DOTA, NOTA). NOTA-based nanogels stably retained (64)Cu in mouse serum and accumulated in tumors in vivo as detected by PET/CT imaging. Measurement of radioactivity in major organs ex vivo confirmed this pattern, revealing a high accumulation (12.3% ID/g and 16.6% ID/g) in tumors at 24 and 48 h following administration, with lower accumulation in the liver (8.5% ID/g at 24 h) and spleen (5.5% ID/g). Nanogels accumulated even more efficiently in metastases (29.9% and 30.4% ID/g at 24 and 48 h). These metal-chelating nanogels hold great promise for future application as bimodal PET/MRI agents; chelation of β-emitting radionuclides could enable radiation therapy. PMID:25553115

  7. Developments in asymmetric catalysis by metal complexes of chiral chelating nitrogen-donor ligands.

    PubMed

    Caputo, Christine A; Jones, Nathan D

    2007-11-01

    In part because of their straightforward and modular syntheses from readily available enantiopure starting materials, and their capacity to bind a wide variety of transition metals, chiral, chelating nitrogen-donor ligands have played a prominent role in asymmetric catalysis. A large number of highly enantioselective transformations rely upon these ligands whose reported classes are built around amine, imine, pyrrole, pyrrolidine, oxazoline and oxazolidine donor groups, among others. In this Perspective, we examine a selection of transformative developments in asymmetric catalysis by metal complexes of bi- and polydentate members of this ligand family. We describe approaches to ligand design and synthesis, structure and bonding in coordination complexes, and limitations and future challenges. PMID:17940641

  8. Effects of trientine, a metal chelator, on defective endothelium-dependent relaxation in the mesenteric vasculature of diabetic rats.

    PubMed

    Inkster, Melanie E; Cotter, Mary A; Cameron, Norman E

    2002-10-01

    Diabetes mellitus compromises endothelium-dependent relaxation of blood vessels. This has been linked to the generation of reactive oxygen species (ROS), which neutralise nitric oxide (NO) and interfere with vasodilator function. Experiments using chelators have emphasised the importance of ROS produced by transition metal catalysed reactions. However, particularly for the small arteries and arterioles that control microcirculatory blood flow, NO is not the only endothelium-derived mediator; endothelium-derived hyperpolarizing factor (EDHF) has a major role. EDHF-mediated vasodilation is severely curtailed by diabetes; however, little information exists on the underlying pathophysiology. Deficits in the EDHF system, alone or in combination with the NO system, are crucial for the development of diabetic microvascular complications. To further elucidate the mechanisms involved, the aim was to examine the effects of diabetes and preventive and intervention chelator therapy with trientine on a preparation that has well-defined NO and EDHF-mediated responses, the rat mesenteric vascular bed. In phenylephrine-preconstricted preparations, maximum vasodilation to acetylcholine was reduced by 35 and 44% after 4 and 8 weeks of streptozotocin-induced diabetes, respectively. Trientine treatment over the first 4 weeks gave 72% protection; intervention therapy over the final 4 weeks prevented deterioration and corrected the initial deficit by 68%. These responses depend on both NO and EDHF. When the latter mechanism was isolated by NO synthase inhibition, diabetic deficits of 53.4 (4 weeks) and 65.4% (8 weeks) were revealed, that were 65% prevented and 50% corrected by trientine treatment. Neither diabetes nor trientine altered vascular smooth muscle responses to the NO donor, sodium nitroprusside (SNP). Thus, the data suggest that metal catalysed ROS production makes a substantial contribution to defects in both the EDHF and NO endothelial mechanisms in diabetes, which has

  9. Effect of keratin on heavy metal chelation and toxicity to aquatic organisms

    SciTech Connect

    Coello, W.F.; Khan, M.A.Q.

    1998-12-31

    The presence of fresh scales and human hair in water can reduce the toxicity of lead nitrate at and above 6 ppb to fish. This ability is lost on drying and storage, but can be restored if dried hair or scales are treated with a solution of amino acids. The chelation ability of keratin in amino acid-treated scales or hair is retained for months on dry storage. Addition of these hair and/or scales to solutions of lead nitrate, mercuric chloride and a mixture of both, and cupric sulfate reduced the toxicity of these solutions to Daphnia magna and Dreissena polymorpha (zebra mussels). Toxicity of 10 ppm solutions of salts of 27 different metals to daphnids was similarly reduced after filtration through scales or hair. A mixture of a 2 ppb concentration of each of these 27 metals also became nonlethal to daphnids in the presence of, or filtration through, treated scales or hair. 0.25 g of treated hair or scale can be used indefinitely, again and again, to remove the mixture of these 27 metals from their fresh solution in 1 L water if the keratin is frequently rinsed with 0.1% nitric acid to remove the bound metals. The keratin in scales, this, may be the most important ectodermal secretion in absorbing metals from polluted environments and in providing protection against their toxic levels.

  10. Enhancing catalytic performance of β-glucosidase via immobilization on metal ions chelated magnetic nanoparticles.

    PubMed

    Chen, Tingting; Yang, Wenjuan; Guo, Yuling; Yuan, Renjun; Xu, Li; Yan, Yunjun

    2014-09-01

    A novel magnetic Fe3O4 nanoparticles (MNPs) coupled with agarose (AMNPs) was synthesized using co-precipitation via alkaline condition and span-80 surfactants in organic solvent. Iminodiacetate was first attached to the MNPs through epichlorohydrin agent and then chelated with metal ions. The morphology and chemical properties of these prepared supports were characterized by scanning electron microscopy (SEM), X-ray power diffraction (XRD), vibrating sample magnetometer (VSM), and Fourier transform infrared spectroscopy (FT-IR). Among them, the Co(2+)-chelated AMNPs (AMNPs-ECH-IDA-Co(2+)) showed the second highest enzyme adsorption capacity of 1.81 mg/g particles, and achieved the largest activity recovery of 117% per protein gram in immobilization of β-glucosidase (BGL). The Michaelis constant (Km) and Vmax of the immobilized BGL were 0.904 mM and 0.057 μmol/min, respectively, and its activation energy was much lower than the free form. Moreover, the immobilized enzyme exhibited enhanced thermostability and operational stability. It still retained more than 90% of its initial activity after being operated for 15 successive batches. This study demonstrates that the immobilized β-glucosidase has a good prospect in industrial applications. PMID:25039060

  11. Enhancing catalytic performance of β-glucosidase via immobilization on metal ions chelated magnetic nanoparticles.

    PubMed

    Chen, Tingting; Yang, Wenjuan; Guo, Yuling; Yuan, Renjun; Xu, Li; Yan, Yunjun

    2014-09-01

    A novel magnetic Fe3O4 nanoparticles (MNPs) coupled with agarose (AMNPs) was synthesized using co-precipitation via alkaline condition and span-80 surfactants in organic solvent. Iminodiacetate was first attached to the MNPs through epichlorohydrin agent and then chelated with metal ions. The morphology and chemical properties of these prepared supports were characterized by scanning electron microscopy (SEM), X-ray power diffraction (XRD), vibrating sample magnetometer (VSM), and Fourier transform infrared spectroscopy (FT-IR). Among them, the Co(2+)-chelated AMNPs (AMNPs-ECH-IDA-Co(2+)) showed the second highest enzyme adsorption capacity of 1.81 mg/g particles, and achieved the largest activity recovery of 117% per protein gram in immobilization of β-glucosidase (BGL). The Michaelis constant (Km) and Vmax of the immobilized BGL were 0.904 mM and 0.057 μmol/min, respectively, and its activation energy was much lower than the free form. Moreover, the immobilized enzyme exhibited enhanced thermostability and operational stability. It still retained more than 90% of its initial activity after being operated for 15 successive batches. This study demonstrates that the immobilized β-glucosidase has a good prospect in industrial applications.

  12. Biomimetic Taste Receptors with Chiral Recognition by Photoluminescent Metal-Organic Frameworks Chelated with Polyaniline Helices.

    PubMed

    Lee, Tu; Lin, Tsung Yan; Lee, Hung Lin; Chang, Yun Hsuan; Tsai, Yee Chen

    2016-01-22

    The adsorption of phenylaniline (Phe) enantiomers on (+)-polyaniline (PAN)-chelated [In(OH)(bdc)]n microcrystals was carefully designed and studied by using the Job titration, circular dichroism, X-ray photoelectron spectroscopy, and photoluminescence to mimic heterotrimeric guanine nucleotide-binding protein (G protein)-coupled receptors in selective, but not specific, ligand binding with chiral recognition and signal transduction. Six essential working principles across different length scales are unraveled: 1) a chiral (+)-PAN (host), 2) specific sites for Phe-(+)/PAN (guest-host) binding, 3) a conformational change of (+)-PAN after binding with Phe enantiomers, 4) different degrees of packing for (+)-PAN, 5) interactions between (+)-PAN and the underlying signal-generating framework (i.e., [In(OH)(bdc)]n microcrystals), and 6) a systematic photoluminescent signal combination by using principal-component analysis from the other three polymer-chelated metal-organic frameworkds (MOFs), such as poly(acrylic acid) (PAA), sodium alginate (SA), and polyvinylpyrrolidone (PVP) to enhance the selectivity and discrimination capabilities.

  13. Determination of toxic heavy metals in sea water by FAAS after preconcentration with a novel chelating resin.

    PubMed

    Manivannan, D; Biju, V M

    2011-01-01

    A solid phase extraction procedure was developed for preconcentration of toxic heavy metals such as cadmium, cobalt, copper, manganese, lead and zinc in sea water samples. A microcolumn packed with 6-[(4-hydroxyphenyl)diazenyl]naphthalene-2,3-diol-formaldehyde (HPDN-F) resin acts as a sorbent to retain the analyte ions by forming metal chelates. The retained trace level metal was subsequently eluted with 1 mol/L HCl and the acid eluent was analysed by Flame Atomic Absorption Spectrophotometer (FAAS). The HPDN-F chelating resin and its metal chelates were characterized by spectral and thermal analysis. The chelating property of the HPDN-F resin towards divalent metal ions was studied as a function of pH and preconcentration flow rate. The recoveries of cadmium, cobalt, copper, manganese, lead and zinc under the optimum working conditions were above 95%. The relative standard deviations were < 2%. The limits of detection were < 0.1 microg/L. The method presented was applied for the determination of cadmium, cobalt, copper, manganese, lead and zinc in sea water samples.

  14. 'Unconventional' coordination chemistry by metal chelating fragments in a metalloprotein active site.

    PubMed

    Martin, David P; Blachly, Patrick G; Marts, Amy R; Woodruff, Tessa M; de Oliveira, César A F; McCammon, J Andrew; Tierney, David L; Cohen, Seth M

    2014-04-01

    The binding of three closely related chelators: 5-hydroxy-2-methyl-4H-pyran-4-thione (allothiomaltol, ATM), 3-hydroxy-2-methyl-4H-pyran-4-thione (thiomaltol, TM), and 3-hydroxy-4H-pyran-4-thione (thiopyromeconic acid, TPMA) to the active site of human carbonic anhydrase II (hCAII) has been investigated. Two of these ligands display a monodentate mode of coordination to the active site Zn(2+) ion in hCAII that is not recapitulated in model complexes of the enzyme active site. This unprecedented binding mode in the hCAII-thiomaltol complex has been characterized by both X-ray crystallography and X-ray spectroscopy. In addition, the steric restrictions of the active site force the ligands into a 'flattened' mode of coordination compared with inorganic model complexes. This change in geometry has been shown by density functional computations to significantly decrease the strength of the metal-ligand binding. Collectively, these data demonstrate that the mode of binding by small metal-binding groups can be significantly influenced by the protein active site. Diminishing the strength of the metal-ligand bond results in unconventional modes of metal coordination not found in typical coordination compounds or even carefully engineered active site models, and understanding these effects is critical to the rational design of inhibitors that target clinically relevant metalloproteins.

  15. 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.

  16. 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. PMID:24824327

  17. Dissolution of metal oxides accumulated in nuclear steam generators: study of solutions containing organic chelating agents

    SciTech Connect

    Gilbert, R.; Ouellet, L.

    1985-03-01

    A study of the reactivity of ethylenediaminetetraacetic acid (EDTA), citric acid, and hydrazine for the dissolution of magnetite particles has allowed some steps of the different mechanisms to be identified. Two mechanisms are suggested: In acidic solutions, the chelating agents are adsorbed at the solid/solution interface followed by desorption of the complexed species FeH /SUB n/ L, where HnL is EDTA or citric acid, whereas in alkaline media, direct dissolution of the oxide particles takes place followed by complexation of the species Fe/sup 3 +//Fe/sup 2 +/ in solution. The hydrazine apparently reduces the Fe/sup 3 +/ ions via a surface complexing reaction involving the N/sub 2/H/sub +//sub 5/ ions, a reaction which is in competition with the protonation of the Fe/sub 3/O/sub 4/ crystal lattice. Finally, regardless of the type of oxide (Fe/sub 3/O/sub 4/, Fe/sub 2/O/sub 3/, FeOOH, CuO, or Cu/sub 2/O) or the composition of the complexing solutions, suspensions of these particles are highly unstable with respect to agglomeration or settling out, more because of the high concentration of chelating agents than their chemical characteristics.

  18. Biodegradation of the chelator 2,6-pyridine dicarboxylic acid (PDA) used for soil metal extraction

    SciTech Connect

    Banerji, S.K.; Regmi, T.P.

    1998-12-31

    In this research the biodegradability of 2,6-pyridine dicarboxylic acid (PDA) was evaluated. This compound has been used as a chelating agent for extraction of metal ions from contaminated soils. Initial experiments indicated that PDA was not biodegraded by unacclimated mixed cultures to any degree. However, acclimated mixed cultures degraded more than 80% of this compound within 12 h under different conditions without showing any sign of inhibition even at high concentrations up to 6 mM (1000 mg/l). The results of PDA biodegradation at all concentrations tested in aqueous solution were very similar to those observed in presence of soil slurry, except that a slight lag of microbial growth occurred at all PDA concentrations in the latter case. No toxicity was evident to the microorganisms during the biodegradation of lead complexed PDA after an initial lag. The PDA complexed with lead was easily available for metabolism by the acclimated mixed culture.

  19. [Functionalized Metal Chelates Based on Diethylenetriaminetetraacetic Acids for Chemical Modification of Proteins and Small Biomolecules].

    PubMed

    Kuprienko, O S; Dubovskaya, L V; Shabunya, P S; Fatykhava, S A; Sviridov, O V

    2015-01-01

    Bifunctional reagents based on diethylenetriaminetetraacetic acid containing a bound metal ion and a reactive functional group for the interaction with proteins and low-molecular-weight substances have been synthesized. An Amino-derivative of a complexonate was obtained by acylation of monosubstituted diamine with diethylenetriaminepentaacetic acid dianhydride followed by deprotection ofthe amino group, purification by anion exchange chromatography and chelation of Eu3+. This metal chelate derivative was used for labeling 17α-hydroxyprogesterone 3-(O-carboxymethyl)oxime and horseradish peroxidase. The enzyme modified with the Eu3+ complexonate at the carbohydrate component and with a cortisol derivative at the polypeptide chain was used in a dissociation-enhanced lanthanide fluorescent immunoassay (DELFIA) as well as in an enzyme immunoassay of the steroid hormone. DELFIA showed that labeled 17α-hydroxyprogesterone retained the affinity for corresponding antibodies. A Eu(3+)-complexonate carboxy-derivative N-succinimide ester was obtained by acylation of the aminochelate with p-phthalic acid di-N-succinimide ester. It was used for modification of amino groups of lysine residues in polypeptide chains of human serum albumin and some immunoglobulins G. Purification of Eu3+ complexonate-protein conjugates by gel-chromatography on a Superose- 12 column allowed to separate the modified proteins from unreacted low molecular weight Eu(3+)-derivatives and to determine a degree of lanthanide inclusion into a protein. The amount of Eu3+ covalently attached to a protein was determined by measuring the fluorescence of a conjugate in the dissociative-enhancement solution. The obtained values correlated well with the results of ICP-MS determination of Eu3+ concentration in a conjugate solution. It was shown that conjugates of monoclonal antibodies obtained by the proposed method possessed the required characteristics of fluorescence intensity, signal-to-noise ratio, sensitivity

  20. Metal chelators coupled with nanoparticles as potential therapeutic agents for Alzheimer's disease

    PubMed Central

    Liu, Gang; Men, Ping; Perry, George; Smith, Mark A.

    2009-01-01

    Alzheimer's disease (AD) is a devastating neuro-degenerative disorder characterized by the progressive and irreversible loss of memory followed by complete dementia. Despite the disease's high prevalence and great economic and social burden, an explicative etiology or viable cure is not available. Great effort has been made to better understand the disease's pathogenesis, and to develop more effective therapeutic agents. However, success is greatly hampered by the presence of the blood-brain barrier that limits a large number of potential therapeutics from entering the brain. Nanoparticle-mediated drug delivery is one of the few valuable tools for overcoming this impediment and its application as a potential AD treatment shows promise. In this review, the current studies on nanoparticle delivery of chelation agents as possible therapeutics for AD are discussed because several metals are found excessive in the AD brain and may play a role in the disease development. Specifically, a novel approach involving transport of iron chelation agents into and out of the brain by nanoparticles is highlighted. This approach may provide a safer and more effective means of simultaneously reducing several toxic metals in the AD brain. It may also provide insights into the mechanisms of AD pathophysiology, and prove useful in treating other iron-associated neurodegenerative diseases such as Friedreich's ataxia, Parkinson's disease, Huntington's disease and Hallervorden-Spatz Syndrome. It is important to note that the use of nanoparticle-mediated transport to facilitate toxicant excretion from diseased sites in the body may advance nanoparticle technology, which is currently focused on targeted drug delivery for disease prevention and treatment. The application of nanoparticle-mediated drug transport in the treatment of AD is at its very early stages of development and, therefore, more studies are warranted. PMID:19936278

  1. Toxicity of synthetic chelators and metal availability in poultry manure amended Cd, Pb and As contaminated agricultural soil.

    PubMed

    Usman, Adel R A; Almaroai, Yaser A; Ahmad, Mahtab; Vithanage, Meththika; Ok, Yong Sik

    2013-11-15

    Chelating agents added to contaminated soils may increase solubility and phytoextraction efficiency of soil metals. However, they can create negative effects on soil biological quality. A 90-day incubation experiment was conducted to evaluate mixed effects of chelating agents and poultry manure on changes in available Cd, Pb and As, CO2-C efflux, microbial biomass C, dissolved organic C (DOC), and N mineralization in metal-polluted agricultural soil. Application of poultry manure resulted in a considerable increase in soil pH, DOC, CO2-C efflux, net N mineralization, net N nitrification, and microbial biomass C compared to those in unmanured soil. Availability of arsenic increased twice in manure amended soil due to changes in pH and DOC. However, adding poultry manure did not affect the concentrations of available Pb and Cd compared to those in control soil. Chelating agents increased CO2-C efflux, DOC, and metal availability but decreased microbial biomass C and net N mineralization. Maximum decrease in microbial biomass C, net N mineralization, and net N nitrification, was observed in EDTA applied soil possibly due to high metal availability to soil microorganisms. Overall results revealed that the application of synthetic chelators in combination with poultry manure enhances available As and demonstrates better environment for soil biota. PMID:23791533

  2. Toxicity of synthetic chelators and metal availability in poultry manure amended Cd, Pb and As contaminated agricultural soil.

    PubMed

    Usman, Adel R A; Almaroai, Yaser A; Ahmad, Mahtab; Vithanage, Meththika; Ok, Yong Sik

    2013-11-15

    Chelating agents added to contaminated soils may increase solubility and phytoextraction efficiency of soil metals. However, they can create negative effects on soil biological quality. A 90-day incubation experiment was conducted to evaluate mixed effects of chelating agents and poultry manure on changes in available Cd, Pb and As, CO2-C efflux, microbial biomass C, dissolved organic C (DOC), and N mineralization in metal-polluted agricultural soil. Application of poultry manure resulted in a considerable increase in soil pH, DOC, CO2-C efflux, net N mineralization, net N nitrification, and microbial biomass C compared to those in unmanured soil. Availability of arsenic increased twice in manure amended soil due to changes in pH and DOC. However, adding poultry manure did not affect the concentrations of available Pb and Cd compared to those in control soil. Chelating agents increased CO2-C efflux, DOC, and metal availability but decreased microbial biomass C and net N mineralization. Maximum decrease in microbial biomass C, net N mineralization, and net N nitrification, was observed in EDTA applied soil possibly due to high metal availability to soil microorganisms. Overall results revealed that the application of synthetic chelators in combination with poultry manure enhances available As and demonstrates better environment for soil biota.

  3. Antioxidant and Metal Chelation-Based Therapies in the Treatment of Prion Disease

    PubMed Central

    Brazier, Marcus W.; Wedd, Anthony G.; Collins, Steven J.

    2014-01-01

    Many neurodegenerative disorders involve the accumulation of multimeric assemblies and amyloid derived from misfolded conformers of constitutively expressed proteins. In addition, the brains of patients and experimental animals afflicted with prion disease display evidence of heightened oxidative stress and damage, as well as disturbances to transition metal homeostasis. Utilising a variety of disease model paradigms, many laboratories have demonstrated that copper can act as a cofactor in the antioxidant activity displayed by the prion protein while manganese has been implicated in the generation and stabilisation of disease-associated conformers. This and other evidence has led several groups to test dietary and chelation therapy-based regimens to manipulate brain metal concentrations in attempts to influence the progression of prion disease in experimental mice. Results have been inconsistent. This review examines published data on transition metal dyshomeostasis, free radical generation and subsequent oxidative damage in the pathogenesis of prion disease. It also comments on the efficacy of trialed therapeutics chosen to combat such deleterious changes. PMID:26784872

  4. Formation Mechanism and Characterization of Ag-Metal Chelate Polymer Prepared by a Wet Chemical Process

    NASA Astrophysics Data System (ADS)

    Huang, Chueh-Jung; Lin, Jiang-Jen; Shieu, Fuh-Sheng

    2005-08-01

    In this study, a metal chelate polymer (MCP) contained Ag(0) was prepared from commercial polyvinyl acetate (PVAc) and silver nitrate (AgNO3) by a wet chemical method using concentrate formic acid (HCOOH) as solvent. The characterization of these MCP materials, and the formation mechanism that involved in the MCP system, were studied by the analyses of Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FESEM). The Ag(I) cations of silver nitrate (AgNO3) were found coordinated with polymer functional groups to form polymer-Ag(I) complexes. The XRD analysis revealed that these complexed Ag(I) ions were in-situ reduced to generate Ag(0) metal by HCOOH solvent in MCP system. The results of FTIR and NMR analyses demonstrated that there are hydrolyzed hydroxyl groups present in the MCP chains. The XPS analysis showed that the oxygen ligands that interacted with the Ag(0) were mostly contributed from the OH groups. The interaction between the reduced Ag(0) metal and the polymer chains was confirmed by transmission electron microscopy (TEM) investigation on the MCP materials.

  5. Distortion Pathways of Transition Metal Coordination Polyhedra Induced by Chelating Topology.

    PubMed

    Alvarez, Santiago

    2015-12-23

    A continuous shape measures analysis of the coordination polyhedra of a host of transition metal complexes with bi- and multidentate ligands discloses the distortion pathway associated with each particular topology of the chelate rings formed. The basic parameter that controls the degree of distortion is the metal-donor atom bond distance that induces nonideal bond angles due to the rigidity of the ligands. Thus, the degree of distortion within each family of complexes depends on the atomic size, on which the high- or low-spin state has a large effect. Special attention is therefore paid to several spin-crossover systems and to the enhanced distortions that go along with the transition from low- to high-spin state affected by temperature, light, or pressure. Several families of complexes show deviations from the expected distortion pathways in the high-spin state that can be associated to the onset of intermolecular interactions such as secondary coordination of counterions or solvent molecules. Also, significant displacement of counterions in an extended solid may result from the changes in metal-ligand bond distances when ligands are involved in intermolecular hydrogen bonding. PMID:26575868

  6. Studies on chelating adsorption properties of novel composite material polyethyleneimine/silica gel for heavy-metal ions

    NASA Astrophysics Data System (ADS)

    Gao, Baojiao; An, Fuqiang; Liu, Kangkai

    2006-12-01

    Firstly, the coordination processes of line-type polyethyleneimine with Cu 2+, Cd 2+ and Zn 2+ were studied by using visible light absorption spectroscopy and chelation conductivity titration method, and the structures of the chelates were determined. Afterwards, polyethyleneimine (PEI) was grafted onto the surface of silica gel particles via the coupling effect of γ-chloropropyl trimethoxysilane (CP), and the novel composite adsorption material PEI/SiO 2 with strong adsorption ability towards heavy-metal ions was prepared. The chelating adsorption properties of PEI/SiO 2 for Cu 2+, Cd 2+ and Zn 2+ were researched by both static (batch) and dynamic (flow) methods. The experiment results show that water-soluble polyamine PEI with line-type structure reacts with Cu 2+, Cd 2+ and Zn 2+ easily and quantitatively, and water-soluble chelates with four ligands are formed. The composite material PEI/SiO 2 possesses very strong chelating adsorption ability for heavy-metal ions, and the saturated adsorption amount can reach 25.94 mg g -1 and 50.01 mg g -1 for Cu 2+ under static and dynamic conditions, respectively. The isothermal adsorption data fit to Langmuir equation, and the adsorption is typical chemical adsorption with monomolecular layer. The adsorbing ability of PEI/SiO 2 towards the three kinds of the ions follows the order of Cu 2+ > Cd 2+ > Zn 2+. The pH value has great influence on the sorption, and at pH 6-7, the adsorption capacity is the greatest. The fact that adsorption capacity increases with temperature rising indicates the adsorbing process of PEI/SiO 2 for metal ions is endothermic. As diluted hydrochloric acid is used as eluent, the adsorbed heavy-metal ions are eluted easily from PEI/SiO 2, and the regeneration and reuse without decreasing sorption for PEI/SiO 2 are demonstrated.

  7. Bioinspired Immobilization of Glycerol Dehydrogenase by Metal Ion-Chelated Polyethyleneimines as Artificial Polypeptides

    PubMed Central

    Zhang, Yonghui; Ren, Hong; Wang, Yali; Chen, Kainan; Fang, Baishan; Wang, Shizhen

    2016-01-01

    In this study, a novel, simple and generally applicable strategy for multimeric oxidoreductase immobilization with multi-levels interactions was developed and involved activity and stability enhancements. Linear polyethyleneimines (PEIs) are flexible cationic polymers with molecular weights that span a wide range and are suitable biomimic polypeptides for biocompatible frameworks for enzyme immobilization. Metal ion-chelated linear PEIs were applied as a heterofunctional framework for glycerol dehydrogenase (GDH) immobilization by hydrogen bonds, electrostatic forces and coordination bonds interactions. Nanoparticles with diameters from 250–650 nm were prepared that exhibited a 1.4-fold enhancement catalytic efficiency. Importantly, the half-life of the immobilized GDH was enhanced by 5.6-folds in aqueous phase at 85 °C. A mechanistic illustration of the formation of multi-level interactions in the PEI-metal-GDH complex was proposed based on morphological and functional studies of the immobilized enzyme. This generally applicable strategy offers a potential technique for multimeric enzyme immobilization with the advantages of low cost, easy operation, high activity reservation and high stability. PMID:27053034

  8. Removal of PCR Error Products and Unincorporated Primers by Metal-Chelate Affinity Chromatography

    PubMed Central

    Kanakaraj, Indhu; Jewell, David L.; Murphy, Jason C.; Fox, George E.; Willson, Richard C.

    2011-01-01

    Immobilized Metal Affinity Chromatography (IMAC) has been used for decades to purify proteins on the basis of amino acid content, especially surface-exposed histidines and “histidine tags” genetically added to recombinant proteins. We and others have extended the use of IMAC to purification of nucleic acids via interactions with the nucleotide bases, especially purines, of single-stranded RNA and DNA. We also have demonstrated the purification of plasmid DNA from contaminating genomic DNA by IMAC capture of selectively-denatured genomic DNA. Here we describe an efficient method of purifying PCR products by specifically removing error products, excess primers, and unincorporated dNTPs from PCR product mixtures using flow-through metal-chelate affinity adsorption. By flowing a PCR product mixture through a Cu2+-iminodiacetic acid (IDA) agarose spin column, 94–99% of the dNTPs and nearly all the primers can be removed. Many of the error products commonly formed by Taq polymerase also are removed. Sequencing of the IMAC-processed PCR product gave base-calling accuracy comparable to that obtained with a commercial PCR product purification method. The results show that IMAC matrices (specifically Cu2+-IDA agarose) can be used for the purification of PCR products. Due to the generality of the base-specific mechanism of adsorption, IMAC matrices may also be used in the purification of oligonucleotides, cDNA, mRNA and micro RNAs. PMID:21264292

  9. [Influences of the mobile phase constitution, salt concentration and pH value on retention characters of proteins on the metal chelate column].

    PubMed

    Li, R; Di, Z M; Chen, G L

    2001-09-01

    The effects of the nature and concentration of salts, pH value and competitive eluent in the mobile phase on the protein retention have been systematically investigated. A mathematical expression describing the protein retention in metal chelate chromatography has been derived. It is proposed that the eluting power of the salt solution can be expressed by the eluent strength exponent epsilon. According to the retention characters of protein under different chromatographic conditions, the interaction between the various metal chelate ligands and proteins is discussed. The protein retention on the metal chelate column is a cooperative interactions of coordination, electrostatic and hydrophobic interaction. For the strong combined metal column with proteins such as IDA-Cu, the coordination is the most important, and the electrostatic interaction is secondary in chromatographic process. However, for the weak combined metal columns with proteins such as IDA-Ni, IDA-Co and IDA-Zn, the electrostatic interaction between the metal chelate ligands and proteins is the chief one, while the coordination is the next in importance. When the mobile phase contains high concentration of salt which can't form complex with the immobilized metal, the hydrophobic interaction between the protein and stationary phase will be increased. As the interaction between the metal chelate ligand and proteins relates to chromatographic operating conditions closely, different elution processes may be selected for different metal chelate columns. The gradient elution is generally performed by the low concentration of salt or different pH for weakly combined columns with proteins, however the competitive elution procedure is commonly utilized for strongly combined column. The experiment showed that NH3 is an excellent competitive eluent. It isn't only give the efficient separation of proteins, but also has the advantages of cheapness, less bleeding of the immobilized metals and ease of controlling NH3

  10. Influence of hydrological and geochemical processes on the transport of chelated metals and chromate in fractured shale bedrock.

    PubMed

    Jardine, P M; Mehlhorn, T L; Larsen, I L; Bailey, W B; Brooks, S C; Roh, Y; Gwo, J P

    2002-03-01

    Field-scale processes governing the transport of chelated radionuclides in groundwater remain conceptually unclear for highly structured, heterogeneous environments. The objectives of this research were to provide an improved understanding and predictive capability of the hydrological and geochemical mechanisms that control the transport behavior of chelated radionuclides and metals in anoxic subsurface environments that are complicated by fracture flow and matrix diffusion. Our approach involved a long-term, steady-state natural gradient field experiment where nonreactive Br- and reactive 57Co(II)EDTA2- 109CdEDTA2-, and 51Cr(VI) were injected into a fracture zone of a contaminated fractured shale bedrock. The spatial and temporal distribution of the tracer and solutes was monitored for 500 days using an array of groundwater sampling wells instrumented within the fast-flowing fracture regime and a slower flowing matrix regime. The tracers were preferentially transported along strike-parallel fractures coupled with the slow diffusion of significant tracer mass into the bedrock matrix. The chelated radionuclides and metals were significantly retarded by the solid phase with the mechanisms of retardation largely due to redox reactions and sorption coupled with mineral-induced chelate-radionuclide dissociation. The formation of significant Fe(III)EDTA byproduct that accompanied the dissociation of the radionuclide-chelate complexes was believed to be the result of surface interactions with biotite which was the only Fe(III)-bearing mineral phase present in these Fe-reducing environments. These results counter current conceptual models that suggest chelated contaminants move conservatively through Fe-reducing environments since they are devoid of Fe-oxyhydroxides that are known to aggressively compete for chelates in oxic regimes. Modeling results further demonstrated that chelate-radionuclide dissociation reactions were most prevalent along fractures where accelerated

  11. METAL BINDING PROPERTIES OF A MONOCLONAL ANTIBODY DIRECTED TOWARDS METAL-CHELATE COMPLEXES. (R824029)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  12. f-Element Ion Chelation in Highly Basic Media - Final Report

    SciTech Connect

    Paine, R.T.

    2000-12-12

    A large body of data has been collected over the last fifty years on the chemical behavior of f-element ions. The ions undergo rapid hydrolysis reactions in neutral or basic aqueous solutions that produce poorly understood oxide-hydroxide species; therefore, most of the fundamental f-element solution chemistry has allowed synthetic and separations chemists to rationally design advanced organic chelating ligands useful for highly selective partitioning and separation of f-element ions from complex acidic solution matrices. These ligands and new examples under development allow for the safe use and treatment of solutions containing highly radioactive species. This DOE/EMSP project was undertaken to address the following fundamental objectives: (1) study the chemical speciation of Sr and lanthanide (Ln) ions in basic aqueous media containing classical counter anions found in waste matrices; (2) prepare pyridine N-oxide phosphonates and phosphonic acids that might act as selective chelator s for Ln ions in model basic pH waste streams; (3) study the binding of the new chelators toward Ln ions and (4) examine the utility of the chelators as decontamination and dissolution agents under basic solution conditions. The project has been successful in attacking selected aspects of the very difficult problems associated with basic pH solution f-element waste chemistry. In particular, the project has (1) shed additional light on the initial stages of Ln ion sol-gel-precipitate formulation under basic solution conditions; (2) generated new families of pyridine phosphonic acid chelators; (3) characterized the function of the chelators and (4) examined their utility as oxide-hydroxide dissolution agents. These findings have contributed significantly to an improved understanding of the behavior of Ln ions in basic media containing anions found in typical waste sludges as well as to the development of sludge dissolution agents. The new chelating reagents are easily made and could be

  13. Role of pH in metal adsorption from aqueous solutions containing chelating agents on chitosan

    SciTech Connect

    Wu, F.C.; Tseng, R.L.; Juang, R.S.

    1999-01-01

    The role of pH in adsorption of Cu(II) from aqueous solutions containing chelating agents on chitosan was emphasized. Four chelating agents including ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, and sodium gluconate were used. It was shown that the adsorption ability of Cu(II) on chitosan from its chelated solutions varied significantly with pH variations. The competition between coordination of Cu(II) with unprotonated chitosan and electrostatic interaction of the Cu(II) chelates with protonated chitosan took place because of the change in solution pH during adsorption. The maximum adsorption capacity was obtained within each optimal pH range determined from titration curves of the chelated solutions. Coordination of Cu(II) with the unprotonated chitosan was found to dominate at pH below such an optimal pH value.

  14. Metal chelate affinity precipitation: purification of BSA using poly(N-vinylcaprolactam-co-methacrylic acid) copolymers.

    PubMed

    Ling, Yuan-Qing; Nie, Hua-Li; Brandford-White, Christopher; Williams, Gareth R; Zhu, Li-Min

    2012-06-01

    This investigation involves the metal chelate affinity precipitation of bovine serum albumin (BSA) using a copper ion loaded thermo-sensitive copolymer. The copolymer of N-vinylcaprolactam with methacrylic acid PNVCL-co-MAA was synthesized by free radical polymerization in aqueous solution, and Cu(II) ions were attached to provide affinity properties for BSA. A maximum loading of 48.1mg Cu(2+) per gram of polymer was attained. The influence of pH, temperature, BSA and NaCl concentrations on BSA precipitation and of pH, ethylenediaminetetraacetic acid (EDTA) and NaCl concentrations on elution were systematically probed. The optimum conditions for BSA precipitation occurred when pH, temperature and BSA concentration were 6.0, 10°C and 1.0 mg/ml, respectively and the most favorable elution conditions were at pH 4.0, with 0.2M NaCl and 0.06 M EDTA. The maximum amounts of BSA precipitation and elution were 37.5 and 33.7 mg BSA/g polymer, respectively. It proved possible to perform multiple precipitation/elution cycles with a minimal loss of polymer efficacy. The results show that PNVCL-co-MAA is a suitable matrix for the purification of target proteins from unfractionated materials.

  15. Phytochemical Analysis and Metal-chelation Activity of Achillea tenuifolia Lam.

    PubMed Central

    Moradkhani, Shirin; Ayatollahi, Abdul Majid; Ghanadian, Mustafa; Moin, Mohammad Reza; Razavizadeh, Masoud; Shahlaei, Mohsen

    2012-01-01

    Achillea tenuifolia Lam. (Asteraceae) afforded a dichloromethane fraction from which three known compounds β-sitosterol (compound1), 5-hydroxy, 4',6,7– trimethoxy flavone (salvigenin compound 2), and methyl-gallate (compound 3) were isolated for the first time. The structure of isolated compounds was elucidated by different spectroscopic methods. Applying the molar-ratio method, the complexation of salvigenin with Fe (III), Cu(II) and Zn(II), the most abundant type of metal ions in the body, were then evaluated. It was determined that stoichiometric ratio of salvigenin with these cations were as Fe(Salvigenin)2 (H2O)2 and Cu(Salvigenin)2(H2O)2 in methanolic solution without pH control, while zinc ions didn`t form significant complexes. The results were confirmed more, by computational molecular modeling of the structure of proposed ligand-complexes by semi-imperical PM3 calculations, which determined negative heat of formation for the complexes Fe(III) and Cu(II) ions as -689.7 and -573.5, respectively and proposed chelating affinity of salvigenin in the following order: Fe(III) > Cu(II) >> Zn(II). PMID:24250440

  16. Stabilizing Protein Motifs with a Genetically Encoded Metal-Ion Chelator.

    PubMed

    Luo, Xiaozhou; Wang, Tsung-Shing Andrew; Zhang, Yong; Wang, Feng; Schultz, Peter G

    2016-09-22

    The N-peptide of HIV gp41 forms a trimeric coiled-coil intermediate during host cell-viral fusion. Stable mimics of this coiled coil could potentially serve as HIV vaccine candidates or inhibitors of viral entry. Therefore, a variety of approaches have been investigated to maintain the N-peptide in its trimeric helical conformation. Here, we utilize a genetic method to incorporate the metal chelating noncanonical amino acid (2,2'-bipyridin-5-yl)alanine (BpyAla) into IZN17, an established trimeric coiled-coil gp41 model. We demonstrate that BpyAla-IZN17 acquires Fe(II) during expression in Escherichia coli, resulting in the formation of a highly stable IZN17 helical trimer with a Tm > 95°C. Removal of Fe(II) results in a 27°C decrease in thermal stability. Replacement of Fe(II) with Zn(II) also affords a Tm > 90°C. Thus, the genetic introduction of BpyAla into polypeptide provides a straightforward method for stabilizing coiled-coil structural motifs in recombinantly engineered proteins. PMID:27662253

  17. In vitro growth inhibition of mastitis causing bacteria by phenolics and metal chelators

    SciTech Connect

    Chew, B.P.; Tjoelker, L.W.; Tanaka, T.S.

    1985-11-01

    Antimicrobial activities of three phenolic compounds and four metal chelators were tested at 0, 250, 500, and 1000 ppm in vitro against four major mastitis-causing bacteria, Streptococcus agalactiae, Staphylococcus aureus, Klebsiella pnuemoniae, and Escherichia coli. Overall, butylated hydroxyanisole and tert-butylhydroquinone showed the greatest antimicrobial activity. These phenolics were bactericidal at 250 to 500 ppm against all four bacteria tested. The butylated hydroxytoluene was bactericidal against the gram-positive bacteria but was ineffective against the coliforms. At 250 ppm, disodium ethylenediaminetetraacetic acid was bactericidal against the gram-positive bacteria but much less effective against the gram-negatives. However, diethylene-triaminepentaacetic acid was more growth inhibitory than ethylenediaminetetraacetic acid against the gram-negative bacteria and especially against Escherichia coli. All other compounds were generally much less effective or ineffective against all four microorganisms. Therefore, butylated hydroxyanisole, butylated hydroxytoluene, tert-butylhydroquinone, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid may have practical implications in the prevention or treatment of bovine mastitis.

  18. Determination of residual fluoroquinolones in honey by liquid chromatography using metal chelate affinity chromatography.

    PubMed

    Yatsukawa, Yoh-Ichi; Ito, Hironobu; Matsuda, Takahiro; Nakamura, Munetomo; Watai, Masatoshi; Fujita, Kazuhiro

    2011-01-01

    A new analytical method for the simultaneous determination of seven fluoroquinolones, namely, norfloxacin, ciprofloxacin, danofloxacin, enrofloxacin, orbifloxacin, sarafloxacin, and difloxacin, especially in dark-colored honey, has been developed. Fluoroquinolone antibiotics were extracted from samples with MacIlvaine buffer solution (pH 4.0) containing EDTA disodium salt dihydrate. The extracts were treated with both a polymeric cartridge and a metal chelate affinity column preloaded with ferric ion (Fe3+). LC separation with fluorescence detection was performed at 40 degrees C using an Inertsil ODS-4 analytical column (150 x 4.6 mm, 3 microm). The mobile phase was composed of 20 mM/L citrate buffer solution (pH 3.1)-acetonitrile mixture (70 + 30, v/v) containing 1 mM/L sodium dodecyl sulfate. Lomefloxacin was used as an internal standard. The developed method was validated according to the criteria of European Commission Decision 2002/657/EC. Decision limits and detection capabilities were below 2.9 and 4.4 microg/kg, respectively.

  19. Antimicrobial Properties of Pyridine-2,6-Dithiocarboxylic Acid, a Metal Chelator Produced by Pseudomonas spp.

    PubMed Central

    Sebat, J. L.; Paszczynski, A. J.; Cortese, M. S.; Crawford, R. L.

    2001-01-01

    Pyridine-2,6-dithiocarboxylic acid (pdtc) is a metal chelator produced by Pseudomonas spp. It has been shown to be involved in the biodegradation of carbon tetrachloride; however, little is known about its biological function. In this study, we examined the antimicrobial properties of pdtc and the mechanism of its antibiotic activity. The growth of Pseudomonas stutzeri strain KC, a pdtc-producing strain, was significantly enhanced by 32 μM pdtc. All nonpseudomonads and two strains of P. stutzeri were sensitive to 16 to 32 μM pdtc. In general, fluorescent pseudomonads were resistant to all concentrations tested. In competition experiments, strain KC demonstrated antagonism toward Escherichia coli. This effect was partially alleviated by 100 μM FeCl3. Less antagonism was observed in mutant derivatives of strain KC (CTN1 and KC657) which lack the ability to produce pdtc. A competitive advantage was restored to strain CTN1 by cosmid pT31, which restores pdtc production. pT31 also enhanced the pdtc resistance of all pdtc-sensitive strains, indicating that this plasmid contains elements responsible for resistance to pdtc. The antimicrobial effect of pdtc was reduced by the addition of Fe(III), Co(III), and Cu(II) and enhanced by Zn(II). Analyses by mass spectrometry determined that Cu(I):pdtc and Co(III):pdtc2 form immediately under our experimental conditions. Our results suggest that pdtc is an antagonist and that metal sequestration is the primary mechanism of its antimicrobial activity. It is also possible that Zn(II), if present, may play a role in pdtc toxicity. PMID:11525988

  20. HIV-1 IN strand transfer chelating inhibitors: a focus on metal binding.

    PubMed

    Bacchi, Alessia; Carcelli, Mauro; Compari, Carlotta; Fisicaro, Emilia; Pala, Nicolino; Rispoli, Gabriele; Rogolino, Dominga; Sanchez, Tino W; Sechi, Mario; Neamati, Nouri

    2011-04-01

    Most active and selective strand transfer HIV-1 integrase (IN) inhibitors contain chelating functional groups that are crucial feature for the inhibition of the catalytic activities of the enzyme. In particular, diketo acids and their derivatives can coordinate one or two metal ions within the catalytic core of the enzyme. The present work is intended as a contribution to elucidate the mechanism of action of the HIV-IN inhibitors by studying the coordinative features of H₂L¹ (L-708,906), an important member of the diketo acids family of inhibitors, and H₂L₂, a model for S-1360, another potent IN inhibitor. Magnesium(II) and manganese(II) complexes of H₂L¹ and H₂L² were isolated and fully characterized in solution and in the solid state. The crystal structures of the manganese complex [Mn(HL₂)₂(CH₃OH)₂]·2CH₃OH were solved by X-ray diffraction analysis. Moreover, the speciation models for H₂L₂ with magnesium(II) and manganese(II) ions were performed and the formation constants of the complexes were measured. M(HL₂)₂ (M = Mg²+, Mn²+) was the most abundant species in solution at physiological pH. All the synthesized compounds were tested for their anti-IN activity, showing good results both for the ligand and the corresponding complexes. From analysis of the speciation models and of the biological data we can conclude that coordination of both metal cofactors could not be strictly necessary and that inhibitors can act as complexes and not only as free ligands.

  1. Effective removal of heavy metals from industrial sludge with the aid of a biodegradable chelating ligand GLDA.

    PubMed

    Wu, Qing; Cui, Yanrui; Li, Qilu; Sun, Jianhui

    2015-01-01

    Tetrasodium of N,N-bis(carboxymethyl) glutamic acid (GLDA), a novel readily biodegradable chelating ligand, was employed for the first time to remove heavy metals from industrial sludge generated from a local battery company. The extraction of cadmium, nickel, copper, and zinc from battery sludge with the presence of GLDA was studied under different experimental conditions such as contact times, pH values, as well as GLDA concentrations. Species distribution of metals in the sludge sample before and after extraction with GLDA was also analyzed. Current investigation showed that (i) GLDA was effective for Cd extraction from sludge samples under various conditions. (ii) About 89% cadmium, 82% nickel and 84% copper content could be effectively extracted at the molar ratio of GLDA:M(II)=3:1 and at pH=4, whereas the removal efficiency of zinc was quite low throughout the experiment. (iii) A variety of parameters, such as contact time, pH values, the concentration of chelating agent, stability constant, as well as species distribution of metals could affect the chelating properties of GLDA.

  2. Functionalization of Cellulose Nanocrystals with PEG-Metal-Chelating Diblock Copolymers via Controlled Conjugation in Aqueous Medium

    NASA Astrophysics Data System (ADS)

    Guo, Melinda

    The surface of cellulose nanocrystals (CNCs) was successfully functionalized with metal chelating diblock copolymers via HyNic-4FB conjugation. Two types of PEG-metal-chelating block polymers with hydrazinonicotinate acetone hydrazine (HyNic) end groups were synthesized: mPEG-PGlu(DTPA) 18-HyNic and mPEG-PGlu(DTPA)25-HyNic. These two polymers both had a methoxy PEG (M ˜ 2000 Da) block that differed in the mean degree of polymerization of the metal-chelating block. They were characterized by 1H NMR spectroscopy and gel-permeation chromatography (GPC). 4-Formylbenzamide (4FB) groups were introduced onto the surface of CNCs and quantified through their reaction with 2-hydrazinopyridine. The polymers were grafted onto the surface of CNCs via bis-aryl hydrazone bond formation, and the kinetics of this reaction was explored by UV/Vis spectroscopy. The CNCs were also labeled with rhodamine and Alexa FluorRTM 488 dyes. Students in our collaborator's group in Pharmacy are examining applications of these materials as radiotherapeutic agents for cancer treatment.

  3. Excited state evolution towards ligand loss and ligand chelation at group 6 metal carbonyl centres.

    PubMed

    Manton, Jennifer C; Amirjalayer, Saeed; Coleman, Anthony C; McMahon, Suzanne; Harvey, Emma C; Greetham, Gregory M; Clark, Ian P; Buma, Wybren Jan; Woutersen, Sander; Pryce, Mary T; Long, Conor

    2014-12-21

    the reactive state responsible for the arrested CO-loss has significant metal-to-carbonyl charge-transfer character. The CO-loss product (η(6)-allylbenzene)Cr(CO)2 formed following irradiation of (η(6)-allylbenzene)Cr(CO)3 reacts further with the pendent alkenyl group to form the chelate product (η(6),η(2)-allylbenzene)Cr(CO)2.

  4. A Practical Guide on the Synthesis of Metal Chelates for Molecular Imaging and Therapy by Means of Click Chemistry.

    PubMed

    Notni, Johannes; Wester, Hans-Jürgen

    2016-08-01

    The copper-catalyzed cycloaddition of organic azides and alkynes (CuAAC) is one of the most popular reactions for rapid assembly of multifunctional molecular frameworks from commercially available building blocks. It is also attractive for synthesis of conjugates of multidentate chelate ligands (chelators) with molecular targeting vectors, such as peptides or proteins, which serve as precursors for labeling with metal radionuclides or are useful as MRI contrast agents after Gd(III) complexation. However, applicability of CuAAC for such purposes is complicated by formation of unwanted copper chelates. The alternative use of copper-free click chemistry, for example, the strain-promoted alkyne-azide cycloaddition (SPAAC) or the Diels-Alder reaction of tetrazines and strained alkenes, entails other specific challenges: Introduction of large, isomerically non-homogeneous and hydrophobic linker groups affects product homogeneity and can severely change pharmacokinetic profiles. Against this background, this review elucidates scope and applicability of both Cu-catalyzed and Cu-free alkyne-azide cycloadditions pertinent to the elaboration of radiometal chelates and MRI contrast agents, with an emphasis on strategies to tackle the problem of copper complexation during CuAAC. PMID:27333118

  5. Impact of donor-acceptor geometry and metal chelation on photophysical properties and applications of triarylboranes.

    PubMed

    Hudson, Zachary M; Wang, Suning

    2009-10-20

    Three-coordinate organoboron compounds have recently found a wide range of applications in materials chemistry as nonlinear optical materials, chemical sensors, and emitters for organic light-emitting diodes (OLEDs). These compounds are excellent electron acceptors due to the empty p(pi) orbital on the boron center. When accompanied by electron donors such as amines, these molecules possess large electronic dipoles, which promote donor-acceptor charge-transfer upon excitation with light. Because of this, donor-acceptor triarylboranes are often highly luminescent both in the solid state and in solution. In this Account, we describe our research to develop donor-acceptor triarylboranes as efficient blue emitters for OLEDs. Through the use of hole-transporting donor groups such as 1-napthylphenylamines, we have prepared multifunctional triarylboranes that can act as the emissive, electron transport, or hole transport layers in OLEDs. We have also examined donor-acceptor compounds based on 2,2'-dipyridylamine or 7-azaindolyl donors, several of which have fluorescent quantum efficiencies approaching 100%. We are also investigating the chemistry of metal-containing triarylboranes. Our studies show that the electron-deficient boryl group can greatly facilitate metal-to-ligand charge-transfer transitions and phosphorescence. In addition, electronegative linker groups such as 2,2'-bipyridine can act in synergy with metal chelation to greatly improve the electron-accepting ability and Lewis acidity of triarylboranes. Donor-acceptor triarylboranes developed in our laboratory can also serve as a series of "switch-on" sensors for fluoride ions. When the donor and acceptor are linked by rigid naphthyl or nonrigid silane linkers, donor-acceptor conjugation is disrupted and charge transfer occurs primarily through space. The binding of fluoride ions to the boron center disrupts this charge transfer, activating alternative pi --> pi* transitions in the molecule and changing the

  6. Commentary on the abuse of metal chelation therapy in patients with autism spectrum disorders.

    PubMed

    Brent, Jeffrey

    2013-12-01

    Approximately half a million patients with autism spectrum disorders are subjected to chelation therapy in the US annually. The overwhelming majority of such cases are chelated for non-accepted medical indications. These patients may seek evaluation when a urine sample is assayed after the administration of a chelating agent and the values obtained have been improperly compared to references ranges for non-chelated urines, causing falsely elevated results. Legitimate practitioners confronted with such data must decide, preferably in consultation with the patient or their guardian(s), whether to do further testing using legitimate methodology or to simply dismiss the results of the improper testing. Bayesian principles tell us that further testing is likely to yield results within normal reference ranges. However, under some circumstances, it is useful to do such testing in order to demonstrate that there is no need for chelation therapy. Unnecessary chelation therapy is expensive, can cause significant acute adverse effects, and may be associated with long-term consequences. PMID:24113859

  7. N-Acetyl-Cysteine as Effective and Safe Chelating Agent in Metal-on-Metal Hip-Implanted Patients: Two Cases

    PubMed Central

    Lonati, Davide; Ragghianti, Benedetta; Ronchi, Anna; Vecchio, Sarah; Locatelli, Carlo Alessandro

    2016-01-01

    Systemic toxicity associated with cobalt (Co) and chromium (Cr) containing metal hip alloy may result in neuropathy, cardiomyopathy, and hypothyroidism. However clinical management concerning chelating therapy is still debated in literature. Here are described two metal-on-metal hip-implanted patients in which N-acetyl-cysteine decreased elevated blood metal levels. A 67-year-old male who underwent Co/Cr hip implant in September 2009 referred to our Poison Control Centre for persisting elevated Co/Cr blood levels (from March 2012 to November 2014). After receiving oral high-dose N-acetyl-cysteine, Co/Cr blood concentrations dropped by 86% and 87% of the prechelation levels, respectively, and persisted at these latter concentrations during the following 6 months of follow-up. An 81-year-old female who underwent Co/Cr hip implant in January 2007 referred to our Centre for detection of high Co and Cr blood levels in June 2012. No hip revision was indicated. After a therapy with oral high-dose N-acetyl-cysteine Co/Cr blood concentrations decreased of 45% and 24% of the prechelation levels. Chelating agents reported in hip-implanted patients (EDTA, DMPS, and BAL) are described in few cases. N-acetyl-cysteine may provide chelating sites for metals and in our cases reduced Co and Cr blood levels and resulted well tolerable. PMID:27148463

  8. Removal of heavy metal species from industrial sludge with the aid of biodegradable iminodisuccinic acid as the chelating ligand.

    PubMed

    Wu, Qing; Duan, Gaoqi; Cui, Yanrui; Sun, Jianhui

    2015-01-01

    High level of heavy metals in industrial sludge was the obstacle of sludge disposal and resource recycling. In this study, iminodisuccinic acid (IDS), a biodegradable chelating ligand, was used to remove heavy metals from industrial sludge generated from battery industry. The extraction of cadmium, copper, nickel, and zinc from battery sludge with aqueous solution of IDS was studied under various conditions. It was found that removal efficiency greatly depends on pH, chelating agent's concentration, as well as species distribution of metals. The results showed that mildly acidic and neutral systems were not beneficial to remove cadmium. About 68 % of cadmium in the sample was extracted at the molar ratio of IDS to heavy metals 7:1 without pH adjustment (pH 11.5). Copper of 91.3 % and nickel of 90.7 % could be removed by IDS (molar ratio, IDS: metals = 1:1) with 1.2 % phosphoric acid effectively. Removal efficiency of zinc was very low throughout the experiment. Based on the experimental results, IDS could be a potentially useful chelant for heavy metal removal from battery industry sludge.

  9. Removal of heavy metal species from industrial sludge with the aid of biodegradable iminodisuccinic acid as the chelating ligand.

    PubMed

    Wu, Qing; Duan, Gaoqi; Cui, Yanrui; Sun, Jianhui

    2015-01-01

    High level of heavy metals in industrial sludge was the obstacle of sludge disposal and resource recycling. In this study, iminodisuccinic acid (IDS), a biodegradable chelating ligand, was used to remove heavy metals from industrial sludge generated from battery industry. The extraction of cadmium, copper, nickel, and zinc from battery sludge with aqueous solution of IDS was studied under various conditions. It was found that removal efficiency greatly depends on pH, chelating agent's concentration, as well as species distribution of metals. The results showed that mildly acidic and neutral systems were not beneficial to remove cadmium. About 68 % of cadmium in the sample was extracted at the molar ratio of IDS to heavy metals 7:1 without pH adjustment (pH 11.5). Copper of 91.3 % and nickel of 90.7 % could be removed by IDS (molar ratio, IDS: metals = 1:1) with 1.2 % phosphoric acid effectively. Removal efficiency of zinc was very low throughout the experiment. Based on the experimental results, IDS could be a potentially useful chelant for heavy metal removal from battery industry sludge. PMID:25115899

  10. Ni (II), Cu (II) and Zn (II) Metal Chelates With Some Thiazole Derived Schiff-Bases: Their Synthesis, Characterization and Bactericidal Properties

    PubMed Central

    Chohan, Zahid H.

    1999-01-01

    A number of thiazole derived tridentate Schiff-bases (LH) and its metal chelates of the type [M(L)2X] where M=Ni(II), Cu(II) and Zn(II), L=substituted salicylaldehyde (5-H, 5-CH3, 5-OCH3, 5-NO2 and 5-Cl) and X=CI have been synthesized and characterized with the help of elemental analyses, conductivity measurements, magnetic moments, UV-Vis, IR and NMR spectral data. An octahedral structure for Ni(II) and Zn(II) and a distorted octahedral structure for Cu(II) chelates have been proposed. All the Schiff-bases and their metal chelates have been screened for their biological activity against Escherichia coli, Staphylococcus aureous , Pseudomonas aeruginosa and Klebsiella pneumonae and in comparison, the metal chelates have been shown to possess more antibacterial activity than the uncomplexed Schiff-bases. PMID:18475884

  11. The use of a biodegradable chelator for enhanced phytoextraction of heavy metals by Festuca arundinacea from municipal solid waste compost and associated heavy metal leaching.

    PubMed

    Zhao, Shulan; Jia, Lina; Duo, Lian

    2013-02-01

    In a column experiment with horizontal permeable barriers, the effects of a biodegradable chelator-nitrilotriacetic acid (NTA) on the uptake of heavy metals from municipal solid waste (MSW) compost by Festuca arundinacea and metal leaching were investigated. The use of NTA was effective in increasing Cu, Pb, and Zn uptakes in shoots of two crops of F. arundinacea. In columns with barriers and treated with 20 mmol NTA per kg MSW compost, metal uptakes by the first and second crop of F. arundinacea were, respectively, 3.8 and 4.0 times for Pb, and 1.8 and 1.7 times for Zn greater with the added NTA than without it. Though NTA application mobilized metals, it caused only slight leaching of metals from MSW compost. Permeable barriers positioned between compost and soil effectively reduced metal leaching. NTA-assisted phytoextraction by turfgrass with permeable barriers to cleanup heavy metal contaminated MSW compost should be environmentally safe.

  12. Molar absorption coefficients and stability constants of metal complexes of 4-(2-pyridylazo)resorcinol (PAR): Revisiting common chelating probe for the study of metalloproteins.

    PubMed

    Kocyła, Anna; Pomorski, Adam; Krężel, Artur

    2015-11-01

    4-(2-Pyridylazo)resorcinol (PAR) is one of the most popular chromogenic chelator used in the determination of the concentrations of various metal ions from the d, p and f blocks and their affinities for metal ion-binding biomolecules. The most important characteristics of such a sensor are the molar absorption coefficient and the metal-ligand complex dissociation constant. However, it must be remembered that these values are dependent on the specific experimental conditions (e.g. pH, solvent components, and reactant ratios). If one uses these values to process data obtained in different conditions, the final result can be under- or overestimated. We aimed to establish the spectral properties and the stability of PAR and its complexes accurately with Zn(2+), Cd(2+), Hg(2+), Co(2+), Ni(2+), Cu(2+), Mn(2+) and Pb(2+) at a multiple pH values. The obtained results account for the presence of different species of metal-PAR complexes in the physiological pH range of 5 to 8 and have been frequently neglected in previous studies. The effective molar absorption coefficient at 492 nm for the ZnHx(PAR)2 complex at pH7.4 in buffered water solution is 71,500 M(-1) cm(-1), and the dissociation constant of the complex in these conditions is 7.08×10(-13) M(2). To confirm these values and estimate the range of the dissociation constants of zinc-binding biomolecules that can be measured using PAR, we performed several titrations of zinc finger peptides and zinc chelators. Taken together, our results provide the updated parameters that are applicable to any experiment conducted using inexpensive and commercially available PAR.

  13. ChelomEx: Isotope-assisted discovery of metal chelates in complex media using high-resolution LC-MS.

    PubMed

    Baars, Oliver; Morel, François M M; Perlman, David H

    2014-11-18

    Chelating agents can control the speciation and reactivity of trace metals in biological, environmental, and laboratory-derived media. A large number of trace metals (including Fe, Cu, Zn, Hg, and others) show characteristic isotopic fingerprints that can be exploited for the discovery of known and unknown organic metal complexes and related chelating ligands in very complex sample matrices using high-resolution liquid chromatography mass spectrometry (LC-MS). However, there is currently no free open-source software available for this purpose. We present a novel software tool, ChelomEx, which identifies isotope pattern-matched chromatographic features associated with metal complexes along with free ligands and other related adducts in high-resolution LC-MS data. High sensitivity and exclusion of false positives are achieved by evaluation of the chromatographic coherence of the isotope pattern within chromatographic features, which we demonstrate through the analysis of bacterial culture media. A built-in graphical user interface and compound library aid in identification and efficient evaluation of results. ChelomEx is implemented in MatLab. The source code, binaries for MS Windows and MAC OS X as well as test LC-MS data are available for download at SourceForge ( http://sourceforge.net/projects/chelomex ).

  14. New biodegradable organic-soluble chelating agents for simultaneous removal of heavy metals and organic pollutants from contaminated media.

    PubMed

    Ullmann, Amos; Brauner, Neima; Vazana, Shlomi; Katz, Zhanna; Goikhman, Roman; Seemann, Boaz; Marom, Hanit; Gozin, Michael

    2013-09-15

    Advanced biodegradable and non-toxic organic chelators, which are soluble in organic media, were synthesized on the basis of the S,S-ethylenediamine-disuccinate (S,S-EDDS) ligand. The modifications suggested in this work include attachment of a lipophilic hydrocarbon chain ("tail") to one or both nitrogen atoms of the S,S-EDDS. The new ligands were designed and evaluated for application in the Sediments Remediation Phase Transition Extraction (SR-PTE) process. This novel process is being developed for the simultaneous removal of both heavy metals and organic pollutants from contaminated soils, sediments or sludge. The new chelators were designed to bind various target metal ions, to promote extraction of these ions into organic solvents. Several variations of attached tails were synthesized and tested. The results for one of them, N,N'-bis-dodecyl-S,S-EDDS (C24-EDDS), showed that the metal-ligand complexes are concentrated in the organic-rich phase in the Phase Transition Extraction process (more than 80%). Preliminary applications of the SR-PTE process with the C24-EDDS ligand were conducted also on actually contaminated sludge (field samples). The extraction of five toxic metals, namely, Cd, Cu, Ni, Pb and Zn was examined. In general, the extraction performance of the new ligand was not less than that of S,S-EDDS when a sufficient ligand-to-extracted ion ratio (about 4:1 was applied.

  15. ChelomEx: Isotope-assisted discovery of metal chelates in complex media using high-resolution LC-MS.

    PubMed

    Baars, Oliver; Morel, François M M; Perlman, David H

    2014-11-18

    Chelating agents can control the speciation and reactivity of trace metals in biological, environmental, and laboratory-derived media. A large number of trace metals (including Fe, Cu, Zn, Hg, and others) show characteristic isotopic fingerprints that can be exploited for the discovery of known and unknown organic metal complexes and related chelating ligands in very complex sample matrices using high-resolution liquid chromatography mass spectrometry (LC-MS). However, there is currently no free open-source software available for this purpose. We present a novel software tool, ChelomEx, which identifies isotope pattern-matched chromatographic features associated with metal complexes along with free ligands and other related adducts in high-resolution LC-MS data. High sensitivity and exclusion of false positives are achieved by evaluation of the chromatographic coherence of the isotope pattern within chromatographic features, which we demonstrate through the analysis of bacterial culture media. A built-in graphical user interface and compound library aid in identification and efficient evaluation of results. ChelomEx is implemented in MatLab. The source code, binaries for MS Windows and MAC OS X as well as test LC-MS data are available for download at SourceForge ( http://sourceforge.net/projects/chelomex ). PMID:25333600

  16. A demonstration model for a selective and recyclable uptake of metals from water: Fe(III) ions complexation and release by a supported natural fluorescent chelator.

    PubMed

    Mureseanu, M; Renard, G; Galarneau, A; Lerner, D A

    2003-06-13

    We describe here the preliminary stage of development of a process aiming at the selective uptake and release of metal ions from water. The process envisioned involves the encapsulation of highly selective natural chelates secreted by bacteria or other living species in mesoporous solids that could be used as usual resins. To demonstrate the feasibility of the concept, we use a model system involving pyoverdin, a natural Fe(III) ions chelator from a Pseudomonas fluorescens strain, encapsulated in a mesoporous templated silica. For this model study, the native fluorescence of the chelator allows a simpler follow-up and quantification of the uptake and release processes. PMID:18969073

  17. N- vs. C-Domain Selectivity of Catalytic Inactivation of Human Angiotensin Converting Enzyme by Lisinopril-Coupled Transition Metal Chelates

    PubMed Central

    Hocharoen, Lalintip; Joyner, Jeff C.; Cowan, J. A.

    2014-01-01

    The N- and C-terminal domains of human somatic Angiotensin I Converting Enzyme (sACE-1) demonstrate distinct physiological functions, with resulting interest in the development of domain-selective inhibitors for specific therapeutic applications. Herein, the activity of lisinopril-coupled transition metal chelates were tested for both reversible binding and irreversible catalytic inactivation of sACE-1. C/N domain binding selectivity ratios ranged from 1 to 350, while rates of irreversible catalytic inactivation of the N- and C-domains were found to be significantly greater for the N-domain, suggesting a more optimal orientation of the M-chelate-lisinopril complexes within the active site of the N-domain of sACE-1. Finally, the combined effect of binding selectivity and inactivation selectivity was assessed for each catalyst (double-filter selectivity factors), and several catalysts were found to cause domain-selective catalytic inactivation. The results of this study demonstrate the ability to optimize the target selectivity of catalytic metallopeptides through both binding and orientation factors (double-filter effect). PMID:24228790

  18. New chelating reagents for preconcentration, separation, determination of metal complexes by high performance liquid chromatography and solid phase extraction

    SciTech Connect

    Qian, Yan wen.

    1991-12-03

    A general scheme is outlined for rapid determination of metal cations by complexation and subsequent HPLC separation. The synthesis and general properties are described for several new thiohydrazone chelating reagents. Solubility considerations suggest that the metal complexes have a positive charge. Excellent chromatographic separations are obtained for mixtures of up to seven metal complexes. Addition of a positively charged additive to the eluent is shown to have a significant effect on both the retention times and sharpness of the chromatographic peaks. Separation of the metal complexes on resins with a permanent charge is also shown to be feasible. Two new hydrazone reagents have been synthesized and characterized. Trace metal ions in aqueous solution are complexed by one of the hydrazones and the resulting metal complexes are solid phase extracted onto a mini cation-exchange or polymeric column. The uptake of metal complexes is complete and the elution step is fast and complete. The quantitative recoveries of metal ions determined by both spectrophotometric method and ICP-MS are very satisfactory and agree with each other.

  19. Resolution and analysis of the components in dual emission of mixed-chelate/ortho-metalate complexes of iridium(III)

    SciTech Connect

    Wilde, A.P.; King, K.A.; Watts, R.J. )

    1991-01-24

    Spectral resolutions of the two components in dual emissions for four mixed-chelate/ortho-metalated complexes of Ir(III) are reported. Resolution of the component emissions from samples of the complexes Ir(bzq){sub 2}(bpy){sup +} and Ir(bzq){sub 2}(phen){sup +} (bzq = benzo(h)quinoline, bpy = 2,2{prime}-bipyridine, phen = 1,10-phenanthroline) in rigid glasses at 77 K has been achieved by time-resolved emission spectroscopy. In each case the lower energy emissions component is assigned to a metal-to-ligand charge-transfer excited state associated with the chelating ligand and the higher energy component to a MLCT excited state associated with the ortho-metalating bzq ligand. Component in the dual emissions of Ir(ppy){sub 2}(bpy){sup +} and Ir(ppy){sub 2}(phen){sup +} (ppy = 2-phenylpyridine) are too similar in their lifetimes to permit full resolution of the two emissions by time-resolved emission spectroscopy when both components are populated by 337-nm excitation.

  20. Confirmation of heavy metal ions in used lubricating oil from a passenger car using chelating self-assembled monolayer.

    PubMed

    Ko, Young Gun; Kim, Choong Hyun

    2006-09-01

    In order to prevent engine failure, the oil must be changed before it loses its protective properties. It is necessary to monitor the actual physical and chemical condition of the oil to reliably determine the optimum oil-change interval. Our study focuses on the condition of the lubricating oil in an operated car engine. Shear stress curves and viscosity curves as a function of the shear rate for fresh and used lubricating oil were examined. Metal nitrate was detected in the lubricating oil from the operated car engine through the use of a chelating self-assembled monolayer.

  1. Structural and spectroscopic insight into the metal binding properties of the o-aminophenol-N,N,O-triacetic acid (APTRA) chelator: implications for design of metal indicators.

    PubMed

    Brady, Michael; Piombo, Sebastian D; Hu, Chunhua; Buccella, Daniela

    2016-08-01

    The o-aminophenol-N,N,O-triacetic acid (APTRA) chelator is employed extensively as a metal-recognition moiety in fluorescent indicators for biological free Mg(2+), as well as in low-affinity indicators for the detection of high levels of cellular Ca(2+). Despite its widespread use in sensor design, the limited metal selectivity of this chelating moiety can lead to binding of competing cations that complicate the fluorescence-based detection of metals of interest in complex samples. Reported herein are the structural characterization of APTRA complexes with various biologically relevant cations, and the thermodynamic analysis of complex formation with Mg(2+), Ca(2+) and Zn(2+). Our results indicate that the low affinity of APTRA for Mg(2+), which makes it a suitable metal-recognition moiety for sensitive analysis of typical millimolar levels of this metal in cells, stems from a much higher enthalpic cost of Mg(2+) binding compared to that of other cations. The results are discussed in the context of indicator design, highlighting the aspects that may aid the future development of fluorescent sensors with enhanced metal selectivity profiles. PMID:27430930

  2. Incorporation of transition metals into Mg-Al layered double hydroxides: Coprecipitation of cations vs. their pre-complexation with an anionic chelator

    SciTech Connect

    Tsyganok, Andrey; Sayari, Abdelhamid . E-mail: Abdel.Sayari@science.uottawa.ca

    2006-06-15

    A comparative study on two different methods for preparing Mg-Al layered double hydroxides (LDH) containing various divalent transition metals M (M=Co, Ni, Cu) has been carried out. The first (conventional) method involved coprecipitation of divalent metals M(II) with Mg(II) and Al(III) cations using carbonate under basic conditions. The second approach was based on the ability of transition metals to form stable anionic chelates with edta{sup 4-} (edta{sup 4-}=ethylenediaminetetraacetate) that were synthesized and further introduced into LDH by coprecipitation with Mg and Al. The synthesized LDHs were characterized by X-ray diffraction (XRD) and X-ray fluorescence (XRF) methods, thermogravimetry with mass-selective detection of decomposition products (TG-MSD), Fourier transform infrared (FTIR) and Raman spectroscopy techniques. The results obtained were discussed in terms of efficiency of transition metal incorporation into the LDH structure, thermal stability of materials and the ability of metal chelates to intercalate the interlayer space of Mg-Al LDH. Vibrational spectroscopy studies confirmed that the integrity of the metal chelates was preserved upon incorporation into the LDH. - Graphical abstract: Two ways for introducing transition metals M(II) into Mg-Al layered double hydroxides (MY{sup 2-} denotes the edta chelate of transition metal M(II)).0.

  3. Multiple function fluorescein probe performs metal chelation, disaggregation, and modulation of aggregated Aβ and Aβ-Cu complex.

    PubMed

    Muthuraj, B; Layek, Sourav; Balaji, S N; Trivedi, Vishal; Iyer, Parameswar Krishnan

    2015-11-18

    An exceptional probe comprising indole-3-carboxaldehyde fluorescein hydrazone (FI) performs multiple tasks, namely, disaggregating amyloid β (Aβ) aggregates in different biomarker environments such as cerebrospinal fluid (CSF), Aβ1-40 fibrils, β-amyloid lysozyme aggregates (LA), and U87 MG human astrocyte cells. Additionally, the probe FI binds with Cu(2+) ions selectively, disrupts the Aβ aggregates that vary from few nanometers to micrometers, and prevents their reaggregation, thereby performing disaggregation and modulation of amyloid-β in the presence as well as absence of Cu(2+) ion. The excellent selectivity of probe FI for Cu(2+) was effectively utilized to modulate the assembly of metal-induced Aβ aggregates by metal chelation with the "turn-on" fluorescence via spirolactam ring opening of FI as well as the metal-free Aβ fibrils by noncovalent interactions. These results confirm that FI has exceptional ability to perform multifaceted tasks such as metal chelation in intracellular conditions using Aβ lysozyme aggregates in cellular environments by the disruption of β-sheet rich Aβ fibrils into disaggregated forms. Subsequently, it was confirmed that FI had the ability to cross the blood-brain barrier and it also modulated the metal induced Aβ fibrils in cellular environments by "turn-on" fluorescence, which are the most vital properties of a probe or a therapeutic agent. Furthermore, the morphology changes were examined by atomic force microscopy (AFM), polarizable optical microscopy (POM), fluorescence microscopy, and dynamic light scattering (DLS) studies. These results provide very valuable clues on the Aβ (CSF Aβ fibrils, Aβ1-40 fibrils, β-amyloid lysozyme aggregates) disaggregation behavior via in vitro studies, which constitute the first insights into intracellular disaggregation of Aβ by "turn-on" method thereby influencing amyloidogenesis.

  4. Separation of selected transition metals by capillary chelation ion chromatography using acetyl-iminodiacetic acid modified capillary polymer monoliths.

    PubMed

    Moyna, Áine; Connolly, Damian; Nesterenko, Ekaterina; Nesterenko, Pavel N; Paull, Brett

    2012-08-01

    Capillary housed laurylmethacrylate-co-ethylene dimethacrylate (LMA-co-EDMA) polymer monoliths were fabricated, functionalised with varying amounts of vinyl azlactone, followed by immobilisation of iminodiacetic acid (IDA), forming a range of acetyl-iminodiacetic acid (AIDA) functionalised monoliths, applied to the chelation ion chromatographic separation of selected transition and heavy metals. A number of monoliths of varying length and ligand density were prepared, resulting in increased cation retention and chromatographic resolution on those displaying the highest capacity. Ligand density and related column capacity were confirmed visually using scanning capacitively coupled contactless conductivity detection (sC(4)D) techniques. Column temperature studies to determine retention mechanism and the effect of temperature on the retention of Mn(II), Cd(II) and Cu(II) was investigated, showing an increase in retention with increased temperature for Cd(II) and Cu(II), whilst a decrease in retention was obtained for Mn(II). Isocratic capillary chelation ion chromatographic separations of Mn(II), Cd(II) and Cu(II) were obtained, with dual peak detection demonstrated using combined on-column C(4)D detection and UV-Visible detection following the post-capillary column reaction of the eluted metals with 4-(2-pyridylazo) resorcinol (PAR).

  5. A tomato stem cell extract, containing antioxidant compounds and metal chelating factors, protects skin cells from heavy metal-induced damages.

    PubMed

    Tito, Annalisa; Carola, Antonietta; Bimonte, Marida; Barbulova, Ani; Arciello, Stefania; de Laurentiis, Francesco; Monoli, Irene; Hill, Jacqueline; Gibertoni, Simone; Colucci, Gabriella; Apone, Fabio

    2011-12-01

    Heavy metals can cause several genotoxic effects on cells, including oxidative stress, DNA sequence breakage and protein modification. Among the body organs, skin is certainly the most exposed to heavy metal stress and thus the most damaged by the toxic effects that these chemicals cause. Moreover, heavy metals, in particular nickel, can induce the over-expression of collagenases (enzymes responsible for collagen degradation), leading to weakening of the skin extracellular matrix. Plants have evolved sophisticated mechanisms to protect their cells from heavy metal toxicity, including the synthesis of metal chelating proteins and peptides, such as metallothioneins and phytochelatins (PC), which capture the metals and prevent the damages on the cellular structures. To protect human skin cells from heavy metal toxicity, we developed a new cosmetic active ingredient from Lycopersicon esculentum (tomato) cultured stem cells. This product, besides its high content of antioxidant compounds, contained PC, effective in the protection of skin cells towards heavy metal toxicity. We have demonstrated that this new product preserves nuclear DNA integrity from heavy metal damages, by inducing genes responsible for DNA repair and protection, and neutralizes the effect of heavy metals on collagen degradation, by inhibiting collagenase expression and inducing the synthesis of new collagen.

  6. Synthesis of an Isomer of the Decalinoyltetramic Acid Methiosetin by a Stereocontrolled IMDA Reaction of a Metal-Chelated 3-Trienoyltetramate.

    PubMed

    Winterer, Markus; Kempf, Karl; Schobert, Rainer

    2016-09-01

    An isomer of the 3-decalinoyltetramic acid methiosetin was synthesized for the first time. The decalin moiety was established by a late-stage intramolecular Diels-Alder cyclization catalyzed by Me2AlCl or La(OTf)3. Its high diastereoselectivity arose from stereoinduction by a well-defined metal O,O-chelate complex of the 3-acyltetramic acid moiety. The nature of the metal and the bulkiness of the residues at the tetramic acid chelator are decisive for the stereochemical outcome.

  7. Synthesis of an Isomer of the Decalinoyltetramic Acid Methiosetin by a Stereocontrolled IMDA Reaction of a Metal-Chelated 3-Trienoyltetramate.

    PubMed

    Winterer, Markus; Kempf, Karl; Schobert, Rainer

    2016-09-01

    An isomer of the 3-decalinoyltetramic acid methiosetin was synthesized for the first time. The decalin moiety was established by a late-stage intramolecular Diels-Alder cyclization catalyzed by Me2AlCl or La(OTf)3. Its high diastereoselectivity arose from stereoinduction by a well-defined metal O,O-chelate complex of the 3-acyltetramic acid moiety. The nature of the metal and the bulkiness of the residues at the tetramic acid chelator are decisive for the stereochemical outcome. PMID:27551958

  8. 13C and 113Cd NMR studies of the chelation of metal ions by the calcium binding protein parvalbumin.

    PubMed

    Bjornson, M E; Corson, D C; Sykes, B D

    1985-10-01

    13C NMR spectra are presented for the calcium binding protein parvalbumin (pI 4.25) from carp muscle in several different metal bound forms: with Ca2+ in both the CD and EF calcium binding sites, with Cd2+ in both sites, with 113Cd2+ in both sites, and with 113Cd2+ in the CD site and Lu3+ in the EF site. The different metals differentially shift the 13C NMR resonances of the protein ligands involved in chelation of the metal ion. In addition, direct 13C-113Cd spin-spin coupling is observed which allows the assignment of protein carbonyl and carboxyl 13C NMR resonances to ligands directly interacting with the metal ions in the CD and EF binding sites. The displacement of 113Cd2+ from the EF site by Lu3+ further allows these resonances to be assigned to the CD or EF site. The occupancy of the two sites in the two cadmium species and in the mixed Cd2+/Lu3+ species is verified by 113Cd NMR. The resolution in these 113Cd NMR spectra is sufficient to demonstrate direct interaction between the two metal binding sites.

  9. Metal chelation, radical scavenging and inhibition of Aβ₄₂ fibrillation by food constituents in relation to Alzheimer's disease.

    PubMed

    Chan, Stephen; Kantham, Srinivas; Rao, Venkatesan M; Palanivelu, Manoj Kumar; Pham, Hoang L; Shaw, P Nicholas; McGeary, Ross P; Ross, Benjamin P

    2016-05-15

    Various food constituents have been proposed as disease-modifying agents for Alzheimer's disease (AD), due to epidemiological evidence of their beneficial effects, and for their ability to ameliorate factors linked to AD pathogenesis, namely by: chelating iron, copper and zinc; scavenging reactive oxygen species; and suppressing the fibrillation of amyloid-beta peptide (Aβ). In this study, nine different food constituents (l-ascorbic acid, caffeic acid, caffeine, curcumin, (-)-epigallocatechin gallate (EGCG), gallic acid, propyl gallate, resveratrol, and α-tocopherol) were investigated for their effects on the above factors, using metal chelation assays, antioxidant assays, and assays of Aβ42 fibrillation. An assay method was developed using 5-Br-PAPS to examine the complexation of Zn(II) and Cu(II). EGCG, gallic acid, and curcumin were identified as a multifunctional compounds, however their poor brain uptake might limit their therapeutic effects. The antioxidants l-ascorbic acid and α-tocopherol, with better brain uptake, deserve further investigation for specifically addressing oxidative stress within the AD brain. PMID:26775960

  10. Metal chelation, radical scavenging and inhibition of Aβ₄₂ fibrillation by food constituents in relation to Alzheimer's disease.

    PubMed

    Chan, Stephen; Kantham, Srinivas; Rao, Venkatesan M; Palanivelu, Manoj Kumar; Pham, Hoang L; Shaw, P Nicholas; McGeary, Ross P; Ross, Benjamin P

    2016-05-15

    Various food constituents have been proposed as disease-modifying agents for Alzheimer's disease (AD), due to epidemiological evidence of their beneficial effects, and for their ability to ameliorate factors linked to AD pathogenesis, namely by: chelating iron, copper and zinc; scavenging reactive oxygen species; and suppressing the fibrillation of amyloid-beta peptide (Aβ). In this study, nine different food constituents (l-ascorbic acid, caffeic acid, caffeine, curcumin, (-)-epigallocatechin gallate (EGCG), gallic acid, propyl gallate, resveratrol, and α-tocopherol) were investigated for their effects on the above factors, using metal chelation assays, antioxidant assays, and assays of Aβ42 fibrillation. An assay method was developed using 5-Br-PAPS to examine the complexation of Zn(II) and Cu(II). EGCG, gallic acid, and curcumin were identified as a multifunctional compounds, however their poor brain uptake might limit their therapeutic effects. The antioxidants l-ascorbic acid and α-tocopherol, with better brain uptake, deserve further investigation for specifically addressing oxidative stress within the AD brain.

  11. Hypoxia inducible factor prolyl hydroxylases as targets for neuroprotection by “antioxidant” metal chelators: from ferroptosis to stroke

    PubMed Central

    Speer, Rachel E.; Karuppagounder, Saravanan S.; Basso, Manuela; Sleiman, Sama; Kumar, Amit; Brand, David; Smirnova, Natalya; Gazaryan, Irina; Khim, Soah J.; Ratan, Rajiv R.

    2015-01-01

    Neurologic conditions including stroke, Alzheimer’s disease, Parkinson’s disease and Huntington’s disease are leading causes of death and long-term disability in the United States, and efforts to develop novel therapeutics for these conditions have historically had poor success in translating from bench to bedside. Hypoxia Inducible Factor-1alpha (HIF-1α) mediates a broad, evolutionarily conserved, endogenous adaptive program to hypoxia, and manipulation of components of the HIF pathway are neuroprotective in a number of human neurological diseases and experimental models. In this review, we discuss molecular components of one aspect of hypoxic adpatation in detail, and provide perspective on which targets within this pathway appear to be ripest for preventing and repairing neurodegeneration. Further, we highlight the role of HIF prolyl hydroxylases as emerging targets for the salutary effects of metal chelators on ferroptosis in vitro as well in animal models of neurological diseases. PMID:23376032

  12. Antioxidant effects of coumarins include direct radical scavenging, metal chelation and inhibition of ROS-producing enzymes.

    PubMed

    Filipský, Tomáš; Říha, Michal; Macáková, Kateřina; Anzenbacherová, Eva; Karlíčková, Jana; Mladěnka, Přemysl

    2015-01-01

    Coumarins represent a large group of 1,2-benzopyrone derivatives which have been identified in many natural sources and synthetized as well. Several studies have shown that their antioxidant capacity is not based only on direct scavenging of reactive oxygen and nitrogen species (RONS) but other mechanisms are also involved. These include: a) the chelation of transient metals iron and copper, which are known to catalyse the Fenton reaction; and b) the inhibition of RONS-producing enzymes (e.g. xanthine oxidase, myeloperoxidase and lipoxygenase), suggesting that mechanism(s) involved on cellular level are complex and synergistic. Moreover, many factors must be taken into account when analysing structure-antioxidant capacity relationships of coumarins due to different in vitro/in vivo methodological approaches. The structural features necessary for the direct RONS scavenging and metal chelation are apparently similar and the ideal structures are 6,7-dihydroxy- or 7,8-dihydroxycoumarins. However, the clinical outcome is unknown, because these coumarins are able to reduce copper and iron, and may thus paradoxically potentiate the Fenton chemistry. The similar structural features appear to be associated with inhibition of lipoxygenase, probably due to interference with iron in its active site. Contrarily, 6,7-dihydroxycoumarin seems to be the most active coumarin in the inhibition of xanthine oxidase while its derivative bearing the 4-methyl group or 7,8-dihydroxycoumarin are less active or inactive. In addition, coumarins may hinder the induction of inducible NO-synthase and cyclooxygenase- 2. Sparse data on inhibition of myeloperoxidase do not enable any clear conclusion, but some coumarins may block it.

  13. Chelation therapy for the management of diabetic complications: a hypothesis and a proposal for clinical laboratory assessment of metal ion homeostasis in plasma.

    PubMed

    Frizzell, Norma; Baynes, John W

    2014-01-01

    In a recent article, we presented the hypothesis that decompartmentalized metal ions are a major contributor to the development of diabetic complications and supported the use of chelation therapy for the treatment of diabetic complications [Nagai R, Murray DB, Metz TO, Baynes JW. Chelation: a fundamental mechanism of action of AGE inhibitors, AGE breakers, and other inhibitors of diabetes complications. Diabetes 2012;61:549-59]. Evidence in support of this hypothesis included the observation that many drugs used in the treatment of diabetes are chelators, that advanced glycation end product (AGE) inhibitors and AGE breakers lack carbonyl-trapping or AGE-breaker activity but are potent chelators, and that simple copper chelators inhibit vascular pathology in diabetes and aging. In the present article, we extend this hypothesis, proposing the interplay between copper and iron in the development of pathology in diabetes and other chronic age-related diseases, including atherosclerosis and neurodegenerative diseases. We also discuss the need and provide a framework for the development of a clinical laboratory test to assess plasma autoxidative catalytic activity and transition metal homeostasis in vivo.

  14. The antioxidant properties of theaflavins and their gallate esters--radical scavengers or metal chelators?

    PubMed

    Miller, N J; Castelluccio, C; Tijburg, L; Rice-Evans, C

    1996-08-19

    The antioxidant properties of theaflavins and their gallate esters were studied by investigating their abilities to scavenge free radicals in the aqueous and lipophilic phases. The total relative antioxidant activities in the aqueous phase were assessed by measuring their direct ABTS.+ radical scavenging abilities, and by their efficacies in inhibiting the degradation of deoxyribose induced by iron. The propensities for enhancing the resistance of LDL to oxidation mediated by Cu2+ were also measured. The results show that the hierarchy of reactivity of these compounds as antioxidants is: theaflavin digallate > 3'-monogallate = 3-monogallate > theaflavin. Spectroscopic studies show that all the compounds chelate iron and copper; enhanced absorbance in the visible region is observed in the case of the iron-digallate complex, but not with copper.

  15. Regeneration of Three-Way Automobile Catalysts using Biodegradable Metal Chelating Agent – S, S-Ethylenediamine Disuccinic Acid (S, S-EDDS)

    EPA Science Inventory

    Regeneration of the activity of three-way catalytic converters (TWCs) was tested for the first time using a biodegradable metal chelating agent (S, S. Ethylenediamine disuccinic acid (S, S-EDDS). The efficiency of this novel environmentally friendly solvent in removing various c...

  16. Recovery of nickel and cobalt from organic acid complexes: adsorption mechanisms of metal-organic complexes onto aminophosphonate chelating resin.

    PubMed

    Deepatana, A; Valix, M

    2006-09-21

    This study examined the recovery of nickel and cobalt from organic acid complexes using a chelating aminophosphonate Purolite S950 resin. These metal complexes are generated by bioleaching nickel laterite ores, a commercial nickel and cobalt mineral oxide, with heterotrophic organism and their metabolites or organic acid products. Equilibrium adsorption tests were conducted as a function of Ni and Co concentrations (15-2000 mg/L), solution pH (0.01 and 0.1 M acids) and three metabolic complexing agents (citrate, malate and lactate). It was shown that the adsorption of the various Ni- and Co-complexes on Purolite were quite low, 16-18 and 5.4-9 mg/g of resin, respectively, in comparison to the smaller nickel ions and nickel sulfate. This was attributed to the bulky organic ligands which promoted crowding effect or steric hindrance. The adsorption of these complexes was further hampered by the strong affinity of the resin to H+ ions under acidic conditions. Mechanisms of adsorption, as inferred from the fitted empirical Langmuir and Freundlich models, were correlated to the proposed steric hindrance and competitive adsorption effects. Nickel and cobalt elution from the resin were found be effective and were independent of the type of metal complexes and metal concentrations. This study demonstrated the relative challenges involved in recovering nickel and cobalt from bioleaching solutions. PMID:16698178

  17. Sequential application of chelating agents and innovative surfactants for the enhanced electroremediation of real sediments from toxic metals and PAHs.

    PubMed

    Hahladakis, John N; Lekkas, Nikolaos; Smponias, Andreas; Gidarakos, Evangelos

    2014-06-01

    This study focused on the sequential application of a chelating agent (citric acid) followed by a surfactant in the simultaneous electroremediation of real contaminated sediments from toxic metals and Polycyclic Aromatic Hydrocarbons (PAHs). Furthermore, the efficiency evaluation of two innovative non-ionic surfactants, commercially known as Poloxamer 407 and Nonidet P40, was investigated. The results indicated a removal efficacy of approximately 43% and 48% for the summation of PAHs (SUM PAHs), respectively for the aforementioned surfactants, much better than the one obtained by the use of Tween 80 (nearly 21%). Individual PAHs (e.g. fluorene) were removed in percentages that reached almost 84% and 92% in the respective electrokinetic experiments when these new surfactants were introduced. In addition, the combined-enhanced sequential electrokinetic treatment with citric acid improved dramatically the removal of Zn and As, compared to the unenhanced run, but did not favor the other toxic metals examined. Since no improvement in metal removal percentages occurred when Tween 80 was used, significant contribution to this matter should also be attributed to the solubilization capacity of these innovative, in electrokinetic remediation, non-ionic surfactants.

  18. Sequential application of chelating agents and innovative surfactants for the enhanced electroremediation of real sediments from toxic metals and PAHs.

    PubMed

    Hahladakis, John N; Lekkas, Nikolaos; Smponias, Andreas; Gidarakos, Evangelos

    2014-06-01

    This study focused on the sequential application of a chelating agent (citric acid) followed by a surfactant in the simultaneous electroremediation of real contaminated sediments from toxic metals and Polycyclic Aromatic Hydrocarbons (PAHs). Furthermore, the efficiency evaluation of two innovative non-ionic surfactants, commercially known as Poloxamer 407 and Nonidet P40, was investigated. The results indicated a removal efficacy of approximately 43% and 48% for the summation of PAHs (SUM PAHs), respectively for the aforementioned surfactants, much better than the one obtained by the use of Tween 80 (nearly 21%). Individual PAHs (e.g. fluorene) were removed in percentages that reached almost 84% and 92% in the respective electrokinetic experiments when these new surfactants were introduced. In addition, the combined-enhanced sequential electrokinetic treatment with citric acid improved dramatically the removal of Zn and As, compared to the unenhanced run, but did not favor the other toxic metals examined. Since no improvement in metal removal percentages occurred when Tween 80 was used, significant contribution to this matter should also be attributed to the solubilization capacity of these innovative, in electrokinetic remediation, non-ionic surfactants. PMID:24321329

  19. Recovery of nickel and cobalt from organic acid complexes: adsorption mechanisms of metal-organic complexes onto aminophosphonate chelating resin.

    PubMed

    Deepatana, A; Valix, M

    2006-09-21

    This study examined the recovery of nickel and cobalt from organic acid complexes using a chelating aminophosphonate Purolite S950 resin. These metal complexes are generated by bioleaching nickel laterite ores, a commercial nickel and cobalt mineral oxide, with heterotrophic organism and their metabolites or organic acid products. Equilibrium adsorption tests were conducted as a function of Ni and Co concentrations (15-2000 mg/L), solution pH (0.01 and 0.1 M acids) and three metabolic complexing agents (citrate, malate and lactate). It was shown that the adsorption of the various Ni- and Co-complexes on Purolite were quite low, 16-18 and 5.4-9 mg/g of resin, respectively, in comparison to the smaller nickel ions and nickel sulfate. This was attributed to the bulky organic ligands which promoted crowding effect or steric hindrance. The adsorption of these complexes was further hampered by the strong affinity of the resin to H+ ions under acidic conditions. Mechanisms of adsorption, as inferred from the fitted empirical Langmuir and Freundlich models, were correlated to the proposed steric hindrance and competitive adsorption effects. Nickel and cobalt elution from the resin were found be effective and were independent of the type of metal complexes and metal concentrations. This study demonstrated the relative challenges involved in recovering nickel and cobalt from bioleaching solutions.

  20. The scientific basis for chelation: animal studies and lead chelation.

    PubMed

    Smith, Donald; Strupp, Barbara J

    2013-12-01

    This presentation summarizes several of the rodent and non-human studies that we have conducted to help inform the efficacy and clinical utility of succimer (meso-2,3-dimercaptosuccincinic acid) chelation treatment. We address the following questions: (1) What is the extent of body lead, and in particular brain lead reduction with chelation, and do reductions in blood lead accurately reflect reductions in brain lead? (2) Can succimer treatment alleviate the neurobehavioral impacts of lead poisoning? And (3) does succimer treatment, in the absence of lead poisoning, produce neurobehavioral deficits? Results from our studies in juvenile primates show that succimer treatment is effective at accelerating the elimination of lead from the body, but chelation was only marginally better than the complete cessation of lead exposure alone. Studies in lead-exposed adult primates treated with a single 19-day course of succimer showed that chelation did not measurably reduce brain lead levels compared to vehicle-treated controls. A follow-up study in rodents that underwent one or two 21-day courses of succimer treatment showed that chelation significantly reduced brain lead levels, and that two courses of succimer were significantly more efficacious at reducing brain lead levels than one. In both the primate and rodent studies, reductions in blood lead levels were a relatively poor predictor of reductions in brain lead levels. Our studies in rodents demonstrated that it is possible for succimer chelation therapy to alleviate certain types of lead-induced behavioral/cognitive dysfunction, suggesting that if a succimer treatment protocol that produced a substantial reduction of brain lead levels could be identified for humans, a functional benefit might be derived. Finally, we also found that succimer treatment produced lasting adverse neurobehavioral effects when administered to non-lead-exposed rodents, highlighting the potential risks of administering succimer or other metal-chelating

  1. A field lysimeter study of heavy metal movement down the profile of soils with multiple metal pollution during chelate-enhanced phytoremediation.

    PubMed

    Hu, Ningjing; Luo, Yongming; Wu, Longhua; Song, Jing

    2007-01-01

    The agricultural soils near a copper smelter in southeast China were found to be highly contaminated with Cu, Pb, Zn, and Cd. Metal migration from the soil to groundwater presents an environmental risk that depends on the physicochemical properties of the contaminated soils. Soil solution samples were obtained using lysimeters from a loam soil with multiple metal pollutions over a period of about 1 yr. A field lysimeter study was also conducted to examine the potential use of (S, S')-ethylenediamine-N, N'-disuccinic acid trisodium salt (EDDSNa3) in chelate-enhanced phytoremedation and to evaluate the leaching of heavy metals. The average heavy metal concentrations in the soil solution (without the addition of EDDS) were high (e.g., 0.15 mg Pb L(-1) at a 50-cm depth) compared to the upper limit for protection of groundwater in China, but varied during the sampling period. Cu concentrations were not correlated with pH or dissolved organic carbon (DOC), but Zn and Cd concentrations were related to soil solution pH. EDDS enhanced metal solubility in the soil, but plant metal uptake by Elsholtzia splendens Nakai did not increase accordingly. There may be an increasing risk of groundwater pollution by Cu and the EDDS enhanced phytoremediation technique needs to be carefully applied to minimize this side effect. PMID:18246705

  2. C-H activation in pyridoxal-5'-phosphate and pyridoxamine-5'-phosphate Schiff bases: effect of metal chelation. A computational study.

    PubMed

    Casasnovas, Rodrigo; Frau, Juan; Ortega-Castro, Joaquin; Donoso, Josefa; Muñoz, Francisco

    2013-02-28

    This study reports the carbon acidities of Cα and C4′ atoms in the Schiff bases of pyridoxal-5′-phosphate (PLP) and pyridoxamine-5′-phosphate (PMP) complexed with several biologically available metal ions (Mg2+, Ni2+, Zn2+, Cu2+, Al3+, and Fe3+). Density functional theory calculations were carried out to determine the free energies of proton exchange reactions of a set of 18 carbon acids and a Schiff base used as a reference species. The experimental pK(a) values of such carbon acids were used to calibrate the computed free energies in a range of 30 pK(a) units. Eventually, the pK(a)s of the chelates were obtained by calculating the corresponding free energies against the same reference species and by considering the previous calibration. The carbon acidity of Cα in the chelates of Mg2+, Ni2+, Zn2+, and Cu2+ varies between pK(a) 22 and pK(a) 13 whereas the pK(a) values of C4′ range between 18 and 7. Chelation of trivalent metals Al3+ and Fe3+ causes further decrease of the pK(a) values of Cα and C4′ down to 10 and 5, respectively. The results highlight the efficiency of the combined action of Schiff base formation and metal chelation to activate the Cα carbon of amino acids (pK(a) 29 for zwitterionic alanine). Our results explain that the experimental increase of transamination rates by Zn2+ chelation is due to stabilization of the reactive Schiff base species with respect to the free ligand under physiological pH conditions. However, the increase in reactivity for transamination due to Cu2+ and Al3+ chelation is mostly due to C–H ligand activation. Each metal ion activates the Cα and C4′ carbon atoms to a different extent, which can be exploited to favor specific reactions on the amino acids in aqueous solution. Metal chelation hinders both intramolecular and intermolecular proton-transfer reactions of the imino, phenol, and carboxylate groups. This is the only apparent inconvenience of metal complexes in enzymatic reactions, which, in turn

  3. Grafting iminodiacetic acid on silica nanoparticles for facilitated refolding of like-charged protein and its metal-chelate affinity purification.

    PubMed

    Liu, Hu; Dong, Xiaoyan; Sun, Yan

    2016-01-15

    A series of highly charged nanoscale chelators were fabricated by grafting of poly(glycidyl methacrylate-iminodiacetic acid) (pGI) chains with iminodiacetic acid (IDA) chelating group on silica nanoparticles (SNPs) via atom transfer radical polymerization (ATRP). The nanoscale chelators, denoted as SNPs-pGI, possessed a nickel ion chelating capacity as high as 2800 μmol/g, 50 times higher than the IDA-modified Sepharose FF (IDA-Sepharose) resin reported in literature and offered a high affinity binding capacity for hexahistidine-tagged enhanced green fluorescence protein (6 × His-EGFP) after nickel ion loading. More importantly, the anionic SNPs-pGI of high charge densities displayed much better performance than IDA-Sepharose in facilitating the refolding of like-charged 6 × His-EGFP from inclusion bodies (IBs). For example, for 0.2mg/mL 6 × His-EGFP IB refolding, addition of 6.2 μL/mL SNPs-pGI with the highest charge density led to a refolding yield of 90%, over 43% higher than that obtained with 460 μL/mL IDA-Sepharose. It is notable that the much higher efficiency of the nanoscale chelator was obtained with a chelator consumption corresponding to only 1.4% of IDA-Sepharose. Moreover, the highly charged SNPs-pGI could efficiently facilitate the refolding of 6 × His-EGFP at higher IB concentrations (0.4 and 0.8 mg/mL). After refolding, nickel ions addition led to the recovery of the refolded 6 × His-EGFP with high yield (80%), purity (96%) and enrichment ratio (1.8). All the results suggest that the SNPs-pGI of high charge densities were promising for cost-effective recovery of His-tagged proteins expressed as IBs with the integrative like-charge facilitated refolding and metal-chelate affinity purification strategy.

  4. Discovery of Metal Ions Chelator Quercetin Derivatives with Potent Anti-HCV Activities.

    PubMed

    Zhong, Dongwei; Liu, Mingming; Cao, Yang; Zhu, Yelin; Bian, Shihui; Zhou, Jiayi; Wu, Fengjie; Ryu, Kum-Chol; Zhou, Lu; Ye, Deyong

    2015-04-16

    Analogues or isosteres of α,γ-diketoacid (DKA) 1a show potent inhibition of hepatitis C virus (HCV) NS5B polymerase through chelation of the two magnesium ions at the active site. The anti-HCV activity of the flavonoid quercetin (2) could partly be attributed to it being a structural mimic of DKAs. In order to delineate the structural features required for the inhibitory effect and improve the anti-HCV potency, two novel types of quercetin analogues, 7-O-arylmethylquercetins and quercetin-3-O-benzoic acid esters, were designed, synthesized and evaluated for their anti-HCV properties in cell-based assays. Among the 38 newly synthesized compounds, 7-O-substituted derivative 3i and 3-O-substituted derivative 4f were found to be the most active in the corresponding series (EC50 = 3.8 μM and 9.0 μΜ, respectively). Docking studies suggested that the quercetin analogues are capable of establishing key coordination with the two magnesium ions as well as interactions with residues at the active site of HCV NS5B.

  5. Metal chelator combined with permeability enhancer ameliorates oxidative stress-associated neurodegeneration in rat eyes with elevated intraocular pressure.

    PubMed

    Liu, P; Zhang, M; Shoeb, M; Hogan, D; Tang, Luosheng; Syed, M F; Wang, C Z; Campbell, G A; Ansari, N H

    2014-04-01

    Because as many as half of glaucoma patients on intraocular pressure (IOP)-lowering therapy continue to experience optic nerve toxicity, it is imperative to find other effective therapies. Iron and calcium ions play key roles in oxidative stress, a hallmark of glaucoma. Therefore, we tested metal chelation by means of ethylenediaminetetraacetic acid (EDTA) combined with the permeability enhancer methylsulfonylmethane (MSM) applied topically on the eye to determine if this noninvasive treatment is neuroprotective in rat optic nerve and retinal ganglion cells exposed to oxidative stress induced by elevated IOP. Hyaluronic acid (HA) was injected into the anterior chamber of the rat eye to elevate the IOP. EDTA-MSM was applied topically to the eye for 3 months. Eyeballs and optic nerves were processed for histological assessment of cytoarchitecture. Protein-lipid aldehyde adducts and cyclooxygenase-2 (COX-2) were detected immunohistochemically. HA administration increased IOP and associated oxidative stress and inflammation. Elevated IOP was not affected by EDTA-MSM treatment. However, oxidative damage and inflammation were ameliorated as reflected by a decrease in formation of protein-lipid aldehyde adducts and COX-2 expression, respectively. Furthermore, EDTA-MSM treatment increased retinal ganglion cell survival and decreased demyelination of optic nerve compared with untreated eyes. Chelation treatment with EDTA-MSM ameliorates sequelae of IOP-induced toxicity without affecting IOP. Because most current therapies aim at reducing IOP and damage occurs even in the absence of elevated IOP, EDTA-MSM has the potential to work in conjunction with pressure-reducing therapies to alleviate damage to the optic nerve and retinal ganglion cells. PMID:24509160

  6. Polymer-cobalt(III) complexes: structural analysis of metal chelates on DNA interaction and comparative cytotoxic activity.

    PubMed

    Nehru, Selvan; Arunachalam, Sankaralingam; Arun, Renganathan; Premkumar, Kumpati

    2014-01-01

    A new series of pendant-type polymer-cobalt(III) complexes, [Co(LL)2(BPEI)Cl](2+), (where BPEI = branched polyethyleneimine, LL = dipyrido[3,2-a:2',3'-c](6,7,8,9-tetrahydro)phenazine (dpqc), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq) and imidazo[4,5-f]1,10-phenanthroline (ip)) each with three different degrees of coordination have been synthesized and characterized. Studies to know the mode and strength of interaction between these polymer-metal complexes and calf thymus DNA have been performed by UV-Visible absorption and emission techniques. Among these series, each polymer metal complex having higher binding strength with DNA has been selected to test against human cancer/normal cell lines. On the basis of these spectral studies, it is proposed that our polymer-metal complexes bind with DNA mainly through intercalation along with some electrostatic binding. The order of binding strength for the complexes with ligand, dpqc > dpq > ip. The analysis of the results suggests that polymer-cobalt(III) complexes with higher degree of coordination effectively binds with DNA due to the presence of large number of positively charged cobalt(III) chelates in the polymer chain which cooperatively act to increase the overall binding strength. These polymer-cobalt(III) complexes with hydrophobic ligands around the cobalt(III) metal centre favour the base stacking interactions via intercalation. All the complexes show very good anticancer activities and increasing of binding strength results in higher inhibition value. The polymer-cobalt(III) complex with dpqc ligand possess two fold increased anticancer activity when compared to complexes with other ligands against MCF-7 cells. Besides, the complexes were insensitive towards the growth of normal cells (HEK-293) at the IC50 concentration.

  7. Comparison of methanol and acetonitrile eluents for the quantitation of chelators specific to soft-metal ions by HPLC.

    PubMed

    Ogawa, Shinya; Yoshimura, Etsuro

    2012-11-15

    HPLC eluent systems employing acetonitrile and methanol were evaluated for the quantitation of glutathione (GSH) and phytochelatin (PC(n)), a family of peptides implicated in heavy-metal detoxification in higher plants. The detection system is based on the dequenching of copper(I)-bathocuproine disulfonate and is specific for soft-metal chelators. Although both elution systems yielded comparable analytical performance for each PC(n), the acetonitrile system had a lower sensitivity for GSH and a steadily increasing baseline. The inferior properties of the acetonitrile system may be due to complex formation between acetonitrile and Cu(I) ions. Both methods were applied to measure peptide levels in the primitive red alga Cyanidioschyzon merolae. Coefficients of variation (CVs) were less than 5%, except for GSH and PC(4) determinations in the acetonitrile system, in cases when CV values were found to be 8.8% and 6.3%, respectively. Recoveries were greater than 96%, except for GSH determination in the acetonitrile system, with a recovery of 84.4%; however, the concentration measured in the acetonitrile system did not differ from that measured in the methanol system at a significance level of 0.05. PMID:23153641

  8. Catalytic properties of endoxylanase fusion proteins from Neocallimastix frontalis and effect of immobilization onto metal-chelate matrix.

    PubMed

    Mesta, Laurent; Heyraud, Alain; Joseleau, Jean Paul; Coulet, Pierre R

    2003-03-20

    The production of hybrid enzymes with novel properties and the research for new methods for enzyme immobilization in bioreactors are of major interest in biotechnology. We report here the second part of a study concerning the improvement of the properties of the endoxylanase XYN3A4 from the anaerobic fungi Neocallimastix frontalis. The effects of gene fusion and immobilization on metal-chelate matrix are also compared for the reference enzymes XYN3, XYN3A, XYN4 used for the construction of the fusion protein XYN3A4. The influence of the metal ion in the immobilization process was first investigated and best immobilization yields were obtained with the Cu(II) ion whereas best coupling efficiencies were reached with the Ni(II) ion. It was also observed that XYN3, XYN3A and XYN34 had a lower rate of hydrolysis when immobilized on Ni(II)-IDA and more difficulties to accomodate small substrates than the soluble enzymes. Nevertheless, a major difference was noted during the hydrolysis of birchwood xylan and it appears that the reaction using the immobilized XYN3A4 chimeric enzyme leads to the accumulation of a specific product. PMID:12615394

  9. Use of metal chelating agents to differentiate among sources of acute aquatic toxicity

    SciTech Connect

    Hockett, J.R.; Mount, D.R.

    1996-10-01

    Metals are common toxicants found in effluents and other environmental samples. Within Toxicity Identification Evaluation methods proposed by the US Environmental Protection Agency and others, addition of ethylenediaminetetraacetic acid (EDTA) is used as an indicator of metal toxicity. Previous experiments showed that addition of sodium thiosulfate, originally included to detect toxicity due to oxidants, was also effective at reducing toxicity from some common metals. in the present study, the authors characterized the effectiveness of both EDTA and thiosulfate in removing the toxicity of 16 different metal ions to Ceriodaphnia dubia. Ethylenediaminetetraacetic acid addition removed toxicity associated with all cationic metals tested except for Cr{sup 3+}, Fe{sup 2+}, Al{sup 3+}, and Ag{sup +}. Thiosulfate addition was less effective than EDTA for Zn{sup 2+}, Mn{sup 2+}, Pb{sup 2+}, and Ni{sup 2+}, but reduced toxicity of both Ag{sup +} and selenite (Se[VI]), which EDTA did not. Results of this research can be used to categorize metal toxicity in unknown samples based on the response to additions of EDTA and thiosulfate.

  10. Chelation in metal intoxication. XIV. Comparative effect of thiol and amino chelators on lead-poisoned rats with normal or damaged kidneys

    SciTech Connect

    Tandon, S.K.; Flora, S.J.; Singh, S.

    1985-06-30

    D-Penicillamine (DPA), diethyldithiocarbamate (DDC), L-cysteine, ethylenediaminetetraacetic acid (EDTA), cyclohexylenediaminetetraacetic acid (CDTA), and diethylene triamine pentaacetic acid (DTPA) were compared for their efficacy to enhance urinary excretion of Pb, to reduce Pb concentration of body organs, and to restore the enhanced urinary excretion of delta-aminolevulinic acid (delta-ALA), the inhibited activities of blood delta-ALA dehydratase, and renal enzymes in Pb-administered rats (10 mg/kg, po, 4 weeks) with normal or experimentally damaged kidneys. The acute renal damage was induced by uranyl acetate (3 mg/kg, sc, once) prior to treatment with the chelators (0.3 mmol/kg, ip, twice) and evaluated by enhanced urinary excretion of diagnostic enzymes and inhibition in their renal activities. Among thiol chelators, DPA was the most effective followed by DDC in enhancing the urinary excretion of Pb, reducing the concentration of Pb in blood, kidneys and liver, and in restoring Pb-induced biological alterations in urine, blood, and kidneys. Among amino carboxylic acids, DTPA was the most effective and EDTA and CDTA were about equally potent in countering Pb toxicity. Protection was more marked in animals with normal kidneys than in those with acutely damaged kidneys.

  11. Application of zone-melting technique to metal chelate systems-XI Refining of tetrakis(di-n-propionylmethanato)zirconium(IV) from hafnium and trace amounts of some other metals.

    PubMed

    Yoshida, I; Kobayashi, H; Ueno, K

    1977-01-01

    The zone-melting method was applied to purification of tetrakis(di-n-propionylmethanato)zirconium(IV) which contained copper(II), nickel(II), cobalt(II and III), iron(III) and hafnium(IV) in the forms of their chelates with the common ligand. All minor components having effective distribution coefficients < 1 in the zirconium(IV) chelate were concentrated toward the terminal end of the refining column. When an aqueous solution of zirconium(IV) containing zinC(II) and manganese(II) in addition to the metal contaminants above was treated with di-n-propionylmethane to precipitate the chelate complexes, only zinc, iron and hafnium were found in the precipitated zirconium chelate. The first two were ettectively removed by zone-melting. Though the separation of hafnium was poorer, the technique was efficient enough for practical purposes. PMID:18962026

  12. Extraction of Micronutrient Metals from Peat-based Media Using Various Chelate-ligand and Iron-source Extractants

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Objectives of the study were to determine effects of chelate-ligand (experiment 1) and iron-source (experiment 2) unbuffrered extractant solutions on substrate pH and Cu, Fe, Mn, and Zn extraction from peat-based media. Chelate-ligand extractants consisted of 5 mM solutions of ethylenediaminedisucc...

  13. Biphasic catalysis using amphiphilic polyphenols-chelated noble metals as highly active and selective catalysts

    PubMed Central

    Mao, Hui; Yu, Hong; Chen, Jing; Liao, Xuepin

    2013-01-01

    In the field of catalysis, it is highly desired to develop novel catalysts that combine the advantages of both homogeneous and heterogeneous catalysts. Here we disclose that the use of plant pholyphenol as amphiphilic large molecule ligand/stabilizer allows for the preparation of noble metal complex and noble metal nanoparticle catalysts. These catalysts are found to be highly selective and active in aqueous-organic biphasic catalysis of cinnamaldehyde and quinoline, and can be reused at least 3 times without significant loss of activity. Moreover, the catalytic activity and reusability of the catalysts can be rationally controlled by simply adjusting the content of polyphenols in the catalysts. Our strategy may be extended to design a wide range of aqueous-organic biphasic catalysis system. PMID:23863916

  14. Orally Bioavailable Metal Chelators and Radical Scavengers: Multifunctional Antioxidants for the Coadjutant Treatment of Neurodegenerative Diseases.

    PubMed

    Kawada, Hiroyoshi; Kador, Peter F

    2015-11-25

    Neurodegenerative diseases are associated with oxidative stress that is induced by the presence of reactive oxygen species and the abnormal cellular accumulation of transition metals. Here, a new series of orally bioavailable multifunctional antioxidants (MFAO-2s) possessing a 2-diacetylamino-5-hydroxypyrimidine moiety is described. These MFAO-2s demonstrate both free radical and metal attenuating properties that are similar to the original published MFAO-1s that are based on 1-N,N'-dimethylsulfamoyl-1-4-(2-pyrimidyl)piperazine. Oral bioavailability studies in C57BL/6 mice demonstrate that the MFAO-2s accumulate in the brain at significantly higher levels than the MFAO-1s while achieving similar neural retina levels. The MFAO-2s protect human neuroblastoma and retinal pigmented epithelial cells against hydroxyl radicals in a dose-dependent manner by maintaining cell viability and intracellular glutathione levels. The MFAO-2s outperform clioquinol, a metal attenuator that has been investigated for the treatment of Alzheimer's disease.

  15. Novel voltammetric and impedimetric sensor for femtomolar determination of lysozyme based on metal-chelate affinity immobilized onto gold nanoparticles.

    PubMed

    Arabzadeh, Abbas; Salimi, Abdollah

    2015-12-15

    In this study, we reported iminodiacetic acid-copper ion complex (IDA-Cu) immobilized onto gold nanoparticles (GNPs)-modified glassy carbon electrode as a novel electrochemical platform for selective and sensitive determination of lysozyme (Lys). IDA-Cu complex acted as an efficient recognition element capable of capturing Lys molecules. GNPs acts as a substrate to immobilize IDA-Cu coordinative complex and its interaction with Lys leds to a great signal amplification through measuring changes in differential pulse voltammetric (DPV) peak current of [Fe(CN)6](3-/4-) redox probe. Upon the recognition of the Lys to the IDA-Cu, the peak current decreased due to the hindered electron transfer reaction on the electrode surface. Under optimum condition, it was found that the proposed method could detect Lys at wide linear concentration range (0.1 pM to 0.10 mM) with detection limit of 60 fM. Furthermore, electrochemical impedance spectroscopy (EIS) detection of Lys was demonstrated as a simple and rapid alternative analytical technique with detection limit of 80 fM at concentration range up to 0.1mM. In addition, the proposed sensor was satisfactorily applied to the determination of Lys in real samples such as hen egg white. The proposed modified electrode showing the high selectivity, good sensitivity and stability toward Lys detection may hold a great promise in developing other electrochemical sensors based on metal-chelate affinity complexes.

  16. Removal effectiveness and mechanisms of naphthalene and heavy metals from artificially contaminated soil by iron chelate-activated persulfate.

    PubMed

    Yan, Dickson Y S; Lo, Irene M C

    2013-07-01

    The effectiveness and mechanisms of naphthalene and metal removal from artificially contaminated soil by FeEDTA/FeEDDS-activated persulfate were investigated through batch experiments. Using FeEDTA-activated persulfate, higher naphthalene removal from the soil at 7 h was achieved (89%), compared with FeEDDS-activated persulfate (75%). The removal was mainly via the dissolution of naphthalene partitioned on mineral surfaces, followed by activated persulfate oxidation. Although EDDS is advantageous over EDTA in terms of biodegradability, it is not preferable for iron chelate-activated persulfate oxidation since persulfate was consumed to oxidize EDDS, resulting in persulfate inadequacy for naphthalene oxidation. Besides, 55 and 40% of naphthalene were removed by FeEDTA and FeEDDS alone, respectively. Particularly, 21 and 9% of naphthalene were degraded in the presence of FeEDTA and FeEDDS alone, respectively, which caused by electrons transfer among dissolved organic matter, Fe(2+)/Fe(3+) and naphthalene. Over 35, 36 and 45% of Cu, Pb and Zn were removed using FeEDTA/FeEDDS-activated persulfate.

  17. Direct measurement of metal-ion chelation in the active site of the AAA+ ATPase magnesium chelatase.

    PubMed

    Viney, Joanne; Davison, Paul A; Hunter, C Neil; Reid, James D

    2007-11-01

    Magnesium chelatase catalyzes the first committed step in chlorophyll biosynthesis. This complex enzyme has at least three substrates and couples ATP hydrolysis to the insertion of Mg2+ into protoporphyrin IX. We directly observed metal-ion chelation fluorometrically, providing the first data describing the on-enzyme reaction. We describe the transient-state kinetics of magnesium chelatase with direct observation of the evolution of an enzyme-product complex EMgDIX. We demonstrate that MgATP2- binding occurs after the rate-determining step. As nucleotide hydrolysis is essential for the overall reaction this must also occur after the rate-determining step. This provides the first evidence for the synchronization of the ATPase and chelatase pathways and suggests a mechanism where nucleotide binding acts to clamp the chelatase in a product complex. Comparison of rate constants for the slow step in the reaction with further transient kinetics under conditions where multiple turnovers can occur reveals that an additional activation step is required to explain the behavior of magnesium chelatase. These data provide a new view of the sequence of events occurring in the reaction catalyzed by magnesium chelatase.

  18. Metal-chelate dye-controlled organization of Cd32S14(SPh)40(4-) nanoclusters into three-dimensional molecular and covalent open architecture.

    PubMed

    Zheng, Nanfeng; Lu, Haiwei; Bu, Xianhui; Feng, Pingyun

    2006-04-12

    Chalcogenide II-VI nanoclusters are usually prepared as isolated clusters and have defied numerous efforts to join them into covalent open-framework architecture with conventional templating methods such as protonated amines or inorganic cations commonly used to direct the formation of porous frameworks. Herein, we report the first templated synthesis of II-VI covalent superlattices from large II-VI tetrahedral clusters (i.e., [Cd32S14(SPh)38]2-). Our method takes advantage of low charge density of metal-chelate dyes that is a unique match with three-dimensional II-VI semiconductor frameworks in charge density, surface hydrophilicity-hydrophobicity, and spatial organization. In addition, metal-chelate dyes also serve to tune the optical properties of resulting dye semiconductor composite materials.

  19. Iron Chelation

    MedlinePlus

    ... iron overload and need treatment. What is iron overload? Iron chelation therapy is used when you have ... may want to perform: How quickly does iron overload happen? This is different for each person. It ...

  20. In Vitro Antioxidant versus Metal Ion Chelating Properties of Flavonoids: A Structure-Activity Investigation

    PubMed Central

    Cherrak, Sabri Ahmed; Mokhtari-Soulimane, Nassima; Berroukeche, Farid; Bensenane, Bachir; Cherbonnel, Angéline; Merzouk, Hafida; Elhabiri, Mourad

    2016-01-01

    Natural flavonoids such as quercetin, (+)catechin and rutin as well as four methoxylated derivatives of quercetin used as models were investigated to elucidate their impact on the oxidant and antioxidant status of human red blood cells (RBCs). The impact of these compounds against metal toxicity was studied as well as their antiradical activities with DPPH assay. Antihemolytic experiments were conducted on quercetin, (+)catechin and rutin with excess of Fe, Cu and Zn (400 μM), and the oxidant (malondialdehyde, carbonyl proteins) and antioxidant (reduced glutathione, catalase activity) markers were evaluated. The results showed that Fe and Zn have the highest prooxidant effect (37 and 33% of hemolysis, respectively). Quercetin, rutin and (+)catechin exhibited strong antioxidant properties toward Fe, but this effect was decreased with respect to Zn ions. However, the Cu showed a weak antioxidant effect at the highest flavonoid concentration (200 μM), while a prooxidant effect was observed at the lowest flavonoid concentration (100 μM). These results are in agreement with the physico-chemical and antiradical data which demonstrated that binding of the metal ions (for FeNTA: (+)Catechin, KLFeNTA = 1.6(1) × 106 M-1 > Rutin, KLFeNTA = 2.0(9) × 105 M-1 > Quercetin, KLFeNTA = 1.0(7) × 105 M-1 > Q35OH, KLFeNTA = 6.3(8.7) × 104 M-1 > Quercetin3’4’OH and Quercetin 3OH, KLFeNTA ~ 2 × 104 M-1) reflects the (anti)oxidant status of the RBCs. This study reveals that flavonoids have both prooxidant and antioxidant activity depending on the nature and concentration of the flavonoids and metal ions. PMID:27788249

  1. Closed vessel miniaturized microwave assisted chelating extraction for determination of trace metals in plant materials

    NASA Astrophysics Data System (ADS)

    Czarnecki, Sezin; Duering, Rolf-Alexander

    2013-04-01

    In recent years, the use of closed vessel microwave assisted extraction (MAE) for plant samples has shown increasing research interest which will probably substitute conventional procedures in the future due to their general disadvantages including consumption of time and solvents. The objective of this study was to demonstrate an innovative miniaturized closed vessel microwave assisted extraction (µMAE) method under the use of EDTA (µMAE-EDTA) to determine metal contents (Cd, Co, Cu, Mn, Ni, Pb, Zn) in plant samples (Lolio-Cynosuretum) by inductively coupled plasma-optical emission spectrometry (ICP-OES). Validation of the method was done by comparison of the results with another miniaturized closed vessel microwave HNO3 method (µMAE-H) and with two other macro scale MAE procedures (MAE-H and MAE-EDTA) which were applied by using a mixture of nitric acid (HNO3) and hydrogen peroxide (H2O2) (MAE-H) and EDTA (MAE-EDTA), respectively. The already established MAE-H method is taken into consideration as a reference validation MAE method for plant material. A conventional plant extraction (CE) method, based on dry ashing and dissolving of the plant material in HNO3, was used as a confidence comparative method. Certified plant reference materials (CRMs) were used for comparison of recovery rates from different extraction protocols. This allowed the validation of the applicability of the µMAE-EDTA procedure. For 36 real plant samples with triplicates each, µMAE-EDTA showed the same extraction yields as the MAE-H in the determination of Cd, Co, Cu, Mn, Ni, Pb, and Zn contents in plant samples. Analytical parameters in µMAE-EDTA should be further investigated and adapted for other metals of interest. By the reduction and elimination of the use of hazardous chemicals in environmental analysis and thus allowing a better understanding of metal distribution and accumulation process in plants and also the metal transfer from soil to plants and into the food chain, µ

  2. Integrative refolding and purification of histidine-tagged protein by like-charge facilitated refolding and metal-chelate affinity adsorption.

    PubMed

    Liu, Hu; Du, Wen-Jie; Dong, Xiao-Yan; Sun, Yan

    2014-05-30

    This work proposed an integrative method of protein refolding and purification by like-charged resin facilitated refolding and metal-chelate affinity adsorption. Hexahistidine-tagged enhanced green fluorescence protein (EGFP) was overexpressed in Escherichia coli as inclusion bodies (IBs), and then the protein was refolded and purified from urea-solubilized IBs by this method. A metal-chelating resin was fabricated by coupling iminodiacetic acid (IDA) to agarose gel (Sepharose FF). The anionic resin was used to facilitate the refolding of like-charged EGFP from IBs. After refolding, nickel ions were introduced for the affinity purification of the target protein by metal-chelating adsorption. It was found that the resin was effective in facilitating EGFP refolding. For 0.1mg/mL EGFP IBs refolding, the fluorescence recovery (FR) by direct dilution was only 64%; addition of only 0.05 g/mL resin increased the FR to over 90%. Moreover, the FR increased with increasing resin concentration. Owning to the shielding effect of the oppositely charged impurities embedded in IBs on the surface charges of the IDA resin, more resin particles were required to exert an aggregation inhibition effect in the IBs protein refolding. Additionally, compared with direct-dilution refolding, inclusion of like-charged resins not only offered an enhanced FR of EGFP, but also bound some opposite-charged contaminant proteins, leading to a preliminary purification effect. Afterwards, the refolded EGFP was recovered by metal-chelating adsorption at an FR of 85% and purity of 93%. This work has thus extended the like-charge facilitated protein refolding strategy to the integrative protein refolding and purification.

  3. CONTINUOUS CHELATION-EXTRACTION PROCESS FOR THE SEPARATION AND PURIFICATION OF METALS

    DOEpatents

    Thomas, J.R.; Hicks, T.E.; Rubin, B.; Crandall, H.W.

    1959-12-01

    A continuous process is presented for separating metal values and groups of metal values from each other. A complex mixture. e.g., neutron-irradiated uranium, can be resolved into component parts. In the present process the values are dissolved in an acidic solution and adjusted to the proper oxidation state. Thenceforth the solution is contacted with an extractant phase comprising a fluorinated beta -diketone in an organic solvent under centain pH conditions whereupon plutonium and zirconium are extracted. Plutonium is extracted from the foregoing extract with reducing aqueous solutions or under specified acidic conditions and can be recovered from the aqueous solution. Zirconium is then removed with an oxalic acid aqueous phase. The uranium is recovered from the residual original solution using hexone and hexone-diketone extractants leaving residual fission products in the original solution. The uranium is extracted from the hexone solution with dilute nitric acid. Improved separations and purifications are achieved using recycled scrub solutions and the "self-salting" effect of uranyl ions.

  4. HPLC method for the determination of phytochelatin synthase activity specific for soft metal ion chelators.

    PubMed

    Ogawa, Shinya; Yoshidomi, Takahiro; Shirabe, Tomoo; Yoshimura, Etsuro

    2010-04-01

    Phytochelatins (PCs) are nonprotein peptides with the general structure (gamma-Glu-Cys)(n)-Gly (PC(n)), where n is greater than or equal to 2. They are synthesized through a reaction catalyzed by phytochelatin synthase (PCS) in the presence of metal cations and using the tripeptide glutathione (gamma-Glu-Cys-Gly) and/or previously synthesized PC(n) as the substrate. Here, a highly sensitive assay for PCS activity was devised, in which the dequenching of Cu(I)-bathocuproinedisulfonate complexes was used in the detection system of a reversed-phase high-performance liquid chromatograph. Using recombinant PCS from the higher plant Arabidopsis thaliana (rAtPCS1), this assay system was capable of determining PCS activity based on an amount of the enzyme preparation that was 100-fold less than that required for the 5,5'-dithiobis(2-nitrobenzoic acid) assay method. Although adsorption of the enzyme onto the reaction vessel hindered accurate activity determination, the inclusion of bovine serum albumin successfully resolved this issue. This method is a powerful tool for investigating PCS enzyme mechanisms with respect to the roles of metal ions. PMID:20074807

  5. Computer-based approach to chelation therapy: a theoretical study of some chelating agents for the selective removal of toxic metal ions from plasma.

    PubMed

    Agarwal, R P; Perrin, D D

    1976-09-01

    COMICS is a computer programme for calculating equilibrium concentrations of metal complexes and reactive species in multi-metal-multi-ligand systems. Its usefulness for analysing metal ion equilibria in blood plasma has been improved by including albumin as a ligand. Using this model system the distribution and removal of copper(II) and zinc ions in histidinaemia, lead poisoning and Wilson's disease have been examined. The efficacy of TRIEN in removing excess copper(II) is shown. The use of specific tripeptides such as Gly-Gly-His methyl ester for the selective removal of copper(II) is suggested. A possible chemoprophylaxis of influenza based on complexation of zinc is discussed. Calculations confirm that thiosemicarbazones such as methisazone and 2-acetylpyridine thiosemicarbazone are effective competitors for heavy metal ions under physiological conditions. PMID:970298

  6. Highly stabilized gadolinium chelates functionalized on metal nanoparticles as magnetic resonance imaging contrast agent

    NASA Astrophysics Data System (ADS)

    Siddiqui, Talha S.

    Magnetic resonance imaging (MRI) is a non-invasive method for imaging and diagnosing tissue damage, organ function and the vascular system. Magnevist(TM) a complex of diethylenetriaminepentaacetic acid (DTPA) and Gd3+ is a clinically approved contrast agent for MRI. A derivative of DTPA was formed by the addition of two cysteine groups (DTPA-L-Cys) through amide linkage. The Gd complex of this ligand bonds with the silver surfaces through the cysteine thiols. GdDTPA-L-Cys was bound to ˜10nm diameter Ag nanoparticles for use as a multifunctional MRI contrast agent. The ligand and complex were characterized by 1H and 13C NMR, ESI-MS and IR spectroscopy. The silver construct was characterized by TEM, TGA and UV-Vis absorption spectra. The per metal complex r1 relaxivity of GdDTPA-L-Cys{Ag} greater than that of Magnavist(TM) with the same molarity for both compounds. The synthesis of a DTPA derivative is described that allows it to bind to silver or gold nanoparticles through a single thiol linkage (DTPASH). The resulting Gd complex, GdDTPASH, was bound to Ag nanoparticles to create a single monolayer on the surface. The construct was further stabilized in buffered solution with the addition of a thiolated PEG chain. The highly stabilized nanoparticle construct delivers a high payload of Gd compelex and is an effective T1 brightening agent. The production of this type of construct opens the way for engineered multimodal MRI contrast agents.

  7. Chelation: a fundamental mechanism of action of AGE inhibitors, AGE breakers, and other inhibitors of diabetes complications.

    PubMed

    Nagai, Ryoji; Murray, David B; Metz, Thomas O; Baynes, John W

    2012-03-01

    This article outlines evidence that advanced glycation end product (AGE) inhibitors and breakers act primarily as chelators, inhibiting metal-catalyzed oxidation reactions that catalyze AGE formation. We then present evidence that chelation is the most likely mechanism by which ACE inhibitors, angiotensin receptor blockers, and aldose reductase inhibitors inhibit AGE formation in diabetes. Finally, we note several recent studies demonstrating therapeutic benefits of chelators for diabetic cardiovascular and renal disease. We conclude that chronic, low-dose chelation therapy deserves serious consideration as a clinical tool for prevention and treatment of diabetes complications.

  8. Supercritical fluid extraction and gas chromatography or electroanalysis of metal chelates from different sample matrices

    PubMed

    Arancibia; Segura; Leiva; Contreras; Valderrama

    2000-01-01

    The supercritical fluid extraction of Pb(DDC)2 and MoO2(acac)2 complexes is performed. The previously formed complexes are used in order to simplify the extraction process. In the extraction cell, 9.0 mg of Pb(DDC)2 or 30.0 mg of MoO2(acac)2 is added. With these two complexes, a study of static and dynamic extraction as a function of pressure (1000-2500 psi), temperature (40-160 degrees C), and presence of modifier (methanol) is performed. Under the best conditions, 5.6 mg of Pb(DDC)2 (2.3 mg of Pb2+) is recovered. The parameters are 2500 psi of pressure, 160 degrees C of temperature, 0.5 mL methanol (placed in a 10-mL extraction cell), 60.0 min of static extraction, and 2.0 min of dynamic extraction. It is necessary to add 3.0 mL of methanol to enhance efficiency on the MoO2(acac)2 complex recovery. Quantitative extractions of MoO2(acac)2 (9.0 mg of MoVI) are obtained when the experiments are carried out under 1000-2500 psi of pressure, 140 degrees C, and times no longer than 10.0 min. Then, the study is carried out forming the in situ complexes. For this purpose, metallic ion and ligand are added. Under these conditions, the Pb2+ recovery decreases from 2.3 to 1.9 mg, and the MoVI recovery decreases from 9.0 to 1.0 mg. When 1.9 mg of Pb2+ and 1.0 mg of MoVI or less is placed in the extraction cell, the recoveries are always 100%. The Pb2+ extracts are directly accomplished using gas chromatography-flame ionization detection (GC-FID), and the MoVI extracts are analyzed using GC-FID and catalytic adsorption voltammetry. The quantitation of pure extracts is carried out by constructing calibration curves with complex solutions and sample solutions using the standard addition method. This method is applied by determination of Pb2+ in sodium alginate extracted from algae and blood, urine, and human milk from patients with diagnosed plumbunemy. MoVI is determined in irrigation water and pasture of animal intake.

  9. An integrated biological approach to guide the development of metal-chelating inhibitors of influenza virus PA endonuclease.

    PubMed

    Stevaert, Annelies; Nurra, Salvatore; Pala, Nicolino; Carcelli, Mauro; Rogolino, Dominga; Shepard, Caitlin; Domaoal, Robert A; Kim, Baek; Alfonso-Prieto, Mercedes; Marras, Salvatore A E; Sechi, Mario; Naesens, Lieve

    2015-02-01

    The influenza virus PA endonuclease, which cleaves capped cellular pre-mRNAs to prime viral mRNA synthesis, is a promising target for novel anti-influenza virus therapeutics. The catalytic center of this enzyme resides in the N-terminal part of PA (PA-Nter) and contains two (or possibly one or three) Mg(2+) or Mn(2+) ions, which are critical for its catalytic function. There is great interest in PA inhibitors that are optimally designed to occupy the active site and chelate the metal ions. We focused here on a series of β-diketo acid (DKA) and DKA-bioisosteric compounds containing different scaffolds, and determined their structure-activity relationship in an enzymatic assay with PA-Nter, in order to build a three-dimensional pharmacophore model. In addition, we developed a molecular beacon (MB)-based PA-Nter assay that enabled us to compare the inhibition of Mn(2+) versus Mg(2+), the latter probably being the biologically relevant cofactor. This real-time MB assay allowed us to measure the enzyme kinetics of PA-Nter or perform high-throughput screening. Several DKA derivatives were found to cause strong inhibition of PA-Nter, with IC50 values comparable to that of the prototype L-742,001 (i.e., below 2 μM). Among the different compounds tested, L-742,001 appeared unique in having equal activity against either Mg(2+) or Mn(2+). Three compounds ( 10: , with a pyrrole scaffold, and 40: and 41: , with an indole scaffold) exhibited moderate antiviral activity in cell culture (EC99 values 64-95 μM) and were proven to affect viral RNA synthesis. Our approach of integrating complementary enzymatic, cellular, and mechanistic assays should guide ongoing development of improved influenza virus PA inhibitors.

  10. Liquid metal Flow Meter - Final Report

    SciTech Connect

    Andersen, C.; Hoogendoom, S.; Hudson, B.; Prince, J.; Teichert, K.; Wood, J.; Chase, K.

    2007-01-30

    Measuring the flow of liquid metal presents serious challenges. Current commercially-available flow meters use ultrasonic, electromagnetic, and other technologies to measure flow, but are inadequate for liquid metal flow measurement because of the high temperatures required by most liquid metals. As a result of the reactivity and high temperatures of most liquid metals, corrosion and leakage become very serious safety concerns. The purpose of this project is to develop a flow meter for Lockheed Martin that measures the flow rate of molten metal in a conduit.

  11. Heavy metal removal from sludge with organic chelators: Comparative study of N, N-bis(carboxymethyl) glutamic acid and citric acid.

    PubMed

    Suanon, Fidèle; Sun, Qian; Dimon, Biaou; Mama, Daouda; Yu, Chang-Ping

    2016-01-15

    The applicability and performance of a new generation of biodegradable chelator, N, N-Bis(carboxymethyl) glutamic acid (GLDA), for extracting heavy metals from sewage sludge was carried out and compared with citric acid (CA). Targeted metals included Cd, Co, Cu, Zn, Ni and Cr, and their contents in the raw sludge were 63.1, 73.4, 1103.2, 2060.3, 483.9 and 604.1 mg kg(-1) (dry sludge basis), respectively. Metals were divided into six fractions including water soluble, exchangeable, carbonates bound, Fe-Mn bound, organic matters bound and residual fraction via chemical fractionation. Washing results showed that in general GLDA exhibited better performance compared with CA, with removal efficiency of 83.9, 87.3, 81.2, 85.6, 89.3 and 90.2% for Cd, Co, Cu, Zn, Ni and Cr, respectively at equilibrium pH = 3.3. Residual metals were better stabilized in the GLAD-washed sludge than in the CA-washed sludge, and were mostly tightly bonded to the residual fraction. Furthermore, CA promoted phosphorus (P) release while GLDA had an opposite effect and tended to retain P within sludge, which could be beneficial for further application in agricultural use. Findings from this study suggested that GLDA could be a potential replacement for refractory and less environmentally-friendly chelators in the extraction of metals from sludge.

  12. Synthesis, structural characterization, in-vitro antibiogram assay and efficient catalytic activities of transition metal(II) chelates incorporating (E)-(2-((2-hydroxybenzylidene)amino)phenyl)(phenyl)methanone ligand

    NASA Astrophysics Data System (ADS)

    Muniyandi, Vellaichamy; Pravin, Narayanaperumal; Mitu, Liviu; Raman, Natarajan

    2015-04-01

    A new tridentate ligand, (E)-(2-((2-hydroxybenzylidene)amino)phenyl)(phenyl)methanone and its four metal(II) chelates have been designed and synthesized. They were structurally characterized by elemental analysis, FT IR, UV-vis, 1H NMR, 13C NMR, mass spectra, EPR, magnetic moment and conductivity measurements. Elemental analysis and molar conductance values reveal that all the chelates are 1:1 stoichiometry of the type [MLCl] having non-electrolytic nature. The metal chelates adopt square planar geometrical arrangements around the metal ions. The DNA-binding properties of these chelates have been investigated by electronic absorption, cyclic voltammetry, differential pulse voltammogram and viscosity measurements. The data indicate that these complexes bind to DNA via an intercalation mode. The oxidative cleavage of the metal complexes with pBR322 DNA has also been investigated by gel electrophoresis. Moreover, the antimicrobial bustle shows that all metal chelates have superior activity than the free ligand. The oxidation of toluene to benzaldehyde is effectively catalyzed by the synthesized chelates.

  13. PDTC, metal chelating compound, induces G1 phase cell cycle arrest in vascular smooth muscle cells through inducing p21Cip1 expression: involvement of p38 mitogen activated protein kinase.

    PubMed

    Moon, Sung-Kwon; Jung, Sun-Young; Choi, Yung-Hyun; Lee, Young-Choon; Patterson, Cam; Kim, Cheorl-Ho

    2004-02-01

    Pyrrolidine dithiocarbamate (PDTC), a metal chelating compound, is known to induce cell death in vascular smooth muscle cells (VSMC). However, the molecular mechanism for PDTC-induced VSMC death is not well understood. Addition of PDTC reduced cell growth and DNA synthesis on VSMC in low density conditions. However, in serum depleted medium, PDTC did not affect the cell viability, suggesting that certain factors in serum may mediate the cytotoxic effect of PDTC. Several metal chelators prevented the cell death induced by PDTC. In a serum-deprived condition, addition of exogenous metals, copper, iron, and zinc, restored the cytotoxic effect of PDTC. These data indicate that metals such as copper, iron, and zinc in serum may mediate the cytotoxic effect of PDTC. At low VSMC density in 10% FBS, treatment of PDTC, which induced a cell-cycle block in G1-phase, induced down-regulation of cyclins and CDKs and up-regulation of the CDK inhibitor p21 expression, whereas up-regulation of p27 or p53 by PDTC was not observed. Finally, we determined PDTC-mediated signaling pathway involved in VSMC death. Among relevant pathways, PDTC induced marked activation of p38MAPK and JNK. Expression of dominant negative p38MAPK and SB203580, a p38MAPK specific inhibitor, blocked PDTC-dependent p38MAPK, growth inhibition, and p21 expression. These data demonstrate that the p38MAPK pathway participates in p21 induction, which consequently leads to decrease of cyclin D1/cdk4 and cyclin E/cdk2 complexes and PDTC-dependent VSMC growth inhibition. In conclusion, an understanding of the molecular mechanisms of PDTC in VSMC provides a theoretical basis for clinical approaches using antioxidant therapies in atherosclerosis. PMID:14603533

  14. Stability and Biodistribution of Thiol-Functionalized and (177)Lu-Labeled Metal Chelating Polymers Bound to Gold Nanoparticles.

    PubMed

    Yook, Simmyung; Lu, Yijie; Jeong, Jenny Jooyoung; Cai, Zhongli; Tong, Lemuel; Alwarda, Ramina; Pignol, Jean-Philippe; Winnik, Mitchell A; Reilly, Raymond M

    2016-04-11

    We are studying a novel radiation nanomedicine approach to treatment of breast cancer using 30 nm gold nanoparticles (AuNP) modified with polyethylene glycol (PEG) metal-chelating polymers (MCP) that incorporate 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelators for complexing the β-particle emitter, (177)Lu. Our objective was to compare the stability of AuNP conjugated to MCP via a single thiol [DOTA-PEG-ortho-pyridyl disulfide (OPSS)], a dithiol [DOTA-PEG-lipoic acid (LA)] or multithiol end-group [PEG-pGlu(DOTA)8-LA4] and determine the elimination and biodistribution of these (177)Lu-labeled MCP-AuNP in mice. Stability to aggregation in the presence of thiol-containing dithiothreitol (DTT), L-cysteine or glutathione was assessed and dissociation of (177)Lu-MCP from AuNP in human plasma measured. Elimination of radioactivity from the body of athymic mice and excretion into the urine and feces was measured up to 168 h post-intravenous (i.v.) injection of (177)Lu-MCP-AuNP and normal tissue uptake was determined. ICP-AES was used to quantify Au in the liver and spleen and these were compared to (177)Lu. Our results showed that PEG-pGlu(DOTA)8-LA4-AuNP were more stable to aggregation in vitro than DOTA-PEG-LA-AuNP and both forms of AuNP were more stable to thiol challenge than DOTA-PEG-OPSS-AuNP. PEG-pGlu((177)Lu-DOTA)8-LA4 was the most stable in plasma. Whole body elimination of (177)Lu was most rapid for mice injected with (177)Lu-DOTA-PEG-OPSS-AuNP. Urinary excretion accounted for >90% of eliminated (177)Lu. All (177)Lu-MCP-AuNP accumulated in the liver and spleen. Liver uptake was lowest for PEG-pGlu((177)Lu-DOTA)8-LA4-AuNP but these AuNP exhibited the greatest spleen uptake. There were differences in Au and (177)Lu in the liver for PEG-pGlu((177)Lu-DOTA)8-LA4-AuNP. These differences were not correlated with in vitro stability of the (177)Lu-MCP-AuNP. We conclude that conjugation of AuNP with PEG-pGlu((177)Lu-DOTA)8-LA4 via a multithiol

  15. Membrane permeability of redox active metal chelators: an important element in reducing hydroxyl radical induced NAD+ depletion in neuronal cells.

    PubMed

    Jayasena, T; Grant, R S; Keerthisinghe, N; Solaja, I; Smythe, G A

    2007-03-01

    There is substantial evidence implicating increased production of the hydroxyl radical and oxidative stress in the pathogenesis of neurodegenerative diseases such as Alzheimer's disease (AD). Significant amounts of hydroxyl radicals will be produced in the presence of hydrogen peroxide and redox active iron via Fenton chemistry. Increased iron levels within the cytoplasm of vulnerable neurons suggest that this may also be an important site of oxidative activity. We investigated the likelihood that intracellular, rather than extracellular chelation of ferrous or ferric iron may be more effective in reducing hydroxyl radical induced cell damage and preserving NAD(+) levels and cell viability. Using intracellular NAD(H) measurements as an indicator of cell viability we found that membrane permeable ferrous chelators were most efficient in preserving cellular NAD(+) levels. Hydrophilic, ferrous or ferric chelators and lipophilic ferric chelators were essentially ineffective in preventing cellular NAD(+) depletion when added at physiological concentrations. We propose that lipophilic ferrous chelators, due to their actions inside the cell, are effective agents for moderating neuronal damage in conditions such as AD where intracellular oxidative stress plays a significant role in disease pathology. PMID:17210195

  16. Paramagnetic relaxation enhancement of membrane proteins by incorporation of the metal-chelating unnatural amino acid 2-amino-3-(8-hydroxyquinolin-3-yl) propanoic acid (HQA)

    PubMed Central

    Park, Sang Ho; Wang, Vivian; Radoicic, Jasmina; De Angelis, Anna A.; Berkamp, Sabrina; Opella, Stanley J.

    2014-01-01

    The use of paramagnetic constraints in protein NMR is an active area of research because of the benefits of long-range distance measurements (>10 Å). One of the main issues in successful execution is the incorporation of a paramagnetic metal ion into diamagnetic proteins. The most common metal ion tags are relatively long aliphatic chains attached to the side chain of a selected cysteine residue with a chelating group at the end where it can undergo substantial internal motions, decreasing the accuracy of the method. An attractive alternative approach is to incorporate an unnatural amino acid (UAA) that binds metal ions at a specific site on the protein using the methods of molecular biology. Here we describe the successful incorporation of the unnatural amino acid 2-amino-3-(8-hydroxyquinolin-3-yl) propanoic acid (HQA) into two different membrane proteins by heterologous expression in E. coli. Fluorescence and NMR experiments demonstrate complete replacement of the natural amino acid with HQA and stable metal chelation by the mutated proteins. Evidence of site-specific intra- and inter-molecular PREs by NMR in micelle solutions sets the stage for the use of HQA incorporation in solid-state NMR structure determinations of membrane proteins in phospholipid bilayers. PMID:25430059

  17. Impact of two iron(III) chelators on the iron, cadmium, lead and nickel accumulation in poplar grown under heavy metal stress in hydroponics.

    PubMed

    Mihucz, Victor G; Csog, Árpád; Fodor, Ferenc; Tatár, Enikő; Szoboszlai, Norbert; Silaghi-Dumitrescu, Luminiţa; Záray, Gyula

    2012-04-15

    Poplar (Populus jacquemontiana var. glauca cv. Kopeczkii) was grown in hydroponics containing 10 μM Cd(II), Ni(II) or Pb(II), and Fe as Fe(III) EDTA or Fe(III) citrate in identical concentrations. The present study was designed to compare the accumulation and distribution of Fe, Cd, Ni and Pb within the different plant compartments. Generally, Fe and heavy-metal accumulation were higher by factor 2-7 and 1.6-3.3, respectively, when Fe(III) citrate was used. Iron transport towards the shoot depended on the Fe(III) chelate and, generally, on the heavy metal used. Lead was accumulated only in the root. The amounts of Fe and heavy metals accumulated by poplar were very similar to those of cucumber grown in an identical way, indicating strong Fe uptake regulation of these two Strategy I plants: a cultivar and a woody plant. The Strategy I Fe uptake mechanism (i.e. reducing Fe(III) followed by Fe(II) uptake), together with the Fe(III) chelate form in the nutrient solution had significant effects on Fe and heavy metal uptake. Poplar appears to show phytoremediation potential for Cd and Ni, as their transport towards the shoot was characterized by 51-54% and 26-48% depending on the Fe(III) supply in the nutrient solution.

  18. Metal-metal multiply bonded complexes of technetium. Final report

    SciTech Connect

    Cotton, F.A.; Haefner, S.C.

    1995-03-30

    The primary objective of this project was to explore and develop the area of technetium metal-metal multiple bond chemistry. At the outset of the project, examples of metal-metal multiply bonded complexes of technetium were primarily limited to those supported by halide and carboxylate ligands. As a result, we intended to significantly expand the number of complexes containing Tc-Tc multiple bonds using ligands other than carboxylates or halides. In order to achieve this goal, the results obtained from years of dirhenium research was used as a guide for the development of new technetium compounds. Our emphasis, however, was on pursuing unanticipated results and exploiting the inherent differences between technetium and rhenium in order to develop chemistry beyond that which exists for rhenium. We have focused our attention on the preparation of dinuclear complexes with ligand sets that are known to support dinuclear metal-metal bonded cores in a variety of different metal oxidation states. Investigation of the consequences of electron addition and removal from metal-metal bonding manifold on the structural and physical properties of such dinuclear species will provide vital information regarding the electronic structure of Tc-Tc multiply bonded compounds.

  19. Heterofunctional Magnetic Metal-Chelate-Epoxy Supports for the Purification and Covalent Immobilization of Benzoylformate Decarboxylase From Pseudomonas Putida and Its Carboligation Reactivity.

    PubMed

    Tural, Servet; Tural, Bilsen; Demir, Ayhan S

    2015-09-01

    In this study, the combined use of the selectivity of metal chelate affinity chromatography with the capacity of epoxy supports to immobilize poly-His-tagged recombinant benzoylformate decarboxylase from Pseudomonas putida (BFD, E.C. 4.1.1.7) via covalent attachment is shown. This was achieved by designing tailor-made magnetic chelate-epoxy supports. In order to selectively adsorb and then covalently immobilize the poly-His-tagged BFD, the epoxy groups (300 µmol epoxy groups/g support) and a very small density of Co(2+)-chelate groups (38 µmol Co(2+)/g support) was introduced onto magnetic supports. That is, it was possible to accomplish, in a simple manner, the purification and covalent immobilization of a histidine-tagged recombinant BFD. The magnetically responsive biocatalyst was tested to catalyze the carboligation reactions. The benzoin condensation reactions were performed with this simple and convenient heterogeneous biocatalyst and were comparable to that of a free-enzyme-catalyzed reaction. The enantiomeric excess (ee) of (R)-benzoin was obtained at 99 ± 2% for the free enzyme and 96 ± 3% for the immobilized enzyme. To test the stability of the covalently immobilized enzyme, the immobilized enzyme was reused in five reaction cycles for the formation of chiral 2-hydroxypropiophenone (2-HPP) from benzaldehyde and acetaldehyde, and it retained 96% of its original activity after five reaction cycles.

  20. A comparative study of the removal of heavy metal ions from water using a silica-polyamine composite and a polystyrene chelator resin

    SciTech Connect

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

    1999-11-01

    The maximum Cu(II), Ni(II), and Co(II) ion capacities of a silica-poly(ethyleneimine) composite (WP-1) are compared with those of the commercially available iminodiacetic acid chelator resin Amberlite IRC-718. Under batch (static) conditions, IRC-718 exhibits better capacities for these metals than WP-1. Dynamic studies, however, revealed that WP-1 possessed a much higher capacity for all three divalent metals than IRC-718, with relative metal capacities in the order CU(II) {gt} CO(II) {approximately} Ni(II). In the presence of the competing chelator ethylenediaminetetraacetic acid, the Cu(II) capacities of WP-1 and IRC-718 lost 48% and 45%, respectively, of their original adsorption values. Even with this decrease, however, WP-1 maintained a higher CU(II) capacity than IRC-718. Repeated cycle testing, using CU(II) solutions at both room temperature and 97 C, was conducted to compare the long-term stability of each material. WP-1 maintained 94% of its original Cu(II) capacity and maintained structural integrity after 3,000 cycles using room temperature copper solutions, while IRC-718 compressed and dropped to 64% of its original capacity. When boiling copper solutions were used, the capacity of WP-1 increased slightly over 1500 cycles, while IRC-718 lost 13% of its original copper capacity and again became compressed, indicating degradation of the polystyrene beads.

  1. Metallization of ferrite ceramic couplings. Final report

    SciTech Connect

    Burden, J

    1992-06-01

    Tests were conducted to determine the optimum sputtering conditions for which the strongest metallization adherence could be achieved for the ferrite safing wheel assemblies. The conditions were varied through four separate test runs with a fifth verification run conducted using parameters selected from the first four runs. The parameters tested were the effects of etching, precleaning, chamber pressures, plating materials, plating thickness, soldering pressures, and cooling rates. The results increased the strength of the metallization to two pounds, well in excess of the required one pound minimum. It was also determined that the gold should be sputtered on and not thermally deposited, which caused cracking in the ferrite material.

  2. Fluid extraction using carbon dioxide and organophosphorus chelating agents

    DOEpatents

    Smart, N.G.; Wai, C.M.; Lin, Y.; Kwang, Y.H.

    1998-11-24

    Methods for extracting metalloid and metal species from a solid or liquid material by exposing the material to a fluid solvent, particularly supercritical CO{sub 2}, and a chelating agent are described. The chelating agent forms a chelate with the species, the chelate being soluble in the fluid to allow removal of the species from the material. In preferred embodiments the extraction solvent is supercritical CO{sub 2} and the chelating agent comprises an organophosphorous chelating agent, particularly sulfur-containing organophosphorous chelating agents, including mixtures of chelating agents. Examples of chelating agents include monothiophosphinic acid, di-thiophosphinic acid, phosphine sulfite, phosphorothioic acid, and mixtures thereof. The method provides an environmentally benign process for removing metal and metalloids from industrial waste solutions, particularly acidic solutions. Both the chelate and the supercritical fluid can be regenerated and the contaminant species recovered to provide an economic, efficient process. 1 fig.

  3. Fluid extraction using carbon dioxide and organophosphorus chelating agents

    DOEpatents

    Smart, Neil G.; Wai, Chien M.; Lin, Yuehe; Kwang, Yak Hwa

    1998-01-01

    Methods for extracting metalloid and metal species from a solid or liquid material by exposing the material to a fluid solvent, particularly supercritical CO.sub.2, and a chelating agent are described. The chelating agent forms a chelate with the species, the chelate being soluble in the fluid to allow removal of the species from the material. In preferred embodiments the extraction solvent is supercritical CO.sub.2 and the chelating agent comprises an organophosphorous chelating agent, particularly sulfur-containing organophosphorous chelating agents, including mixtures of chelating agents. Examples of chelating agents include monothiophosphinic acid, di-thiophosphinic acid, phosphine sulfite, phosphorothioic acid, and mixtures thereof. The method provides an environmentally benign process for removing metal and metalloids from industrial waste solutions, particularly acidic solutions. Both the chelate and the supercritical fluid can be regenerated and the contaminant species recovered to provide an economic, efficient process.

  4. Synthesis and coordination chemistry of two N2-donor chelating di(indazolyl)methane ligands: structural characterization and comparison of their metal chelation aptitudes.

    PubMed

    Pettinari, Claudio; Marinelli, Alessandro; Marchetti, Fabio; Ngoune, Jean; Galindo, Agustín; Álvarez, Eleuterio; Gómez, Margarita

    2010-11-15

    The N(2)-donor bidentate ligands di(1H-indazol-1-yl)methane (L(1)) and di(2H-indazol-2-yl)methane (L(2)) (L in general) have been synthesized, and their coordination behavior toward Zn(II), Cd(II), and Hg(II) salts has been studied. Reaction of L(1) and L(2) with ZnX(2) (X = Cl, Br, or I) yields [ZnX(2)L] species (1-6), that, in the solid state, show a tetrahedral structure with dihapto ligand coordination via the pyrazolyl arms. The reaction of L(1) and L(2) with Zn(NO(3))(2)·6H(2)O is strongly dependent on the reaction conditions and on the ligand employed. Reaction of L(1) with equimolar quantities of Zn(NO(3))(2)·6H(2)O yields the neutral six-coordinate species [Zn(NO(3))(2)(L(1))], 7. On the other hand the use of L(1) excess gives the 2:1 adduct [Zn(NO(3))(2)(L(1))(2)], 8 where both nitrates act as a unidentate coordinating ligand. Analogous stoichiometry is found in the compound obtained from the reaction of L(2) with Zn(NO(3))(2)·6H(2)O which gives the ionic [Zn(NO(3))(L(2))(2)](NO(3)), 10. Complete displacement of both nitrates from the zinc coordination sphere is observed when the reaction between L(1) excess and the zinc salt was carried out in hydrothermal conditions. The metal ion type is also determining structure and stoichiometry: the reaction of L(2) with CdCl(2) gave the 2:1 adduct [CdCl(2)(L(2))(2)] 11 where both chlorides complete the coordination sphere of the six-coordinate cadmium center; on the other hand from the reaction of L(1) with CdBr(2) the polynuclear [CdBr(2)(L(1))](n) 12 is obtained, the Br(-) anion acting as bridging ligands in a six-coordinate cadmium coordination environment. The reaction of L(1) and L(2) with HgX(2) (X = Cl, I, SCN) is also dependent on the reaction conditions and the nature of X, two different types of adducts being formed [HgX(L)] (14: L = L(1), 16, 17: L = L(1) or L(2), X = I, 19: L = L(2), X = SCN) and [HgX(L)(2)] (15: L = L(2), X = Cl, 18: L = L(1), X = SCN). The X-ray diffraction analyses of compounds 1

  5. Enhanced anaerobic digestion of food waste by trace metal elements supplementation and reduced metals dosage by green chelating agent [S, S]-EDDS via improving metals bioavailability.

    PubMed

    Zhang, Wanli; Zhang, Lei; Li, Aimin

    2015-11-01

    This study aimed at investigating the effects of trace metals on methane production from food waste and examining the feasibility of reducing metals dosage by ethylenediamine-N,N'-disuccinic acid (EDDS) via improving metals bioavailability. The results indicated that the effects of metal elements highly depended on the supplemental concentrations. Trace metals supplemented under moderate concentrations greatly enhanced the methane yield. However, the excessive supplementation of Fe (1000 mg/L) and Ni (50 mg/L) exhibited the obvious toxicity to methanogens. The combinations of trace metals exhibited remarkable synergistic effects. The supplementation of Fe (100 mg/L) + Co (1 mg/L) + Mo (5 mg/L) + Ni (5 mg/L) obtained the greatest methane yield of 504 mL/g VSadded and the highest increment of 35.5% compared to the reactor without metals supplementation (372 mL/g VSadded). The changes of metals speciation showed the reduction of metals bioavailability during anaerobic digestion, which might weaken the stimulative effects of trace metals. However, the addition of EDDS improved metals bioavailability for microbial uptake and stimulated the activity of methanogens, and therefore, strengthened the stimulative effects of metals on anaerobic digestion of food waste. The batch and semi-continuous experiments confirmed that the addition of EDDS (20 mg/L) bonded to trace metals prior to their supplementation could obtain a 50% reduction of optimal metals dosage. This study provided a feasible method to reduce trace metals dosage without the degeneration of process performance of anaerobic digestion.

  6. A general chelate-assisted co-assembly to metallic nanoparticles-incorporated ordered mesoporous carbon catalysts for Fischer-Tropsch synthesis.

    PubMed

    Sun, Zhenkun; Sun, Bo; Qiao, Minghua; Wei, Jing; Yue, Qin; Wang, Chun; Deng, Yonghui; Kaliaguine, Serge; Zhao, Dongyuan

    2012-10-24

    The organization of different nano objects with tunable sizes, morphologies, and functions into integrated nanostructures is critical to the development of novel nanosystems that display high performances in sensing, catalysis, and so on. Herein, using acetylacetone as a chelating agent, phenolic resol as a carbon source, metal nitrates as metal sources, and amphiphilic copolymers as a template, we demonstrate a chelate-assisted multicomponent coassembly method to synthesize ordered mesoporous carbon with uniform metal-containing nanoparticles. The obtained nanocomposites have a 2-D hexagonally arranged pore structure, uniform pore size (~4.0 nm), high surface area (~500 m(2)/g), moderate pore volume (~0.30 cm(3)/g), uniform and highly dispersed Fe(2)O(3) nanoparticles, and constant Fe(2)O(3) contents around 10 wt %. By adjusting acetylacetone amount, the size of Fe(2)O(3) nanoparticles is readily tunable from 8.3 to 22.1 nm. More importantly, it is found that the metal-containing nanoparticles are partially embedded in the carbon framework with the remaining part exposed in the mesopore channels. This unique semiexposure structure not only provides an excellent confinement effect and exposed surface for catalysis but also helps to tightly trap the nanoparticles and prevent aggregating during catalysis. Fischer-Tropsch synthesis results show that as the size of iron nanoparticles decreases, the mesoporous Fe-carbon nanocomposites exhibit significantly improved catalytic performances with C(5+) selectivity up to 68%, much better than any reported promoter-free Fe-based catalysts due to the unique semiexposure morphology of metal-containing nanoparticles confined in the mesoporous carbon matrix.

  7. Synthesis and evaluation of selegiline derivatives as monoamine oxidase inhibitor, antioxidant and metal chelator against Alzheimer's disease.

    PubMed

    Xie, Shishun; Chen, Jie; Li, Xiruo; Su, Tao; Wang, Yali; Wang, Zhiren; Huang, Ling; Li, Xingshu

    2015-07-01

    A series of compounds with monoamine oxidase inhibition and biometal chelation activities were designed, synthesised and evaluated as agents against Alzheimer's disease. The in vitro assay shows that most target compounds exhibit good MAO-B activities with submicromolar IC50 values and antioxidant activity (1.49-5.67 ORAC-FL values). The selected compounds were used to determine the biometal chelating ability using UV-vis spectrometry and high-resolution mass spectrometry, which confirm that they can effectively interact with copper(II), iron(II) and zinc(II). The ThT fluorescence binding assay indicates that the synthetic compounds can inhibit Cu(II)-induced Aβ1-42 aggregation. The parallel artificial membrane permeation assay shows that most target compounds can cross the BBB. Based on these results, compound 8a was selected as a potential multifunctional agent for the treatment of AD.

  8. Cyclotron production of high specific activity 55Co and in vivo evaluation of the stability of 55Co metal-chelate-peptide complexes

    PubMed Central

    Mastren, Tara; Marquez, Bernadette V.; Sultan, Deborah E.; Bollinger, Elizabeth; Eisenbeis, Paul; Voller, Tom; Lapi, Suzanne E.

    2016-01-01

    This work describes the production of high-specific activity 55Co and the evaluation of the stability of 55Co-metal-chelate-peptide complexes in vivo. 55Co was produced via the 58Ni(p,α)55Co reaction and purified using anion exchange chromatography with an average recovery of 92% and an average specific activity of 1.96GBq/µmol. 55Co-DO3A and 55Co-NO2A peptide complexes were radiolabelled at 3.7MBq/µg and injected into HCT-116 tumor xenografted mice. PET imaging and biodistribution studies were performed at 24 and 48 hours post injection and compared with that of 55CoCl2. Both 55Co-metal-chelate complexes demonstrated good in vivo stability by reducing the radiotracers’ uptake in the liver by 6-fold at 24 with ~1% ID/g and at 48 hours with ~0.5% ID/g, and reducing uptake in the heart by 4-fold at 24 hours with ~0.7% ID/g and 7-fold at 48 hours with ~0.35% ID/g. These results support the use of 55Co as a promising new radiotracer for Positron Emission Tomography (PET) imaging of cancer and other diseases. PMID:26505224

  9. Cyclotron Production of High-Specific Activity 55Co and In Vivo Evaluation of the Stability of 55Co Metal-Chelate-Peptide Complexes.

    PubMed

    Mastren, Tara; Marquez, Bernadette V; Sultan, Deborah E; Bollinger, Elizabeth; Eisenbeis, Paul; Voller, Tom; Lapi, Suzanne E

    2015-01-01

    This work describes the production of high-specific activity 55Co and the evaluation of the stability of 55Co-metal-chelate-peptide complexes in vivo. 55Co was produced via the 58Ni(p,α)55Co reaction and purified using anion exchange chromatography with an average recovery of 92% and an average specific activity of 1.96 GBq/μmol. 55Co-DO3A and 55Co-NO2A peptide complexes were radiolabeled at 3.7 MBq/μg and injected into HCT-116 tumor xenografted mice. Positron emission tomography (PET) and biodistribution studies were performed at 24 and 48 hours postinjection and compared to those of 55CoCl2. Both 55Co-metal-chelate complexes demonstrated good in vivo stability by reducing the radiotracers' uptake in the liver by sixfold at 24 hours with ~ 1% ID/g and at 48 hours with ~ 0.5% ID/g and reducing uptake in the heart by fourfold at 24 hours with ~ 0.7% ID/g and sevenfold at 48 hours with ~ 0.35% ID/g. These results support the use of 55Co as a promising new radiotracer for PET imaging of cancer and other diseases.

  10. Multitarget-directed benzylideneindanone derivatives: anti-β-amyloid (Aβ) aggregation, antioxidant, metal chelation, and monoamine oxidase B (MAO-B) inhibition properties against Alzheimer's disease.

    PubMed

    Huang, Ling; Lu, Chuanjun; Sun, Yang; Mao, Fei; Luo, Zonghua; Su, Tao; Jiang, Huailei; Shan, Wenjun; Li, Xingshu

    2012-10-11

    A novel series of benzylideneindanone derivatives were designed, synthesized, and evaluated as multitarget-directed ligands against Alzheimer's disease. The in vitro studies showed that most of the molecules exhibited a significant ability to inhibit self-induced β-amyloid (Aβ(1-42)) aggregation (10.5-80.1%, 20 μM) and MAO-B activity (IC(50) of 7.5-40.5 μM), to act as potential antioxidants (ORAC-FL value of 2.75-9.37), and to function as metal chelators. In particular, compound 41 had the greatest ability to inhibit Aβ(1-42) aggregation (80.1%), and MAO-B (IC(50) = 7.5 μM) was also an excellent antioxidant and metal chelator. Moreover, it is capable of inhibiting Cu(II)-induced Aβ(1-42) aggregation and disassembling the well-structured Aβ fibrils. These results indicated that compound 41 is an excellent multifunctional agent for the treatment of AD.

  11. Luminescent lanthanide chelates and methods of use

    DOEpatents

    Selvin, Paul R.; Hearst, John

    1997-01-01

    The invention provides lanthanide chelates capable of intense luminescence. The celates comprise a lanthanide chelator covalently joined to a coumarin-like or quinolone-like sensitizer. Exemplary sensitzers include 2- or 4-quinolones, 2- or 4-coumarins, or derivatives thereof e.g. carbostyril 124 (7-amino-4-methyl-2-quinolone), coumarin 120 (7-amino-4-methyl-2-coumarin), coumarin 124 (7-amino-4-(trifluoromethyl)-2-coumarin), aminomethyltrimethylpsoralen, etc. The chelates form high affinity complexes with lanthanides, such as terbium or europium, through chelator groups, such as DTPA. The chelates may be coupled to a wide variety of compounds to create specific labels, probes, diagnostic and/or therapeutic reagents, etc. The chelates find particular use in resonance energy transfer between chelate-lanthanide complexes and another luminescent agent, often a fluorescent non-metal based resonance energy acceptor. The methods provide useful information about the structure, conformation, relative location and/or interactions of macromolecules.

  12. Purification of monoclonal antibodies, IgG1, from cell culture supernatant by use of metal chelate convective interaction media monolithic columns.

    PubMed

    Rajak, Poonam; Vijayalakshmi, M A; Jayaprakash, N S

    2012-12-01

    Monoclonal antibodies (MAbs) have diverse applications in diagnostics and therapeutics. The recent advancement in hybridoma technology for large-scale production of MAbs in bioreactors demands rapid and efficient purification methods. Conventional affinity purification systems have drawbacks of low flow rates and denaturation of antibodies owing to harsh elution conditions. Here, we attempted purification of MAbs by use of a high-throughput metal-chelate methacrylate monolithic system. Monolithic macroporous convective interaction media-iminodiacetate (CIM-IDA) disks immobilized with four different metal ions (Cu²⁺, Ni²⁺, Zn²⁺ and Co²⁺) were used and evaluated for purification of anti-human serum albumin IgG1 mouse MAbs from cell culture supernatant after precipitation with 50% ammonium sulfate. Elution with 10 mM imidazole in the equilibration buffer (25 mM MMA = MOPS (Morpholino propane sulfonic acid) + MES (Morpholino ethane sulfonic acid) + Acetate + 0.5 M NaCl, pH 7.4) resulted in a purification of 25.7 ± 2.9-fold and 32.5 ± 2.6-fold in experiments done using Zn²⁺ and Co²⁺ metal ions, respectively. The highest recovery of 85.4 ± 1.0% was obtained with a CIM-IDA-Zn(II) column. SDS-PAGE, ELISA and immuno-blot showed that the antibodies recovered were pure, with high antigen-binding efficiency. Thus, metal chelate CIM monoliths could be a potential alternative to conventional systems for fast and efficient purification of MAbs from the complex cell culture supernatant. PMID:22362585

  13. Final Report: Metal Perhydrides for Hydrogen Storage

    SciTech Connect

    Hwang, J-Y.; Shi, S.; Hackney, S.; Swenson, D.; Hu, Y.

    2011-07-26

    Hydrogen is a promising energy source for the future economy due to its environmental friendliness. One of the important obstacles for the utilization of hydrogen as a fuel source for applications such as fuel cells is the storage of hydrogen. In the infrastructure of the expected hydrogen economy, hydrogen storage is one of the key enabling technologies. Although hydrogen possesses the highest gravimetric energy content (142 KJ/g) of all fuels, its volumetric energy density (8 MJ/L) is very low. It is desired to increase the volumetric energy density of hydrogen in a system to satisfy various applications. Research on hydrogen storage has been pursed for many years. Various storage technologies, including liquefaction, compression, metal hydride, chemical hydride, and adsorption, have been examined. Liquefaction and high pressure compression are not desired due to concerns related to complicated devices, high energy cost and safety. Metal hydrides and chemical hydrides have high gravimetric and volumetric energy densities but encounter issues because high temperature is required for the release of hydrogen, due to the strong bonding of hydrogen in the compounds. Reversibility of hydrogen loading and unloading is another concern. Adsorption of hydrogen on high surface area sorbents such as activated carbon and organic metal frameworks does not have the reversibility problem. But on the other hand, the weak force (primarily the van der Waals force) between hydrogen and the sorbent yields a very small amount of adsorption capacity at ambient temperature. Significant storage capacity can only be achieved at low temperatures such as 77K. The use of liquid nitrogen in a hydrogen storage system is not practical. Perhydrides are proposed as novel hydrogen storage materials that may overcome barriers slowing advances to a hydrogen fuel economy. In conventional hydrides, e.g. metal hydrides, the number of hydrogen atoms equals the total valence of the metal ions. One Li

  14. Effect of soil washing with only chelators or combining with ferric chloride on soil heavy metal removal and phytoavailability: Field experiments.

    PubMed

    Guo, Xiaofang; Wei, Zebin; Wu, Qitang; Li, Chunping; Qian, Tianwei; Zheng, Wei

    2016-03-01

    In a field experiment on multi-metal contaminated soil, we investigated the efficiency of Cd, Pb, Zn, and Cu removal by only mixture of chelators (MC) or combining with FeCl3. After washing treatment, a co-cropping system was performed for heavy metals to be extracted by Sedum alfredii and to produce safe food from Zea mays. We analyzed the concentration of heavy metals in groundwater to evaluate the leashing risk of soil washing with FeCl3 and MC. Results showed that addition of FeCl3 was favorable to the removal of heavy metals in the topsoil. Metal leaching occurred mainly in rain season during the first co-cropping. The removal rates of Cd, Zn, Pb, and Cu in topsoil were 28%, 53%, 41%, and 21% with washing by FeCl3+MC after first harvest. The application of FeCl3 reduced the yield of S. alfredii and increased the metals concentration of Z. mays in first harvest. However, after amending soil, the metals concentration of Z. mays in FeCl3+MC treatment were similar to that only washing by MC. The grains and shoots of Z. mays were safe for use in feed production. Soil washing did not worsen groundwater contamination during the study period. But the concentration of Cd in groundwater was higher than the limit value of Standard concentrations for Groundwater IV. This study suggests that soil washing using FeCl3 and MC for the remediation of multi-metal contaminated soil is potential feasibility. However, the subsequent measure to improve the washed soil environment for planting crop is considered.

  15. Separation and determination of heavy metals associated with low molecular weight chelators in xylem saps of Indian mustard (Brassica juncea) by size exclusion chromatography and atomic absorption spectrometry.

    PubMed

    Wei, Zhenggui G; Wong, Jonathan Woonchung C; Zhao, Haiyan Y; Zhang, Huijuan J; Li, Huixin X; Hu, Feng

    2007-08-01

    To elucidate the role of low molecular weight chelators in long-distance root-to-shoot transport of heavy metals in Indian mustard, an "off-line" size exclusion high-performance liquid chromatography-graphite furnace atomic absorption spectrometry was developed to investigate heavy metals associated with low molecular weight chelators in xylem saps of Indian mustard (Brassica juncea). The size exclusion chromatogram presented only the peaks with molecular weight for all xylem saps and directly indicated the long-distance transport of phytochelatins (PCs) of Indian mustard under Cd stress. In the absence of Cd stress, only organic acids and inorganic anions participated in the long-distance transport of Cd, but organic acids, inorganic anions, glutathione (GSH), and cysteine might relate to the long-distance transport of Cu or Zn. In the presence of Cd stress, PCs were induced, and Cd ions in xylem saps were associated with the induced PCs. As the Cd levels in nutrient solution increased, more Cd in xylem saps adopted the form of PC-Cd. Although PCs might participate in the long-distance transport of Cd under Cd stress, the majority of Cd was still transported by organic acids and inorganic anions in xylem vessels. Moreover, results indicated the existence of complexation competition for GSH and cysteine between Cd and Cu (or Zn) and complexation competition for Cd between PCs and GSH (or cysteine) in xylem vessels. Our work might be very useful for understanding the mechanism of long-distance transport of heavy metals in hyperaccumulator.

  16. Biotinylated polyacrylamide-based metal-chelating polymers and their influence on antigen recognition following conjugation to a trastuzumab Fab fragment.

    PubMed

    Liu, Peng; Boyle, Amanda J; Lu, Yijie; Reilly, Raymond M; Winnik, Mitchell A

    2012-09-10

    We report the synthesis and characterization of metal-chelating polymers (MCPs) with a terminal biotin and a polyacrylamide backbone harboring multiple diethylenetriaminepentaacetic acid (DTPA) chelating sites. These polymers are conjugated to a streptavidin (SAv)-modified Fab fragment of trastuzumab (tmFab) and subsequently complexed with (111)In through DTPA. Trastuzumab has specific targeting ability toward human epidermal growth factor receptor-2 (HER2), which is overexpressed on some types of breast cancer cells and ovarian cancer cells. (111)In can generate Auger electrons which cause lethal DNA double strand breaks. The radioimmunoconjugates (RICs) were designed to target HER2 overexpressing cancer cells and carry multiple copies of (111)In to these cells. The mole maximum specific activities of these polymers were investigated by loading the polymers with (111)In at an increasing (111)In to polymer ratio. The polymers show 55-fold to 138-fold higher maximum specific activity than DTPA modified tmFab-SAv. Moreover, the HER2 immunoreactivities of these RICs were evaluated by measuring their specific binding ability toward HER2 overexpressing SKOV-3 ovarian cancer cells. The results demonstrate that although in the presence of polymer there is increased nonspecific binding, HER2 targeting ability was retained, ensuring the radionuclide delivery ability of these RICs.

  17. Synthesis, characterization and application of a new chelating resin for solid phase extraction, preconcentration and determination of trace metals in some dairy samples by flame atomic absorption spectrometry.

    PubMed

    Daşbaşı, Teslima; Saçmacı, Şerife; Çankaya, Nevin; Soykan, Cengiz

    2016-11-15

    In this study, a simple and rapid solid phase extraction/preconcentration procedure was developed for determination of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Pb(II), and Zn(II) trace metals by flame atomic absorption spectrometry (FAAS). A new chelating resin, poly(N-cyclohexylacrylamide-co-divinylbenzene-co-2-acrylamido-2-methyl-1-propanesulfonic acid) (NCA-co-DVB-co-AMPS) (hereafter CDAP) was synthesized and characterized. The influences of the analytical parameters such as pH of the sample solution, type and concentration of eluent, flow rates of the sample and eluent, volume of the sample and eluent, amount of chelating resin, and interference of ions were examined. The limit of detection (LOD) of analytes were found (3s) to be in the range of 0.65-1.90μgL(-1). Preconcentration factor (PF) of 200 and the relative standard deviation (RSD) of ⩽2% were achieved (n=11). The developed method was applied for determination of analytes in some dairy samples and certified reference materials. PMID:27283608

  18. Light-induced copper(II) coordination by a bicyclic tetraaza chelator through a ligand-to-metal charge-transfer reaction.

    PubMed

    Holm-Jørgensen, Jacob R; Jensen, Mikael; Bjerrum, Morten J

    2011-12-19

    To enable utilization of the broad potential of copper isotopes in nuclear medicine, rapid and robust chelation of the copper is required. Bowl adamanzanes (bicyclic tetraaza ligands) can form kinetically stable copper complexes, but they are usually formed at low rates unless high pH values and high temperatures are applied. We have investigated the effects of the variation in the pH, different anions, and UV irradiation on the chelation rate. UV spectra of mixtures of Cu(2+) and [2(4).3(1)]adz in water show the existence of a long-lived two-coordinated copper(II) intermediate (only counting coordinated amine groups) at pH above 6. These findings are supported by pH titrations of mixtures of Cu(2+) and [2(4).3(1)]adz in water. Irradiation of this complex in the ligand-to-metal charge-transfer (LMCT) band by a diode-array spectrophotometer leads to photodeprotonation and subsequently to formation of the four-coordinated copper(II) complex at a rate up to 7800-fold higher at 25 °C than in the dark. Anions in the solution were found to have three major effects: competitive inhibition due to Cu(II) binding anions, inhibition of the photoinduced transchelation from UV-absorbing anions, and photoredox inhibition from acido ligands capable of acting as electron donors in LMCT reactions. Dissolved O(2) was also found to result in photoredox inhibition.

  19. Biotinylated polyacrylamide-based metal-chelating polymers and their influence on antigen recognition following conjugation to a trastuzumab Fab fragment.

    PubMed

    Liu, Peng; Boyle, Amanda J; Lu, Yijie; Reilly, Raymond M; Winnik, Mitchell A

    2012-09-10

    We report the synthesis and characterization of metal-chelating polymers (MCPs) with a terminal biotin and a polyacrylamide backbone harboring multiple diethylenetriaminepentaacetic acid (DTPA) chelating sites. These polymers are conjugated to a streptavidin (SAv)-modified Fab fragment of trastuzumab (tmFab) and subsequently complexed with (111)In through DTPA. Trastuzumab has specific targeting ability toward human epidermal growth factor receptor-2 (HER2), which is overexpressed on some types of breast cancer cells and ovarian cancer cells. (111)In can generate Auger electrons which cause lethal DNA double strand breaks. The radioimmunoconjugates (RICs) were designed to target HER2 overexpressing cancer cells and carry multiple copies of (111)In to these cells. The mole maximum specific activities of these polymers were investigated by loading the polymers with (111)In at an increasing (111)In to polymer ratio. The polymers show 55-fold to 138-fold higher maximum specific activity than DTPA modified tmFab-SAv. Moreover, the HER2 immunoreactivities of these RICs were evaluated by measuring their specific binding ability toward HER2 overexpressing SKOV-3 ovarian cancer cells. The results demonstrate that although in the presence of polymer there is increased nonspecific binding, HER2 targeting ability was retained, ensuring the radionuclide delivery ability of these RICs. PMID:22871127

  20. Hyperaccumulator oilcake manure as an alternative for chelate-induced phytoremediation of heavy metals contaminated alluvial soils.

    PubMed

    Mani, Dinesh; Kumar, Chitranjan; Patel, Niraj Kumar

    2015-01-01

    The ability of hyperaccumulator oilcake manure as compared to chelates was investigated by growing Calendula officinalis L for phytoremediation of cadmium and lead contaminated alluvial soil. The combinatorial treatment T6 [2.5 g kg(-1) oilcake manure+5 mmol kg(-1) EDDS] caused maximum cadmium accumulation in root, shoot and flower up to 5.46, 4.74 and 1.37 mg kg(-1) and lead accumulation up to 16.11, 13.44 and 3.17 mg kg(-1), respectively at Naini dump site, Allahabad (S3). The treatment showed maximum remediation efficiency for Cd (RR=0.676%) and Pb (RR=0.202%) at Mumfordganj contaminated site (S2). However, the above parameters were also observed at par with the treatment T5 [2.5 g kg(-1) oilcake manure +2 g kg(-1) humic acid]. Applied EDDS altered chlorophyll-a, chlorophyll-b, and carotene contents of plants while application of oilcake manure enhanced their contents in plant by 3.73-8.65%, 5.81-17.65%, and 7.04-17.19%, respectively. The authors conclude that Calendula officinalis L has potential to be safely grown in moderately Cd and Pb-contaminated soils and application of hyperaccumulator oilcake manure boosts the photosynthetic pigments of the plant, leading to enhanced clean-up of the cadmium and lead-contaminated soils. Hence, the hyperaccumulator oilcake manure should be preferred over chelates for sustainable phytoremediation through soil-plant rhizospheric process.

  1. Oxidation-Induced Degradable Nanogels for Iron Chelation

    PubMed Central

    Liu, Zhi; Wang, Yan; Purro, Max; Xiong, May P.

    2016-01-01

    Iron overload can increase cellular oxidative stress levels due to formation of reactive oxygen species (ROS); untreated, it can be extremely destructive to organs and fatal to patients. Since elevated oxidative stress levels are inherent to the condition in such patients, oxidation-induced degradable nanogels for iron chelation were rationally designed by simultaneously polymerizing oxidation-sensitive host-guest crosslinkers between β-cyclodextrin (β-CD) and ferrocene (Fc) and iron chelating moieties composed of deferoxamine (DFO) into the final gel scaffold in reverse emulsion reaction chambers. UV-Vis absorption and atomic absorption spectroscopy (AAS) was used to verify iron chelating capability of nanogels. These materials can degrade into smaller chelating fragments at rates proportional to the level of oxidative stress present. Conjugating DFO reduces the cytotoxicity of the chelator in the macrophage cells. Importantly, the nanogel can effectively reduce cellular ferritin expression in iron overloaded cells and regulate intracellular iron levels at the same time, which is important for maintaining a homeostatic level of this critical metal in cells. PMID:26868174

  2. Theoretical analysis of the inflection point on the logarithm of the distribution ratio vs pH plot for metal solvent extraction with chelating extractants

    SciTech Connect

    Tanaka, Mikiya; Koyama, Kazuya

    1996-11-01

    The general shape of the log D vs pH plot for metal solvent extraction equilibrium with chelating extractants, which is obtained under constant initial molarities of the extractant and target metal cation, has been mathematically investigated on the basis of simplified assumptions. The molarity of the metal ion ranges from dilute to concentrated regions. The log D vs pH plot is classified into three types depending on the ratios of the amount of the initial target metal cation to the extraction capacity of the organic phase, R; that is, (1) 0 < R < 1, (2) R = 1, and (3) R > 1. The difference among these types is the slope of the asymptote of the log D vs pH plot when the pH approaches infinity. There is an inflection point only on the plot of type 1. At the inflection point, the extractant molarity is equal to the geometric mean of the extractant molarities when the extraction percentages are 0% and 100%. The log D vs pH plot showing an inflection point is symmetric with respect to the inflection point. The locus of the inflection point with a variation in R lies on the straight line identical to the asymptote of the log D vs pH plot when R is equal to unity and the pH approaches infinity. These results are verified by numerical calculation.

  3. Multifunctional coumarin derivatives: monoamine oxidase B (MAO-B) inhibition, anti-β-amyloid (Aβ) aggregation and metal chelation properties against Alzheimer's disease.

    PubMed

    Huang, Ming; Xie, Sai-Sai; Jiang, Neng; Lan, Jin-Shuai; Kong, Ling-Yi; Wang, Xiao-Bing

    2015-02-01

    A series of coumarin derivatives were designed, synthesized, and evaluated as novel multifunctional agents against Alzheimer's disease (AD). In vitro studies showed that most of these compounds exhibited significant potency to inhibit hMAO-B selectively and self-induced Aβ1-42 aggregation. In particular, compound 13 presented the greatest potential to inhibit hMAO-B (IC50=0.081μM, SI >1234) and good inhibition of Aβ1-42 aggregation (52.9% at 20μM). Moreover, compound 13 could function as a metal-chelator, penetrate the blood-brain barrier (BBB) and show low cell toxicity in rat pheochromocytoma (PC12) and SH-SY5Y cells. Taken together, these results suggested that compound 13 might be a promising multifunctional agent for AD treatment. PMID:25542589

  4. Multifunctional coumarin derivatives: monoamine oxidase B (MAO-B) inhibition, anti-β-amyloid (Aβ) aggregation and metal chelation properties against Alzheimer's disease.

    PubMed

    Huang, Ming; Xie, Sai-Sai; Jiang, Neng; Lan, Jin-Shuai; Kong, Ling-Yi; Wang, Xiao-Bing

    2015-02-01

    A series of coumarin derivatives were designed, synthesized, and evaluated as novel multifunctional agents against Alzheimer's disease (AD). In vitro studies showed that most of these compounds exhibited significant potency to inhibit hMAO-B selectively and self-induced Aβ1-42 aggregation. In particular, compound 13 presented the greatest potential to inhibit hMAO-B (IC50=0.081μM, SI >1234) and good inhibition of Aβ1-42 aggregation (52.9% at 20μM). Moreover, compound 13 could function as a metal-chelator, penetrate the blood-brain barrier (BBB) and show low cell toxicity in rat pheochromocytoma (PC12) and SH-SY5Y cells. Taken together, these results suggested that compound 13 might be a promising multifunctional agent for AD treatment.

  5. Natural chelating agents for radionuclide decorporation

    DOEpatents

    Premuzic, E.T.

    1985-06-11

    This invention relates to the production of metal-binding compounds useful for the therapy of heavy metal poisoning, for biological mining and for decorporation of radionuclides. The present invention deals with an orderly and effective method of producing new therapeutically effective chelating agents. This method uses challenge biosynthesis for the production of chelating agents that are specific for a particular metal. In this approach, the desired chelating agents are prepared from microorganisms challenged by the metal that the chelating agent is designed to detoxify. This challenge induces the formation of specific or highly selective chelating agents. The present invention involves the use of the challenge biosynthetic method to produce new complexing/chelating agents that are therapeutically useful to detoxify uranium, plutonium, thorium and other toxic metals. The Pseudomonas aeruginosa family of organisms is the referred family of microorganisms to be used in the present invention to produce the new chelating agent because this family is known to elaborate strains resistant to toxic metals.

  6. Hyperaccumulator oilcake manure as an alternative for chelate-induced phytoremediation of heavy metals contaminated alluvial soils.

    PubMed

    Mani, Dinesh; Kumar, Chitranjan; Patel, Niraj Kumar

    2015-01-01

    The ability of hyperaccumulator oilcake manure as compared to chelates was investigated by growing Calendula officinalis L for phytoremediation of cadmium and lead contaminated alluvial soil. The combinatorial treatment T6 [2.5 g kg(-1) oilcake manure+5 mmol kg(-1) EDDS] caused maximum cadmium accumulation in root, shoot and flower up to 5.46, 4.74 and 1.37 mg kg(-1) and lead accumulation up to 16.11, 13.44 and 3.17 mg kg(-1), respectively at Naini dump site, Allahabad (S3). The treatment showed maximum remediation efficiency for Cd (RR=0.676%) and Pb (RR=0.202%) at Mumfordganj contaminated site (S2). However, the above parameters were also observed at par with the treatment T5 [2.5 g kg(-1) oilcake manure +2 g kg(-1) humic acid]. Applied EDDS altered chlorophyll-a, chlorophyll-b, and carotene contents of plants while application of oilcake manure enhanced their contents in plant by 3.73-8.65%, 5.81-17.65%, and 7.04-17.19%, respectively. The authors conclude that Calendula officinalis L has potential to be safely grown in moderately Cd and Pb-contaminated soils and application of hyperaccumulator oilcake manure boosts the photosynthetic pigments of the plant, leading to enhanced clean-up of the cadmium and lead-contaminated soils. Hence, the hyperaccumulator oilcake manure should be preferred over chelates for sustainable phytoremediation through soil-plant rhizospheric process. PMID:25397984

  7. Synthesis of 4-substituted-trans-1,2-diaminocyclohexyl polyaminocarboxylate metal chelating agents for the preparation of stable radiometal antibody immunoconjugates for therapy and SPECT and PET imaging

    DOEpatents

    Mease, R.C.; Kolsky, K.L.; Mausner, L.F.; Srivastava, S.C.

    1997-06-03

    Cyclohexyl chelating agents useful in forming antibody-metal conjugates which are used for diagnostic and therapeutic purposes are synthesized. New compounds and processes of forming these compounds are disclosed including 4-haloacetamido-trans-1,2-diaminocyclohexyl polyaminocarboxylate and 4-isothiocyanato-trans-1,2-diamino cyclohexane-N,N,N{prime},N{prime}-tetra acetic acid.

  8. Synthesis of 4-substituted-trans-1,2-diaminocyclohexyl polyaminocarboxylate metal chelating agents for the preparation of stable radiometal antibody immunoconjugates for therapy and spect and pet imaging

    DOEpatents

    Mease, Ronnie C.; Kolsky, Kathryn L.; Mausner, Leonard F.; Srivastava, Suresh C.

    1997-06-03

    Cyclohexyl chelating agents useful in forming antibody-metal conjugates useful for diagnostic and therapeutic purposes. New compounds and processes of forming these compounds are disclosed including 4-haloacetamido-trans-1,2-diaminocyclohexyl polyaminocarboxylate and 4-isothiocyanato-trans-1,2-diamino cyclohexane-N, N, N', N'-tetra acetic acid.

  9. High-capacity chitosan-based chelating resin for on-line collection of transition and rare-earth metals prior to inductively coupled plasma-atomic emission spectrometry measurement.

    PubMed

    Katarina, Rosi Ketrin; Oshima, Mitsuko; Motomizu, Shoji

    2009-10-15

    High-capacity chitosan-based chelating resin, N-(2-hydroxyethyl)glycine-type chitosan, was synthesized using chloromethyloxirane (CMO) as a cross-linker and a coupling arms and hydroxylethylamine and bromoacetic acid as a synthesizer for the N-(2-hydroxyethyl)glycine chelating moiety. The CMO could bind with both of hydroxyl and amino group of the chitosan resin, and then couple with the chelating moiety. Increasing the amounts of chelating moiety could increase the capacity of the resin toward metal ions. Most transition and rare-earth metals could adsorb quantitatively on the resin at wide pH ranges and could be separated from alkaline and alkaline-earth metals. The resin was packed in a mini-column (40 mm length x 2 mm i.d.) which was installed in a Multi-Auto-Pret system. The Multi-Auto-Pret system coupled with ICP-AES was successfully applied to the determination of transition and rare-earth metals in river water samples.

  10. Hydroxypyridonate chelating agents

    DOEpatents

    Raymond, Kenneth N.; Scarrow, Robert C.; White, David L.

    1987-01-01

    Chelating agents having 1-hydroxy-2-pyridinone (HOPO) and related moieties incorporated within their structures, including polydentate HOPO-substituted polyamines such as spermidine and spermine, and HOPO-substituted desferrioxamine. The chelating agents are useful in selectively removing certain cations from solution, and are particularly useful as ferric ion and actinide chelators. Novel syntheses of the chelating agents are provided.

  11. Separation and recovery of lead from a mixture of some heavy metals using Amberlite IRC 718 chelating resin.

    PubMed

    Agrawal, Archana; Sahu, K K

    2006-05-20

    A weakly acidic ion exchanger resin containing the iminodiacetate group has been used to separate and recover metal ion from their mixtures. Batch and column methods were applied for the separation studies. Previous study on the kinetics and thermodynamics shows that the selectivity of this resin for transition metals was quite high as compared to that of alkaline earth metals. The efficiency of this resin in different experimental conditions was established and because of the large difference in the distribution coefficient values separation of the metal ions from their mixture was performed.

  12. Consolidated Incineration Facility metals partitioning test. Final report

    SciTech Connect

    Burns, D.B.

    1993-08-31

    Test burns were conducted at Energy and Environmental Research Corporation`s rotary kiln simulator, the Solid Waste Incineration Test Facility, using surrogate CIF wastes spiked with hazardous metals and organics. The primary objective for this test program was measuring heavy metals partition between the kiln bottom ash, scrubber blowdown solution, and incinerator stack gas. Also, these secondary waste streams were characterized to determine waste treatment requirements prior to final disposal. These tests were designed to investigate the effect of several parameters on metals partitioning: incineration temperature; waste chloride concentration; waste form (solid or liquid); and chloride concentration in the scrubber water. Tests were conducted at three kiln operating temperatures. Three waste simulants were burned, two solid waste mixtures (paper, plastic, latex, and one with and one without PVC), and a liquid waste mixture (containing benzene and chlorobenzene). Toxic organic and metal compounds were spiked into the simulated wastes to evaluate their fate under various combustion conditions. Kiln offgases were sampled for volatile organic compounds (VOC), semi-volatile organic compounds (SVOC), polychlorinated dibenz[p]dioxins and polychlorinated dibenzofurans (PCDD/PCDF), metals, particulate loading and size distribution, HCl, and combustion products. Stack gas sampling was performed to determine additional treatment requirements prior to final waste disposal. Significant test results are summarized below.

  13. Intracellular routing in breast cancer cells of streptavidin-conjugated trastuzumab Fab fragments linked to biotinylated doxorubicin-functionalized metal chelating polymers.

    PubMed

    Liu, Peng; Cai, Zhongli; Kang, Jae W; Boyle, Amanda J; Adams, Jarret; Lu, Yijie; Ngo Ndjock Mbong, Ghislaine; Sidhu, Sachdev; Reilly, Raymond M; Winnik, Mitchell A

    2014-03-10

    We describe the synthesis of a heterotelechelic metal-chelating polymer (Bi-MCP-Dox), a polyacrylamide with a number average degree of polymerization DPn = 50 (PDI = 1.2), with biotin (Bi) and doxorubicin (Dox) as functional chain ends and diethylenetriaminepentaacetic acid (DTPA) pendant groups as the binding sites for metal ions. We compared its behavior in cell-uptake experiments with a similar polymer (Bi-MCP) without Dox. These MCPs were complexed with trastuzumab Fab (tmFab) fragments covalently linked to streptavidin (SAv) to form tmFab-SAv-Bi-MCP-Dox and tmFab-SAv-Bi-MCP via the strong affinity between Bi and SAv. tmFab targets human epidermal growth factor receptor-2 (HER2), which is overexpressed on certain human breast cancer cells. Surface plasmon resonance (SPR) experiments with the extracellular domain (ECD) of HER2 showed that incorporation of the MCPs in these complexes had no significant effect on the association or dissociation rate with the HER2 ECD and the dissociation constants. The tmFab-complexed MCPs were subsequently labeled with (111)In (an Auger electron emitting radionuclide). Auger electrons can cause lethal DNA double strand breaks (DSBs) but only if they are emitted intracellularly and especially, in close proximity to the nucleus. To evaluate the cellular and nuclear uptake of tmFab-SAv-Bi-MCP-Dox, we incubated HER2+ SK-BR-3 human breast cancer cells with the complexes saturated with stable In(3+) and visualized their distribution by confocal fluorescence microscopy, monitoring the fluorescence of Dox. In parallel, we carried out cell fractionation studies on tmFab-SAv-Bi-MCP-Dox and on tmFab-SAv-Bi-MCP labeled with (111)In. Both radiolabeled complexes showed cell internalization and nuclear localization. We conclude that metal-chelating polymers with this composition appear to encourage internalization, nuclear uptake, and chromatin (DNA) binding of trastuzumab fragments modified with streptavidin in human breast cancer cells

  14. Synthesis, characterization, and antipathogenic studies of some transition metal complexes with N,O-chelating Schiff's base ligand incorporating azo and sulfonamide Moieties

    NASA Astrophysics Data System (ADS)

    Alaghaz, Abdel-Nasser M. A.; Bayoumi, Hoda A.; Ammar, Yousry A.; Aldhlmani, Sharah A.

    2013-03-01

    Chromium(III), Manganese(II), Cobalt(II), nickel(II), copper(II) and cadmium(II) complexes of 4-[4-hydroxy-3-(phenyliminomethyl)-phenylazo]benzenesulfonamide, were prepared and characterized on the basis of elemental analyses, spectral, magnetic, molar conductance and thermal analysis. Square planar, tetrahedral and octahedral geometries have been assigned to the prepared complexes. Dimeric complexes are obtained with 2:2 molar ratio except chromium(III) complex is monomeric which is obtained with 1:1 molar ratios. The IR spectra of the prepared complexes were suggested that the Schiff base ligand(HL) behaves as a bi-dentate ligand through the azomethine nitrogen atom and phenolic oxygen atom. The crystal field splitting, Racah repulsion and nepheloauxetic parameters and determined from the electronic spectra of the complexes. Thermal studies suggest a mechanism for degradation of HL and its metal complexes as function of temperature supporting the chelation modes. Also, the activation thermodynamic parameters, such as ΔE*, ΔH*, ΔS* and ΔG* for the different thermal decomposition steps of HL and its metal complexes were calculated. The pathogenic activities of the synthesized compounds were tested in vitro against the sensitive organisms Staphylococcus aureus (RCMB010027), Staphylococcus epidermidis (RCMB010024) as Gram positive bacteria, Klebsiella pneumonia (RCMB 010093), Shigella flexneri (RCMB 0100542), as Gram negative bacteria and Aspergillus fumigates (RCMB 02564), Aspergillus clavatus (RCMB 02593) and Candida albicans (RCMB05035) as fungus strain, and the results are discussed.

  15. EFFECTS OF OXIDATION OF IMMOBILIZED POLY-L-CYSTEINE ON TRACE METAL CHELATION AND PRECONCENTRATION. (R826694C651)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  16. Microscopic and Thermal Characterization of Hydrogen Peroxide Killing and Lysis of Spores and Protection by Transition Metal Ions, Chelators, and Antioxidants

    PubMed Central

    Shin, Soon-Young; Calvisi, Elizabeth G.; Beaman, Teofila C.; Pankratz, H. Stuart; Gerhardt, Philipp; Marquis, Robert E.

    1994-01-01

    Killing of bacterial spores by H2O2 at elevated but sublethal temperatures and neutral pH occurred without lysis. However, with prolonged exposure or higher concentrations of the agent, secondary lytic processes caused major damage successively to the coat, cortex, and protoplast, as evidenced by electron and phase contrast microscopy. These processes were also reflected in changes in differential scanning calorimetric profiles for H2O2-treated spores. Endothermic transitions in the profiles occurred at lower temperatures than usual as a result of H2O2 damage. Thus, H2O2 sensitized the cells to heat damage. Longer exposure to H2O2 resulted in total disappearance of the transitions, indicative of major disruptions of cell structure. Spores but not vegetative cells were protected against the lethal action of H2O2 by the transition metal cations Cu+, Cu2+, Co2+, Co3+, Fe2+, Fe3+, Mn2+, Ti3+, and Ti4+. The metal chelator EDTA was also somewhat protective, while o-phenanthroline, citrate, deferoxamine, and ethanehydroxydiphosphonate were only marginally so. Superoxide dismutase and a variety of other free-radical scavengers were not protective. In contrast, reducing agents such as sulfhydryl compounds and ascorbate at concentrations of 20 to 50 mM were highly protective. Decoating or demineralization of the spores had only minor effects. The marked dependence of H2O2 sporicidal activity on moderately elevated temperature and the known low reactivity of H2O2 itself suggest that radicals are involved in its killing action. However, the protective effects of a variety of oxidized or reduced transition metal ions indicate that H2O2 killing of spores is markedly different from that of vegetative cells. Images PMID:16349375

  17. Preparation of High-Efficiency Cytochrome c-Imprinted Polymer on the Surface of Magnetic Carbon Nanotubes by Epitope Approach via Metal Chelation and Six-Membered Ring.

    PubMed

    Qin, Ya-Ping; Li, Dong-Yan; He, Xi-Wen; Li, Wen-You; Zhang, Yu-Kui

    2016-04-27

    A novel epitope molecularly imprinted polymer on the surface of magnetic carbon nanotubes (MCNTs@EMIP) was successfully fabricated to specifically recognize target protein cytochrome c (Cyt C) with high performance. The peptides sequences corresponding to the surface-exposed C-terminus domains of Cyt C was selected as epitope template molecule, and commercially available zinc acrylate and ethylene glycol dimethacrylate (EGDMA) were employed as functional monomer and cross-linker, respectively, to synthesize MIP via free radical polymerization. The epitope was immobilized via metal chelation and six-membered ring formed between the functional monomer and the hydroxyl and amino groups of the epitope. The resulting MCNTs@EMIP exhibited specific recognition ability toward target Cyt C including more satisfactory imprinting factor (about 11.7) than that of other reported imprinting methods. In addition, the MCNTs@EMIP demonstrated a high adsorption amount (about 780.0 mg g(-1)) and excellent selectivity. Besides, the magnetic property of the support material made the processes easy and highly efficient by assistance of an external magnetic field. High-performance liquid chromatography analysis of Cyt C in bovine blood real sample and protein mixture indicated that the specificity was not affected by other competitive proteins, which forcefully stated that the MCNTs@EMIP had potential to be applied in bioseparation area. In brief, this study provided a new protocol to detect target protein in complex sample via epitope imprinting approach and surface imprinting strategy.

  18. Synthesis, spectroscopic, thermal and anticancer studies of metal-antibiotic chelations: Ca(II), Fe(III), Pd(II) and Au(III) chloramphenicol complexes

    NASA Astrophysics Data System (ADS)

    Al-Khodir, Fatima A. I.; Refat, Moamen S.

    2016-09-01

    Four Ca(II), Fe(III), Pd(II) and Au(III) complexes of chloramphenicol drug have been synthesized and well characterized using elemental analyses, (infrared, electronic, and 1H-NMR) spectra, magnetic susceptibility measurement, and thermal analyses. Infrared spectral data show that the chloramphenicol drug coordinated to Ca(II), Pd(II) and Au(III) metal ions through two hydroxyl groups with 1:1 or 1:2 M ratios, but Fe(III) ions chelated towards chloramphenicol drug via the oxygen and nitrogen atoms of amide group with 1:2 ratio based on presence of keto↔enol form. The X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) techniques were used to identify the nano-size particles of both iron(III) and gold(III) chloramphenicol complexes. The antimicrobial assessments of the chloramphenicol complexes were scanned and collected the results against of some kind of bacteria and fungi. The cytotoxic activity of the gold(III) complex was tested against the human colon carcinoma (HCT-116) and human hepatocellular carcinoma (HepG-2) tumor cell lines.

  19. Compression and immersion tests and leaching of radionuclides, stable metals, and chelating agents from cement-solidified decontamination waste collected from nuclear power stations

    SciTech Connect

    Akers, D.W.; Kraft, N.C.; Mandler, J.W.

    1994-06-01

    A study was performed for the Nuclear Regulatory Commission (NRC) to evaluate structural stability and leachability of radionuclides, stable metals, and chelating agents from cement-solidified decontamination ion-exchange resin wastes collected from seven commercial boiling water reactors and one pressurized water reactor. The decontamination methods used at the reactors were the Can-Decon, AP/Citrox, Dow NS-1, and LOMI processes. Samples of untreated resin waste and solidified waste forms were subjected to immersion and compressive strength testing. Some waste-form samples were leach-tested using simulated groundwaters and simulated seawater for comparison with the deionized water tests that are normally performed to assess waste-form leachability. This report presents the results of these tests and assesses the effects of the various decontamination methods, waste form formulations, leachant chemical compositions, and pH of the leachant on the structural stability and leachability of the waste forms. Results indicate that releases from intact and degraded waste forms are similar and that the behavior of some radionuclides such as {sup 55}Fe, {sup 60}Co, and {sup 99}Tc were similar. In addition, the leachability indexes are greater than 6.0, which meets the requirement in the NRC`s ``Technical Position on Waste Form,`` Revision 1.

  20. Coordination of two high-affinity hexamer peptides to copper(II) and palladium(II) models of the peptide-metal chelation site on IMAC resins

    SciTech Connect

    Chen, Y.; Pasquinelli, R.; Ataai, M.; Koepsel, R.R.; Kortes, R.A.; Shepherd, R.E.

    2000-03-20

    The coordination of peptides Ser-Pro-His-His-Gly-Gly (SPHHGG) and (His){sub 6} (HHHHHH) to [Pd{sup II}(mida)(D{sub 2}O)] (mida{sup 2{minus}} = N-methyliminodiacetate) was studied by {sup 1}H NMR as model reactions for Cu{sup II}(iminodiacetate)-immobilized metal affinity chromatography (IMAC) sites. This is the first direct physical description of peptide coordination for IMAC. A three-site coordination is observed which involves the first, third, and fourth residues along the peptide chain. The presence of proline in position 2 of SPHHGG achieves the best molecular mechanics and bonding angles in the coordinated peptide and enhances the interaction of the serine amino nitrogen. Histidine coordination of H{sub 1}, H{sub 3}, and H{sub 4} of (His){sub 6} and H{sub 3} and H{sub 4} of SPHHGG was detected by {sup 1}H NMR contact shifts and H/D exchange of histidyl protons. The EPR spectra of SPHHGG and HHHHHH attached to the [Cu{sup II}(mida)] unit were obtained for additional modeling of IMAC sites. EPR parameters of the parent [Cu(mida)(H{sub 2}O){sub 2}] complex are representative: g{sub zz} = 2.31; g{sub yy} = 2.086; g{sub xx} = 2.053; A{sub {vert_bar}{vert_bar}} = 161 G; A{sub N} = 19G (three line, one N coupling). Increased rhombic distortion is detected relative to the starting aqua complex in the order of [Cu(mida)L] for distortion of HHHHHH > SPHHGG > (H{sub 2}O){sub 2}. The lowering of symmetry is also seen in the decrease in the N-shf coupling, presumably to the imino nitrogen of mida{sup 2{minus}} in the order 19 G (H{sub 2}O), 16 G (SPHHGG) and 11 G (HHHHHH). Visible spectra of the [Cu(mida)(SPHHGG)] and [Cu(mida)(HHHHHH)] as a function of pH indicate coordination of one histidyl donor at ca. 4.5, two in the range of pH 5--7, and two chelate ring attachments involving the terminal amino donor for SPHHGG or another histidyl donor of HHHHHH in the pH domain of 7--8 in agreement with the [Pd{sup II}(mida)L] derivatives which form the two-chelate

  1. Characterization of a novel chelating resin of enhanced hydrophilicity and its analytical utility for preconcentration of trace metal ions.

    PubMed

    Islam, Aminul; Laskar, Mohammad Asaduddin; Ahmad, Akil

    2010-06-15

    A stable extractor of metal ions was synthesized through azo linking of p-hydroxybenzoic acid with Amberlite XAD-4 and was characterized by elemental analyses, infrared spectral and thermal studies. Its water regain value and hydrogen ion capacity were found to be 15.80 and 7.52mmolg(-1), respectively. Both batch and column methods were employed to study the sorption behavior for the metal ions which were subsequently determined by flame atomic absorption spectrophotometry. The optimum pH range for Co(II), Ni(II), Cu(II), Zn(II), and Pb(II) ions were 10.0, 8.0-9.0, 7.0, 7.0-8.0 and 7.0-8.0, respectively. The half-loading time, t(1/2), are 6.0, 8.0, 8.0, 8.0 and 4.0min, respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>75%). The breakthrough capacities for Co(II), Ni(II), Cu(II), Zn(II), and Pb(II) ions were found to be 0.46, 0.43, 0.42, 0.09 and 0.06mmolg(-1) with the corresponding preconcentration factor of 460, 460, 460, 360 and 260, respectively. The limit of preconcentration was in the range of 4.3-7.6microgL(-1). The detection limit for Co(II), Ni(II), Cu(II), Zn(II) and Pb(II) were found to be 0.47, 0.45, 0.50, 0.80, and 1.37microgL(-1), respectively. The Student's t (t-test) values for the analysis of standard reference materials were found to be less than the critical Student's t values at 95% confidence level. The AXAD-4-HBA has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil and fish.

  2. Hydroxynaphthyridine-derived group III metal chelates: wide band gap and deep blue analogues of green Alq3 (tris(8-hydroxyquinolate)aluminum) and their versatile applications for organic light-emitting diodes.

    PubMed

    Liao, Szu-Hung; Shiu, Jin-Ruei; Liu, Shun-Wei; Yeh, Shi-Jay; Chen, Yu-Hung; Chen, Chin-Ti; Chow, Tahsin J; Wu, Chih-I

    2009-01-21

    A series of group III metal chelates have been synthesized and characterized for the versatile application of organic light-emitting diodes (OLEDs). These metal chelates are based on 4-hydroxy-1,5-naphthyridine derivates as chelating ligands, and they are the blue version analogues of well-known green fluorophore Alq(3) (tris(8-hydroxyquinolinato)aluminum). These chelating ligands and their metal chelates were easily prepared with an improved synthetic method, and they were facially purified by a sublimation process, which enables the materials to be readily available in bulk quantity and facilitates their usage in OLEDs. Unlike most currently known blue analogues of Alq(3) or other deep blue materials, metal chelates of 4-hydroxy-1,5-naphthyridine exhibit very deep blue fluorescence, wide band gap energy, high charge carrier mobility, and superior thermal stability. Using a vacuum-thermal-deposition process in the fabrication of OLEDs, we have successfully demonstrated that the application of these unusual hydroxynaphthyridine metal chelates can be very versatile and effective. First, we have solved or alleviated the problem of exciplex formation that took place between the hole-transporting layer and hydroxynaphthyridine metal chelates, of which OLED application has been prohibited to date. Second, these deep blue materials can play various roles in OLED application. They can be a highly efficient nondopant deep blue emitter: maximum external quantum efficiency eta(ext) of 4.2%; Commision Internationale de L'Eclairage x, y coordinates, CIE(x,y) = 0.15, 0.07. Compared with Alq(3), Bebq(2) (beryllium bis(benzoquinolin-10-olate)), or TPBI (2,2',2''-(1,3,5-phenylene)tris(1-phenyl-1H-benzimidazole), they are a good electron-transporting material: low HOMO energy level of 6.4-6.5 eV and not so high LUMO energy level of 3.0-3.3 eV. They can be ambipolar and possess a high electron mobility of 10(-4) cm(2)/V s at an electric field of 6.4 x 10(5) V/cm. They are a

  3. On the mechanism of divalent metal ion chelator induced activation of the 7S nerve growth factor esteropeptidase. Activation by 2,2',2''-terpyridine and by 8-hydroxyquinoline 5-sulfonic acid.

    PubMed

    Pattison, S E; Dunn, M F

    1976-08-24

    Our previous studies (Pattison, S. E., and Dunn, M. F. (1975), Biochemistry 14, 2733) have shown that the reaction of divalent metal ion chelators with the 140 000 mol wt mouse submaxillary nerve growth factor protein (7S NGF) activates the iota-subunit esteropeptidase activity ca. sevenfold. Ultraviolet-visible spectral studies with the chelator 2,2',2''-terpyridine (terpyridine) and fluorescence emission studies with 8-hydroxyquinoline-5-sulfonic acid (HQSA) in combination with both conventional and rapid-mixing stopped-flow kinetic techniques have been employed in the present study to investigate (a) the mechanism of the chelator-induced activation process, and (b) the identity of the divalent metal ion involved. The spectral studies confirm the presence of stoichiometrically significant amounts of tightly bound zinc ion in native 7S NGF (1-2 g-atoms of An2+/mol of 7S NGF). The kinetic studies show that the reaction of terpyridine with 7S NGF occurs via a two-step process involving first a rapid, apparent second-order step (k1 = 1 x 10(6) M-1 s-1) to form a 7S NGF-Zn2+-chelator monocomplex, then a slow step to form a bis(terpyridine)-Zn(II) complex and activated 7S NGF in an apparent first-order process (kobsd = 0.10 min-1). This rate is, within experimental error, identical with the apparent first-order rate constant for the chelator-induced activation process (monitored by the rate of change in the steady-state rate of hydrolysis of chromophoric substrate, alpha-N-benzoyl-D,L-arginine-p-nitroanilide). Kinetic studies of the reaction of HQSA with native 7S NGF show that, under the same conditions of concentration, the rate of formation of the tris(HQSA)-Zn(II) complex is identical with the rate of the HQSA-induced activation of the 7S NGF esteropeptidase. Thus, these studies unambiguously establish that zinc ion is the metal ion involved in the chelator-induced activation process, and that activation involves removal of zinc ion from native 7S NGF.

  4. Rapid screening method for quinolone residues in livestock and fishery products using immobilised metal chelate affinity chromatographic clean-up and liquid chromatography-fluorescence detection.

    PubMed

    Takeda, N; Gotoh, M; Matsuoka, T

    2011-09-01

    An efficient LC method was developed for screening the presence of quinolones (QLs)--comprising fluoroquinolones (FQs) and acidic quinolones (AQs)--residues in various livestock and fishery products. Targeted analytes were for nine FQs of marbofloxacin (MAR), ofloxacin (OFL), norfloxacin (NOR), ciprofloxacin (CIP), enrofloxacin (ENR), danofloxacin (DAN), orbifloxacin (ORB), difloxacin (DIF) and sarafloxacin (SAR), and three AQs of oxolinic acid (OXA), nalidixic acid (NAL) and flumequine (FMQ). Samples comprised ten different food products covering five matrices: muscle (cattle, swine and chicken), liver (chicken), raw fish (shrimp and salmon), egg (chicken), and processed food (ham, sausage and fish sausage). This method involved a simple extraction with (1:1) acetonitrile-methanol, a highly selective clean-up with an immobilised metal chelate affinity column charged with Fe(3+), a fast isocratic LC analysis using a short column (20 mm × 4.6 mm, 3 µm) with a mobile phase of (15:85:0.1) methanol/water/formic acid, and fluorescence detection (excitation/emission wavelengths of 295 nm/455 nm for FQs (495 nm for MAR), and 320 nm/365 nm for AQs). Among FQs, pairs of NOR/OFL, ORB/DIF and ENR/DAN were incompletely resolved. A confirmatory LC run with a Mg(2+) containing methanolic mobile phase was also proposed for the samples suspected of being positive. The optimised method gave satisfactory recoveries of 88.5% (56.1-108.6%) and 78.7% (44.1-99.5%) for intra- and inter-day assays with relative standard deviations of 7.2% (0.7-18.4%) and 6.8% (1.4-16.6%), respectively. Limits of quantitation ranged from 0.8 µg kg(-1) (DAN) to 6.5 µg kg(-1) (SAR). This method was successfully employed to analyse 113 real samples and two positive samples were found: fish sausage (CIP 990 µg kg(-1)) and shrimp (ENR 20 µg kg(-1)).

  5. Rapid screening method for quinolone residues in livestock and fishery products using immobilised metal chelate affinity chromatographic clean-up and liquid chromatography-fluorescence detection.

    PubMed

    Takeda, N; Gotoh, M; Matsuoka, T

    2011-09-01

    An efficient LC method was developed for screening the presence of quinolones (QLs)--comprising fluoroquinolones (FQs) and acidic quinolones (AQs)--residues in various livestock and fishery products. Targeted analytes were for nine FQs of marbofloxacin (MAR), ofloxacin (OFL), norfloxacin (NOR), ciprofloxacin (CIP), enrofloxacin (ENR), danofloxacin (DAN), orbifloxacin (ORB), difloxacin (DIF) and sarafloxacin (SAR), and three AQs of oxolinic acid (OXA), nalidixic acid (NAL) and flumequine (FMQ). Samples comprised ten different food products covering five matrices: muscle (cattle, swine and chicken), liver (chicken), raw fish (shrimp and salmon), egg (chicken), and processed food (ham, sausage and fish sausage). This method involved a simple extraction with (1:1) acetonitrile-methanol, a highly selective clean-up with an immobilised metal chelate affinity column charged with Fe(3+), a fast isocratic LC analysis using a short column (20 mm × 4.6 mm, 3 µm) with a mobile phase of (15:85:0.1) methanol/water/formic acid, and fluorescence detection (excitation/emission wavelengths of 295 nm/455 nm for FQs (495 nm for MAR), and 320 nm/365 nm for AQs). Among FQs, pairs of NOR/OFL, ORB/DIF and ENR/DAN were incompletely resolved. A confirmatory LC run with a Mg(2+) containing methanolic mobile phase was also proposed for the samples suspected of being positive. The optimised method gave satisfactory recoveries of 88.5% (56.1-108.6%) and 78.7% (44.1-99.5%) for intra- and inter-day assays with relative standard deviations of 7.2% (0.7-18.4%) and 6.8% (1.4-16.6%), respectively. Limits of quantitation ranged from 0.8 µg kg(-1) (DAN) to 6.5 µg kg(-1) (SAR). This method was successfully employed to analyse 113 real samples and two positive samples were found: fish sausage (CIP 990 µg kg(-1)) and shrimp (ENR 20 µg kg(-1)). PMID:21749230

  6. Synthesis, characterization and biological approach of metal chelates of some first row transition metal ions with halogenated bidentate coumarin Schiff bases containing N and O donor atoms.

    PubMed

    Prabhakara, Chetan T; Patil, Sangamesh A; Toragalmath, Shivakumar S; Kinnal, Shivashankar M; Badami, Prema S

    2016-04-01

    The impregnation of halogen atoms in a molecule is an emerging trend in pharmaceutical chemistry. The presence of halogens (Cl, Br, I and F) increases the lipophilic nature of molecule and improves the penetration of lipid membrane. The presence of electronegative halogen atoms increases the bio- activity of core moiety. In the present study, Co(II), Ni(II) and Cu(II) complexes are synthesised using Schiff bases (HL(I) and HL(II)), derived from 8-formyl-7-hydroxy-4-methylcoumarin/3-chloro-8-formyl-7-hydroxy-4-methylcoumarin with 2,4-difluoroaniline/o-toluidine respectively. The synthesized compounds were characterized by spectral (IR, NMR, UV-visible, Mass, ESI-MS, ESR), thermal, fluorescence and molar conductivity studies. All the synthesized metal complexes are completely soluble in DMF and DMSO. The non-electrolytic nature of the metal complexes was confirmed by molar conductance studies. Elemental analysis study suggest [ML2(H2O)2] stoichiometry, here M=Co(II), Ni(II) and Cu(II), L=deprotonated ligand. The obtained IR data supports the binding of metal ion to Schiff base. Thermal study suggests the presence of coordinated water molecules. Electronic spectral results reveal six coordinated geometry for the synthesized metal complexes. The Schiff bases and their metal complexes were evaluated for antibacterial (Pseudomonas aureginosa and Proteus mirabilis), antifungal (Aspergillus niger and Rhizopus oryzae), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activities. PMID:26874303

  7. Synthesis, characterization and biological approach of metal chelates of some first row transition metal ions with halogenated bidentate coumarin Schiff bases containing N and O donor atoms.

    PubMed

    Prabhakara, Chetan T; Patil, Sangamesh A; Toragalmath, Shivakumar S; Kinnal, Shivashankar M; Badami, Prema S

    2016-04-01

    The impregnation of halogen atoms in a molecule is an emerging trend in pharmaceutical chemistry. The presence of halogens (Cl, Br, I and F) increases the lipophilic nature of molecule and improves the penetration of lipid membrane. The presence of electronegative halogen atoms increases the bio- activity of core moiety. In the present study, Co(II), Ni(II) and Cu(II) complexes are synthesised using Schiff bases (HL(I) and HL(II)), derived from 8-formyl-7-hydroxy-4-methylcoumarin/3-chloro-8-formyl-7-hydroxy-4-methylcoumarin with 2,4-difluoroaniline/o-toluidine respectively. The synthesized compounds were characterized by spectral (IR, NMR, UV-visible, Mass, ESI-MS, ESR), thermal, fluorescence and molar conductivity studies. All the synthesized metal complexes are completely soluble in DMF and DMSO. The non-electrolytic nature of the metal complexes was confirmed by molar conductance studies. Elemental analysis study suggest [ML2(H2O)2] stoichiometry, here M=Co(II), Ni(II) and Cu(II), L=deprotonated ligand. The obtained IR data supports the binding of metal ion to Schiff base. Thermal study suggests the presence of coordinated water molecules. Electronic spectral results reveal six coordinated geometry for the synthesized metal complexes. The Schiff bases and their metal complexes were evaluated for antibacterial (Pseudomonas aureginosa and Proteus mirabilis), antifungal (Aspergillus niger and Rhizopus oryzae), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activities.

  8. Antimalarial properties of orally active iron chelators.

    PubMed

    Heppner, D G; Hallaway, P E; Kontoghiorghes, G J; Eaton, J W

    1988-07-01

    The appearance of widespread multiple drug resistance in human malaria has intensified the search for new antimalarial compounds. Metal chelators, especially those with high affinity for iron, represent one presently unexploited class of antimalarials. Unfortunately the use of previously identified chelators as antimalarials has been precluded by their toxicity and, in the case of desferrioxamine, the necessity for parenteral administration. The investigators now report that a new class of orally active iron chelators, namely the derivatives of alpha-ketohydroxypyridines (KHPs), are potent antimalarials against cultured Plasmodium falciparum. The KHPs evidently exert this effect by sequestering iron because a preformed chelator:iron complex has no antimalarial action. The pool(s) of iron being sequestered by the chelators have not been identified but may not include serum transferrin. Preincubation of human serum with KHPs followed by removal of the drug results in the removal of greater than 97% of total serum iron. Nonetheless, this serum effectively supports the growth of P falciparum cultures. Therefore the KHPs may exert antimalarial effect through chelation of erythrocytic rather than serum iron pool(s). The investigators conclude that these powerful, orally active iron chelators may form the basis of a new class of antimalarial drugs. PMID:3291984

  9. Macrocyclic bifunctional chelating agents

    DOEpatents

    Meares, Claude F.; DeNardo, Sally J.; Cole, William C.; Mol, Min K.

    1987-01-01

    A copper chelate conjugate which is stable in human serum. The conjugate includes the copper chelate of a cyclic tetraaza di-, tri-, or tetra-acetic acid, a linker attached at one linker end to a ring carbon of the chelate, and a biomolecule joined at the other end of the linker. The conjugate, or the linker-copper chelate compound used in forming the conjugate, are designed for use in diagnostic and therapeutic applications which involve Cu(II) localization via the systemic route.

  10. Final report for the DOE Metal Hydride Center of Excellence.

    SciTech Connect

    Keller, Jay O.; Klebanoff, Leonard E.

    2012-01-01

    This report summarizes the R&D activities within the U.S. Department of Energy Metal Hydride Center of Excellence (MHCoE) from March 2005 to June 2010. The purpose of the MHCoE has been to conduct highly collaborative and multi-disciplinary applied R&D to develop new reversible hydrogen storage materials that meet or exceed DOE 2010 and 2015 system goals for hydrogen storage materials. The MHCoE combines three broad areas: mechanisms and modeling (which provide a theoretically driven basis for pursuing new materials), materials development (in which new materials are synthesized and characterized) and system design and engineering (which allow these new materials to be realized as practical automotive hydrogen storage systems). This Final Report summarizes the organization and execution of the 5-year research program to develop practical hydrogen storage materials for light duty vehicles. Major results from the MHCoE are summarized, along with suggestions for future research areas.

  11. Magnetically controlled deposition of metals using gas plasma. Final report

    SciTech Connect

    1998-04-02

    This is the first phase of a project that has the objective to develop a method of spraying materials on a substrate in a controlled manner to eliminate the waste and hazardous material generation inherent in present plating processes. The project is considering plasma spraying of metal on a substrate using magneto-hydrodynamics to control the plasma/metal stream. The process being developed is considering the use of commercially available plasma torches to generate the plasma/metal stream. The plasma stream is collimated, and directed using magnetic forces to the extent required for precise control of the deposition material. The project will be completed in phases. Phase one of the project, the subject of this grant, is the development of an analytical model that can be used to determine the feasibility of the process and to design a laboratory scale demonstration unit. The contracted time is complete, and the research is still continuing. This report provides the results obtained to date. As the model and calculations are completed those results will also be provided. This report contains the results of the computer code that have been completed to date. Results from a ASMEE Benchmark problem, flow over a backward step with heat transfer, Couette flow with magnetic forces, free jet flow are presented along with several other check calculations that are representative of the cases that were calculated in the course of the development process. The final cases that define a velocity field in the exit of a plasma spray torch with and without a magnetic field are in process. A separate program (SPRAY) has been developed that can track the plating material to the substrate and describe the distribution of the material on the substrate. When the jet calculations are complete SPRAY will be used to compare the distribution of material on the substrate with and without the effect of the magnetic focus.

  12. Copper Chelation in Alzheimer's Disease Protein

    NASA Astrophysics Data System (ADS)

    Rose, Frisco; Hodak, Miroslav; Bernholc, Jerry

    2013-03-01

    Alzheimer's disease (AD) is a neurodegenerative disorder affecting millions of people in the U.S. AD is primarily characterized at the cellular level by densely tangled fibrils of amyloid- β protein. These protein clusters have been found in association with elevated levels of multiple transition metals, with copper being the most egregious. Interestingly, metal chelation has shown promise in attenuating the symptoms of AD in recent clinical studies. We investigate this process by constructing an atomistic model of the amyloid- β-copper complex and profile the energetic viability in each of its subsequent disassociation stages. Our results indicate that five energetic barriers must be overcome for full metal chelation. The energy barriers are biologically viable in the presence water mediated bond and proton transfer between the metal and the protein. We model the chelation reaction using a consecutive path nudged elastic band method implemented in our ab initio real-space multi-grid code to obtain a viable sequence. This reaction model details a physically consistent explanation of the chelation process that could lead to the discovery of more effective chelation agents in the treatment of AD.

  13. Zn(II)- and Cu(II)-induced non-fibrillar aggregates of amyloid-beta (1-42) peptide are transformed to amyloid fibrils, both spontaneously and under the influence of metal chelators.

    PubMed

    Tõugu, Vello; Karafin, Ann; Zovo, Kairit; Chung, Roger S; Howells, Claire; West, Adrian K; Palumaa, Peep

    2009-09-01

    Aggregation of amyloid-beta (Abeta) peptides is a central phenomenon in Alzheimer's disease. Zn(II) and Cu(II) have profound effects on Abeta aggregation; however, their impact on amyloidogenesis is unclear. Here we show that Zn(II) and Cu(II) inhibit Abeta(42) fibrillization and initiate formation of non-fibrillar Abeta(42) aggregates, and that the inhibitory effect of Zn(II) (IC(50) = 1.8 micromol/L) is three times stronger than that of Cu(II). Medium and high-affinity metal chelators including metallothioneins prevented metal-induced Abeta(42) aggregation. Moreover, their addition to preformed aggregates initiated fast Abeta(42) fibrillization. Upon prolonged incubation the metal-induced aggregates also transformed spontaneously into fibrils, that appear to represent the most stable state of Abeta(42). H13A and H14A mutations in Abeta(42) reduced the inhibitory effect of metal ions, whereas an H6A mutation had no significant impact. We suggest that metal binding by H13 and H14 prevents the formation of a cross-beta core structure within region 10-23 of the amyloid fibril. Cu(II)-Abeta(42) aggregates were neurotoxic to neurons in vitro only in the presence of ascorbate, whereas monomers and Zn(II)-Abeta(42) aggregates were non-toxic. Disturbed metal homeostasis in the vicinity of zinc-enriched neurons might pre-dispose formation of metal-induced Abeta aggregates, subsequent fibrillization of which can lead to amyloid formation. The molecular background underlying metal-chelating therapies for Alzheimer's disease is discussed in this light. PMID:19619132

  14. The Chelate Effect Redefined.

    ERIC Educational Resources Information Center

    da Silva, J. J. R. Frausto

    1983-01-01

    Discusses ambiguities of the accepted definition of the chelate effect, suggesting that it be defined in terms of experimental observation rather than mathematical abstraction. Indicates that the effect depends on free energy change in reaction, ligand basicity, pH of medium, type of chelates formed, and concentration of ligands in solution. (JN)

  15. Assessing bioavailability levels of metals in effluent-affected rivers: effect of Fe(III) and chelating agents on the distribution of metal speciation.

    PubMed

    Han, Shuping; Naito, Wataru; Masunaga, Shigeki

    2016-01-01

    To assess the effects of Fe(III) and anthropogenic ligands on the bioavailability of Ni, Cu, Zn, and Pb, concentrations of bioavailable metals were measured by the DGT (diffusive gradients in thin films) method in some urban rivers, and were compared with concentrations calculated by a chemical equilibrium model (WHAM 7.0). Assuming that dissolved Fe(III) (<0.45 μm membrane filtered) was in equilibrium with colloidal iron oxide, the WHAM 7.0 model estimated that bioavailable concentrations of Ni, Cu, and Zn were slightly higher than the corresponding values estimated assuming that dissolved Fe(III) was absent. In contrast, lower levels of free Pb were predicted by the WHAM 7.0 model when dissolved Fe(III) was included. Estimates showed that most of the dissolved Pb was present as colloidal iron-Pb complex. Ethylene-diamine-tetra-acetic acid (EDTA) concentrations at sampling sites were predicted from the relationship between EDTA and the calculated bioavailable concentration of Zn. When both colloidal iron and predicted EDTA concentrations were included in the WHAM 7.0 calculations, dissolved metals showed a strong tendency to form EDTA complexes, in the order Ni > Cu > Zn > Pb. With the inclusion of EDTA, bioavailable concentrations of Ni, Cu, and Zn predicted by WHAM 7.0 were different from those predicted considering only humic substances and colloidal iron. PMID:27533864

  16. Reactive oxygen species-mediated loss of bovine sperm motility in egg yolk Tris extender: protection by pyruvate, metal chelators and bovine liver or oviductal fluid catalase.

    PubMed

    Bilodeau, Jean-François; Blanchette, Sophie; Cormier, Nathaly; Sirard, Marc-André

    2002-02-01

    Improvement of bovine semen cryopreservation requires a better understanding of the properties of the currently used extenders. At present, about half of the spermatozoa die or become immotile following cryopreservation. The implication of an oxidative stress during or following the process of cryopreservation has been suspected to alter sperm functions. However, insufficient information is available on the effect of oxidative stress on sperm functions in their surrounding environment, the extender, such as the one based on egg yolk, Tris and glycerol. In this study, we investigated the effects of hydrogen peroxide (H2O2) and superoxide anion (O2*-) on bovine sperm motility in a widely used egg yolk Tris glycerol (EYTG) extender in comparison to a reference medium, the Tyrode's albumen lactate pyruvate (TALP). Bovine sperm were incubated for 6 h with or without concentrations of H2O2 ranging from 12.5 microM to 1.25 mM and with the hypoxanthine/xanthine oxidase system (X/XOD) that generates O2*-. Sperm motility was established by computer assisted semen analysis (CASA) in four similar experiments using the same frozen pool of semen. We have found that sperm motility was reduced significantly by H2O2 concentrations 20-fold lower in EYTG than in TALP medium. The differential resistance of the two media was explained by pyruvate present in TALP that acts as an antioxidant and metals ions, chelated by ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DETAPAC), found in egg yolk that might react with H2O2. Addition of only 5 U/ml of bovine liver catalase or oviductal fluid catalase (OFC) were sufficient to overcome the loss of sperm motility caused by 100 microM H2O2 in both EYTG and TALP. However, OFC was the most effective of the two catalases in EYTG. In addition to maintain sperm motility, catalase (5 U/ml) and pyruvate (5 mM) increased the intracellular sperm ATP level in comparison to sperm incubated alone for 6 h at 38.5 degrees C in

  17. Chelation Treatment for Autism Spectrum Disorders: A Systematic Review

    ERIC Educational Resources Information Center

    Davis, Tonya N.; O'Reilly, Mark; Kang, Soyeon; Lang, Russell; Rispoli, Mandy; Sigafoos, Jeff; Lancioni, Giulio; Copeland, Daelynn; Attai, Shanna; Mulloy, Austin

    2013-01-01

    Chelation treatment is used to eliminate specific metals from the body, such as mercury. It has been hypothesized that mercury poisoning may be a factor in autism and data suggest that perhaps 7% of individuals with autism spectrum disorder (ASD) have received chelation treatment. It would therefore seem timely to review studies investigating the…

  18. Nanoparticle and Iron Chelators as a Potential Novel Alzheimer Therapy

    PubMed Central

    Liu, Gang; Men, Ping; Perry, George; Smith, Mark A.

    2010-01-01

    Current therapies for Alzheimer disease (AD) such as the acetylcholinesterase inhibitors and the latest NMDA receptor inhibitor, Namenda, provide moderate symptomatic delay at various stages of the disease, but do not arrest the disease progression or bring in meaningful remission. New approaches to the disease management are urgently needed. Although the etiology of AD is largely unknown, oxidative damage mediated by metals is likely a significant contributor since metals such as iron, aluminum, zinc, and copper are dysregulated and/or increased in AD brain tissue and create a pro-oxidative environment. This role of metal ion-induced free radical formation in AD makes chelation therapy an attractive means of dampening the oxidative stress burden in neurons. The chelator desferrioxamine, FDA approved for iron overload, has shown some benefit in AD, but like many chelators, it has a host of adverse effects and substantial obstacles for tissue-specific targeting. Other chelators are under development and have shown various strengths and weaknesses. Here, we propose a novel system of chelation therapy through the use of nanoparticles. Nanoparticles conjugated to chelators show unique ability to cross the blood–brain barrier (BBB), chelate metals, and exit through the BBB with their corresponding complexed metal ions. This method may provide a safer and more effective means of reducing the metal load in neural tissue, thus attenuating the harmful effects of oxidative damage and its sequelae. Experimental procedures are presented in this chapter. PMID:20013176

  19. Chelation: A Fundamental Mechanism of Action of AGE Inhibitors, AGE Breakers, and Other Inhibitors of Diabetes Complications

    SciTech Connect

    Nagai, Rhoji; Murray, David B.; Metz, Thomas O.; Baynes, John

    2012-03-01

    Advanced glycation or glycoxidation end-products (AGE) increase in tissue proteins with age, and their rate of accumulation is increased in diabetes, nephropathy and inflammatory diseases. AGE inhibitors include a range of compounds that are proposed to act by trapping carbonyl and dicarbonyl intermediates in AGE formation. However, some among the newer generation of AGE inhibitors lack reactive functional groups that would trap reaction intermediates, indicating an alternative mechanism of action. We propose that AGE inhibitors function primarily as chelators, inhibiting metal-catalyzed oxidation reactions. The AGE-inhibitory activity of angiotensin-converting enzyme inhibitors and angiotensin receptor blockers is also consistent with their chelating activity. Finally, compounds described as AGE breakers, or their hydrolysis products, also have strong chelating activity, suggesting that these compounds also act through their chelating activity. We conclude that chelation is the common, and perhaps the primary, mechanism of action of AGE inhibitors and breakers, and that chronic, mild chelation therapy should prove useful in treatment of diabetes and age-related diseases characterized by oxidative stress, inflammation and increased chemical modification of tissue proteins by advanced glycoxidation and lipoxidation end-products.

  20. Remediation of metal contaminated soil by EDTA incorporating electrochemical recovery of metal and EDTA

    SciTech Connect

    Allen, H.E.; Chen, P.H. )

    1993-11-01

    Removal of toxic heavy metals from a soil matrix by the addition of ethylenediamine tetraacetic acid (EDTA) is an effective means of remediation. The liquid stream containing the metal and chelating agent is amenable to further treatment by electrolysis in which the metal can be separated from the chelating agent. This provides a separated metal than can be removed for reuse or treated for final disposal by conventional technologies and a reclaimed EDTA stream that can be used again for treatment of contaminated soil. Under the diffusion controlled conditions of polarography or voltammetry, the authors observed reduction of cadmium, copper and lead ions and their protonated EDTA complexes (MHY[sup [minus

  1. Metal-Chelating Polymers (MCPs) with Zwitterionic Pendant Groups Complexed to Trastuzumab Exhibit Decreased Liver Accumulation Compared to Polyanionic MCP Immunoconjugates.

    PubMed

    Liu, Peng; Boyle, Amanda J; Lu, Yijie; Adams, Jarrett; Chi, Yuechuan; Reilly, Raymond M; Winnik, Mitchell A

    2015-11-01

    Metal-chelating polymers (MCPs) can amplify the radioactivity delivered to cancer cells by monoclonal antibodies or their Fab fragments. We focus on trastuzumab (tmAb), which is used to target cancer cells that overexpress human epidermal growth factor receptor 2 (HER2). We report the synthesis and characterization of a biotin (Bi) end-capped MCP, Bi-PAm(DET-DTPA)36, a polyacrylamide with diethylenetriaminepentaacetic acid (DTPA) groups attached as monoamides to the polymer backbone by diethylenetriamine (DET) pendant groups. We compared its behavior in vivo and in vitro to a similar MCP with ethylenediamine (EDA) pendant groups (Bi-PAm(EDA-DTPA)40). These polymers were complexed to a streptavidin-modified Fab fragment of tmAb, then labeled with (111)In to specifically deliver multiple copies of (111)In to HER2+ cancer cells. Upon decay, (111)In emits γ-rays that can be used in single-photon emission computed tomography radioimaging, as well as Auger electrons that cause lethal double strand breakage of DNA. Our previous studies in Balb/c mice showed that radioimmunoconjugates (RICs) containing the Bi-PAm(EDA-DTPA)40 polymer had extremely short blood circulation time and high liver uptake and were, thus, unsuitable for in vivo studies. The polymer Bi-PAm(EDA-DTPA)40 carries negative charges on each pendant group at neutral pH and a net charge of (-1) on each pendant group when saturated with stable In(3+). To test our hypothesis that charge associated with the polymer repeat unit is a key factor affecting its biodistribution profile, we examined the biodistribution of RICs containing Bi-PAm(DET-DTPA)36. While this polymer is also negatively charged at neutral pH, it becomes a zwitterionic MCP upon saturation of the DTPA groups with stable In(3+) ions. In both nontumor bearing Balb/c mice and athymic mice implanted with HER2+ SKOV-3 human ovarian cancer tumors, we show that the zwitterionic MCP has improved biodistribution, higher blood levels of radioactivity

  2. Metal-Chelating Polymers (MCPs) with Zwitterionic Pendant Groups Complexed to Trastuzumab Exhibit Decreased Liver Accumulation Compared to Polyanionic MCP Immunoconjugates.

    PubMed

    Liu, Peng; Boyle, Amanda J; Lu, Yijie; Adams, Jarrett; Chi, Yuechuan; Reilly, Raymond M; Winnik, Mitchell A

    2015-11-01

    Metal-chelating polymers (MCPs) can amplify the radioactivity delivered to cancer cells by monoclonal antibodies or their Fab fragments. We focus on trastuzumab (tmAb), which is used to target cancer cells that overexpress human epidermal growth factor receptor 2 (HER2). We report the synthesis and characterization of a biotin (Bi) end-capped MCP, Bi-PAm(DET-DTPA)36, a polyacrylamide with diethylenetriaminepentaacetic acid (DTPA) groups attached as monoamides to the polymer backbone by diethylenetriamine (DET) pendant groups. We compared its behavior in vivo and in vitro to a similar MCP with ethylenediamine (EDA) pendant groups (Bi-PAm(EDA-DTPA)40). These polymers were complexed to a streptavidin-modified Fab fragment of tmAb, then labeled with (111)In to specifically deliver multiple copies of (111)In to HER2+ cancer cells. Upon decay, (111)In emits γ-rays that can be used in single-photon emission computed tomography radioimaging, as well as Auger electrons that cause lethal double strand breakage of DNA. Our previous studies in Balb/c mice showed that radioimmunoconjugates (RICs) containing the Bi-PAm(EDA-DTPA)40 polymer had extremely short blood circulation time and high liver uptake and were, thus, unsuitable for in vivo studies. The polymer Bi-PAm(EDA-DTPA)40 carries negative charges on each pendant group at neutral pH and a net charge of (-1) on each pendant group when saturated with stable In(3+). To test our hypothesis that charge associated with the polymer repeat unit is a key factor affecting its biodistribution profile, we examined the biodistribution of RICs containing Bi-PAm(DET-DTPA)36. While this polymer is also negatively charged at neutral pH, it becomes a zwitterionic MCP upon saturation of the DTPA groups with stable In(3+) ions. In both nontumor bearing Balb/c mice and athymic mice implanted with HER2+ SKOV-3 human ovarian cancer tumors, we show that the zwitterionic MCP has improved biodistribution, higher blood levels of radioactivity

  3. EDTA Chelation Therapy, Without Added Vitamin C, Decreases Oxidative DNA Damage and Lipid Peroxidation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Chelation therapy is thought to not only remove contaminating metals, but also to decrease free radical production. However, in standard EDTA chelation therapy high doses of vitamin C with potential prooxidant effects are often added to the chelation solution. We demonstrated previously that the in...

  4. Biologically Active Transition Metal Chelates of Ni(II), Cu(II) and Zn(II) With 2-Aminothiazole-Derived Schiff-bases: Their Synthesis, Characterization and the Role of Anions (NO3, SO42-, C2O42-and CH3CO2-) on Their Antibacterial Properties

    PubMed Central

    Chohan, Zahid H.

    1999-01-01

    Biologically active nickel(ll), copper(ll) and zinc(ll) chelates with thiazole-derived nitro- and chlorosalicylaldehyde Schiff-bases having the same metal ion but different anions, e.g. nitrate, sulfate, oxalate and acetate have been synthesized and characterized on the basis of their physical, spectral and analytical data. In order to evaluate the possible participating role of anions on the antibacterial properties, these ligands and their synthesized metal chelates with various anions have been screened against bacterial species Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus. PMID:18472911

  5. Medical toxicology case presentations: to chelate or not to chelate, is that the question?

    PubMed

    McKay, Charles A

    2013-12-01

    Four case studies described in this article were presented to a panel of physicians participating in the ACMT "Use and Misuse of Metal Chelation Therapy" Symposium in February 2012. The individuals who participated in the panel are listed in the appendix. These cases highlight some of the practical questions facing medical providers when issues of metal toxicity and its treatment arise. Medical toxicologists are valuable resources for information, public debate, consultation, and treatment of patients with concerns about heavy metal exposure.

  6. Medical toxicology case presentations: to chelate or not to chelate, is that the question?

    PubMed

    McKay, Charles A

    2013-12-01

    Four case studies described in this article were presented to a panel of physicians participating in the ACMT "Use and Misuse of Metal Chelation Therapy" Symposium in February 2012. The individuals who participated in the panel are listed in the appendix. These cases highlight some of the practical questions facing medical providers when issues of metal toxicity and its treatment arise. Medical toxicologists are valuable resources for information, public debate, consultation, and treatment of patients with concerns about heavy metal exposure. PMID:24243289

  7. Antagonism of a Zinc Metalloprotease Using a Unique Metal-Chelating Scaffold: Tropolones as Inhibitors of P. aeruginosa Elastase†‡

    PubMed Central

    Fullagar, Jessica L.; Garner, Amanda L.; Struss, Anjali K.; Day, Joshua A.; Martin, David P.; Yu, Jing; Cai, Xiaoqing

    2013-01-01

    Tropolone emerged from the screening of a chelator fragment library (CFL) as an inhibitor of the Zn2+-dependent virulence factor, Pseudomonas aeruginosa elastase (LasB). Based on this initial hit, a series of substituted tropolone-based LasB inhibitors was prepared, and a compound displaying potent activity in vitro and in a bacterial swarming assay was identified. Importantly, this inhibitor was found to be specific for LasB over other metalloenzymes, validating the usage of tropolone as a viable scaffold for identifying first-in-class LasB inhibitors. PMID:23482955

  8. SO2 surface chemistry on metal substrates. Final report

    SciTech Connect

    Sun, Y.M.; Sloan, D.; White, J.M.

    1995-12-31

    The surface chemistry, induced by thermal and non-thermal methods, of SO2 on metal substrates is reviewed. The substrate temperature during dosing is important; regardless of metal, adsorption is dissociative at 300 K and molecular at 100 K. On Ni, Pd, and Pt, molecular adsorption occurs through the S and one O atom, and the molecular plane is perpendicular to the surface. However, on Ag and Cu, adsorption occurs only through the S with the molecular plane perpendicular to the surface. The differences can be attributed to the structure of the metal`s molecular orbitals and their interactions with the SO2 orbitals. Upon heating, SO2 dissociates on all transition metal surfaces with the exception of Ag, Au, and Cu, where only molecular desorption occurs. On Pt, Fe, and Pd, additional reactions are observed between SO2 and its dissociation products. The nonthermal reactions induced by photons and electrons for monolayer coverages of SO2 on Ag (111) are dominated by molecular desorption. Desorption cross sections for 313 nm photons and 50 eV electrons were 2.8 x 10(exp {minus}20) sq cm and approx. 1 x 10(exp {minus}16) sq cm, respectively. Nonthermal excitation mechanisms and quenching processes as well as interesting characteristics of SO2 under irradiation are also reviewed.

  9. Extracting metals directly from metal oxides

    DOEpatents

    Wai, Chien M.; Smart, Neil G.; Phelps, Cindy

    1997-01-01

    A method of extracting metals directly from metal oxides by exposing the oxide to a supercritical fluid solvent containing a chelating agent is described. Preferably, the metal is an actinide or a lanthanide. More preferably, the metal is uranium, thorium or plutonium. The chelating agent forms chelates that are soluble in the supercritical fluid, thereby allowing direct removal of the metal from the metal oxide. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones, halogenated .beta.-diketones, phosphinic acids, halogenated phosphinic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof. In especially preferred embodiments, at least one of the chelating agents is fluorinated. The method provides an environmentally benign process for removing metals from metal oxides without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the metal recovered, to provide an economic, efficient process.

  10. Extracting metals directly from metal oxides

    DOEpatents

    Wai, C.M.; Smart, N.G.; Phelps, C.

    1997-02-25

    A method of extracting metals directly from metal oxides by exposing the oxide to a supercritical fluid solvent containing a chelating agent is described. Preferably, the metal is an actinide or a lanthanide. More preferably, the metal is uranium, thorium or plutonium. The chelating agent forms chelates that are soluble in the supercritical fluid, thereby allowing direct removal of the metal from the metal oxide. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of {beta}-diketones, halogenated {beta}-diketones, phosphinic acids, halogenated phosphinic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof. In especially preferred embodiments, at least one of the chelating agents is fluorinated. The method provides an environmentally benign process for removing metals from metal oxides without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the metal recovered, to provide an economic, efficient process. 4 figs.

  11. Lead chelation to immobilised Symphytum officinale L. (comfrey) root tannins.

    PubMed

    Chin, Lily; Leung, David W M; Harry Taylor, H

    2009-07-01

    Reported correlations between tannin level and metal accumulation within plant tissues suggest that metal-chelating tannins may help plants to tolerate toxic levels of heavy metal contaminants. This paper supports such correlations using a new method that demonstrated the ability of plant tannins to chelate heavy metals, and showed that the relative levels of tannins in tissues were quantitatively related to lead chelation in vitro. Using this in vitro metal chelation method, we showed that immobilised tannins prepared from lateral roots of Symphytum officinale L., that contained high tannin levels, chelated 3.5 times more lead than those from main roots with lower tannin levels. This trend was confirmed using increasing concentrations of tannins from a single root type, and using purified tannins (tannic acid) from Chinese gallnuts. This study presents a new, simple, and reliable method that demonstrates direct lead-tannin chelation. In relation to phytoremediation, it also suggests that plant roots with more 'built-in' tannins may advantageously accumulate more lead. PMID:19477483

  12. N,N',N"-tris(dihydroxyphosphorylmethyl)-1,4,7-triazacyclononane (Deofix) - a high-affinity, high-specificity chelator for first transition series metal cations with significant deodorant, antimicrobial, and antioxidant activity.

    PubMed

    Laden, Karl; Zaklad, Haim; Simhon, Elliot D; Klein, Joseph Y; Cyjon, Rosa L; Winchell, Harry S

    2003-01-01

    Deofix, N,N',N"-tris(dihydroxyphosphorylmethyl)-1,4,7-triazacyclononane, is a high-affinity, high-specificity chelator for first transition series cations such as iron, zinc, manganese, and copper. A 1% solution in 50% ethanol was found to be significantly better at reducing underarm malodor than a solution of 0.3% Triclosan in 50% ethanol. Compared to a 50% alcohol control, Deofix was found to produce a significant reduction in malodor for at least 48 hours. Deofix appears to work by reducing the concentration of first transition series metal ions below the levels needed for microbial cell reproduction and by inhibiting oxidative processes by interfering with catalytic formation of free radicals. Deofix has very low levels of toxicity when measured via a number of screening techniques.

  13. Synthesis, Characterization and Biological Properties of Tridentate NNO, NNS and NNN Donor Thiazole-Derived Furanyl, Thiophenyl and Pyrrolyl Schiff Bases and Their Co(II), Cu(II), Ni(II) and Zn(II) Metal Chelates

    PubMed Central

    Kausar, Samina

    2000-01-01

    2-Aminothiazole undergoes condensation reactions with furane-, thiophene- and pyrrole-2-carboxylaldehyde to give tridentate NNO, NNS and NNN Schiff bases respectively. These tridentate Schiff bases formed complexes of the type [M (L)2]X2 where [M=Co(II), Cu(II), Ni(II) or Zn(II), L=N-(2-furanylmethylene)-2-aminothiazole (L1), N-(2-thiophenylmethylene)-2-aminothiazole (L2, N-(2-pyrrolylmethylene)-2-aminothiazole (L3) and X=Cl. The structures of these Schiff bases and of their complexes have been determined on the basis of their physical, analytical and spectral data. The screening results of these compounds indicated them to possess excellent antibacterial activity against tested pathogenic bacterial organisms e.g., Escherichia coli, Staphylococcus aureous and Pseudomonas aeruginosa. However, in comparison, their metal chelates have been shown to possess more antibacterial activity than the uncomplexed Schiff bases. PMID:18475919

  14. Synthesis, Characterization and Biological Properties of Tridentate NNO, NNS and NNN Donor Thiazole-Derived Furanyl, Thiophenyl and Pyrrolyl Schiff Bases and Their Co(II), Cu(II), Ni(II) and Zn(II) Metal Chelates.

    PubMed

    Chohan, Z H; Kausar, S

    2000-01-01

    2-Aminothiazole undergoes condensation reactions with furane-, thiophene- and pyrrole-2-carboxylaldehyde to give tridentate NNO, NNS and NNN Schiff bases respectively. These tridentate Schiff bases formed complexes of the type [M (L)(2)]X(2) where [M=Co(II), Cu(II), Ni(II) or Zn(II), L=N-(2-furanylmethylene)-2-aminothiazole (L(1)), N-(2-thiophenylmethylene)-2-aminothiazole (L(2), N-(2-pyrrolylmethylene)-2-aminothiazole (L(3)) and X=Cl. The structures of these Schiff bases and of their complexes have been determined on the basis of their physical, analytical and spectral data. The screening results of these compounds indicated them to possess excellent antibacterial activity against tested pathogenic bacterial organisms e.g., Escherichia coli, Staphylococcus aureous and Pseudomonas aeruginosa. However, in comparison, their metal chelates have been shown to possess more antibacterial activity than the uncomplexed Schiff bases.

  15. EDTA Chelation Therapy to Reduce Cardiovascular Events in Persons with Diabetes.

    PubMed

    Ouyang, Pamela; Gottlieb, Sheldon H; Culotta, Valerie L; Navas-Acien, Ana

    2015-11-01

    The Trial to Assess Chelation Therapy (TACT) was a randomized double-blind placebo-controlled trial enrolling patients age ≥50 years with prior myocardial infarction. TACT used a 2 × 2 factorial design to study ethylene diamine tetraacetic acid (EDTA) chelation and high-dose vitamin supplementation. Chelation provided a modest but significant reduction in cardiovascular endpoints. The benefit was stronger and significant among participants with diabetes but absent in those without diabetes. Mechanisms by which chelation might reduce cardiovascular risk in persons with diabetes include the effects of EDTA chelation on transition and toxic metals. Transition metals, particularly copper and iron, play important roles in oxidative stress pathways. Toxic metals, in particular cadmium and lead, are toxic for the cardiovascular system. This review discusses the epidemiologic evidence and animal and human studies supporting the role of these metals in the development of diabetes and ischemic heart disease and potential ways by which EDTA chelation could confer cardiovascular benefit.

  16. Changes in worldwide demand for metals (final). Open File report

    SciTech Connect

    Faucett, J.G.; Chmelynski, H.J.

    1986-08-01

    Worldwide demand for metals was analyzed to identify the important factors that explain differences in the level of demand among world countries. The per capita demand for steel, aluminum, copper, and total nonferrous metals was investigated for 40 to 50 countries over a 22-year period. These countries have been further grouped into four world regions for purposes of making generalizations about the importance of these factors for countries in different stages of development and with dissimilar levels of per capita gross domestic product (GDP). Intercountry and intertemporal differences are explained largely by differences in per capita GDP and changes over time in per capita GDP, oil real prices, and to a lesser extent, metal real prices. The trend in world consumption is dramatically different in the last decade than the previous one. In 1962-73, per capita consumption increased in all areas and consumption intensity (consumption divided by (GDP) increased in most areas). In 1973-84, per capita consumption fell in most areas and intensity fell dramatically, except in developing nations.

  17. 76 FR 61342 - Magnesium Metal from the Russian Federation: Amended Final Results of Antidumping Duty...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-04

    ... Results of Antidumping Duty Administrative Review, 76 FR 56396 (September 13, 2011) (Final Results). We... Antidumping and Countervailing Duty Proceedings: Assessment of Antidumping Duties, 68 FR 23954 (May 6, 2003... International Trade Administration Magnesium Metal from the Russian Federation: Amended Final Results...

  18. Affinity purification of copper chelating peptides from chickpea protein hydrolysates.

    PubMed

    Megías, Cristina; Pedroche, Justo; Yust, Maria M; Girón-Calle, Julio; Alaiz, Manuel; Millan, Francisco; Vioque, Javier

    2007-05-16

    Chickpea protein hydrolysates obtained with alcalase and flavourzyme were used for purification of copper chelating peptides by affinity chromatography using copper immobilized on solid supports. The chelating activity of purified peptides was indirectly measured by the inhibition of beta-carotene oxidation in the presence of copper. Two protein hydrolysates, obtained after 10 and 100 min of hydrolysis, were the most inhibitory of beta-carotene oxidation. Purified copper chelating peptides from these protein hydrolysates contained 19.7 and 35.1% histidine, respectively, in comparison to 2.7 and 2.6% in the protein hydrolysates. Chelating peptides from hydrolysate obtained after 10 min of hydrolysis were the most antioxidative being 8.3 times more antioxidative than the hydrolysate, while chelating peptides purified from protein hydrolysate obtained after 100 min were 3.1 times more antioxidative than its hydrolysate. However, the histidine content was higher in peptides derived from the 100 min hydrolysate (19.7 against 35.1% in 10 min hydrolysate), indicating that this amino acid is not the only factor involved in the antioxidative activity, and other factors such as peptide size or amino acid sequence are also determinant. This manuscript shows that affinity chromatography is a useful procedure for purification of copper chelating peptides. This method can be extended to other metals of interest in nutrition, such as calcium, iron, or zinc. Purified chelating peptides, in addition to their antioxidative properties, may also be useful in food mineral fortification for increasing the bioavailability of these metals.

  19. Metal ion complexation by ionizable crown ethers. Final report, January 1, 1988--June 30, 1994

    SciTech Connect

    Bartsch, R.A.

    1994-12-31

    During the report period a variety of new lipophilic ionizable crown ethers with pendent proton-ionizable groups has been synthesized. The ligands possess one or more ionizable group (carboxylic acid, phosphonic acid monoethyl ester, para-nitrophenol, phosphonic acid) attached to crown ether, monoazacrown ether or diazacrown ether frameworks. These novel chelating agents have either pendent or inward-facing proton-ionizable groups. Such lipophilic proton-ionizable crown ethers are designed for use in multiphase metal ion separations (solvent extraction, liquid membrane transport). In addition a series of proton-ionizable crown ethers without lipophilic groups was prepared to study how structural variations within the ligand influence metal ion complexation in homogeneous media as assessed by NMR spectroscopy or titration calorimetry. A third class of new metal ion-complexing agents is a series of lipophilic acyclic polyether dicarboxylic acids. Competitive solvent extractions of alkali metal and alkaline earth cations and of the mixed species have been conducted to reveal the influence of ring size, nature and attachment site of the lipophilic group, sidearm length, and proton-ionizable group identity and location upon the selectivity and efficiency of metal ion complexation. In addition to such studies of structural variation within the lipophilic proton-ionizable crown ether, the effect of changing the organic solvent and variation of the stripping conditions have been assessed. The influence of structural variations within lipophilic acyclic polyether dicarboxylic acids upon competitive solvent extraction of alkaline earth cations has been probed. Also a new chromogenic, di-ionizable crown ether with extremely high selectivity for Hg{sup 2+} has been discovered.

  20. Final Report: Sintered CZTS Nanoparticle Solar Cells on Metal Foil; July 26, 2011 - July 25, 2012

    SciTech Connect

    Leidholm, C.; Hotz, C.; Breeze, A.; Sunderland, C.; Ki, W.; Zehnder, D.

    2012-09-01

    This is the final report covering 12 months of this subcontract for research on high-efficiency copper zinc tin sulfide (CZTS)-based thin-film solar cells on flexible metal foil. Each of the first three quarters of the subcontract has been detailed in quarterly reports. In this final report highlights of the first three quarters will be provided and details will be given of the final quarter of the subcontract.

  1. Federal regulation of unapproved chelation products.

    PubMed

    Lee, Charles E

    2013-12-01

    Chelation products can be helpful in the treatment of metal poisoning. However, many unapproved products with unproven effectiveness and safety are marketed to consumers, frequently via the internet. This paper describes the primary responsibility of the Health Fraud and Consumer Outreach Branch of the United States Food and Drug Administration to identify and address health fraud products. Efforts to prevent direct and indirect hazards to the population's health through regulatory actions are described.

  2. The Initial-Final Mass Relation and its Dependence with Metallicity

    NASA Astrophysics Data System (ADS)

    Romero, A. D.; Campos, F.; Kepler, S. O.

    2015-06-01

    We present a study of the low end of the initial-final mass relation and its dependence on metallicity. We computed a grid of full evolutionary models, from the Main Sequence, trough the Asymptotic Giant Branch phase, to low luminosity stages on the white dwarf cooling curve. We consider metallicity values from Z=0.0001 to Z=0.04 with initial masses between 0.8 and 3M⊙. We found that the spreading in the observations can be explained by means of different metallicities of the environment. We also found a strong dependence of the pre-white dwarf age with metallicity.

  3. Rigid bifunctional chelating agents

    DOEpatents

    Sweet, Mark P.; Mease, Ronnie C.; Srivastava, Suresh C.

    2000-02-08

    Bicyclo[2.2.2]octane-2,3 diamine-N,N,N',N'-tetraacetic acids (BODTA) and bicyclo[2.2.1]heptane-2,3 diamine-N,N,N',N'-tetraacetic acid (BHDTA) are chelating agents useful in forming detectably labeled bioconjugate compounds for diagnostic and therapeutic purposes. New compounds and processes of forming BODTA and BHDTA are disclosed. Radioimmunoconjugates of the present invention show high and prolonged tumor uptake with low normal tissue uptakes.

  4. Rigid bifunctional chelating agents

    DOEpatents

    Sweet, M.P.; Mease, R.C.; Srivastava, S.C.

    1998-07-21

    Bicyclo[2.2.2] octane-2,3 diamine-N,N,N`,N`-tetraacetic acids (BODTA) and bicyclo[2.2.1] heptane-2,3 diamine-N,N,N`,N`-tetraacetic acid (BHDTA) are chelating agents useful in forming detectably labeled bioconjugate compounds for diagnostic and therapeutic purposes. New compounds and processes of forming BODTA and BHDTA are disclosed. Radioimmunoconjugates of the present invention show high and prolonged tumor uptake with low normal tissue uptakes.

  5. Rigid bifunctional chelating agents

    DOEpatents

    Sweet, Mark P.; Mease, Ronnie C.; Srivastava, Suresh C.

    1998-07-21

    Bicyclo›2.2.2! octane-2,3 diamine-N,N,N',N'-tetraacetic acids (BODTA) and bicyclo›2.2.1! heptane-2,3 diamine-N,N,N',N'-tetraacetic acid (BHDTA) are chelating agents useful in forming detectably labeled bioconjugate compounds for diagnostic and therapeutic purposes. New compounds and processes of forming BODTA and BHDTA are disclosed. Radioimmunoconjugates of the present invention show high and prolonged tumor uptake with low normal tissue uptakes.

  6. Radiation damage of transition metal carbides. Final technical report

    SciTech Connect

    Dixon, G.

    1991-12-31

    In this grant period we have investigated electrical properties of transition metal carbides and radiation-induced defects produced by low-temperature electron irradiation in them. Special attention has been given to the composition VC{sub 0.88} in which the vacancies on the carbon sublattice of this fcc crystal order to produce a V{sub 8}C{sub 7} superlattice. The existence of this superlattice structure was found to make the crystal somewhat resistant to radiation damage at low doses and/or at ambient temperature. At larger doses significant changes in the resistivity are produced. Annealing effects were observed which we believe to be connected with the reconstitution of the superlattice structure.

  7. Stability of Bulk Metallic Glass Structure. Final Report

    SciTech Connect

    Jain, H.; Williams, D. B.

    2003-06-01

    The fundamental origins of the stability of the (Pd-Ni){sub 80}P{sub 20} bulk metallic glasses (BMGs), a prototype for a whole class of BMG formers, were explored. While much of the properties of their BMGs have been characterized, their glass-stability have not been explained in terms of the atomic and electronic structure. The local structure around all three constituent atoms was obtained, in a complementary way, using extended X-ray absorption fine structure (EXAFS), to probe the nearest neighbor environment of the metals, and extended energy loss fine structure (EXELFS), to investigate the environment around P. The occupied electronic structure was investigated using X-ray photoelectron spectroscopy (XPS). The (Pd-Ni){sub 80}P{sub 20} BMGs receive their stability from cumulative, and interrelated, effects of both atomic and electronic origin. The stability of the (Pd-Ni){sub 80}P{sub 20} BMGs can be explained in terms of the stability of Pd{sub 60}Ni{sub 20}P{sub 20} and Pd{sub 30}Ni{sub 50}P{sub 20}, glasses at the end of BMG formation. The atomic structure in these alloys is very similar to those of the binary phosphide crystals near x=0 and x=80, which are trigonal prisms of Pd or Ni atoms surrounding P atoms. Such structures are known to exist in dense, randomly-packed systems. The structure of the best glass former in this series, Pd{sub 40}Ni{sub 40}P{sub 20} is further described by a weighted average of those of Pd{sub 30}Ni{sub 50}P{sub 20} and Pd{sub 60}Ni{sub 20}P{sub 20}. Bonding states present only in the ternary alloys were found and point to a further stabilization of the system through a negative heat of mixing between Pd and Ni atoms. The Nagel and Tauc criterion, correlating a decrease in the density of states at the Fermi level with an increase in the glass stability, was consistent with greater stability of the Pd{sub x}Ni{sub 80-x}P{sub 20} glasses with respect to the binary alloys of P. A valence electron concentration of 1.8 e/a, which

  8. 75 FR 20812 - Silicon Metal from Brazil: Amended Final Results of Administrative Review Pursuant to Court Decision

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-04-21

    ... Metal from Brazil for the period of review beginning July 1, 1996, through June 30, 1997. See Silicon Metal from Brazil: Notice of Final Results of Antidumping Duty Administrative Review, 64 FR 6305... International Trade Administration Silicon Metal from Brazil: Amended Final Results of Administrative...

  9. Flame Atomic Absorption Spectrometric Determination of Trace Metal Ions in Environmental and Biological Samples After Preconcentration on a Newly Developed Amberlite XAD-16 Chelating Resin Containing p-Aminobenzene Sulfonic Acid.

    PubMed

    Islam, Aminul; Ahmad, Akil; Laskar, Mohammad Asaduddin

    2015-01-01

    Amberlite® XAD-16 was functionalized with p-aminobenzene sulfonic acid via an azo spacer in order to prepare a new chelating resin, which was then characterized by water regain value, hydrogen ion capacity, elemental analyses, and IR spectral and thermal studies. The maximum uptake of Cu(II), Ni(II), Zn(II), Co(II), Cr(III), Fe(III), and Pb(II) ions was observed in the pH range 4.0-6.0 with the corresponding half-loading times of 6.5, 7.0, 8.0, 9.0, 11.0, 8.5, and 16.5 min. The sorption data followed Langmuir isotherms and a pseudo-second-order model. Thermodynamic quantities, ΔH and ΔS, based on the variation of the distribution coefficient with temperature were also evaluated. High preconcentration factors of 60-100 up to a low preconcentration limit of 4.0-6.6 μg/L have been achieved for the metal ions. The validity of the method was checked by analyzing standard reference materials and recoveries of trace metals after spiking. The analytical applications of the method were explored by analyzing natural water, mango pulp, mint leaves, and fish. PMID:25857893

  10. Cast Metals Coalition Technology Transfer and Program Management Final Report

    SciTech Connect

    Gwyn, Mike

    2009-03-31

    The Cast Metals Coalition (CMC) partnership program was funded to ensure that the results of the Department of Energy's (DOE) metalcasting research and development (R&D) projects are successfully deployed into industry. Specifically, the CMC program coordinated the transfer and deployment of energy saving technologies and process improvements developed under separately funded DOE programs and projects into industry. The transition of these technologies and process improvements is a critical step in the path to realizing actual energy savings. At full deployment, DOE funded metalcasting R&D results are projected to save 55% of the energy used by the industry in 1998. This closely aligns with DOE's current goal of driving a 25% reduction in industrial energy intensity by 2017. In addition to benefiting DOE, these energy savings provide metalcasters with a significant economic advantage. Deployment of already completed R&D project results and those still underway is estimated to return over 500% of the original DOE and industry investment. Energy savings estimates through December 2008 from the Energy-Saving Melting and Revert Reduction Technology (E-SMARRT) portfolio of projects alone are 12 x 1012 BTUs, with a projection of over 50 x 1012 BTUs ten years after program completion. These energy savings and process improvements have been made possible through the unique collaborative structure of the CMC partnership. The CMC team consists of DOE's Office of Industrial Technology, the three leading metalcasting technical societies in the U.S: the American Foundry Society; the North American Die Casting Association; and the Steel Founders Society of America; and the Advanced Technology Institute (ATI), a recognized leader in distributed technology management. CMC provides collaborative leadership to a complex industry composed of approximately 2,100 companies, 80% of which employ less than 100 people, and only 4% of which employ more than 250 people. Without collaboration

  11. Synthesis, spectral, thermal, fluorescence, antimicrobial, anthelmintic and DNA cleavage studies of mononuclear metal chelates of bi-dentate 2H-chromene-2-one Schiff base.

    PubMed

    Prabhakara, Chetan T; Patil, Sangamesh A; Kulkarni, Ajaykumar D; Naik, Vinod H; Manjunatha, M; Kinnal, Shivshankar M; Badami, Prema S

    2015-07-01

    The Co(II), Ni(II) and Cu(II) complexes have been synthesized with Schiff base (HL), derived from 8-formyl-7-hydroxy-4-methylcoumarin with benzylamine. The Schiff base and its metal complexes were structurally characterized based on IR, (1)H NMR, (13)C NMR, UV-visible, ESR, magnetic, thermal, fluorescence, mass and ESI-MS studies. The complexes are completely soluble in DMF and DMSO. The molar conductance values indicate that, all synthesized metal complexes are non-electrolytic in nature. Elemental analysis reveals [ML2(H2O)2] stoichiometry, here MCo(II), Ni(II) and Cu(II), L=deprotonated ligand. The coordination between metal ion and Schiff base was supported by IR data, through deprotonation of phenolic oxygen of coumarin and azomethine nitrogen atoms. Solution electronic spectral results unveiled that all the synthesized complexes posses six coordinated geometry around metal ion. Thermal studies suggest the presence of coordinated water molecules. The Schiff base and its metal complexes have been screened for their antibacterial (Escherichia coli, Pseudomonas aureginosa, Klebsiella pneumoniae and Staphylococcus aureus) and antifungal (Penicillium chrysogenum and Aspergillus niger), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activities.

  12. Natural chelates for radionuclide decorporation

    DOEpatents

    Premuzic, E.T.

    1983-08-25

    This invention relates to the method and resulting chelates of desorbing a radionuclide selected from thorium, uranium, and plutonium containing cultures in a bioavailable form involving pseudomonas or other microorganisms. A preferred microorganism is Pseudomonas aeruginosa which forms multiple chelates with thorium in the range of molecular weight 1000 to 1000 and also forms chelates with uranium of molecular weight in the area of 100 to 1000 and 1000 to 2000.

  13. Chelation of cadmium.

    PubMed Central

    Andersen, O

    1984-01-01

    The toxicity of cadmium is determined by chelation reactions: in vivo, Cd2+ exists exclusively in coordination complexes with biological ligands, or with administered chelating agents. The Cd2+ ion has some soft character, but it is not a typical soft ion. It has a high degree of polarizability, and its complexes with soft ligands have predominantly covalent bond characteristics. Cd2+ forms the most stable complexes with soft donor atoms (S much greater than N greater than 0). The coordination stereochemistry of Cd2+ is unusually varied, including coordination numbers from 2 to 8. Even though the Cd2+ ion is a d10 ion, disturbed coordination geometries are often seen. Generally, the stability of complexes increases with the number of coordination groups contributed by the ligand; consequently, complexes of Cd2+ with polydentate ligands containing SH groups are very stable. Cd2+ in metallothionein (MT) is coordinated with 4 thiolate groups, and the log stability constant is estimated to 25.5. Complexes between Cd2+ and low molecular weight monodentate or bidentate ligands, e.g., free amino acids (LMW-Cd), seem to exist very briefly, and Cd2+ is rapidly bound to high molecular weight proteins, mainly serum albumin. These complexes (HMW-Cd) are rapidly scavenged from blood, mainly by the liver, and Cd2+ is redistributed to MT. After about 1 day the Cd-MT complex (MT-Cd) almost exclusively accounts for the total retained dose of Cd2+, independent of the route of exposure. MT-Cd is slowly transferred to and accumulated in kidney cortex. The acute toxicity and interorgan distribution of parenterally administered Cd2+ are strongly influenced by preceding MT induction, or decreased capacity for MT synthesis; however, the gastrointestinal (GI) uptake of Cd2+ seems unaffected by preceding MT induction resulting in considerable capacity for Cd2+ chelation in intestinal mucosa, and this finding indicates that endogenous MT is not involved in Cd2+ absorption. The toxicity of

  14. Synthesis and characterization of ligational behavior of curcumin drug towards some transition metal ions: Chelation effect on their thermal stability and biological activity

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.

    2013-03-01

    Complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with curcumin ligand as antitumor activity were synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV-Vis, IR, Raman, ESR, 1H-NMR spectroscopy, X-ray diffraction analysis of powdered samples and thermal analysis, and screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as a monobasic bidentate ligand towards the central metal ion with an oxygen's donor atoms sequence of both sbnd OH and Cdbnd O groups under keto-enol structure. From the microanalytical data, the stoichiometry of the complexes 1:2 (metal:ligand) was found. The ligand and their metal complexes were screened for antibacterial activity against Escherichia Coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa and fungicidal activity against Aspergillus flavus and Candida albicans.

  15. COMPARISON OF SILICA IMMOBILIZED POLY-L-CYSTEINE AND 8-HYDROXYQUINOLINE FOR TRACE METAL CHELATION AND PRECONCENTRATION. (R826694C651)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  16. Synthesis of 4-substituted-trans-1, 2-diaminocyclohexyl polyaminocarboxylate metal chelating agents for the preparation of stable radiometal antibody immunoconjugates for therapy and spect and pet imaging

    DOEpatents

    Mease, Ronnie C.; Mausner, Leonard F.; Srivastava, Suresh C.

    1994-01-01

    Cyclo agents useful in forming antibody-metal conjugates useful for diagnostic and therapeutic purposes. New compounds and processes of forming these compounds are disclosed including 4-haloacetamido-trans-1,2-diaminocyclohexyl polyaminocarboxylate and 4-isothiocyanato-trans-1,2-diamino cyclohexane-N,N,N',N'-tetra acetic acid.

  17. Synthesis of 4-substituted-trans-1, 2-diaminocyclohexyl polyaminocarboxylate metal chelating agents for the preparation of stable radiometal antibody immunoconjugates for therapy and SPECT and PET imaging

    DOEpatents

    Mease, R.C.; Mausner, L.F.; Srivastava, S.C.

    1994-03-08

    Cyclo agents are described which are useful in forming antibody-metal conjugates which are used for diagnostic and therapeutic purposes. New compounds and processes of forming these compounds are disclosed including 4-haloacetamido-trans-1,2diaminocyclohexyl polyaminocarboxylate and 4-isothiocyanato-trans-1,2diamino cyclohexane-N,N,N',N'-tetra acetic acid. No Drawings

  18. Predicting stability constants of various chelating agents using QSAR technology

    SciTech Connect

    Okey, R.W.; Lin, S.W.; Hong, P.K.A.

    1995-12-31

    The practice of capturing metals from contaminated soil slurry often involves the use of organics as chelators. This work was undertaken to develop information on the molecular characteristics which optimize the removal or the complexation of cadmium, copper, lead and zinc. Quantitative structure-activity relationship (QSAR) technology was employed using special techniques developed for the determination of the correct set of variables. The linear free energy relationship was applied using a 183 case data set to obtain regression coefficients. Equations obtained are provided. The differences in the coefficients and variables may be used as a guide in selecting the optimum chelator for a specific metal. The use of QSAR technology appears effective in furthering the understanding of metal-chelator relationships. A variable set combining molecular connectivity indices and fragments or groups can be used to minimize the size of the data set required for a valid regression and for the avoidance of collinearity problems.

  19. Synthesis and characterization of dihexyldithiocarbamate as a chelating agent in extraction of gold(III)

    NASA Astrophysics Data System (ADS)

    Fatimah, Soja Siti; Bahti, Husein H.; Hastiawan, Iwan; Permanasari, Anna

    2016-02-01

    The use of dialkyldithiocarbamates as chelating agents of transition metals have been developing for decades. Many chelating agents have been synthesized and used in the extraction of the metals. Studies on particular aspects of extraction of the metals, such as the effect of increasing hydrophobicity of chelating agents on the effectiveness of the extraction, have been done. However, despite the many studies on the synthesis and applications of this type of chelating agents, interests in the aspect of molecular structure of the synthesized ligands and of their complexes, have been limited. This study aimed at synthesizing and characterizing dihexylthiocarbamate, and using the ligand for the extraction of gold III). Characterization of the ligand and of its metal complex were done by using elemental analysis, DTG, and spectroscopic methods to include NMR, (1H, and 13C), FTIR, and MS-ESI. Data on the synthesis, characterization, and the application of the ligand as a chelating agent are presented.

  20. 3-hydroxy-2(1H)-pyridinone chelating agents

    DOEpatents

    Raymond, Kenneth; Xu, Jide

    1999-01-01

    Disclosed is a series of improved chelating agents and the chelates formed from these agents, which are highly effective upon both injection and oral administration. Several of the most effective are of low toxicity. These chelating agents incorporate within their structure 3-hydroxy-2-pyridinone (3,2-HOPO) moieties with a substituted carbamoyl group ortho to the hydroxy group of the hydroxypyridinone ring. The electron-withdrawing carbamoyl group increases the acidity, as well as the chemical stability towards oxidation and reduction, of the hydroxypyridinones. In the metal complexes of the chelating agents, the amide protons form very strong hydrogen bonds with the adjacent HOPO oxygen donor, making these complexes very stable at physiological conditions. The terminal N-substituents provide a certain degree of lipophilicity to the 3,2-HOPO, increasing oral activity.

  1. 3-hydroxy-2(1H)-pyridinone chelating agents

    DOEpatents

    Raymond, K.; Xu, J.

    1999-04-06

    Disclosed is a series of improved chelating agents and the chelates formed from these agents, which are highly effective upon both injection and oral administration. Several of the most effective are of low toxicity. These chelating agents incorporate within their structure 3-hydroxy-2-pyridinone (3,2-HOPO) moieties with a substituted carbamoyl group ortho to the hydroxy group of the hydroxypyridinone ring. The electron-withdrawing carbamoyl group increases the acidity, as well as the chemical stability towards oxidation and reduction, of the hydroxypyridinones. In the metal complexes of the chelating agents, the amide protons form very strong hydrogen bonds with the adjacent HOPO oxygen donor, making these complexes very stable at physiological conditions. The terminal N-substituents provide a certain degree of lipophilicity to the 3,2-HOPO, increasing oral activity. 2 figs.

  2. Comparing potential copper chelation mechanisms in Parkinson's disease protein

    NASA Astrophysics Data System (ADS)

    Rose, Frisco; Hodak, Miroslav; Bernholc, Jerry

    2011-03-01

    We have implemented the nudged elastic band (NEB) as a guided dynamics framework for our real-space multigrid method of DFT-based quantum simulations. This highly parallel approach resolves a minimum energy pathway (MEP) on the energy hypersurface by relaxing intermediates in a chain-of-states. As an initial application we present an investigation of chelating agents acting on copper ion bound to α -synuclein, whose misfolding is implicated in Parkinson's disease (PD). Copper ions are known to act as highly effective misfolding agents in a-synuclein and are thus an important target in understanding PD. Furthermore, chelation therapy has shown promise in the treatment of Alzheimer's and other neuro-degenerative diseases with similar metal-correlated pathologies. At present, our candidate chelating agents include nicotine, curcumin and clioquinol. We examine their MEP activation barriers in the context of a PD onset mechanism to assess the viability of various chelators for PD remediation.

  3. CCCCC pentadentate chelates with planar Möbius aromaticity and unique properties

    PubMed Central

    Zhu, Congqing; Yang, Caixia; Wang, Yongheng; Lin, Gan; Yang, Yuhui; Wang, Xiaoyong; Zhu, Jun; Chen, Xiaoyuan; Lu, Xin; Liu, Gang; Xia, Haiping

    2016-01-01

    The coordinating atoms in polydentate chelates are primarily heteroatoms. We present the first examples of pentadentate chelates with all binding atoms of the chelating agent being carbon atoms, denoted as CCCCC chelates. Having up to five metal-carbon bonds in the equatorial plane has not been previously observed in transition metal chemistry. Density functional theory calculations showed that the planar metallacycle has extended Craig-Möbius aromaticity arising from 12-center–12-electron dπ-pπ π-conjugation. These planar chelates have broad absorption in the ultraviolet-visible–near-infrared region and, thus, notable photothermal performance upon irradiation by an 808-nm laser, indicating that these chelates have potential applications in photothermal therapy. The combination of facile synthesis, high stability, and broad absorption of these complexes could make the polydentate carbon chain a novel building block in coordination chemistry. PMID:27574707

  4. CCCCC pentadentate chelates with planar Möbius aromaticity and unique properties.

    PubMed

    Zhu, Congqing; Yang, Caixia; Wang, Yongheng; Lin, Gan; Yang, Yuhui; Wang, Xiaoyong; Zhu, Jun; Chen, Xiaoyuan; Lu, Xin; Liu, Gang; Xia, Haiping

    2016-08-01

    The coordinating atoms in polydentate chelates are primarily heteroatoms. We present the first examples of pentadentate chelates with all binding atoms of the chelating agent being carbon atoms, denoted as CCCCC chelates. Having up to five metal-carbon bonds in the equatorial plane has not been previously observed in transition metal chemistry. Density functional theory calculations showed that the planar metallacycle has extended Craig-Möbius aromaticity arising from 12-center-12-electron dπ-pπ π-conjugation. These planar chelates have broad absorption in the ultraviolet-visible-near-infrared region and, thus, notable photothermal performance upon irradiation by an 808-nm laser, indicating that these chelates have potential applications in photothermal therapy. The combination of facile synthesis, high stability, and broad absorption of these complexes could make the polydentate carbon chain a novel building block in coordination chemistry. PMID:27574707

  5. Minimal role of metallothionein in decreased chelator efficacy for cadmium.

    PubMed

    Waalkes, M P; Watkins, J B; Klaassen, C D

    1983-05-01

    Chelator efficacy in Cd poisoning drops precipitously if therapy is not commenced almost immediately after exposure. Metallothionein (MT), a low-molecular-weight metal-binding protein with high affinity for Cd, may be important for this phenomenon. To more fully assess this role of MT in the acute drop in chelator efficacy following Cd poisoning, rats were injected iv with radioisotopic Cd (1mg/kg as CdCl2; 50 muCi/kg) followed by diethylenetriaminepentaacetic acid (DTPA; 90 mg/kg ip) at various times (0, 15, 30, 60, and 120 min) after Cd. Ther percentage of the Cd dose remaining in major organs 24 hr following Cd was determined. Although DTPA reduced Cd content in the various organs when given immediately after Cd, the chelator was ineffective at all later times. Increases in hepatic and renal MT did not occur until 2 hr after Cd, and did not coincide with the earlier drop in chelator efficacy. Blockade of MT synthesis by actinomycin D treatment (1.25 mg/kg, 1 hr before Cd) failed to prolong the chelators effectiveness. Furthermore, newborn rats have high levels of hepatic MT which had no effect on the time course of chelator effectiveness since DTPA still decreased Cd organ contents if given immediately following Cd but had no effect if given 2 hr after Cd. Therefore, if appears that MT does not have an important role in the acute decrease in efficacy of chelation therapy for Cd poisoning. The quick onset of chelator ineffectiveness may be due to the rapid uptake of Cd into tissues which makes it relatively unavailable of chelation.

  6. The ability of subsoils to attenuate metals in coal pile leachate. Final report

    SciTech Connect

    Zelmanowitz, S.; Boyle, W.C.; Armstrong, D.E.; Park, J.K.

    1992-09-01

    Research was performed to investigate potential groundwater contamination due to coal pile leachates. Laboratory-generated and field-collected coal pile leachates were analyzed for dissolved organic carbon (DOC), dissolved ions, pH, and chelation potential of the organic acids. Two soil column studies were performed. Column study 1 involved leaching three soils (sand, a silt loam, and a silt loam with 4% CaCO{sub 3} added) with dilute sulfuric acid solutions at pH 1.5, 3.5, and 5.6. Column leachates were analyzed for pH, dissolved silica, cations, and anions. During the second column study pH 1.5 synthetic coal pile leachate was leached through the three soils. Redox potential, pH, dissolved cations and anions of column leachates were determined. A batch experiment was performed in which Plano silt loam with and without CaCO{sub 3} was equilibrated with synthetic coal pile leachate containing 0, 50 or 100 mg/L fulvic acids (FAs). Equilibrated solutions were analyzed for pH, DOC, Fe, Zn and Cd. Field-collected coal pile leachate was more acidic and generally contained higher metals concentrations than did the laboratory-generated leachates. The DOC of the field leachate was lower than levels likely to leach out of surface soils. Both silt loam soils were able to buffer pH 3.5 acid, but the sand was not. None of the soils were able to buffer pH 1.5 acid for the entire leaching period. The sand exhibited the lowest buffering ability and the silt loam at low flowrate and silt loam with CaCO{sub 3} showed the most buffering. Breakthrough of metals in synthetic coal pile leachate corresponded with soil buffering capacity. Metals were most mobile on the sand and least mobile on the silt loam with CaCO{sub 3}. For all soils, metals in column effluents reached input levels or above during leaching. In the batch study, FAs at 50 and 100 mg/L decreased iron and zinc attenuation on silt loam with CaCO{sub 3}, did not affect metals attenuation on silt loam without CaCO{sub 3}.

  7. Microwave assisted synthesis, characterization and biocidal activities of some new chelates of carbazole derived Schiff bases of cadmium and tin metals

    NASA Astrophysics Data System (ADS)

    Yadav, Manju; Mishra, Neelima; Sharma, Nutan; Chandra, Sulekh; Kumar, Dinesh

    2014-11-01

    This study is planned to report the advancement of green microwave approach in the fabrication of a new series of biologically potent (N^X, where X = O/S) donor Schiff bases and their cadmium(II) and tin(II) complexes. The ligands and their metal complexes have been characterized in terms of elemental analysis, molar ionic conductance, magnetic moment and spectral (IR, UV-Vis, NMR (1H, 119Sn), FAB-mass, thermal and XRD) data. The data revealed that the ligands coordinated to the metal center via nitrogen and oxygen/sulfur atoms and form an octahedral arrangement of the ligands around central metal atom. All compounds were evaluated for their in vitro antimicrobial activities against two pathogenic bacteria Bacillus subtilis and Escherichia coli and two fungi Aspergillus niger and Aspergillus flavus by standard disc diffusion method. The discs were stored in an incubator at 37 °C. The compounds were dissolved in DMF at 500 and 1000 ppm concentrations for screening biocidal activity. The compounds were dissolved in DMF to get the 100 and 200 ppm concentration of test solutions for screening fungicidal activity. The inhibition zone around each disc was measured (in mm) after 24 h and 96 h for biocidal and fungicidal activities respectively.

  8. Microwave assisted synthesis, characterization and biocidal activities of some new chelates of carbazole derived Schiff bases of cadmium and tin metals.

    PubMed

    Yadav, Manju; Mishra, Neelima; Sharma, Nutan; Chandra, Sulekh; Kumar, Dinesh

    2014-11-11

    This study is planned to report the advancement of green microwave approach in the fabrication of a new series of biologically potent (N^X, where X=O/S) donor Schiff bases and their cadmium(II) and tin(II) complexes. The ligands and their metal complexes have been characterized in terms of elemental analysis, molar ionic conductance, magnetic moment and spectral (IR, UV-Vis, NMR ((1)H, (119)Sn), FAB-mass, thermal and XRD) data. The data revealed that the ligands coordinated to the metal center via nitrogen and oxygen/sulfur atoms and form an octahedral arrangement of the ligands around central metal atom. All compounds were evaluated for their in vitro antimicrobial activities against two pathogenic bacteria Bacillus subtilis and Escherichia coli and two fungi Aspergillus niger and Aspergillus flavus by standard disc diffusion method. The discs were stored in an incubator at 37°C. The compounds were dissolved in DMF at 500 and 1000 ppm concentrations for screening biocidal activity. The compounds were dissolved in DMF to get the 100 and 200 ppm concentration of test solutions for screening fungicidal activity. The inhibition zone around each disc was measured (in mm) after 24 h and 96 h for biocidal and fungicidal activities respectively.

  9. Grafted-double walled carbon nanotubes as electrochemical platforms for immobilization of antibodies using a metallic-complex chelating polymer: Application to the determination of adiponectin cytokine in serum.

    PubMed

    Ojeda, Irene; Barrejón, Myriam; Arellano, Luis M; González-Cortés, Araceli; Yáñez-Sedeño, Paloma; Langa, Fernando; Pingarrón, José M

    2015-12-15

    An electrochemical immunosensor for adiponectin (APN) using screen printed carbon electrodes (SPCEs) modified with functionalized double-walled carbon nanotubes (DWCNTs) as platforms for immobilization of the specific antibodies is reported. DWCNTs were functionalized by treatment with 4-aminobenzoic acid (HOOC-Phe) in the presence of isoamylnitrite resulting in the formation of 4-carboxyphenyl-DWCNTs. The oriented binding of specific antibodies toward adiponectin was accomplished by using the metallic-complex chelating polymer Mix&Go™. The HOOC-Phe-DWCNTs-modified SPCEs were characterized by cyclic voltammetry and compared with HOOC-Phe-SWCNTs/SPCE. The different variables affecting the performance of the developed immunosensor were optimized. Under the selected conditions, a calibration plot for APN was constructed showing a range of linearity extending between 0.05 and 10.0 μg/mL which is adequate for the determination of the cytokine in real samples. A detection limit of 14.5 ng/mL was achieved. The so prepared immunosensor exhibited a good reproducibility for the APN measurements, excellent storage stability and selectivity, and a much shorter assay time than the available ELISA kits. The usefulness of the immunosensor for the analysis of real samples was demonstrated by analyzing human serum from female or male healthy patients.

  10. Influence of pH, metal chelator, free radical scavenger and interfacial characteristics on the oxidative stability of β-carotene in conjugated whey protein-pectin stabilised emulsion.

    PubMed

    Xu, Duoxia; Yuan, Fang; Gao, Yanxiang; McClements, D Julian; Decker, Eric A

    2013-08-15

    The influence of whey protein isolate (WPI)-beet pectin conjugates formed by dry-heating on the oxidative stability of β-carotene in O/W emulsions was studied. It was mainly focused on the influence of pH, metal chelator, free radical scavenger and interfacial characteristics on the degradation of β-carotene in the emulsion stabilised by conjugate. The conjugate increased the oxidative stability of β-carotene in the emulsion as compared to their unconjugated mixture at pH 7.0. The desferoxamine retarded β-carotene degradation at pH 4.0 more effectively than pH 7.0 and more effectively in the emulsion with the conjugate than the unconjugated mixture (p<0.05). The addition of 200 mg/kg α-tocopherol significantly improved the stability of β-carotene in the conjugate stabilised emulsion. The emulsions were washed to remove conjugate not absorbed to the emulsion droplet interface, indicating that unabsorbed emulsifiers could protect β-carotene. It suggested that WPI-pectin conjugate could be used to protect bioactive lipids in emulsions.

  11. Polycatecholamide chelating agents

    DOEpatents

    Weitl, Frederick L.; Raymond, Kenneth N.

    1984-01-01

    Novel polybenzamide compounds useful for in vitro or in vivo chelation are described. The compounds have the formula ##STR1## Polyamines are reacted with 2,3-dimethoxy benzoyl chloride unsubstituted or substituted with SO.sub.3 H, SO.sub.3 M, NO.sub.2, CO.sub.2 H or CO.sub.2 M as desired is reacted with a polyamine in an inert solvent then demethylated with BBr.sub.3 or BCl.sub.3 in an inert solvent. Where compounds symmetrically substituted on the terminal N's are desired, the polyamine is first reductively alkylated by reaction with an aldehyde or ketone and the resulting Schiff base is hydrogenated.

  12. Novel polycatecholamide chelating agents

    DOEpatents

    Weitl, F.L.; Raymond, K.N.

    1981-08-24

    Novel polybenzamide compounds useful for in vitro or in vivo chelation are described. Formulas of the compounds are given. To prepare them polyamines are reacted with 2,3-dimethoxy benzoyl chloride unsubstituted or substituted with SO/sub 3/H, SO/sub 3/M, NO/sub 2/, CO/sub 2/H or CO/sub 2/M as desired is reacted with a polyamine in an inert solvent then demethylated with BBr/sub 3/ or BCl/sub 3/ in an inert solvent. Where compounds symmetrically substituted on the terminal N's are desired, the polyamine is first reductively alkylated by reaction with an aldehyde or ketone and the resulting Schiff base is hydrogenated.

  13. Polycatecholamide chelating agents

    DOEpatents

    Weitl, F.L.; Raymond, K.N.

    1984-04-10

    Novel polybenzamide compounds useful for in vitro or in vivo chelation are described. The compounds have the formula given in patent. Polyamines are reacted with 2,3-dimethoxy benzoyl chloride unsubstituted or substituted with SO[sub 3]H, SO[sub 3]M, NO[sub 2], CO[sub 2]H or CO[sub 2]M as desired is reacted with a polyamine in an inert solvent then demethylated with BBr[sub 3] or BCl[sub 3] in an inert solvent. Where compounds symmetrically substituted on the terminal N's are desired, the polyamine is first reductively alkylated by reaction with an aldehyde or ketone and the resulting Schiff base is hydrogenated. No Drawings

  14. Bifunctional chelating agent for the design and development of site specific radiopharmaceuticals and biomolecule conjugation strategy

    DOEpatents

    Katti, Kattesh V.; Prabhu, Kandikere R.; Gali, Hariprasad; Pillarsetty, Nagavara Kishore; Volkert, Wynn A.

    2003-10-21

    There is provided a method of labeling a biomolecule with a transition metal or radiometal in a site specific manner to produce a diagnostic or therapeutic pharmaceutical compound by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radio metal or a transition metal, and covalently linking the resulting metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. Also provided is a method of synthesizing the --PR.sub.2 containing biomolecules by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radiometal or a transition metal, and covalently linking the resulting radio metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. There is provided a therapeutic or diagnostic agent comprising a --PR.sub.2 containing biomolecule.

  15. Quercetin glycosides and chlorogenic acid in highbush blueberry leaf decoction prevent cataractogenesis in vivo and in vitro: Investigation of the effect on calpains, antioxidant and metal chelating properties.

    PubMed

    Ferlemi, Anastasia-Varvara; Makri, Olga E; Mermigki, Penelope G; Lamari, Fotini N; Georgakopoulos, Constantinos D

    2016-04-01

    The present study investigates whether highbush blueberry leaf polyphenols prevent cataractogenesis and the underlying mechanisms. Chlorogenic acid, quercetin, rutin, isoquercetin and hyperoside were quantified in Vaccinium corymbosum leaf decoction (BBL) using HPLC-DAD. Wistar rats were injected subcutaneously with 20 μmol selenite (Na2SeO3)/kg body weight on postnatal (PN) day 10 (Se, n = 8-10/group) only or also intraperitoneally with 100 mg dry BBL/kg body weight on PN days 11 and 12 (SeBBL group, n = 10). Control group received only normal saline (C). Cataract evaluation revealed that BBL significantly prevented lens opacification. It, also, protected lens from selenite oxidative attack and prevented calpain activation, as well as protein loss and aggregation. In vitro studies showed that quercetin attenuated porcine lens turbidity caused by [Formula: see text] or Ca(2+) and interacted efficiently with those ions according to UV-Vis titration experiments. Finally, rutin, isoquercetin and hyperoside moderately inhibited pure human μ-calpain. Conclusively, blueberry leaf extract, a rich source of bioactive polyphenols, prevents cataractogenesis by their strong antioxidant, chelating properties and through direct/indirect inhibition of lens calpains.

  16. 76 FR 7811 - Silicon Metal From the People's Republic of China: Amended Final Results of Antidumping Duty...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-02-11

    ... Partial Rescission of the 2008-2009 Administrative Review of the Antidumping Duty Order, 76 FR 3084... International Trade Administration Silicon Metal From the People's Republic of China: Amended Final Results of... the final results of the antidumping duty administrative review of silicon metal from the...

  17. Technetium-99m chelators in nuclear medicine. A review.

    PubMed

    Hjelstuen, O K

    1995-03-01

    Nuclear medicine is a branch of medical imaging that uses radioactive tracers to examine the function of body systems. The radionuclide used in about 90% of all examinations is 99Tcm, which is available from 99Mo/99Tcm generators at most nuclear medicine departments. In aqueous medium, technetium is chemically stable as pertechnetate, 99TcmO4-. Injected into the human body, pertechnetate will be absorbed by the thyroid gland because of the similarity to iodide in its radius and charge. To reach targets in the human body other than glandula thyreoidea, 99Tcm needs a carrier molecule, usually a chelating agent. Many chelators that form stable complexes with 99Tcm have affinities for certain tissues in the human body. Other chelators can be manipulated by pharmaceutical formation to be retained in certain body systems. In order to form bonds with technetium, the chelator must contain electron donors like nitrogen, oxygen and sulfur. Space between multiple electron donor atoms is required to allow several bonds to form with the central metal. The stability of the complex increases with increasing number of bonds. Today, chelators for the use with 99Tcm exist for a number of highly sensitive scintigraphic studies of the brain, heart, skeleton, kidneys, hepatobiliary system and lungs. This includes chelators such as dimercaptosuccinic acid, 1,2-ethylenediylbis-L-cysteine diethyl ester, methylenediphosphonate, hexamethylpropyleneamineoxime and hexakis(methoxy isobutyl isonitrile).

  18. The effect of various metal ions and chelating agents on the formation of noncovalently and covalently linked IgM polymers.

    PubMed

    Eskeland, T

    1977-01-01

    The influence of various concentrations of Mg2+, Ca2+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, EDTA, or 8-hydroxyquinoline-5-sulfonic acid on the formation in vitro of polymeric IgM from reduced and dissociated IgM has been investigated. 4-200muM Zn, Cd, or Hg ions in the dialysis buffer used for reassociation resulted in the formation of a homogeneous polymer peak sedimenting as 19S IgM, whereas the other metal ions resulted in the formation of polymers sedimenting mostly as tetramers, pentamers (19S IgM), and hexamers. Dialysis in the presence of 1 and 3mM EDTA or 8-hydroxyquinoline-5-sulfonic acid gave slight polymer formation; 10 mM of the agents gave none. Ca, Mg, Fe, Ni, Zn, Cd, or Hg ions regularly gave only noncovalently linked polymers, whereas Cu ions in particular, but also Co and, to a minor extent, Mn ions catalyzed the formation of covalently linked polymers. Experiments performed with Mg, Ca, Ni, and Zn ions or with Cu and Zn ions in the same buffer during reassociation showed that Zn ions inhibit the effect of the other ions on polymer assembly and covalent stabilization.

  19. Overproduction of Thermus sp. Strain T2 β-Galactosidase in Escherichia coli and Preparation by Using Tailor-Made Metal Chelate Supports

    PubMed Central

    Pessela, Benevides C. C.; Vian, Alejandro; Mateo, César; Fernández-Lafuente, Roberto; García, José L.; Guisán, José M.; Carrascosa, Alfonso V.

    2003-01-01

    A novel thermostable chimeric β-galactosidase was constructed by fusing a poly-His tag to the N-terminal region of the β-galactosidase from Thermus sp. strain T2 to facilitate its overexpression in Escherichia coli and its purification by immobilized metal-ion affinity chromatography (IMAC). The poly-His tag fusion did not affect the activation, kinetic parameters, and stability of the β-galactosidase. Copper-iminodiacetic acid (Cu-IDA) supports enabled the most rapid adsorption of the His-tagged enzyme, favoring multisubunit interactions, but caused deleterious effects on the enzyme stability. To improve the enzyme purification a selective one-point adsorption was achieved by designing tailor-made low-activated Co-IDA or Ni-IDA supports. The new enzyme was not only useful for industrial purposes but also has become an excellent model to study the purification of large multimeric proteins via selective adsorption on tailor-made IMAC supports. PMID:12676671

  20. Stereochemistry of new nitrogen containing heterocyclic aldehyde. Part XI. Novel ligational behaviour of quinoline as chelate ligand toward transition metal ions

    NASA Astrophysics Data System (ADS)

    El-Sonbati, A. Z.; Al-Shihri, A. S.; El-Bindary, A. A.

    2004-07-01

    Novel complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and UO 2(II) with a new Schiff base derived from 8-hydroxy-7-quinolinecarboxaldehyde and 2-aminoethanethiol (LH 2) (system name: 2-(8-hydroxy-7-carboxalimino)ethanethiol.) have been prepared and characterized on the basis of analytical, thermal, magnetic moment, infrared, electronic, NMR and EPR spectral data. From the analytical, NMR and thermal data and stoichiometry of the complexes indicate that LH 2 act as a dibasic tridentate ligand with ONS donors towards all the metal ions. The magnetic moment, electronic and EPR spectral data commensurate that the Mn(II), Fe(II), Ni(II) and UO 2(II) complexes are dimeric with octahedral configuration while the Cu(II) and Zn(II) complexes are monomeric with square-planar and tetrahedral geometries, respectively. Various ligand field parameters Dq, B and β for complex 5 was calculated. The complexes 3+ 4 have lower symmetries and the amount of distortion in terms of DT/DQ applying NSH "Hamiltonian Theory" has been evaluated which indicate that the complexes are moderately distorted.

  1. Study of the chemical chelates and anti-microbial effect of some metal ions in nanostructural form on the efficiency of antibiotic therapy "norfloxacin drug"

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Hawary, W. F.; Mohamed, Mahmoud A.

    2012-04-01

    This paper has reviewed the chemical and biological impact resulting from the interaction between norfloxacin (norH) antibiotic drug and two lanthanide (lanthanum(III) and cerium(III)) metal ions, which prepared in normal and nano-features. La(III) and Ce(III) complexes were synthesized with chemical formulas [La(nor)3]·3H2O and [Ce(nor)3]·2H2O. Lanthanum and cerium(III) ions coordinated toward norH with a hexadentate geometry. The norH acts as deprotonated bidentate ligand through the oxygen atom of carbonyl group and the oxygen atom of carboxylic group. Elemental analysis, FT-IR spectral, electrical conductivity, thermal analysis (TG/DTA), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) measurements have been used to characterize the mentioned isolated complexes. The Coats-Redfern and Horowitz-Metzger integral methods are used to estimate the kinetic parameters for the major successive steps detectable in the TG curve. The brightness side in this study is to take advantage for the preparation and characterization of single phases of La2O3 and CeO2 nanoparticles using urea as precursors via a solid-state decomposition procedure. The norH ligand in comparison with both cases (normal and nano-particles) of lanthanide complexes were screened against for antibacterial (Escherichia Coli, Staphylococcus Aureus, Bacillus subtilis and Pseudomonas aeruginosa) and antifungal (Aspergillus Flavus and Candida Albicans) activities. The highest antibacterial and antifungal activities data of the nano-particles complexes were observed with more potent than the free norH and normal lanthanide complexes.

  2. Chelation ion chromatography as a method for trace elemental analysis in complex environmental and biological samples

    SciTech Connect

    Siriraks, A.; Kingston, H.M. ); Riviello, J.M. )

    1990-06-01

    The development and evaluation of a new method for the determination of trace transition and rare-earth elements based on the combination of chelation and ion chromatography are described. The new method, chelation ion chromatography (Chelation IC), uses a chelating column to concentrate and separate transition and rare-earth elements from the common alkali and alkaline-earth metals, as well as other matrix components, prior to analysis by ion chromatography. The sample fraction from the chelating column contains only the concentrated analyte ions, thus eliminating interfering matrix components from complex matrices such as seawater and digested biological, botanical, and geological materials. This combination of chelation and ion chromatography provides a technique that makes possible the determination of trace elements in complex matrices that have proven to be difficult or impossible to analyze by ion chromatography or conventional atomic spectroscopy techniques.

  3. Alteration of tissue disposition of cadmium by chelating agents.

    PubMed Central

    Klaassen, C D; Waalkes, M P; Cantilena, L R

    1984-01-01

    administering chelators daily for 5 days starting 48 hr after Cd. DTPA, EDTA, DMSA and BAL significantly increased the urinary elimination of Cd. Thus, mobilization of Cd into urine occurs with repeated chelation therapy, which may decrease tissue concentrations of Cd and reduce the toxicity of the metal. PMID:6734558

  4. 3-hydroxy-2(1H)-pyridinone chelating agents

    DOEpatents

    Raymond, Kenneth N.; Xu, Jide

    1997-01-01

    Disclosed is a series of improved metal chelating agents, which are highly effective upon both injection and oral administration; several of the most effective are of low toxicity. These chelating agents incorporate within their structure 1-hydroxy-2-pyridinone (1,2-HOPO) and 3-hydroxy-2-pyridinone (3,2-HOPO) moieties with a substituted carbamoyl group ortho to the hydroxy or oxo groups of the hydroxypyridinone ring. The electron-withdrawing carbamoyl group increases the acidity of the hydroxypyridinones. In the metal complexes of said chelating agents, the amide protons form very strong hydrogen bonds with its adjacent HOPO oxygen donor, making these complexes very stable at physiological conditions. The terminal N-substituents provides a certain degree of lipophilicity to said 3,2-HOPO, increasing oral activity. Also disclosed is a method of making the chelating agents and a method of producing a known compound, 3-hydroxy-1-alkyl-2(1H)pyridinone, used as a precursor to the chelating agent, safely and in large quantities.

  5. Ab initio coordination chemistry for nickel chelation motifs.

    PubMed

    Sudan, R Jesu Jaya; Kumari, J Lesitha Jeeva; Sudandiradoss, C

    2015-01-01

    Chelation therapy is one of the most appreciated methods in the treatment of metal induced disease predisposition. Coordination chemistry provides a way to understand metal association in biological structures. In this work we have implemented coordination chemistry to study nickel coordination due to its high impact in industrial usage and thereby health consequences. This paper reports the analysis of nickel coordination from a large dataset of nickel bound structures and sequences. Coordination patterns predicted from the structures are reported in terms of donors, chelate length, coordination number, chelate geometry, structural fold and architecture. The analysis revealed histidine as the most favored residue in nickel coordination. The most common chelates identified were histidine based namely HHH, HDH, HEH and HH spaced at specific intervals. Though a maximum coordination number of 8 was observed, the presence of a single protein donor was noted to be mandatory in nickel coordination. The coordination pattern did not reveal any specific fold, nevertheless we report preferable residue spacing for specific structural architecture. In contrast, the analysis of nickel binding proteins from bacterial and archeal species revealed no common coordination patterns. Nickel binding sequence motifs were noted to be organism specific and protein class specific. As a result we identified about 13 signatures derived from 13 classes of nickel binding proteins. The specifications on nickel coordination presented in this paper will prove beneficial for developing better chelation strategies.

  6. 3-hydroxy-2(1H)-pyridinone chelating agents

    DOEpatents

    Raymond, K.N.; Xu, J.

    1997-04-29

    Disclosed is a series of improved metal chelating agents, which are highly effective upon both injection and oral administration; several of the most effective are of low toxicity. These chelating agents incorporate within their structure 1-hydroxy-2-pyridinone (1,2-HOPO) and 3-hydroxy-2-pyridinone (3,2-HOPO) moieties with a substituted carbamoyl group ortho to the hydroxy or oxo groups of the hydroxypyridinone ring. The electron-withdrawing carbamoyl group increases the acidity of the hydroxypyridinones. In the metal complexes of the chelating agents, the amide protons form very strong hydrogen bonds with its adjacent HOPO oxygen donor, making these complexes very stable at physiological conditions. The terminal N-substituents provides a certain degree of lipophilicity to the 3,2-HOPO, increasing oral activity. Also disclosed is a method of making the chelating agents and a method of producing a known compound, 3-hydroxy-1-alkyl-2(1H)pyridinone, used as a precursor to the chelating agent, safely and in large quantities. 2 figs.

  7. Ab initio coordination chemistry for nickel chelation motifs.

    PubMed

    Sudan, R Jesu Jaya; Kumari, J Lesitha Jeeva; Sudandiradoss, C

    2015-01-01

    Chelation therapy is one of the most appreciated methods in the treatment of metal induced disease predisposition. Coordination chemistry provides a way to understand metal association in biological structures. In this work we have implemented coordination chemistry to study nickel coordination due to its high impact in industrial usage and thereby health consequences. This paper reports the analysis of nickel coordination from a large dataset of nickel bound structures and sequences. Coordination patterns predicted from the structures are reported in terms of donors, chelate length, coordination number, chelate geometry, structural fold and architecture. The analysis revealed histidine as the most favored residue in nickel coordination. The most common chelates identified were histidine based namely HHH, HDH, HEH and HH spaced at specific intervals. Though a maximum coordination number of 8 was observed, the presence of a single protein donor was noted to be mandatory in nickel coordination. The coordination pattern did not reveal any specific fold, nevertheless we report preferable residue spacing for specific structural architecture. In contrast, the analysis of nickel binding proteins from bacterial and archeal species revealed no common coordination patterns. Nickel binding sequence motifs were noted to be organism specific and protein class specific. As a result we identified about 13 signatures derived from 13 classes of nickel binding proteins. The specifications on nickel coordination presented in this paper will prove beneficial for developing better chelation strategies. PMID:25985439

  8. Ab Initio Coordination Chemistry for Nickel Chelation Motifs

    PubMed Central

    Jesu Jaya Sudan, R.; Lesitha Jeeva Kumari, J.; Sudandiradoss, C.

    2015-01-01

    Chelation therapy is one of the most appreciated methods in the treatment of metal induced disease predisposition. Coordination chemistry provides a way to understand metal association in biological structures. In this work we have implemented coordination chemistry to study nickel coordination due to its high impact in industrial usage and thereby health consequences. This paper reports the analysis of nickel coordination from a large dataset of nickel bound structures and sequences. Coordination patterns predicted from the structures are reported in terms of donors, chelate length, coordination number, chelate geometry, structural fold and architecture. The analysis revealed histidine as the most favored residue in nickel coordination. The most common chelates identified were histidine based namely HHH, HDH, HEH and HH spaced at specific intervals. Though a maximum coordination number of 8 was observed, the presence of a single protein donor was noted to be mandatory in nickel coordination. The coordination pattern did not reveal any specific fold, nevertheless we report preferable residue spacing for specific structural architecture. In contrast, the analysis of nickel binding proteins from bacterial and archeal species revealed no common coordination patterns. Nickel binding sequence motifs were noted to be organism specific and protein class specific. As a result we identified about 13 signatures derived from 13 classes of nickel binding proteins. The specifications on nickel coordination presented in this paper will prove beneficial for developing better chelation strategies. PMID:25985439

  9. Hydroxypyridonate chelating agents and synthesis thereof

    DOEpatents

    Raymond, K.N.; Scarrow, R.C.; White, D.L.

    1985-11-12

    Chelating agents having 1-hydroxy-2-pyridinone (HOPO) and related moieties incorporated within their structures, including polydentate HOPO-substituted polyamines such as spermidine and spermine, and HOPO-substituted desferrioxamine. The chelating agents are useful in selectively removing certain cations from solution, and are particularly useful as ferric ion and actinide chelators. Novel syntheses of the chelating agents are provided. 4 tabs.

  10. Metal based pharmacologically active agents: Synthesis, structural characterization, molecular modeling, CT-DNA binding studies and in vitro antimicrobial screening of iron(II) bromosalicylidene amino acid chelates

    NASA Astrophysics Data System (ADS)

    Abdel-Rahman, Laila H.; El-Khatib, Rafat M.; Nassr, Lobna A. E.; Abu-Dief, Ahmed M.; Ismael, Mohamed; Seleem, Amin Abdou

    2014-01-01

    flavus and Trichotheium rosium. The results of these studies indicated that the metal complexes exhibit a stronger antibacterial and antifungal efficiency than their corresponding Schiff base amino acid ligands.

  11. Metal based pharmacologically active agents: synthesis, structural characterization, molecular modeling, CT-DNA binding studies and in vitro antimicrobial screening of iron(II) bromosalicylidene amino acid chelates.

    PubMed

    Abdel-Rahman, Laila H; El-Khatib, Rafat M; Nassr, Lobna A E; Abu-Dief, Ahmed M; Ismael, Mohamed; Seleem, Amin Abdou

    2014-01-01

    and Trichotheium rosium. The results of these studies indicated that the metal complexes exhibit a stronger antibacterial and antifungal efficiency than their corresponding Schiff base amino acid ligands.

  12. Final results of the XR2-1 BWR metallic melt relocation experiment

    SciTech Connect

    Gauntt, R.O.; Humphries, L.L.

    1997-08-01

    This report documents the final results of the XR2-1 boiling water reactor (BWR) metallic melt relocation experiment, conducted at Sandia National Laboratories for the U.S. Nuclear Regulatory Commission. The objective of this experiment was to investigate the material relocation processes and relocation pathways in a dry BWR core following a severe nuclear reactor accident such as an unrecovered station blackout accident. The imposed test conditions (initial thermal state and the melt generation rates) simulated the conditions for the postulated accident scenario and the prototypic design of the lower core test section (in composition and in geometry) ensured that thermal masses and physical flow barriers were modeled adequately. The experiment has shown that, under dry core conditions, the metallic core materials that melt and drain from the upper core regions can drain from the core region entirely without formation of robust coherent blockages in the lower core. Temporary blockages that suspended pools of molten metal later melted, allowing the metals to continue draining downward. The test facility and instrumentation are described in detail. The test progression and results are presented and compared to MERIS code analyses. 6 refs., 55 figs., 4 tabs.

  13. 75 FR 1592 - Silicon Metal from the People's Republic of China: Final Results and Partial Rescission of...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-01-12

    ... International Trade Administration A-570-806 Silicon Metal from the People's Republic of China: Final Results... administrative review of the antidumping duty order on silicon metal from the People's Republic of China (``PRC... From the People's Republic of China: Preliminary Results and Preliminary Rescission, in Part,...

  14. 75 FR 15412 - Silicon Metal From the People's Republic of China: Notice of Amended Final Results of New Shipper...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-29

    ... (``the Department'') determination of the appropriate surrogate value for silica fume in Silicon Metal From the People's Republic of China: Notice of Final Results of 2005/2006 New Shipper Reviews, 72 FR 58... International Trade Administration Silicon Metal From the People's Republic of China: Notice of Amended...

  15. 75 FR 50992 - Magnesium Metal from the People's Republic of China: Extension of Time for the Final Results of...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-18

    ..., 2009. See Magnesium Metal from the People's Republic of China: Preliminary Results of the 2008-2009 Antidumping Duty Administrative Review, 75 FR 20817 (April 21, 2010). The final results of review are... International Trade Administration Magnesium Metal from the People's Republic of China: Extension of Time...

  16. The role of chelation in the treatment of arsenic and mercury poisoning.

    PubMed

    Kosnett, Michael J

    2013-12-01

    Chelation for heavy metal intoxication began more than 70 years ago with the development of British anti-lewisite (BAL; dimercaprol) in wartime Britain as a potential antidote the arsenical warfare agent lewisite (dichloro[2-chlorovinyl]arsine). DMPS (unithiol) and DMSA (succimer), dithiol water-soluble analogs of BAL, were developed in the Soviet Union and China in the late 1950s. These three agents have remained the mainstay of chelation treatment of arsenic and mercury intoxication for more than half a century. Animal experiments and in some instances human data indicate that the dithiol chelators enhance arsenic and mercury excretion. Controlled animal experiments support a therapeutic role for these chelators in the prompt treatment of acute poisoning by arsenic and inorganic mercury salts. Treatment should be initiated as rapidly as possible (within minutes to a few hours), as efficacy declines or disappears as the time interval between metal exposure and onset of chelation increases. DMPS and DMSA, which have a higher therapeutic index than BAL and do not redistribute arsenic or mercury to the brain, offer advantages in clinical practice. Although chelation following chronic exposure to inorganic arsenic and inorganic mercury may accelerate metal excretion and diminish metal burden in some organs, potential therapeutic efficacy in terms of decreased morbidity and mortality is largely unestablished in cases of chronic metal intoxication.

  17. The role of chelation in the treatment of arsenic and mercury poisoning.

    PubMed

    Kosnett, Michael J

    2013-12-01

    Chelation for heavy metal intoxication began more than 70 years ago with the development of British anti-lewisite (BAL; dimercaprol) in wartime Britain as a potential antidote the arsenical warfare agent lewisite (dichloro[2-chlorovinyl]arsine). DMPS (unithiol) and DMSA (succimer), dithiol water-soluble analogs of BAL, were developed in the Soviet Union and China in the late 1950s. These three agents have remained the mainstay of chelation treatment of arsenic and mercury intoxication for more than half a century. Animal experiments and in some instances human data indicate that the dithiol chelators enhance arsenic and mercury excretion. Controlled animal experiments support a therapeutic role for these chelators in the prompt treatment of acute poisoning by arsenic and inorganic mercury salts. Treatment should be initiated as rapidly as possible (within minutes to a few hours), as efficacy declines or disappears as the time interval between metal exposure and onset of chelation increases. DMPS and DMSA, which have a higher therapeutic index than BAL and do not redistribute arsenic or mercury to the brain, offer advantages in clinical practice. Although chelation following chronic exposure to inorganic arsenic and inorganic mercury may accelerate metal excretion and diminish metal burden in some organs, potential therapeutic efficacy in terms of decreased morbidity and mortality is largely unestablished in cases of chronic metal intoxication. PMID:24178900

  18. Questions and Answers on Unapproved Chelation Products

    MedlinePlus

    ... OTC) to prevent or treat diseases. Companies are marketing unapproved OTC chelation therapy products to patients with ... 4. Why did FDA take this action? Companies marketing unapproved OTC chelation products with unsubstantiated treatment claims ...

  19. Hydroxypyridonate and hydroxypyrimidinone chelating agents

    DOEpatents

    Raymond, Kenneth N.; Doble, Daniel M.; Sunderland, Christopher J.; Thompson, Marlon

    2005-01-25

    The present invention provides hydroxypyridinone and hydroxypyrimidone chelating agents. Also provides are Gd(III) complexes of these agents, which are useful as contrast enhancing agents for magnetic resonance imaging. The invention also provides methods of preparing the compounds of the invention, as well as methods of using the compounds in magnetic resonance imaging applications.

  20. Natural chelating agents for radionuclide decorporation

    DOEpatents

    Premuzic, Eugene T.

    1988-01-01

    This invention relates to the preparation of new, naturally produced chelating agents as well as to the method and resulting chelates of desorbing cultures in a bioavailable form involving Pseudomonas species or other microorganisms. A preferred microorganism is Pseudomonas aeruginosa which forms multiple chelates with thorium in the range of molecular weight 100-1,000 and also forms chelates with uranium of molecular weight in the area of 100-1,000 and 1,000-2,000.

  1. Iron chelation and multiple sclerosis

    PubMed Central

    Weigel, Kelsey J.; Lynch, Sharon G.; LeVine, Steven M.

    2014-01-01

    Histochemical and MRI studies have demonstrated that MS (multiple sclerosis) patients have abnormal deposition of iron in both gray and white matter structures. Data is emerging indicating that this iron could partake in pathogenesis by various mechanisms, e.g., promoting the production of reactive oxygen species and enhancing the production of proinflammatory cytokines. Iron chelation therapy could be a viable strategy to block iron-related pathological events or it can confer cellular protection by stabilizing hypoxia inducible factor 1α, a transcription factor that normally responds to hypoxic conditions. Iron chelation has been shown to protect against disease progression and/or limit iron accumulation in some neurological disorders or their experimental models. Data from studies that administered a chelator to animals with experimental autoimmune encephalomyelitis, a model of MS, support the rationale for examining this treatment approach in MS. Preliminary clinical studies have been performed in MS patients using deferoxamine. Although some side effects were observed, the large majority of patients were able to tolerate the arduous administration regimen, i.e., 6–8 h of subcutaneous infusion, and all side effects resolved upon discontinuation of treatment. Importantly, these preliminary studies did not identify a disqualifying event for this experimental approach. More recently developed chelators, deferasirox and deferiprone, are more desirable for possible use in MS given their oral administration, and importantly, deferiprone can cross the blood–brain barrier. However, experiences from other conditions indicate that the potential for adverse events during chelation therapy necessitates close patient monitoring and a carefully considered administration regimen. PMID:24397846

  2. Effects of zinc supplementation and zinc chelation on in vitro β-cell function in INS-1E cells

    PubMed Central

    2014-01-01

    Background Zinc is essential for the activities of pancreatic β-cells, especially insulin storage and secretion. Insulin secretion leads to co-release of zinc which contributes to the paracrine communication in the pancreatic islets. Zinc-transporting proteins (zinc-regulated transporter, iron-regulated transporter-like proteins [ZIPs] and zinc transporters [ZnTs]) and metal-buffering proteins (metallothioneins, MTs) tightly regulate intracellular zinc homeostasis. The present study investigated how modulation of cellular zinc availability affects β-cell function using INS-1E cells. Results Using INS-1E cells, we found that zinc supplementation and zinc chelation had significant effects on insulin content and insulin secretion. Supplemental zinc within the physiological concentration range induced insulin secretion. Insulin content was reduced by zinc chelation with N,N,N’,N-tektrakis(2-pyridylmethyl)-ethylenediamine. The changes in intracellular insulin content following exposure to various concentrations of zinc were reflected by changes in the expression patterns of MT-1A, ZnT-8, ZnT-5, and ZnT-3. Furthermore, high zinc concentrations induced cell necrosis while zinc chelation induced apoptosis. Finally, cell proliferation was sensitive to changes in zinc the concentration. Conclusion These results indicate that the β-cell-like function and survival of INS-1E cells are dependent on the surrounding zinc concentrations. Our results suggest that regulation of zinc homeostasis could represent a pharmacological target. PMID:24502363

  3. Regeneration of the heart in diabetes by selective copper chelation.

    PubMed

    Cooper, Garth J S; Phillips, Anthony R J; Choong, Soon Y; Leonard, Bridget L; Crossman, David J; Brunton, Dianne H; Saafi, 'Etuate L; Dissanayake, Ajith M; Cowan, Brett R; Young, Alistair A; Occleshaw, Christopher J; Chan, Yih-Kai; Leahy, Fiona E; Keogh, Geraldine F; Gamble, Gregory D; Allen, Grant R; Pope, Adèle J; Boyd, Peter D W; Poppitt, Sally D; Borg, Thomas K; Doughty, Robert N; Baker, John R

    2004-09-01

    Heart disease is the major cause of death in diabetes, a disorder characterized by chronic hyperglycemia and cardiovascular complications. Although altered systemic regulation of transition metals in diabetes has been the subject of previous investigation, it is not known whether changed transition metal metabolism results in heart disease in common forms of diabetes and whether metal chelation can reverse the condition. We found that administration of the Cu-selective transition metal chelator trientine to rats with streptozotocin-induced diabetes caused increased urinary Cu excretion compared with matched controls. A Cu(II)-trientine complex was demonstrated in the urine of treated rats. In diabetic animals with established heart failure, we show here for the first time that 7 weeks of oral trientine therapy significantly alleviated heart failure without lowering blood glucose, substantially improved cardiomyocyte structure, and reversed elevations in left ventricular collagen and beta(1) integrin. Oral trientine treatment also caused elevated Cu excretion in humans with type 2 diabetes, in whom 6 months of treatment caused elevated left ventricular mass to decline significantly toward normal. These data implicate accumulation of elevated loosely bound Cu in the mechanism of cardiac damage in diabetes and support the use of selective Cu chelation in the treatment of this condition.

  4. Copper and Zinc Chelation as a Treatment of Alzheimer's Disease

    NASA Astrophysics Data System (ADS)

    Hodak, Miroslav; Bernholc, Jerry

    2014-03-01

    Alzheimer's disease (AD) is a neurodegenerative disorder affecting millions of people in the U.S. The cause of the disease remains unknown, but amyloid- β (A β), a short peptide, is considered causal its pathogenesis. At cellular level, AD is characterized by deposits mainly composed of A β that also contain elevated levels of transition metals ions. Targeting metals is a promising new strategy for AD treatment, which uses moderately strong metal chelators to sequester them from A β or the environment. PBT2 is a chelating compound that has been the most promising in clinical trials. In our work, we use computer simulations to investigate complexes of a close analog of PBT2 with Cu2+ and Zn2+ ions. The calculations employ KS/FD DFT method, which combines Kohn-Sham DFT with the frozen-density DFT to achieve efficient description of explicit solvent beyond the first solvation shell. Our work is based on recent experiments and examines both 1:1 and 2:1 chelator-metal stochiometries detected experimentally. The results show that copper attaches more strongly than zinc, find that 1:1 complexes involve water in the first coordination shell and determine which one of several possible 2:1 geometries is the most preferable.

  5. Persulfate oxidation for in situ remediation of TCE. II. Activated by chelated ferrous ion.

    PubMed

    Liang, Chenju; Bruell, Clifford J; Marley, Michael C; Sperry, Kenneth L

    2004-06-01

    In situ chemical oxidation (ISCO) is a technique used to remediate contaminated soil and groundwater systems. It has been postulated that sodium persulfate (Na2S2O8) can be activated by transition metal ions such as ferrous ion (Fe2+) to produce a powerful oxidant known as the sulfate free radical (SO4-*) with a redox potential of 2.6 V, which can potentially destroy organic contaminants. In this laboratory study persulfate oxidation of dissolved trichloroethylene (TCE) was investigated in aqueous and soil slurry systems under a variety of experimental conditions. A chelating agent (i.e., citric acid) was used in attempt to manipulate the quantity of ferrous ion in solution by providing an appropriate chelate/Fe2+ molar ratio. In an aqueous system a chelate/Fe2+ molar ratio of 1/5 (e.g., S2O8(2)-/chelate/Fe2+/TCE ratio of 20/2/10/1) was found to be the lowest acceptable ratio to maintain sufficient quantities of Fe2+ activator in solution resulting in nearly complete TCE destruction after only 20 min. The availability of Fe2+ appeared to be controlled by adjusting the molar ratio of chelate/Fe2+. In general, high levels of chelated ferrous ion concentrations resulted in faster TCE degradation and more persulfate decomposition. However, if initial ferrous ion contents are relatively low, sufficient quantities of chelate must be provided to ensure the chelation of a greater percentage of the limited ferrous ion present. Citric acid chelated ferrous ion appeared effective for TCE degradation within soil slurries but required longer reaction times. Additionally, the use of citric acid without the addition of supplemental Fe2+ in soil slurries, where the citric acid apparently extracted native metals from the soil, appeared to be somewhat effective at enhancing persulfate oxidation of TCE over extended reaction times. A comparison of different chelating agents revealed that citric acid was the most effective.

  6. Multidentate terephthalamidate and hydroxypyridonate ligands: towards new orally active chelators.

    PubMed

    Abergel, Rebecca J; Raymond, Kenneth N

    2011-01-01

    The limitations of current therapies for the treatment of iron overload or radioisotope contamination have stimulated efforts to develop new orally bioavailable iron and actinide chelators. Siderophore-inspired tetradentate, hexadentate and octadentate terephthalamidate and hydroxypyridonate ligands were evaluated in vivo as selective and efficacious iron or actinide chelating agents, with several metal loading and ligand assessment procedures, using (59)Fe, (238)Pu, and (241)Am as radioactive tracers. The compounds presented in this study were compared to commercially available therapeutic sequestering agents [deferoxamine (DFO) for iron and diethylenetriaminepentaacetic acid (DPTA) for actinides] and are unrivaled in terms of affinity, selectivity and decorporation efficacy, which attests to the fact that high metal affinity may overcome the low bioavailability properties commonly associated to multidenticity. PMID:21599440

  7. MULTIDENTATE TEREPHTHALAMIDATE AND HYDROXYPYRIDONATE LIGANDS: TOWARDS NEW ORALLY ACTIVE CHELATORS

    SciTech Connect

    Abergel, Rebecca J.; Raymond, Kenneth N.

    2011-07-13

    The limitations of current therapies for the treatment of iron overload or radioisotope contamination have stimulated efforts to develop new orally bioavailable iron and actinide chelators. Siderophore-inspired tetradentate, hexadentate and octadentate terephthalamidate and hydroxypyridonate ligands were evaluated in vivo as selective and efficacious iron or actinide chelating agents, with several metal loading and ligand assessment procedures, using {sup 59}Fe, {sup 238}Pu, and {sup 241}Am as radioactive tracers. The compounds presented in this study were compared to commercially available therapeutic sequestering agents [deferoxamine (DFO) for iron and diethylenetriaminepentaacetic acid (DPTA) for actinides] and are unrivaled in terms of affinity, selectivity and decorporation efficacy, which attests to the fact that high metal affinity may overcome the low bioavailability properties commonly associated to multidenticity.

  8. Pressure-assisted chelation extraction of lead from contaminated soil.

    PubMed

    Hong, P K Andy; Cai, Xiaoxiao; Cha, Zhixiong

    2008-05-01

    Soil contamination by metallic elements including lead occurs frequently. Contaminant metals in soil pose a serious risk to public health and groundwater supplies. Extraction using chelants is seen as a remediation option; however, it is often hampered by access to the contaminants that are shielded by the soil matrix. We have developed a novel extraction technique that utilizes a mildly elevated pressure in consecutive cycles of compression and decompression along with a chelating agent for the soil slurry. Complete extraction of 3300 mg/kg of Pb from soil was achieved by 100 mM of EDTA (ethylenediaminetetraacetic acid) in 10 min using 20 pressure cycles at 150 psi (10 atm). Extraction was studied according to pressure, number of pressure cycles, chelant concentration, solid content, pH, agitation, and use of consecutive washings. Heightened extraction is attributed to fracturing of the soil particles that leads to enhanced contaminant exposure to the chelating agent.

  9. Final-state diffraction effects in angle-resolved photoemission at an organic-metal interface

    NASA Astrophysics Data System (ADS)

    Bocquet, F. C.; Giovanelli, L.; Amsalem, P.; Petaccia, L.; Topwal, D.; Gorovikov, S.; Abel, M.; Koch, N.; Porte, L.; Goldoni, A.; Themlin, J.-M.

    2011-12-01

    In this paper it is shown that angle-resolved photoemission performed using low-energy photons on an organic-metal interface allows to clearly distinguish genuine interface states from features of substrate photoelectrons diffracted by the molecular lattice. As a model system an ordered monolayer of Zn-phthalocyanine is used as a diffraction lattice to probe the electronic band structure of a Ag(110) substrate. Photoemission close to normal emission geometry reveals strongly dispersive features absent in the pristine substrate spectra. Density functional theory modeling helped identifying these as bulk sp direct transitions undergoing surface-umklapp processes. The present results establish the important role of final-state diffraction effects in photoemission experiments at organic-inorganic interfaces.

  10. Evaluation of non-metallic fiber reinforced concrete in new full depth pcc pavements. Final report

    SciTech Connect

    Ramakrishnan, V.; Tolmare, N.S.

    1998-12-30

    This final report presents the construction and performance evaluation of a new full depth pavement, constructed with a new type non-metallic fiber reinforced concrete (NMFRC). The mixture proportions used, the quality control tests conducted for the evaluation of the fresh and hardened concrete properties, the procedure used for mixing, transporting, placing, consolidating, finishing, and curing of the concrete are described. Periodic inspection of the full depth pavement was done and this report includes the results of these inspections. The feasibility of using this NMFRC in the construction of highway structures has been discussed. The new NMFRC with enhanced fatigue, impact resistance, modulus of rupture, ductility and toughness properties is suitable for the construction of full depth pavements. However, a life-cycle cost analysis shows that NMFRC is not a favorable choice, because of it`s high initial cost.

  11. Immobilized iminodiacetic acid (IDA)-type Cu2+ -chelating membrane affinity chromatography for purification of bovine liver catalase.

    PubMed

    Yang, L; Jia, L; Zou, H; Zhang, Y

    1999-05-01

    A metal ion chelating membrane medium based on iminodiacetate-substituted modified short cotton cellulose was examined for the purification of bovine liver catalase (BLC). The effect of buffer pH, chelator surface density, initial concentration of crude enzyme and flow rate on BLC binding efficiency to the copper ion chelating membrane adsorbent were examined. Under the chromatographic conditions chosen, 67.7% recovery of BLC was attained with an overall 4.2-fold increase in specific activity in a single step. After performance of BLC purification, the chelating membrane adsorbent can be easily regenerated by imidazole or EDTA buffer with higher reviving effectiveness with the latter. PMID:10375124

  12. Copper chelators: chemical properties and bio-medical applications.

    PubMed

    Tegoni, M; Valensin, D; Toso, L; Remelli, M

    2014-01-01

    Copper is present in different concentrations and chemical forms throughout the earth crust, surface and deep water and even, in trace amounts, in the atmosphere itself. Copper is one of the first metals used by humans, the first artifacts dating back 10,000 years ago. Currently, the world production of refined copper exceeds 16,000 tons/year. Copper is a micro-element essential to life, principally for its red-ox properties that make it a necessary cofactor for many enzymes, like cytochrome-c oxidase and superoxide dismutase. In some animal species (e.g. octopus, snails, spiders, oysters) copper-hemocyanins also act as carriers of oxygen instead of hemoglobin. However, these red-ox properties also make the pair Cu(+)/Cu(2+) a formidable catalyst for the formation of reactive oxygen species, when copper is present in excess in the body or in tissues. The treatment of choice in cases of copper overloading or intoxication is the chelation therapy. Different molecules are already in clinical use as chelators or under study or clinical trial. It is worth noting that chelation therapy has also been suggested to treat some neurodegenerative diseases or cardiovascular disorders. In this review, after a brief description of the homeostasis and some cases of dyshomeostasis of copper, the main (used or potential) chelators are described; their properties in solution, even in relation to the presence of metal or ligand competitors, under physiological conditions, are discussed. The legislation of the most important Western countries, regarding both the use of chelating agents and the limits of copper in foods, drugs and cosmetics, is also outlined.

  13. Final report to USAMP on the use of EBPVD in the light metal die casting industry

    SciTech Connect

    Heestand, G.M.

    1996-02-02

    This is the final report to the United States Automotive Materials Partnership (USAMP) on the use of Electron Beam Physical Vapor Deposition (EBPVD) to make rapid tooling for functional prototyping of metal mold processes. Historically this process has been successfully applied to the production of mold inserts for the plastics injection mold industry. Our approach for this project was to use the same technique to produce dies which could be used to make a few thousand light metal (aluminum and magnesium) prototype parts. The difficulty encountered in this project was that the requirements for the die casting industry, both in size and material requirements, were considerably more stringent than those encountered in the plastics injection industry. Consequently our technique, within the allotted time and budget constraints, was not able to meet the requirements set forth by USAMP. The remainder of this report is organized into five sections. The first discusses the technique in some detail while the second discusses a successful application. The third section discusses issues with this process while the fourth specifically discusses the work done in this project. The last is a short summary and conclusion section.

  14. Dust survey following the final shutdown of TEXTOR: metal particles and fuel retention

    NASA Astrophysics Data System (ADS)

    Fortuna-Zaleśna, E.; Weckmann, A.; Grzonka, J.; Rubel, M.; Esser, H. G.; Freisinger, M.; Kreter, A.; Sergienko, G.; Ström, P.

    2016-02-01

    The work presents results of a broad TEXTOR dust survey in terms of its composition, structure, distribution and fuel content. The dust particles were collected after final shutdown of TEXTOR in December 2013. Fuel retention, as determined by thermal desorption, varied significantly, even by two orders of magnitude, dependent on the dust location in the machine. Dust structure was examined by means of scanning electron microscopy combined with energy-dispersive x-ray spectroscopy, focused ion beam and scanning transmission electron microscopy. Several categories of dust have been identified. Carbon-based stratified and granular deposits were dominating, but the emphasis in studies was on metal dust. They were found in the form of small particles, small spheres, flakes and splashes which formed ‘comet’-like structures, clearly indicating directional effects in the impact on surfaces of plasma-facing components. Nickel-rich alloys from the Inconel liner and iron-based ones from various diagnostic holders were the main components of metal-containing dust, but also molybdenum and tungsten debris were detected. Their origin is discussed.

  15. EFFECT OF TEMPERATURE ON THE SORPTION OF CHELATED RADIONUCLIDES.

    USGS Publications Warehouse

    Maest, Ann S.; Crerar, David A.; Dillon, Edward C.; Trehu, Stephen M.; Rountree, Tamara N.; ,

    1985-01-01

    Temperature effects in the near-field radioactive waste disposal environment can result in changes in the adsorptive capacity and character of the substrate and the chemistry of the reacting fluids. This work examines the effect of temperature on 1) the kinetics of radionuclide sorption onto clays from 25 degree -75 degree C and 2) the degradation and metal-binding ability of two organic complexing agents found in chelated radioactive wastes and natural groundwaters.

  16. Chelators for investigating zinc metalloneurochemistry.

    PubMed

    Radford, Robert J; Lippard, Stephen J

    2013-04-01

    The physiology and pathology of mobile zinc signaling has become an important topic in metalloneurochemistry. To study the action of mobile zinc effectively, specialized tools are required that probe the temporal and positional changes of zinc ions within live tissue and cells. In the present article we describe the design and implementation of selective zinc chelators as antagonists to interrogate the function of mobile zinc, with an emphasis on the pools of vesicular zinc in the terminals of hippocampal mossy fiber buttons.

  17. Experimental investigation on the mechanism of chelation-assisted, copper(II) acetate-accelerated azide-alkyne cycloaddition.

    PubMed

    Kuang, Gui-Chao; Guha, Pampa M; Brotherton, Wendy S; Simmons, J Tyler; Stankee, Lisa A; Nguyen, Brian T; Clark, Ronald J; Zhu, Lei

    2011-09-01

    A mechanistic model is formulated to account for the high reactivity of chelating azides (organic azides capable of chelation-assisted metal coordination at the alkylated azido nitrogen position) and copper(II) acetate (Cu(OAc)(2)) in copper(II)-mediated azide-alkyne cycloaddition (AAC) reactions. Fluorescence and (1)H NMR assays are developed for monitoring the reaction progress in two different solvents, methanol and acetonitrile. Solvent kinetic isotopic effect and premixing experiments give credence to the proposed different induction reactions for converting copper(II) to catalytic copper(I) species in methanol (methanol oxidation) and acetonitrile (alkyne oxidative homocoupling), respectively. The kinetic orders of individual components in a chelation-assisted, copper(II)-accelerated AAC reaction are determined in both methanol and acetonitrile. Key conclusions resulting from the kinetic studies include (1) the interaction between copper ion (either in +1 or +2 oxidation state) and a chelating azide occurs in a fast, pre-equilibrium step prior to the formation of the in-cycle copper(I)-acetylide, (2) alkyne deprotonation is involved in several kinetically significant steps, and (3) consistent with prior experimental and computational results by other groups, two copper centers are involved in the catalysis. The X-ray crystal structures of chelating azides with Cu(OAc)(2) suggest a mechanistic synergy between alkyne oxidative homocoupling and copper(II)-accelerated AAC reactions, in which both a bimetallic catalytic pathway and a base are involved. The different roles of the two copper centers (a Lewis acid to enhance the electrophilicity of the azido group and a two-electron reducing agent in oxidative metallacycle formation, respectively) in the proposed catalytic cycle suggest that a mixed valency (+2 and +1) dinuclear copper species be a highly efficient catalyst. This proposition is supported by the higher activity of the partially reduced Cu(OAc)(2) in

  18. Chelating agents and cadmium intoxication

    SciTech Connect

    Shinobu, L.A.

    1985-01-01

    A wide range of conventional chelating agents have been screened for (a) antidotal activity in acute cadmium poisoning and (b) ability to reduce aged liver and kidney deposits of cadmium. Chelating agents belonging to the dithiocarbamate class have been synthesized and tested in both the acute and chronic modes of cadmium intoxication. Several dithiocarbamates, not only provide antidotal rescue, but also substantially decrease the intracellular deposits of cadmium associated with chronic cadmium intoxication. Fractionating the cytosol from the livers and kidneys of control and treated animals by Sephadex G-25 gel filtration clearly demonstrates that the dithiocarbamates are reducing the level of metallothionein-bound cadmium. However, the results of cell culture (Ehrlich ascites) studies designed to investigate the removal of cadmium from metallothionein and subsequent transport of the resultant cadmium complex across the cell membrane were inconclusive. In other in vitro investigations, the interaction between isolated native Cd, Zn-metallothionein and several chelating agents was explored. Ultracentrifugation, equilibrium dialysis, and Sephadex G-25 gel filtration studies have been carried out in an attempt to determine the rate of removal of cadmium from metallothionein by these small molecules. Chemical shifts for the relevant cadmium-dithiocarbamate complexes have been determined using natural abundance Cd-NMR.

  19. X-ray line shapes of metals: Exact solutions of a final-state interaction model

    NASA Astrophysics Data System (ADS)

    Swarts, Coenraad A.; Dow, John D.

    2005-10-01

    By means of model calculations for an independent-electron metal, we obtain exact line shapes for the photon absorption, emission, and photoemission spectra of core states, including electronic relaxation. In all cases we find an x-ray edge anomaly. For the absorption and emission spectra this anomaly is superposed on a continuum resembling Elliott exciton theory. We display how the spectra evolve from the exciton limit to the free-electron limit as the final-state interaction strength is decreased or the Fermi energy increased. We compare the spectra obtained for different final-state interactions and find that different types of interactions produce different spectral shapes. Away from threshold the absorption and emission profiles show an enhancement of the free-electron result, as predicted by the screened-exciton theory. Our results offer potential explanations for (i) incompatibilities between threshold exponents and exponents extracted from other data, (ii) the occurrence of nearly symmetric x-ray photoemission lines, and (iii) the lack of mirror symmetry of absorption and emission edges.

  20. 78 FR 29322 - Silicon Metal From the People's Republic of China: Final Results and Final No Shipments...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-05-20

    ... Administrative Review; 2011- 2012, 78 FR 13321 (February 27, 2013) (``Preliminary Results''). DATES: Effective... People's Republic of China: Continuation of Antidumping Duty Order, 77 FR 23660 (April 20, 2012). Final... CBP based on our final results.\\4\\ \\3\\ See Preliminary Results, 78 FR at 13321. \\4\\ See...

  1. Potentiometric, spectroscopic, electrochemical and DFT characterization of oxovanadium(IV) complexes formed by citrate and tartrates in aqueous solution at high ligand to metal molar ratios: the effects of the trigonal bipyramidal distortion in bis-chelated species and biological implications.

    PubMed

    Lodyga-Chruscinska, Elzbieta; Sanna, Daniele; Garribba, Eugenio; Micera, Giovanni

    2008-09-28

    The complexation of VO(IV) ion with citrate (L3-), D-, L- and DL-tartrate (L2-) at high ligand to metal molar ratios was studied in aqueous solution through the combined application of potentiometric, spectroscopic (UV-vis and EPR) and electrochemical (cyclic voltammetry) techniques. Unlike in equimolar solution, mononuclear and not dinuclear species are formed with the binding of carboxylate-COO- and alcoholate-O- donors yielding mono- and bis-chelated species with VOLH, VOL, VOLH(-1) and VOL2H(-2) composition; for tartrates also the "sugar-like" (O-, O-) coordination is involved in the vanadium binding at basic pH values giving rise to the formation of VOL2H(-3) and VOL2H(-4) complexes. Among the species formed, VOL2H(-2) is characterised by a strong distortion towards the trigonal bipyramid with the two V-O(alcoholate) bonds in the equatorial and the two V-O(carboxylate) bonds in the axial positions. The geometry and electronic absorption spectra of such complexes were simulated by DFT methods and it was found that in aqueous solution the distortion follows the steric hindrance of the substituents on the alpha-carbon atom and the hydrophobicity of the ligands. The results were compared with those displayed by simple alpha-hydroxycarboxylates (glycolate, 2-hydroxyisobutyrate, 2-ethyl-2-hydroxybutyrate and benzilate). The trigonal bipyramidal distortion was correlated with the values of: i) Deltalambda = lambda2-lambda3, where lambda2 and lambda3 are the central bands in the electronic absorption spectrum; ii) |A(x)-A(y)|, where A(x) and A(y) are the 51V hyperfine coupling constants along the x and y axes in the anisotropic EPR spectrum; iii) the half-wave potential E(1/2) of oxidation of VO(IV) to the corresponding VO2(V) species in the cyclic voltammogram. Finally, a discussion on the possible form of VO(IV)-citrate complexes in blood serum is presented, where it is found that the most relevant species under physiological conditions should be [VO(citrH(-1))]2-.

  2. Desferrithiocin: A Search for Clinically Effective Iron Chelators

    PubMed Central

    2015-01-01

    The successful search for orally active iron chelators to treat transfusional iron-overload diseases, e.g., thalassemia, is overviewed. The critical role of iron in nature as a redox engine is first described, as well as how primitive life forms and humans manage the metal. The problems that derive when iron homeostasis in humans is disrupted and the mechanism of the ensuing damage, uncontrolled Fenton chemistry, are discussed. The solution to the problem, chelator-mediated iron removal, is clear. Design options for the assembly of ligands that sequester and decorporate iron are reviewed, along with the shortcomings of the currently available therapeutics. The rationale for choosing desferrithiocin, a natural product iron chelator (a siderophore), as a platform for structure–activity relationship studies in the search for an orally active iron chelator is thoroughly developed. The study provides an excellent example of how to systematically reengineer a pharmacophore in order to overcome toxicological problems while maintaining iron clearing efficacy and has led to three ligands being evaluated in human clinical trials. PMID:25207964

  3. High-temperature thermochemistry of transition metal borides, silicides and related compounds. Final report

    SciTech Connect

    Klemppa, Ole J.

    2000-10-01

    Earlier this year in collaboration with Dr. Susan V. Meschel we prepared a major review paper which gives a comprehensive summary of what our laboratory has accomplished with support from DOE. This paper is No.43 in the List of Publications provided. It was presented to TMS at its National Meeting in Nashville, TN last March. A copy of the manuscript of this paper was recently mailed to DOE. It has been submitted for publication in Journal of Alloys and Compounds. This review paper summarizes our observed trends in the enthalpies of formation of TR-X and RE-X compounds (where X is a IIIB or IVB element) in their dependence of the atomic number of the transition metal (TR) and the lanthanide metal (RE). In this paper our measured enthalpies of formation for each alloy family are compared for the 3d, 4d and 5d transition metal elements. We also compare our experimental results with predicted values based on Miedema's semi-empirical model. Data are presented for the carbides, silicides, germanides and stannides in Group IVB, and for the borides and aluminides in Group IIIB. During the past year (1999-2000) we have extended our work to compounds of the 3d, 4d and 5d elements with gallium (see papers No.40, No.41, and No.45 in the List of Publications). Fig. 1 (taken from No.45) presents a systematic picture of our experimental values for the most exothermic gallide compounds formed with the transition elements. This figure is characteristic of the other systematic pictures which we have found for the two other IIIB elements which we have studied and for the four IVB elements. These figures are all presented in Ref. No.43. This paper also illustrates how the enthalpy of formation of compounds of the IIIB and IVB elements with the lanthanide elements (with the exception of Pm, Eu and Yb) depend on the atomic number of RE. Finally our results for the RE-X compounds are compared with the predictions of Gschneidner (K.A. Gschneidner, Jr., J. Less Common Metals 17, 1

  4. Hydroxypyri(mi)dine-based chelators as antidotes of toxicity due to aluminum and actinides.

    PubMed

    Santos, M A; Esteves, M A; Chaves, S

    2012-01-01

    This review is focused on recent developments on hydroxypyri(mi)dines, as aluminum and actinide chelating agents to combat the toxicity due to accumulations of these metal ions in human body resulting from excessive metal exposure. After a brief update revision of the most common processes of aluminum (Al) exposure, as well as the associated toxicities and pathologies, we will focus on the current available Al chelators and future perspective as potential antidotes of Al toxicity. Due to the similarity between Al and Fe, a major emphasis is given to the hydroxypyridinone and hydroxypyrimidinone chelators, since they are analogues of the current iron chelators in clinical use (DFP and DFO). This review includes issues such as molecular design strategies and corresponding effects on the associated physico-chemical properties, lipo-hydrophilic balance, toxicity, in vivo bioassays and current clinical applications. The hydroxypyri(mi)dine chelators are also suitable for other hard metal ions, such as the radiotoxic actinides, and so a brief review is included on the applications of these chelators in actinides scavenging.

  5. Isomerism in benzyl-DOTA derived bifunctional chelators: implications for molecular imaging.

    PubMed

    Payne, Katherine M; Woods, Mark

    2015-02-18

    The bifunctional chelator IB-DOTA has found use in a range of biomedical applications given its ability to chelate many metal ions, but in particular the lanthanide(III) ions. Gd(3+) in particular is of interest in the development of new molecular imaging agents for MRI and is highly suitable for chelation by IB-DOTA. Given the long-term instability of the aryl isothiocyanate functional group we have used the more stable nitro derivative (NB-DOTA) to conduct a follow-up study of some of our previous work on the coordination chemistry of chelates of these BFCs. Using a combination of NMR and HPLC to study the Eu(3+) and Yb(3+) chelates of NB-DOTA, we have demonstrated that this ligand will produce two discrete regioisomeric chelates at the point at which the metal ion is introduced into the BFC. These regioisomers are defined by the position of the benzylic substituent on the macrocyclic ring: adopting an equatorial position either at the corner or the side of the [3333] ring conformation. These regioisomers are incapable of interconversion and are distinct, separate structures with different SAP/TSAP ratios. The side isomer exhibits an increased population of the TSAP isomer, pointing to more rapid water exchange kinetics in this regioisomer. This has potential ramifications for the use of these two regioisomers of Gd(3+)-BFC chelates in MRI applications. We have also found that, remarkably, there is little or no freedom of rotation about the first single bond extending from the macrocyclic ring to the benzylic substituent. Since this is the linkage through which the chelate is conjugated to the remainder of the molecular imaging probe, this result implies that there may be reduced local rotation of the Gd(3+) chelate within a molecular imaging probe. This implies that this type of BFC could exhibit higher relaxivities than other types of BFC.

  6. Chelating ionic liquids for reversible zinc electrochemistry.

    PubMed

    Kar, Mega; Winther-Jensen, Bjorn; Forsyth, Maria; MacFarlane, Douglas R

    2013-05-21

    Advanced, high energy-density, metal-air rechargeable batteries, such as zinc-air, are of intense international interest due to their important role in energy storage applications such as electric and hybrid vehicles, and to their ability to deal with the intermittency of renewable energy sources such as solar and wind. Ionic liquids offer a number of ideal thermal and physical properties as potential electrolytes in such large-scale energy storage applications. We describe here the synthesis and characterisation of a family of novel "chelating" ILs designed to chelate and solubilize the zinc ions to create electrolytes for this type of battery. These are based on quaternary alkoxy alkyl ammonium cations of varying oligo-ether side chains and anions such as p-toluene sulfonate, bis(trifluoromethylsulfonyl)amide and dicyanoamides. This work shows that increasing the ether chain length in the cation from two to four oxygens can increase the ionic conductivity and reduce the melting point from 67 °C to 15 °C for the tosylate system. Changing the anion also plays a significant role in the nature of the zinc deposition electrochemistry. We show that zinc can be reversibly deposited from [N(222(20201))][NTf2] and [N(222(202020201))][NTf2] beginning at -1.4 V and -1.7 V vs. SHE, respectively, but not in the case of tosylate based ILs. This indicates that the [NTf2] is a weaker coordinating anion with the zinc cation, compared to the tosylate anion, allowing the coordination of the ether chain to dominate the behavior of the deposition and stripping of zinc ions. PMID:23558696

  7. Structure-Reactivity Relationships in Multi-Component Transition Metal Oxide Catalysts FINAL Report

    SciTech Connect

    Altman, Eric I.

    2015-10-06

    The focus of the project was on developing an atomic-level understanding of how transition metal oxide catalysts function. Over the course of several renewals the specific emphases shifted from understanding how local structure and oxidation state affect how molecules adsorb and react on the surfaces of binary oxide crystals to more complex systems where interactions between different transition metal oxide cations in an oxide catalyst can affect reactivity, and finally to the impact of cluster size on oxide stability and reactivity. Hallmarks of the work were the use of epitaxial growth methods to create surfaces relevant to catalysis yet tractable for fundamental surface science approaches, and the use of scanning tunneling microscopy to follow structural changes induced by reactions and to pinpoint adsorption sites. Key early findings included the identification of oxidation and reduction mechanisms on a tungsten oxide catalyst surface that determine the sites available for reaction, identification of C-O bond cleavage as the rate limiting step in alcohol dehydration reactions on the tungsten oxide surface, and demonstration that reduction does not change the favored reaction pathway but rather eases C-O bond cleavage and thus reduces the reaction barrier. Subsequently, a new reconstruction on the anatase phase of TiO2 relevant to catalysis was discovered and shown to create sites with distinct reactivity compared to other TiO2 surfaces. Building on this work on anatase, the mechanism by which TiO2 enhances the reactivity of vanadium oxide layers was characterized and it was found that the TiO2 substrate can force thin vanadia layers to adopt structures they would not ordinarily form in the bulk which in turn creates differences in reactivity between supported layers and bulk samples. From there, the work progressed to studying well-defined ternary oxides where synergistic effects between the two cations can induce

  8. Suppression of electron emission from metal electrodes : LDRD 28771 final report.

    SciTech Connect

    Stygar, William A.; Savage, Mark Edward; Ives, Harry Crockett, III; Johnson, David J.; Fowler, William E.

    2003-11-01

    This research consisted of testing surface treatment processes for stainless steel and aluminum for the purpose of suppressing electron emission over large surface areas to improve the pulsed high voltage hold-off capabilities of these metals. Improvements to hold-off would be beneficial to the operation of the vacuum-insulator grading rings and final self-magnetically insulated transmission line on the ZR-upgrade machine and other pulsed power applications such as flash radiograph and pulsed-microwave machines. The treatments tested for stainless steel include the Z-protocol (chemical polish, HVFF, and gold coating), pulsed E-beam surface treatments by IHCE, Russia, and chromium oxide coatings. Treatments for aluminum were anodized and polymer coatings. Breakdown thresholds also were measured for a range of surface finishes and gap distances. The study found that: (1.) Electrical conditioning and solvent cleaning in a filtered air environment each improve HV hold-off 30%. (2.) Anodized coatings on aluminum give a factor of two improvement in high voltage hold-off. However, anodized aluminum loses this improvement when the damage is severe. Chromium oxide coatings on stainless steel give a 40% and 20% improvement in hold-off before and after damage from many arcs. (3.) Bare aluminum gives similar hold-off for surface roughness, R{sub a}, ranging from 0.08 to 3.2 {micro}m. (4.) The various EBEST surfaces tested give high voltage hold-off a factor of two better than typical machined and similar to R{sub a} = 0.05 {micro}m polished stainless steel surfaces. (5.) For gaps > 2 mm the hold-off voltage increases as the square root of the gap for bare metal surfaces. This is inconsistent with the accepted model for metals that involves E-field induced electron emission from dielectric inclusions. Micro-particles accelerated across the gap during the voltage pulse give the observed voltage dependence. However the similarity in observed breakdown times for large and small

  9. FY07 LDRD Final Report Synthesis under High Pressure and Temperature of New Metal Nitrides

    SciTech Connect

    Crowhurst, J C; Sadigh, B; Aberg, D; Zaug, J M; Goncharov, A F

    2008-09-23

    The original aim of this LDRD was to determine with unprecedented precision the melting curve of iron to geophysically relevant pressures. In the course of developing much of the technology and techniques required to obtain this information we have encountered and studied novel chemical reactions some of whose products are stable or metastable under ambient conditions. Specifically we have synthesized nitrides of the platinum group metals including platinum, iridium, and palladium. We have also carried out in depth first principles theoretical investigations into the nature of these materials. We believed that the scientific impact of continuing this work would be greater than that of the original goals of this project. Indeed the work has led to a number of high profile publications with additional publications in preparation. While nitrides of the transition metals are generally of tremendous technological importance, those of the noble metals in particular have enjoyed much experimental and theoretical attention in the very short time since they were first synthesized. The field was and clearly remains open for further study. While the scientific motivation for this research is different from that originally proposed, many of the associated methods in which we have now gained experience are similar or identical. These include use of the diamond anvil cell combined with technologies to generate high temperatures, the in-situ technique of Raman scattering using our purpose-built, state-of-the-art system, analytical techniques for determining the composition of recovered samples such as x-ray photoelectron spectroscopy, and finally synchrotron-based techniques such as x-ray diffraction for structural and equation of state determinations. Close interactions between theorists and experimentalists has and will continue to allow our group to rapidly and reliably interpret complicated results on the structure and dynamics of these compounds and also additional novel

  10. Effectiveness of chelation therapy with time after acute uranium intoxication

    SciTech Connect

    Domingo, J.L.; Ortega, A.; Llobet, J.M.; Corbella, J. )

    1990-01-01

    The effect of increasing the time interval between acute uranium exposure and chelation therapy was studied in male Swiss mice. Gallic acid, 4,5-dihydroxy-1,3- benzenedisulfonic acid (Tiron), diethylenetriaminepentaacetic acid (DTPA), and 5-aminosalicylic acid (5-AS) were administered ip at 0, 0.25, 1, 4, and 24 hr after sc injection of 10 mg/kg of uranyl acetate dihydrate. Chelating agents were given at doses equal to one-fourth of their respective LD50 values. Daily elimination of uranium into urine and feces was determined for 4 days after which time the mice were killed, and the concentration of uranium was measured in kidney, spleen, and bone. The excretion of uranium was especially rapid in the first 24 hr. Treatment with Tiron or gallic acid at 0, 0.25, or 1 hr after uranium exposure significantly increased the total excretion of the metal. In kidney and bone, only administration of Tiron at 0, 0.25, or 1 hr after uranium injection, or gallic acid at 1 hr after uranium exposure significantly reduced tissue uranium concentrations. Treatment at later times (4 to 24 hr) did not increase the total excretion of the metal and did not decrease the tissue uranium concentrations 4 days after uranyl acetate administration. The results show that the length of time before initiating chelation therapy for acute uranium intoxication greatly influences the effectiveness of this therapy.

  11. Generation, Fractionation, and Characterization of Iron-Chelating Protein Hydrolysate from Palm Kernel Cake Proteins.

    PubMed

    Zarei, Mohammad; Ghanbari, Rahele; Tajabadi, Naser; Abdul-Hamid, Azizah; Bakar, Fatimah Abu; Saari, Nazamid

    2016-02-01

    Palm kernel cake protein was hydrolyzed with different proteases namely papain, bromelain, subtilisin, flavourzyme, trypsin, chymotrypsin, and pepsin to generate different protein hydrolysates. Peptide content and iron-chelating activity of each hydrolysate were evaluated using O-phthaldialdehyde-based spectrophotometric method and ferrozine-based colorimetric assay, respectively. The results revealed a positive correlation between peptide contents and iron-chelating activities of the protein hydrolysates. Protein hydrolysate generated by papain exhibited the highest peptide content of 10.5 mM and highest iron-chelating activity of 64.8% compared with the other hydrolysates. Profiling of the papain-generated hydrolysate by reverse phase high performance liquid chromatography fractionation indicated a direct association between peptide content and iron-chelating activity in most of the fractions. Further fractionation using isoelectric focusing also revealed that protein hydrolysate with basic and neutral isoelectric point (pI) had the highest iron-chelating activity, although a few fractions in the acidic range also exhibited good metal chelating potential. After identification and synthesis of papain-generated peptides, GGIF and YLLLK showed among the highest iron-chelating activities of 56% and 53%, whereas their IC50 were 1.4 and 0.2 μM, respectively.

  12. Determination of trace metal ions via on-line separation and preconcentration by means of chelating Sepharose beads in a sequential injection lab-on-valve (SI-LOV) system coupled to electrothermal atomic absorption spectrometric detection.

    PubMed

    Long, Xiangbao; Hansen, Elo Harald; Miró, Manuel

    2005-06-15

    The analytical performance of an on-line sequential injection lab-on-valve (SI-LOV) system using chelating Sepharose beads as sorbent material for the determination of ultra-trace levels of Cd(II), Pb(II) and Ni(II) by electrothermal atomic absorption spectrometry (ETAAS) is described and discussed. The samples are adjusted to pH 5.0 on-line in the system for optimum operation. The target ions are adsorbed by chelation on the surface of the beads, contained in a 20mul microcolumn within the LOV, and following elution by 50mul 2M nitric acid, the eluate is, as sandwiched by air segments, introduced into the ETAAS. Based on the consumption of 1.8ml sample solution, retention efficiencies of 95, 75 and 90%, enrichment factors of 34, 27 and 32, and determination limits of 0.001, 0.07 and 0.02mugl(-1) were obtained for Cd(II), Pb(II) and Ni(II), respectively. The beads can be used repeatedly for at least 20 times without decrease of performance, yet can be replaced at will if the circumstances should so dictate. The optimized procedural parameters showed that 12 samples per hour could be prepared and successfully analyzed. The results obtained for three standard reference materials agreed very well with the certified values.

  13. Chelation technology: a promising green approach for resource management and waste minimization.

    PubMed

    Chauhan, Garima; Pant, K K; Nigam, K D P

    2015-01-01

    Green chemical engineering recognises the concept of developing innovative environmentally benign technologies to protect human health and ecosystems. In order to explore this concept for minimizing industrial waste and for reducing the environmental impact of hazardous chemicals, new greener approaches need to be adopted for the extraction of heavy metals from industrial waste. In this review, a range of conventional processes and new green approaches employed for metal extraction are discussed in brief. Chelation technology, a modern research trend, has shown its potential to develop sustainable technology for metal extraction from various metal-contaminated sites. However, the interaction mechanism of ligands with metals and the ecotoxicological risk associated with the increased bioavailability of heavy metals due to the formation of metal-chelant complexes is still not sufficiently explicated in the literature. Therefore, a need was felt to provide a comprehensive state-of-the-art review of all aspects associated with chelation technology to promote this process as a green chemical engineering approach. This article elucidates the mechanism and thermodynamics associated with metal-ligand complexation in order to have a better understanding of the metal extraction process. The effects of various process parameters on the formation and stability of complexes have been elaborately discussed with respect to optimizing the chelation efficiency. The non-biodegradable attribute of ligands is another important aspect which is currently of concern. Therefore, biotechnological approaches and computational tools have been assessed in this review to illustrate the possibility of ligand degradation, which will help the readers to look for new environmentally safe mobilizing agents. In addition, emerging trends and opportunities in the field of chelation technology have been summarized and the diverse applicability of chelation technology in metal extraction from

  14. Acute prooxidant effects of vitamin C in EDTA chelation therapy and long-term antioxidant benefits of therapy.

    PubMed

    Hininger, Isabelle; Waters, Robert; Osman, Mireille; Garrel, Catherine; Fernholz, Karen; Roussel, Anne Marie; Anderson, Richard A

    2005-06-15

    Chelation therapy is thought to not only remove contaminating metals but also to decrease free radical production. EDTA chelation therapy, containing high doses of vitamin C as an antioxidant, is often used in the treatment of diseases such as diabetes and cardiovascular diseases but the effectiveness of this treatment may be variable and its efficacy has not been demonstrated conclusively. The objective of this work was to determine if the vitamin C added to standard chelation therapy cocktails was prooxidant. We administered a standard EDTA cocktail solution with or without 5 g of sodium ascorbate. One hour following the standard chelation therapy, there were highly significant prooxidant effects on lipids, proteins, and DNA associated with decreased activities of RBC glutathione peroxidase and superoxide dismutase while in the absence of sodium ascorbate, there were no acute signs of oxidative damage. After 16 sessions of standard chelation therapy, the acute prooxidant effects of vitamin C remained, but, even in the absence of nutrient supplements, there were beneficial long-term antioxidant effects of chelation therapy and plasma peroxide levels decreased. In conclusion, multiple sessions of EDTA chelation therapy protect lipids against oxidative damage. However, standard high amounts of vitamin C added to EDTA chelation solutions also display short term prooxidant effects. The added benefits of lower levels of vitamin C in chelation therapy need to be documented.

  15. A pro-chelator triggered by hydrogen peroxide inhibits iron-promoted hydroxyl radical formation.

    PubMed

    Charkoudian, Louise K; Pham, David M; Franz, Katherine J

    2006-09-27

    The synthesis and structural characterization of a new pro-chelating agent, isonicotinic acid [2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzylidene]-hydrazide (BSIH), are presented. BSIH only weakly interacts with iron unless hydrogen peroxide (H2O2) is present to remove the boronic ester protecting group to reveal a phenol that is a key metal-binding group of tridentate salicylaldehyde isonicotinoyl hydrazone (SIH). BSIH prevents deoxyribose degradation caused by hydroxyl radicals that are generated from H2O2 and redox-active iron by sequestering Fe3+ and preventing iron-promoted hydroxyl radical formation. The rate-determining step for iron sequestration is conversion of BSIH to SIH, followed by rapid Fe3+ complexation. The pro-chelate approach of BSIH represents a promising strategy for chelating a specific pool of detrimental metal ions without disturbing healthy metal ion distribution.

  16. A pro-chelator triggered by hydrogen peroxide inhibits iron-promoted hydroxyl radical formation.

    PubMed

    Charkoudian, Louise K; Pham, David M; Franz, Katherine J

    2006-09-27

    The synthesis and structural characterization of a new pro-chelating agent, isonicotinic acid [2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzylidene]-hydrazide (BSIH), are presented. BSIH only weakly interacts with iron unless hydrogen peroxide (H2O2) is present to remove the boronic ester protecting group to reveal a phenol that is a key metal-binding group of tridentate salicylaldehyde isonicotinoyl hydrazone (SIH). BSIH prevents deoxyribose degradation caused by hydroxyl radicals that are generated from H2O2 and redox-active iron by sequestering Fe3+ and preventing iron-promoted hydroxyl radical formation. The rate-determining step for iron sequestration is conversion of BSIH to SIH, followed by rapid Fe3+ complexation. The pro-chelate approach of BSIH represents a promising strategy for chelating a specific pool of detrimental metal ions without disturbing healthy metal ion distribution. PMID:16984186

  17. Is lead chelation therapy effective for chronic kidney disease? A meta-analysis.

    PubMed

    Yang, Shi-Kun; Xiao, Li; Song, Pan-Ai; Xu, Xiao-Xuan; Liu, Fu-You; Sun, Lin

    2014-01-01

    The heavy metal lead (Pb) is a major environmental and occupational hazard. Epidemiological studies have demonstrated a strong association between lead exposure and the presence of chronic kidney injury. Some studies have suggested that chelation therapy with calcium disodium ethylenediaminetetraacetic acid (calcium disodium EDTA) might help decrease the progression of chronic kidney disease among patients with measurable body lead burdens. However, calcium disodium EDTA chelation in lead exposure is controversial due to the potential for adverse effects such as acute tubular necrosis. Therefore, we investigated the available randomized controlled trials assessing the renoprotective effects of calcium disodium EDTA chelation therapy. Our meta-analysis shows that calcium disodium EDTA chelation therapy can effectively delay the progression of chronic kidney disease in patients with measurable body lead burdens reflected by increasing the levels of estimated glomerular filtration rate (eGFR) and creatinine clearance rate (Ccr). There appears to be no conclusive evidence that calcium disodium EDTA can decrease proteinuria.

  18. EDTA chelation therapy, without added vitamin C, decreases oxidative DNA damage and lipid peroxidation.

    PubMed

    Roussel, Anne Marie; Hininger-Favier, Isabelle; Waters, Robert S; Osman, Mireille; Fernholz, Karen; Anderson, Richard A

    2009-03-01

    Chelation therapy is thought to not only remove contaminating metals but also to decrease free radical production. However, in standard ethylene diamine tetracetic acid (EDTA) chelation therapy, high doses of vitamin C with potential pro-oxidant effects are often added to the chelation solution. The authors demonstrated previously that the intravenous administration of the standard chelation cocktail, containing high amounts of vitamin C, resulted in an acute transitory pro-oxidant burst that should be avoided in the treatment of pathologies at risk of increased oxidative stress such as diabetes and cardiovascular disease. The current study was designed to determine the acute and chronic biochemical effects of chelation therapy on accepted clinical, antioxidant variables. An EDTA chelation cocktail not containing ascorbic acid was administered to six adult patients for five weeks (10 sessions of chelation therapy); antioxidant indicators were monitored. Immediately after the initial chelation session, in contrast with the data previously reported with the standard cocktail containing high doses of vitamin C, none of the oxidative stress markers were adversely modified. After five weeks, plasma peroxide levels, monitored by malondialdehyde, decreased by 20 percent, and DNA damage, monitored by formamidopyrimidine-DNA glycosylase (Fpg) sensitive sites, decreased by 22 percent. Remaining antioxidant-related variables did not change. In summary, this study demonstrates that multiple sessions of EDTA chelation therapy in combination with vitamins and minerals, but without added ascorbic acid, decreases oxidative stress. These results should be beneficial in the treatment of diseases associated with increased oxidative stress such as diabetes and cardiovascular diseases.

  19. Alteration of tissue disposition of cadmium by chelating agents. [Mice; rats

    SciTech Connect

    Klaassen, C.D.; Waalkes, M.P.; Cantilena, L.R. Jr.

    1984-03-01

    The effect of several chelating agents (diethyldithiocarbamic acid, DDC; nitrilotriacetic acid, NTA; 2,3-dimercaptopropanol, BAL; d,l-penicillamine, PEN; 2,3-dimercaptosuccinic acid, DMSA; ethylenediaminetetraacetic acid, EDTA; and diethylenetriaminepentaacetic acid, DTPA) on the toxicity, distribution and excretion of cadmium (Cd) was determined in mice. When chelators were administered immediately after Cd, significant increases in survival were noted after treatment with DMSA, EDTA, and DTPA. DTPA, followed by EDTA and then DMSA, were consistently the most effective in decreasing the tissue concentrations of Cd and increasing the excretion of Cd. NTA, BAL, DDC and PEN had no beneficial effects. To determine the role of MT in the acute decrease in chelator efficacy following Cd poisoning, rats were injected IV with Cd followed by DTPA at various times after Cd. Although DTPA reduced Cd content in the various organs when given immediately after Cd, the chelator was ineffective at all later times. Increases in hepatic and renal metallothionein (MT) did not occur until 2 hr after Cd, and did not coincide with the earlier drop in chelator efficacy. Blockade of MT synthesis by actinomycin D failed to eliminate this decreased DTPA effectiveness. Therefore, it appears that MT does not play an important role in the acute decrease in efficacy of chelation therapy for Cd poisoning. The effect of repeated daily administration of chelators on the distribution and excretion of Cd was studied by administering chelators daily for 5 days starting 48 hr after Cd. DTPA, EDTA, DMSA and BAL significantly increased the urinary elimination of Cd. Thus, mobilization of Cd into urine occurs with repeated chelation therapy, which may decrease tissue concentrations of Cd and reduce the toxicity of the metal. 4 references, 15 figures, 2 tables.

  20. Composite metal-hydrogen electrodes for metal-hydrogen batteries. Final report, October 1, 1993--April 15, 1997

    SciTech Connect

    Ruckman, M.W.; Strongin, M.; Weismann, H.

    1997-04-01

    The purpose of this project is to develop and conduct a feasibility study of metallic thin films (multilayered and alloy composition) produced by advanced sputtering techniques for use as anodes in Ni-metal hydrogen batteries that would be deposited as distinct anode, electrolyte and cathode layers in thin film devices. The materials could also be incorporated in secondary consumer batteries (i.e. type AF(4/3 or 4/5)) which use electrodes in the form of tapes. The project was based on pioneering studies of hydrogen uptake by ultra-thin Pd-capped Nb films, these studies suggested that materials with metal-hydrogen ratios exceeding those of commercially available metal hydride materials and fast hydrogen charging and discharging kinetics could be produced. The project initially concentrated on gas phase and electrochemical studies of Pd-capped niobium films in laboratory-scale NiMH cells. This extended the pioneering work to the wet electrochemical environment of NiMH batteries and exploited advanced synchrotron radiation techniques not available during the earlier work to conduct in-situ studies of such materials during hydrogen charging and discharging. Although batteries with fast charging kinetics and hydrogen-metal ratios approaching unity could be fabricated, it was found that oxidation, cracking and corrosion in aqueous solutions made pure Nb films and multilayers poor candidates for battery application. The project emphasis shifted to alloy films based on known elemental materials used for NiMH batteries. Although commercial NiMH anode materials contain many metals, it was found that 0.24 {mu}m thick sputtered Zr-Ni films cycled at least 50 times with charging efficiencies exceeding 95% and [H]/[M] ratios of 0.7-1.0. Multilayered or thicker Zr-Ni films could be candidates for a thin film NiMH battery that may have practical applications as an integrated power source for modern electronic devices.

  1. Iron Chelation Therapy in Myelodysplastic Syndromes

    PubMed Central

    Messa, Emanuela; Cilloni, Daniela; Saglio, Giuseppe

    2010-01-01

    Myelodysplastic syndromes (MDS) are a heterogeneous disorder of the hematopoietic stem cells, frequently characterized by anemia and transfusion dependency. In low-risk patients, transfusion dependency can be long lasting, leading to iron overload. Iron chelation therapy may be a therapeutic option for these patients, especially since the approval of oral iron chelators, which are easier to use and better accepted by the patients. The usefulness of iron chelation in MDS patients is still under debate, mainly because of the lack of solid prospective clinical trials that should take place in the future. This review aims to summarize what is currently known about the incidence and clinical consequences of iron overload in MDS patients and the state-of the-art of iron chelation therapy in this setting. We also give an overview of clinical guidelines for chelation in MDS published to date and some perspectives for the future. PMID:20672005

  2. Characterization of the effect of serum and chelating agents on Staphylococcus aureus biofilm formation; chelating agents augment biofilm formation through clumping factor B

    NASA Astrophysics Data System (ADS)

    Abraham, Nabil Mathew

    Staphylococcus aureus is the causative agent of a diverse array of acute and chronic infections, and some these infections, including infective endocarditis, joint infections, and medical device-associated bloodstream infections, depend upon its capacity to form tenacious biofilms on surfaces. Inserted medical devices such as intravenous catheters, pacemakers, and artificial heart valves save lives, but unfortunately, they can also serve as a substrate on which S. aureus can form a biofilm, attributing S. aureus as a leading cause of medical device-related infections. The major aim of this work was take compounds to which S. aureus would be exposed during infection and to investigate their effects on its capacity to form a biofilm. More specifically, the project investigated the effects of serum, and thereafter of catheter lock solutions on biofilm formation by S. aureus. Pre-coating polystyrene with serum is frequently used as a method to augment biofilm formation. The effect of pre-coating with serum is due to the deposition of extracellular matrix components onto the polystyrene, which are then recognized by MSCRAMMs. We therefore hypothesized that the major component of blood, serum, would induce biofilm formation. Surprisingly, serum actually inhibited biofilm formation. The inhibitory activity was due to a small molecular weight, heat-stable, non-proteinaceous component/s of serum. Serum-mediated inhibition of biofilm formation may represent a previously uncharacterized aspect of host innate immunity that targets the expression of a key bacterial virulence factor: the ability to establish a resistant biofilm. Metal ion chelators like sodium citrate are frequently chosen to lock intravenous catheters because they are regarded as potent inhibitors of bacterial biofilm formation and viability. We found that, while chelating compounds abolished biofilm formation in most strains of S. aureus, they actually augmented the phenotype in a subset of strains. We

  3. Chelating ligands for nanocrystals' surface functionalization.

    PubMed

    Querner, Claudia; Reiss, Peter; Bleuse, Joël; Pron, Adam

    2004-09-22

    A new family of ligands for the surface functionalization of CdSe nanocrystals is proposed, namely alkyl or aryl derivatives of carbodithioic acids (R-C(S)SH). The main advantages of these new ligands are as follows: they nearly quantitatively exchange the initial surface ligands (TOPO) in very mild conditions; they significantly improve the resistance of nanocrystals against photooxidation because of their ability of strong chelate-type binding to metal atoms; their relatively simple preparation via Grignard intermediates facilitates the development of new bifunctional ligands containing, in addition to the anchoring carbodithioate group, a second function, which enables the grafting of molecules or macromolecules of interest on the nanocrystal surface. To give an example of this approach, we report, for the first time, the grafting of an electroactive oligomer from the polyaniline family-aniline tetramer-on CdSe nanocrystals after their functionalization with 4-formyldithiobenzoic acid. The grafting proceeds via a condensation reaction between the aldehyde group of the ligand and the terminal primary amine group of the tetramer. The resulting organic/inorganic hybrid exhibits complete extinction of the fluorescence of its constituents, indicating efficient charge or energy transfer between the organic and the inorganic semiconductors.

  4. Development of metal-coated ceramic anodes for molten carbonate fuel cells. Final report

    SciTech Connect

    Khandkar, A.C.; Elangovan, S.; Marianowski, L.G.

    1990-03-01

    This report documents the developmental efforts on metal coating of various ceramic substrates (LiAlO{sub 2}, SrTiO{sub 3}, and LiFeO{sub 2}) and the critical issues associated with fabricating anodes using metal-coated LiAlO{sub 2} substrates. Electroless Ni and Cu coating technology was developed to achieve complete metal coverage on LiAlO{sub 2} powder substrates. Metal coated SrTiO{sub 3} powders were fabricated into anodes by a process identical to that reported in the GE literature. Microstructural examination revealed that the grains of the ceramic had fused together, with the metal having dewetted from the surface of the ceramic. Alternate substrates that might allow for better wetting of the metal on the ceramic such as LiFeO{sub 2} and Li{sub 2}MnO{sub 3} were identified. Cu/Ni-coated (50:50 mol ratio, 50 w/o metal loading) LiFeO{sub 2} anodes were optimized to meet the MCFC anode specifications. Metal-coated gamma-LiAlO{sub 2} substrates were also developed. By using suitable chemical surface modification methods, the gamma-UAlO{sub 2} substrate surface may be modified to allow a stable metal coated anode to be fabricated. Creep testing of the metal coated ceramic anodes were conducted at IGT. It was determined that the predominant creep mechanism is due to particle rearrangement. The anode porosity, and mean pore size had significant effect on the creep of the anode. Lower porosity and pore size consistent with performance criteria are desired to reduce creep. Lower metal loading with uniformity of coverage will result in lower creep behavior of the anode. Of the two substrates evaluated, LiFeO{sub 2} in general exhibited lower creep which was attributed to superior metal adhesion.

  5. Antimicrobial action of chelating agents: repercussions on the microorganism development, virulence and pathogenesis.

    PubMed

    Santos, A L S; Sodre, C L; Valle, R S; Silva, B A; Abi-Chacra, E A; Silva, L V; Souza-Goncalves, A L; Sangenito, L S; Goncalves, D S; Souza, L O P; Palmeira, V F; d'Avila-Levy, C M; Kneipp, L F; Kellett, A; McCann, M; Branquinha, M H

    2012-01-01

    Infections caused by resistant microorganisms often fail to respond to conventional therapy, resulting in prolonged illness, increased treatment costs and greater risk of death. Consequently, the development of novel antimicrobial drugs is becoming more demanding every day since the existing drugs either have too many side-effects or they tend to lose effectiveness due to the selection of resistant strains. In view of these facts, a number of new strategies to obstruct vital biological processes of a microbial cell have emerged; one of these is focused on the use of metal-chelating agents, which are able to selectively disturb the essential metal metabolism of the microorganism by interfering with metal acquisition and bioavailability for crucial reactions. The chelation activity is able to inhibit the biological role of metal-dependent proteins (e.g., metalloproteases and transcription factors), disturbing the microbial cell homeostasis and culminating in the blockage of microbial nutrition, growth and development, cellular differentiation, adhesion to biotic (e.g., extracellular matrix components, cell and/or tissue) and abiotic (e.g., plastic, silicone and acrylic) structures as well as controlling the in vivo infection progression. Interestingly, chelating agents also potentiate the activity of classical antimicrobial compounds. The differences between the microorganism and host in terms of the behavior displayed in the presence of chelating agents could provide exploitable targets for the development of an effective chemotherapy for these diseases. Consequently, metal chelators represent a novel group of antimicrobial agents with potential therapeutic applications. This review will focus on the anti-fungal and anti-protozoan action of the most common chelating agents, deciphering and discussing their mode of action.

  6. Elucidating Interactions between DMSO and Chelate-Based Ionic Liquids.

    PubMed

    Chen, Hang; Wang, Xinyu; Yao, Jia; Chen, Kexian; Guo, Yan; Zhang, Pengfei; Li, Haoran

    2015-12-21

    The C-D bond stretching vibrations of deuterated dimethyl sulfoxide ([D6 ]DMSO) and the C2 -H bond stretching vibrations of 1,1,1,5,5,5-hexafluoropentane-2,4-dione (hfac) ligand in anion are chosen as probes to elucidate the solvent-solute interaction between chelate-based ionic liquids (ILs) and DMSO by vibrational spectroscopic studies. The indirect effect from the interaction of the adjacent S=O functional group of DMSO with the cation [C10 mim](+) and anion [Mn(hfac)3 ](-) of the ILs leads to the blue-shift of the C-D stretching vibrations of DMSO. The C2 -H bond stretching vibrations in hfac ligand is closely related to the ionic hydrogen bond strength between the cation and anion of chelate-based ILs. EPR studies reveal that the crystal field of the central metal is kept when the chelate-based ILs are in different microstructure environment in the solution.

  7. The evaluation of the use of metal alloy fuels in pressurized water reactors. Final report

    SciTech Connect

    Lancaster, D.

    1992-10-26

    The use of metal alloy fuels in a PWR was investigated. It was found that it would be feasible and competitive to design PWRs with metal alloy fuels but that there seemed to be no significant benefits. The new technology would carry with it added economic uncertainty and since no large benefits were found it was determined that metal alloy fuels are not recommended. Initially, a benefit was found for metal alloy fuels but when the oxide core was equally optimized the benefit faded. On review of the optimization of the current generation of ``advanced reactors,`` it became clear that reactor design optimization has been under emphasized. Current ``advanced reactors`` are severely constrained. The AP-600 required the use of a fuel design from the 1970`s. In order to find the best metal alloy fuel design, core optimization became a central effort. This work is ongoing.

  8. Targeting Chelatable Iron as a Therapeutic Modality in Parkinson's Disease

    PubMed Central

    Moreau, Caroline; Devedjian, Jean Christophe; Kluza, Jérome; Petrault, Maud; Laloux, Charlotte; Jonneaux, Aurélie; Ryckewaert, Gilles; Garçon, Guillaume; Rouaix, Nathalie; Duhamel, Alain; Jissendi, Patrice; Dujardin, Kathy; Auger, Florent; Ravasi, Laura; Hopes, Lucie; Grolez, Guillaume; Firdaus, Wance; Sablonnière, Bernard; Strubi-Vuillaume, Isabelle; Zahr, Noel; Destée, Alain; Corvol, Jean-Christophe; Pöltl, Dominik; Leist, Marcel; Rose, Christian; Defebvre, Luc; Marchetti, Philippe; Cabantchik, Z. Ioav; Bordet, Régis

    2014-01-01

    Abstract Aims: The pathophysiological role of iron in Parkinson's disease (PD) was assessed by a chelation strategy aimed at reducing oxidative damage associated with regional iron deposition without affecting circulating metals. Translational cell and animal models provided concept proofs and a delayed-start (DS) treatment paradigm, the basis for preliminary clinical assessments. Results: For translational studies, we assessed the effect of oxidative insults in mice systemically prechelated with deferiprone (DFP) by following motor functions, striatal dopamine (HPLC and MRI-PET), and brain iron deposition (relaxation-R2*-MRI) aided by spectroscopic measurements of neuronal labile iron (with fluorescence-sensitive iron sensors) and oxidative damage by markers of protein, lipid, and DNA modification. DFP significantly reduced labile iron and biological damage in oxidation-stressed cells and animals, improving motor functions while raising striatal dopamine. For a pilot, double-blind, placebo-controlled randomized clinical trial, early-stage Parkinson's patients on stabilized dopamine regimens enrolled in a 12-month single-center study with DFP (30 mg/kg/day). Based on a 6-month DS paradigm, early-start patients (n=19) compared to DS patients (n=18) (37/40 completed) responded significantly earlier and sustainably to treatment in both substantia nigra iron deposits (R2* MRI) and Unified Parkinson's Disease Rating Scale motor indicators of disease progression (p<0.03 and p<0.04, respectively). Apart from three rapidly resolved neutropenia cases, safety was maintained throughout the trial. Innovation: A moderate iron chelation regimen that avoids changes in systemic iron levels may constitute a novel therapeutic modality for PD. Conclusions: The therapeutic features of a chelation modality established in translational models and in pilot clinical trials warrant comprehensive evaluation of symptomatic and/or disease-modifying potential of chelation in PD. Antioxid

  9. Development of Iron-Chelating Poly(ethylene terephthalate) Packaging for Inhibiting Lipid Oxidation in Oil-in-Water Emulsions.

    PubMed

    Johnson, David R; Tian, Fang; Roman, Maxine J; Decker, Eric A; Goddard, Julie M

    2015-05-27

    Foods such as bulk oils, salad dressings, and nutritionally fortified beverages that are susceptible to oxidative degradation are often packaged in poly(ethylene terephthalate) (PET) bottles with metal chelators added to the food to maintain product quality. In the present work, a metal-chelating active packaging material is designed and characterized, in which poly(hydroxamic acid) (PHA) metal-chelating moieties were grafted from the surface of PET. Biomimetic PHA groups were grafted in a two-step UV-initiated process without the use of a photoinitiator. Surface characterization of the films by attenuated total reflective Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM) suggested successful grafting and conversion of poly(hydroxyethyl acrylate) (PHEA) to PHA chelating moieties from the surface of PET. Colorimetric (ferrozine) and inductively coupled plasma mass spectroscopy (ICP-MS) assays demonstrated the ability of PET-g-PHA to chelate iron in a low-pH (3.0) environment containing a competitive metal chelator (citric acid). Lipid oxidation studies demonstrated the antioxidant activity of PET-g-PHA films in inhibiting iron-promoted oxidation in an acidified oil-in-water (O/W) emulsion model system (pH 3.0). Particle size and ζ-potential analysis indicated that the addition of PET-g-PHA films did not affect the physical stability of the emulsion system. This work suggests that biomimetic chelating moieties can be grafted from PET and effectively inhibit iron-promoted degradation reactions, enabling removal of metal-chelating additives from product formulations.

  10. Development of Iron-Chelating Poly(ethylene terephthalate) Packaging for Inhibiting Lipid Oxidation in Oil-in-Water Emulsions.

    PubMed

    Johnson, David R; Tian, Fang; Roman, Maxine J; Decker, Eric A; Goddard, Julie M

    2015-05-27

    Foods such as bulk oils, salad dressings, and nutritionally fortified beverages that are susceptible to oxidative degradation are often packaged in poly(ethylene terephthalate) (PET) bottles with metal chelators added to the food to maintain product quality. In the present work, a metal-chelating active packaging material is designed and characterized, in which poly(hydroxamic acid) (PHA) metal-chelating moieties were grafted from the surface of PET. Biomimetic PHA groups were grafted in a two-step UV-initiated process without the use of a photoinitiator. Surface characterization of the films by attenuated total reflective Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM) suggested successful grafting and conversion of poly(hydroxyethyl acrylate) (PHEA) to PHA chelating moieties from the surface of PET. Colorimetric (ferrozine) and inductively coupled plasma mass spectroscopy (ICP-MS) assays demonstrated the ability of PET-g-PHA to chelate iron in a low-pH (3.0) environment containing a competitive metal chelator (citric acid). Lipid oxidation studies demonstrated the antioxidant activity of PET-g-PHA films in inhibiting iron-promoted oxidation in an acidified oil-in-water (O/W) emulsion model system (pH 3.0). Particle size and ζ-potential analysis indicated that the addition of PET-g-PHA films did not affect the physical stability of the emulsion system. This work suggests that biomimetic chelating moieties can be grafted from PET and effectively inhibit iron-promoted degradation reactions, enabling removal of metal-chelating additives from product formulations. PMID:25985711

  11. Improvement of Oxidative and Metabolic Parameters by Cellfood Administration in Patients Affected by Neurodegenerative Diseases on Chelation Treatment

    PubMed Central

    Fulgenzi, Alessandro; Giuseppe, Rachele De; Bamonti, Fabrizia; Ferrero, Maria Elena

    2014-01-01

    Objective. This prospective pilot study aimed at evaluating the effects of therapy with antioxidant compounds (Cellfood, and other antioxidants) on patients affected by neurodegenerative diseases (ND), who displayed toxic metal burden and were subjected to chelation treatment with the chelating agent calcium disodium ethylenediaminetetraacetic acid (CaNa2EDTA or EDTA). Methods. Two groups of subjects were studied: (a) 39 patients affected by ND and (b) 11 subjects unaffected by ND (controls). The following blood parameters were analyzed before and after three months' treatment with chelation + Cellfood or chelation + other antioxidants: oxidative status (reactive oxygen species, ROS; total antioxidant capacity, TAC; oxidized LDL, oxLDL; glutathione), homocysteine, vitamin B12, and folate. Results. After 3-months' chelation + Cellfood administration oxLDL decreased, ROS levels were significantly lower, and TAC and glutathione levels were significantly higher than after chelation + other antioxidants treatment, both in ND patients and in controls. Moreover, homocysteine metabolism had also improved in both groups. Conclusions. Chelation + Cellfood treatment was more efficient than chelation + other antioxidants improving oxidative status and homocysteine metabolism significantly in ND patients and controls. Although limited to a small number of cases, this study showed how helpful antioxidant treatment with Cellfood was in improving the subjects' metabolic conditions. PMID:25114898

  12. Preorganized and immobilized ligands for metal ion separations. Final report, June, 1994--May, 1997

    SciTech Connect

    Paine, R.T.

    1997-12-01

    Historically, much of the interest shown in f-element ion coordination chemistry has been driven by practical needs to devise separation schemes for lanthanide (Ln) and actinide (An) ions. However, few of the separations are completely satisfactory, and the basic chemical framework needed to achieve improvements is still poorly developed. As a result, studies of the fundamental aspects of f-element coordination chemistry are still pertinent not only to the evolution of improved separations, but also waste remediation, biological and medical applications of Ln ions, biochemistry of An ion decorporation, and new solid state materials preparations. The research objectives during the present grant period were to (1) synthesize new bifunctional and trifunctional chelating ligands, particularly in the class of new phosphonopyridine N-oxides; (2) characterize the structural features of the Ln and An coordination complexes formed by these ligands; (3) determine the extraction efficacy of these ligands; and (4) explore synthetic approaches for formation of dendritic polymers containing phosphoryl terminating groups. Some highlights of recently accomplished work and still-in-progress research are outlined.

  13. National Metal Casting Research Institute final report. Volume 4, Plan for technology transfer

    SciTech Connect

    Griffee, W.B.; Davis, S.

    1994-04-01

    This project was developed because of growing concern over the decline of the US metal casting industry; it springs from the Public Law 101-425 ``Department of Energy Metal Casting Competitiveness Research Act of 1990.`` The project sought the opinion of two groups in the metal casting industry: the operating users (foundries, other producers), and information purveyors. They were asked what was working, what was not, and what were some promising, innovative programs that are taking place or should be tried. Results and recommendations are given.

  14. Chelation therapy and cardiovascular disease: connecting scientific silos to benefit cardiac patients.

    PubMed

    Peguero, Julio G; Arenas, Ivan; Lamas, Gervasio A

    2014-08-01

    Medical practitioners have treated atherosclerotic disease with chelation therapy for over 50 years. Lack of strong of evidence led conventional practitioners to abandon its use in the 1960s and 1970s. This relegated chelation therapy to complementary and alternative medicine practitioners, who reported good anecdotal results. Concurrently, the epidemiologic evidence linking xenobiotic metals with cardiovascular disease and mortality gradually accumulated, suggesting a plausible role for chelation therapy. On the basis of the continued use of chelation therapy without an evidence base, the National Institutes of Health released a Request for Applications for a definitive trial of chelation therapy. The Trial to Assess Chelation Therapy (TACT) was formulated as a 2 × 2 factorial randomized controlled trial of intravenous EDTA-based chelation vs. placebo and high-dose oral multivitamins and multiminerals vs. oral placebo. The composite primary endpoint was death, reinfarction, stroke, coronary revascularization, or hospitalization for angina. A total of 1708 post-MI patients who were 50 years or older with a creatinine of 2.0 or less were enrolled and received 55,222 infusions of disodium EDTA or placebo with a median follow-up of 55 months. Patients were on evidence-based post-MI medications including statins. EDTA proved to be safe. EDTA chelation therapy reduced cardiovascular events by 18%, with a 5-year number needed to treat (NNT) of 18. Prespecified subgroup analysis revealed a robust benefit in patients with diabetes mellitus with a 41% reduction in the primary endpoint (5-year NNT = 6.5), and a 43% 5-year relative risk reduction in all-cause mortality (5-year NNT = 12). The magnitude of benefit is such that it suggests urgency in replication and implementation, which could, due to the excellent safety record, occur simultaneously.

  15. Chelation and mobilization of cellular iron by different classes of chelators.

    PubMed

    Zanninelli, G; Glickstein, H; Breuer, W; Milgram, P; Brissot, P; Hider, R C; Konijn, A M; Libman, J; Shanzer, A; Cabantchik, Z I

    1997-05-01

    Iron chelators belonging to three distinct chemical families were assessed in terms of their physicochemical properties and the kinetics of iron chelation in solution and in two biological systems. Several hydroxypyridinones, reversed siderophores, and desferrioxamine derivatives were selected to cover agents with different iron-binding stoichiometry and geometry and a wide range of lipophilicity, as determined by the octanol-water partition coefficients. The selection also included highly lipophilic chelators with potentially cell-cleavable ester groups that can serve as precursors of hydrophilic and membrane-impermeant chelators. Iron binding was determined by the chelator capacity for restoring the fluorescence of iron-quenched calcein (CA), a dynamic fluorescent metallosensor. The iron-scavenging properties of the chelators were assessed under three different conditions: (a) in solution, by mixing iron salts with free CA; (b) in resealed red cell ghosts, by encapsulation of CA followed by loading with iron; and (c) in human erythroleukemia K562 cells, by loading with the permeant CA-acetomethoxy ester, in situ formation of free CA, and binding of cytosolic labile iron. The time-dependent recovery of fluorescence in the presence of a given chelator provided a continuous measure for the capacity of the chelator to access the iron/CA-containing compartment. The resulting rate constants of fluorescence recovery indicated that chelation in solution was comparable for the members of each family of chelators, whereas chelation in either biological system was largely dictated by the lipophilicity of the free chelator. For example, desferrioxamine was among the fastest and most efficient iron scavengers in solution but was essentially ineffective in either biological system when used at < or = 200 microM over a 2-hr period at 37 degrees. On the other hand, the highly lipophilic and potentially cell-cleavable hydroxypyridinones and reversed siderophores were highly

  16. Metal wastage design guidelines for bubbling fluidized-bed combustors. Final report

    SciTech Connect

    Lyczkowski, R.W.; Podolski, W.F.; Bouillard, J.X.; Folga, S.M.

    1992-11-01

    These metal wastage design guidelines identify relationships between metal wastage and (1) design parameters (such as tube size, tube spacing and pitch, tube bundle and fluidized-bed height to distributor, and heat exchanger tube material properties) and (2) operating parameters (such as fluidizing velocity, particle size, particle hardness, and angularity). The guidelines are of both a quantitative and qualitative nature. Simplified mechanistic models are described, which account for the essential hydrodynamics and metal wastage processes occurring in bubbling fluidized beds. The empirical correlational approach complements the use of these models in the development of these design guidelines. Data used for model and guideline validation are summarized and referenced. Sample calculations and recommended design procedures are included. The influences of dependent variables on metal wastage, such as solids velocity, bubble size, and in-bed pressure fluctuations, are discussed.

  17. Metal cation inhibitors for controlling denting corrosion in steam generators. Final report. [PWR

    SciTech Connect

    Leidheiser, H. Jr.; Granata, R.D.; Simmons, G.W.; Music, S.; Vedage, H.L.

    1982-12-01

    Metal cations of arsenic, antimony, tin, manganese, zinc, cadmium, indium, and thallium have been evaluated in a preliminary way as possible3 inhibitors for controlling denting corrision observed in steam generators used with pressurized water reactors (PWR). The rationale for this approach was based upon the well-known inhibition effects of metal cations on corrosion rates in electrolyte/metal systems. A review of corrosion inhibition by metal cations (H. Leidheiser, Jr., Corrosion 36, 339 (1982)) has identified eleven inhibition mechanisms. The major test methods used for this evaluation were: (1) Isothermal capsule tests of carbon/steel/Inconel 600 tube bulging rates at temperatures up to 288/sup 0/C in seawater/copper-nickel chloride bulge-accelerating solutions. (2) Immersion weight-loss tests of steel coupled to Inconel 600 in boiling (102/sup 0/C) 3% sodium chloride solutions. In addition, electrochemical measuremens and surface analyses were performed. The major findings of this investigation are presented.

  18. FINAL REPORT FOR VERIFICATION OF THE METAL FINISHING FACILITY POLLUTION PREVENTION TOOL (MFFPPT)

    EPA Science Inventory

    The United States Environmental Protection Agency (USEPA) has prepared a computer process simulation package for the metal finishing industry that enables users to predict process outputs based upon process inputs and other operating conditions. This report documents the developm...

  19. Mobility of Source Zone Heavy Metals and Radionuclides: The Mixed Roles of Fermentative Activity on Fate and Transport of U and Cr. Final Report

    SciTech Connect

    Gerlach, Robin; Peyton, Brent M.; Apel, William A.

    2014-01-29

    Various U. S. Department of Energy (DOE) low and medium-level radioactive waste sites contain mixtures of heavy metals, radionuclides and assorted organic materials. In addition, there are numerous sites around the world that are contaminated with a mixture of organic and inorganic contaminants. In most sites, over time, water infiltrates the wastes, and releases metals, radionuclides and other contaminants causing transport into the surrounding environment. We investigated the role of fermentative microorganisms in such sites that may control metal, radionuclide and organics migration from source zones. The project was initiated based on the following overarching hypothesis: Metals, radionuclides and other contaminants can be mobilized by infiltration of water into waste storage sites. Microbial communities of lignocellulose degrading and fermenting microorganisms present in the subsurface of contaminated DOE sites can significantly impact migration by directly reducing and immobilizing metals and radionuclides while degrading complex organic matter to low molecular weight organic compounds. These low molecular weight organic acids and alcohols can increase metal and radionuclide mobility by chelation (i.e., certain organic acids) or decrease mobility by stimulating respiratory metal reducing microorganisms. We demonstrated that fermentative organisms capable of affecting the fate of Cr6+, U6+ and trinitrotoluene can be isolated from organic-rich low level waste sites as well as from less organic rich subsurface environments. The mechanisms, pathways and extent of contaminant transformation depend on a variety of factors related to the type of organisms present, the aqueous chemistry as well as the geochemistry and mineralogy. This work provides observations and quantitative data across multiple scales that identify and predict the coupled effects of fermentative carbon and electron flow on the transport of radionuclides, heavy metals and organic contaminants in

  20. Electrolytic technology in the metals industry: A scoping study: Final report

    SciTech Connect

    Sabatini, J.S.; Field, E.L.; Shanley, E.S.; Weiler, D.A.

    1989-01-01

    The overall purpose of the study was twofold: (1) to evaluate technologies with respect to the recovery of selected metals from both primary and secondary resources, as well as waste resources, and (2) to identify opportunities that might permit consideration for joint development by industry and EPRI. The technologies of interest are classified as ''electrolytic technologies'' and include electrorefining, electrowinning, and fused-salt electrolysis. In the course of this effort, more than 40 metal/commodities were screened and reviewed. Seven metal commodities selected for inclusion in this study were copper, iron/steel, lead, magnesium, sodium, titanium, and zinc. Sectors considered in this analysis included extraction from ore (''primary industry'') and recovery from scrap metal (''secondary industry'') as well as waste products. Using readily available data for these seven metals, market, industry, and current production overviews were developed, followed by the identification and evaluation of over 60 potential electrolytic processes in nine research categories. In addition, ''capsule summaries'' on markets and technologies were prepared for ten metals of secondary interest to this study: antimony, chromium, manganese, molybdenum, nickel, rare earth oxides, silicon, silver, tin and zirconium. 254 refs., 10 figs., 11 tabs.

  1. Melamine-formaldehyde-NTA chelating gel resin: Synthesis, characterization and application for copper(II) ion removal from synthetic wastewater.

    PubMed

    Baraka, Ahmad; Hall, P J; Heslop, M J

    2007-02-01

    A new chelating resin was synthesised by anchoring nitrilotriacetic acid (NTA) to melamine during the melamine-formaldehyde gelling reaction in the presence of water, using acetone and guaiacol as a porogen mixture. This technique gives a porous chelating gel resin capable of removing heavy metals from wastewater. FT-IR, XRD, elemental analysis, surface area and water regain measurements were conducted for characterization of the new chelating gel resin. A comprehensive adsorption study (kinetics isotherm, and thermodynamics) of Cu(II) removal from synthetic acidic aqueous solutions by adsorption on this resin was conducted regarding the effects of time, temperature, initial pH and copper(II) initial concentration.

  2. Increased Uptake of Chelated Copper Ions by Lolium perenne Attributed to Amplified Membrane and Endodermal Damage

    PubMed Central

    Johnson, Anthea; Singhal, Naresh

    2015-01-01

    The contributions of mechanisms by which chelators influence metal translocation to plant shoot tissues are analyzed using a combination of numerical modelling and physical experiments. The model distinguishes between apoplastic and symplastic pathways of water and solute movement. It also includes the barrier effects of the endodermis and plasma membrane. Simulations are used to assess transport pathways for free and chelated metals, identifying mechanisms involved in chelate-enhanced phytoextraction. Hypothesized transport mechanisms and parameters specific to amendment treatments are estimated, with simulated results compared to experimental data. Parameter values for each amendment treatment are estimated based on literature and experimental values, and used for model calibration and simulation of amendment influences on solute transport pathways and mechanisms. Modeling indicates that chelation alters the pathways for Cu transport. For free ions, Cu transport to leaf tissue can be described using purely apoplastic or transcellular pathways. For strong chelators (ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA)), transport by the purely apoplastic pathway is insufficient to represent measured Cu transport to leaf tissue. Consistent with experimental observations, increased membrane permeability is required for simulating translocation in EDTA and DTPA treatments. Increasing the membrane permeability is key to enhancing phytoextraction efficiency. PMID:26512647

  3. Iron-chelation therapy: an update.

    PubMed

    Franchini, Massimo; Veneri, Dino

    2004-01-01

    Chronically transfused patients develop iron overload that leads to organ damage and ultimately to death. The introduction of the iron-chelating agent, desferrioxamine mesylate, dramatically improved the life expectancy of these patients. However, the very demanding nature of this treatment (subcutaneous continuous infusion via a battery-operated portable pump) has been the motivation for attempts to develop alternative forms of treatment that would facilitate the patients' compliance. In this review, we describe the most important advances in iron-chelating therapy. In particular, we analyze a new method of administering desferrioxamine mesylate (twice daily subcutaneous bolus injections) and a novel, orally active iron chelator (ICL670A). We also present a meta-analysis of the largest trials on the oral iron chelator deferiprone and the results of combined therapy (deferiprone and desferrioxamine).

  4. 77 FR 73979 - Magnesium Metal From the Russian Federation: Notice of Reinstated Final Results of Administrative...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-12-12

    ... Russian Federation: Final Results of Antidumping Duty Administrative Review, 73 FR 52642 (September 10... period April 1, 2006, through March 31, 2007. See Final Results, 73 FR at 52643. The CIT remanded the... Administrative Review Pursuant to Court Decision, 76 FR 13355 (March 11, 2011). On July 27, 2012, the...

  5. Pyrolysed N{sub 4}-chelates: Novel electrocatalysts for chemical and biosensors

    SciTech Connect

    Atanasov, P.; Wilkins, E.; Gamburzev, S.

    1996-12-31

    During the last few years the use of different types of N{sub 4}-metal chelates (especially phtalocyanines and phorphyrins) for electroanalytical and biosensor applications has been attracting increasing attention. Electroanalytical application of such catalysts is generally based on their use as electrode modifiers. The use of N{sub 4}-metal chelates offers several advantages: they show high catalytic activity combined with some analyte selectivity; they are suitable for forming thin layers over an inert electrode; they demonstrate compatibility with enzymes and different immobilization reagents; the electrode modification procedures can be arranged as a step in the sensor micromanufacturing procedure. Oxygen reduction as well as redox properties of numerous organic compounds have been studied on electrodes modified with N{sub 4}-metal chelates. Some of the N{sub 4}-metal chelates have been employed as catalysts for oxygen electroreduction and the electrochemical oxidation of hydrogen peroxide. During the work described, catalysts were prepared by deposition of CoTMPP or H{sub 2} TMPP on non-carbon dispersed carrier, followed by the pyrolysis of the compound and by removal of the carrier. Both pyrolysis products possess high electrocatalytic activity for oxygen reduction and hydrogen peroxide reduction and oxidation.

  6. Comparison of the antibacterial activity of chelating agents using the agar diffusion method

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The agar diffusion assay was used to examine antibacterial activity of 2 metal chelators. Concentrations of 0 to 40 mM of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine-N,N’-disuccinic acid (EDDS) were prepared in 1.0 M potassium hydroxide (KOH). The pH of the solutions was adjusted to 1...

  7. Oxide-supported metal carbonyls: novel catalysts for the liquefaction of coal. Final technical report

    SciTech Connect

    Melson, G.A.

    1985-01-01

    Coal liquefaction, hydrodesulfurization (HDS), and hydrodenitrogenation (HDN) catalysts have been investigated increasingly in recent years because of the need to understand how to develop more selective and stable materials for coal utilization. One catalyst that has been used extensively for HDS and subjected to numerous characterization and model reaction studies is Co-Mo/Al/sub 2/O/sub 3/. In these studies, the catalyst preparation technique has usually involved the incipient-wetness impregnation of ..gamma..-Al/sub 2/O/sub 3/ with ammonium molybdates and cobalt nitrates. Such a technique leads to a variety of surface species, bulk-like and monolayer forms, which have been described and can be controlled by alterations in the preparation techniques and materials. However, certain structural and chemical factors of the catalysts, e.g., Co and Mo reducibility and dispersion or surface speciation at low and high metal concentrations, seem to be independent of such alterations. To investigate whether these factors can be affected by preparation techniques and to develop oxide-supported, metal catalysts having controlled metal dispersions and speciation, a catalyst preparation technique using metal carbonyls with an extraction process to metal-load oxide supports has been developed (J.E. Crawford, G.A. Melson, L.E. Makovsky, F.R. Brown, J. Catal., 83: 454 (1983)). This report discusses the surface and bulk characterization, and presents initial HDS and liquefaction results, for these catalysts. 7 refs., 4 figs., 1 tab.

  8. Removal of Technetium, Carbon Tetrachloride, and Metals from DOE Properties - Final Report

    SciTech Connect

    Mallouk, Thomas E.

    2000-09-01

    This research is a three year project involving close collaboration between chemists at Pennsylvania State University and materials scientists at Pacific Northwest National Laboratory (PNNL). The goal of the project is the development and characterization of supported reducing agents, and solid waste forms derived from them, which will be effective in remediation of aqueous wastes. The work follows the recent discovery that zero-valent metals, such as iron, are effective decontaminants for waste streams containing chlorinated hydrocarbons. Preliminary data, obtained at Penn State and elsewhere, have shown that the same strategy will be effective in reducing soluble compounds containing toxic metals (technetium, lead, mercury, and chromium) to insoluble forms. The Penn State group has prepared a new class of powerful reducing agents, called Ferragels, which consist of finely divided zero-valent metals on high surface area supports. Because the rate of the surface oxidation-reduction reaction depends on available surface area, Ferragels are more effective in every case tested to date than unsupported metals. The project will further develop and investigate the application of these composite materials to problems relevant to the DOE-EM mission, namely the detoxification of waste streams containing technetium, carbon tetrachloride, and toxic metal ions. The Penn State group will work closely with the PNNL group to prepare materials that are compatible with the highly corrosive liquid fraction of Hanford site tank waste, to conduct tests with waste simulants containing technetium, and to formulate and characterize vitrified waste forms derived from these materials.

  9. Potentials and drawbacks of chelate-enhanced phytoremediation of soils.

    PubMed

    Römkens, Paul; Bouwman, Lucas; Japenga, Jan; Draaisma, Cathrina

    2002-01-01

    Chelate-enhanced phytoremediation has been proposed as an effective tool for the extraction of heavy metals from soils by plants. However, side-effects related to the addition of chelates, e.g. metal leaching and effects on soil micro-organisms, were usually neglected. Therefore, greenhouse and lysimeter studies were conducted to study the phytoremedation potential of EDGA and citric acid and to evaluate its effects on microbial activity and leaching of Cd, Zn Cu and Pb. Grass, lupine and yellow mustard were grown on a moderately polluted acid (pH 4.5) sandy soil that contained 2 mg kg(-1) Cd and 200 mg kg(-1) Zn. Citric acid appeared to be degraded microbially within a few days after addition which limited its potential for long-lasting remediation studies. EDGA enhanced metal solubility but plant uptake did not increase accordingly. The metal shoot:root ratio increased upon addition of EDGA but it also reduced the net shoot and root biomass production of both lupine and yellow mustard. Bacterial biomass was higher in both the citric and EDGA treated pots but bacterial activity remained unaffected. The number of microbivorous nematodes was greatly reduced upon addition of EDGA which was most likely related to the reduced biomass production and, to a smaller extent, to the changes in the composition of the available food. Furthermore, EDGA enhanced metal leaching in the lysimeter study which could lead to groundwater pollution. To prevent these unwanted side-effects, careful management of phytoremediation methods, therefore, seems necessary.

  10. A study of the metal content of municipal solid waste. Final report

    SciTech Connect

    Churney, K.L.; Domalski, E.S.

    1998-01-01

    Knowledge of the content of toxic components, so called pollutant precursors, in the municipal solid waste (MSW) stream is essential to development of the strategies for source reduction and reuse, recycling, composting and disposal. Data are scarce; trends in composition for any locality even more so. In a previous study the total and water soluble chlorine content of the components of municipal solid waste were determined from sampling studies at two sites, Baltimore County, MD, and Brooklyn, NY, each for a five day period. The total sulfur content of the combined combustible components was also determined. Because of the scarcity of data and synergistic effects, it seemed appropriate to determine the heavy metal content of the preceding material prior to its disposal. The metals chosen were the so-called priority pollutant metals (PPM): antimony, arsenic, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, thallium, and zinc.

  11. The magnesium chelation step in chlorophyll biosynthesis

    SciTech Connect

    Weinstein, J.

    1990-11-01

    In photosynthetic organisms, the biogenesis of energy transducing membranes requires the coordinate synthesis of prosthetic groups, proteins, and various lipids. Two of the major prosthetic groups, chlorophyll and heme, share a common biosynthetic pathway that diverges at the point of metal insertion into protoporphyrin IX (Proto). Insertion of iron leads to the formation of hemes, while insertion of magnesium is the first step unique to chlorophyll formation. This project is directed toward identifying the enzyme(s) responsible for magnesium chelation and elucidating the mechanism which regulates the flux of precursors through the branch point enzymes in isolated chloroplasts. Using intact chloroplasts from greening cucumber cotyledons, we have confirmed the ATP requirement for Mg-Proto formation. Use of non-hydrolyzable ATP analogs, uncouplers and ionophores has led to the conclusions that ATP hydrolysis is necessary, but that this hydrolysis is not linked to the requirement for membrane intactness by transmembrane ion gradients or electrical potentials. The enzyme(s) are flexible with respect to the porphyrin substrate specificity, accepting porphyrins with -vinyl, -ethyl, or -H substituents at the 2 and 4 positions. The activity increases approximately four-fold during greening. Possible physiological feedback inhibitors such as heme, protochlorophyllide, and chlorophyllide had no specific effect on the activity. The activity has now been assayed in barely, corn and peas, with the system from peas almost ten-fold more active than the cucumber system. Work is continuing in pea chloroplasts with the development of a continuous assay and investigation of the feasibility of characterizing an active, organelle-free preparation. 6 figs.

  12. ECLSS Sustaining Metal Materials Compatibility Final Report, Electrochemical and Crevice Corrosion Test Results

    NASA Technical Reports Server (NTRS)

    Lee, R. E.

    2015-01-01

    Electrochemical test results are presented for six noble metals evaluated in two acidic test solutions which are representative of waste liquids processed in the Environmental Control and Life Support System (ECLSS) aboard the International Space Station (ISS). The two test solutions consisted of fresh waste liquid which had been modified with a proposed or alternate pretreatment formulation and its associated brine concentrate. The six test metals included three titanium grades, (Commercially Pure, 6Al-4V alloy and 6Al-4V Low Interstitial alloy), two nickel-chromium alloys (Inconel® 625 and Hastelloy® C276), and one high tier stainless steel (Cronidur® 30).

  13. Energy requirements for metals production: comparison between ocean nodules and land-based resources. Final report

    SciTech Connect

    Not Available

    1980-09-01

    A methodology was developed to compare the energy requirements of technologies for production of metals from ocean nodules with production of same metals from land based ores using conventional processes. The energy requirements for production of copper, nickel, cobalt, and manganese from ocean nodules are based on an ocean mining operation of 3 million tons per year of dry nodules. A linear relationship exists between the amount of nodules processed and the total energy so that the energy can be easily converted to other processing rates if desired.

  14. Toxicity of heavy metals and metal-containing nanoparticles on plants.

    PubMed

    Mustafa, Ghazala; Komatsu, Setsuko

    2016-08-01

    Plants are under the continual threat of changing climatic conditions that are associated with various types of abiotic stresses. In particular, heavy metal contamination is a major environmental concern that restricts plant growth. Plants absorb heavy metals along with essential elements from the soil and have evolved different strategies to cope with the accumulation of heavy metals. The use of proteomic techniques is an effective approach to investigate and identify the biological mechanisms and pathways affected by heavy metals and metal-containing nanoparticles. The present review focuses on recent advances and summarizes the results from proteomic studies aimed at understanding the response mechanisms of plants under heavy metal and metal-containing nanoparticle stress. Transport of heavy metal ions is regulated through the cell wall and plasma membrane and then sequestered in the vacuole. In addition, the role of different metal chelators involved in the detoxification and sequestration of heavy metals is critically reviewed, and changes in protein profiles of plants exposed to metal-containing nanoparticles are discussed in detail. Finally, strategies for gaining new insights into plant tolerance mechanisms to heavy metal and metal-containing nanoparticle stress are presented. This article is part of a Special Issue entitled: Plant Proteomics--a bridge between fundamental processes and crop production, edited by Dr. Hans-Peter Mock. PMID:26940747

  15. Toxicity of heavy metals and metal-containing nanoparticles on plants.

    PubMed

    Mustafa, Ghazala; Komatsu, Setsuko

    2016-08-01

    Plants are under the continual threat of changing climatic conditions that are associated with various types of abiotic stresses. In particular, heavy metal contamination is a major environmental concern that restricts plant growth. Plants absorb heavy metals along with essential elements from the soil and have evolved different strategies to cope with the accumulation of heavy metals. The use of proteomic techniques is an effective approach to investigate and identify the biological mechanisms and pathways affected by heavy metals and metal-containing nanoparticles. The present review focuses on recent advances and summarizes the results from proteomic studies aimed at understanding the response mechanisms of plants under heavy metal and metal-containing nanoparticle stress. Transport of heavy metal ions is regulated through the cell wall and plasma membrane and then sequestered in the vacuole. In addition, the role of different metal chelators involved in the detoxification and sequestration of heavy metals is critically reviewed, and changes in protein profiles of plants exposed to metal-containing nanoparticles are discussed in detail. Finally, strategies for gaining new insights into plant tolerance mechanisms to heavy metal and metal-containing nanoparticle stress are presented. This article is part of a Special Issue entitled: Plant Proteomics--a bridge between fundamental processes and crop production, edited by Dr. Hans-Peter Mock.

  16. Development of an Innovative Laser-Assisted Coating Process for Extending Lifetime of Metal Casting Dies. Final Report

    SciTech Connect

    Madhav Rao Gonvindaraju

    1999-10-18

    Die casting dies used in the metal casting industry fail due to thermal fatigue cracking accompanied by the presence of residual tensile stresses, corrosion, erosion and wear of die surfaces. This phase 1 SBIR Final Report summarize Karta Technologies research involving the development of an innovative laser coating technology for metal casting dies. The process involves depositing complex protective coatings of nanocrystalline powders of TiC followed by a laser shot peening. The results indicate a significant improvement in corrosion and erosion resistance in molten aluminum for H13 die casting die steels. The laser-coated samples also showed improved surface finish, a homogeneous and uniform coating mircrostructure. The technology developed in this research can have a significant impact on the casting industry by saving the material costs involved in replacing dies, reducing downtime and improving the quality.

  17. Impact of histidine residue on chelating ability of 2'-deoxyriboadenosine.

    PubMed

    Lodyga-Chruścińska, Elżbieta; Ołdziej, Stanisław; Sochacka, Elżbieta; Korzycka, Karolina; Chruściński, Longin; Micera, Giovanni; Sanna, Daniele; Turek, Monika; Pawlak, Justyna

    2011-09-01

    Copper(II) complexes with a new chelator-type nucleoside-histidine modified 2'-deoxyriboadenosine (N-[(9-β-D-2'-deoxyribofuranosylpurin-6-yl)-carbamoyl]histidine) were studied by potentiometric and spectroscopic (UV-visible, CD, EPR) techniques, in conjunction with computer modeling optimization. The ligand can act as bidentate or tridentate depending on pH range. In acidic pH a very stable dimeric complex Cu(2)L(2) predominates with coordination spheres of both metal ions composed of oxygen atoms from carboxylic groups, one oxygen atom from ureido group and two nitrogen atoms derived from purine base and histidine ring. Above pH 5, deprotonation of carbamoyl nitrogens leads to the formation of CuL(2), Cu(2)L(2)H(-1) and Cu(2)L(2)H(-2) species. The CuL(2)H(-1) and CuL(2)H(-2) complexes with three or four nitrogens in Cu(II) coordination sphere have been detected in alkaline medium. Our findings suggest that N-[(9-beta-D-2'-deoxyribofuranosylpurin-6-yl)-carbamoyl]histidine chelates copper(II) ions very efficiently. The resulting complex might be used as an alternative base-pairing mode in which hydrogen-bonded base pairs present in natural DNA are replaced by metal-mediated ones. PMID:21723807

  18. Impact of histidine residue on chelating ability of 2'-deoxyriboadenosine.

    PubMed

    Lodyga-Chruścińska, Elżbieta; Ołdziej, Stanisław; Sochacka, Elżbieta; Korzycka, Karolina; Chruściński, Longin; Micera, Giovanni; Sanna, Daniele; Turek, Monika; Pawlak, Justyna

    2011-09-01

    Copper(II) complexes with a new chelator-type nucleoside-histidine modified 2'-deoxyriboadenosine (N-[(9-β-D-2'-deoxyribofuranosylpurin-6-yl)-carbamoyl]histidine) were studied by potentiometric and spectroscopic (UV-visible, CD, EPR) techniques, in conjunction with computer modeling optimization. The ligand can act as bidentate or tridentate depending on pH range. In acidic pH a very stable dimeric complex Cu(2)L(2) predominates with coordination spheres of both metal ions composed of oxygen atoms from carboxylic groups, one oxygen atom from ureido group and two nitrogen atoms derived from purine base and histidine ring. Above pH 5, deprotonation of carbamoyl nitrogens leads to the formation of CuL(2), Cu(2)L(2)H(-1) and Cu(2)L(2)H(-2) species. The CuL(2)H(-1) and CuL(2)H(-2) complexes with three or four nitrogens in Cu(II) coordination sphere have been detected in alkaline medium. Our findings suggest that N-[(9-beta-D-2'-deoxyribofuranosylpurin-6-yl)-carbamoyl]histidine chelates copper(II) ions very efficiently. The resulting complex might be used as an alternative base-pairing mode in which hydrogen-bonded base pairs present in natural DNA are replaced by metal-mediated ones.

  19. 77 FR 54563 - Silicon Metal from the People's Republic of China: Final Results of Antidumping Duty...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-09-05

    ... Fair Value: Silicon Metal from the People's Republic of China, 56 FR 18570, 18571-2 (April 23, 1991... Duty Administrative Review, 77 FR 13534 (March 7, 2012) (``Preliminary Results''). On March 27, 2012... Shanghai Jinneng meets the criteria for a separate rate. \\14\\ See Preliminary Results, 77 FR at...

  20. Constructed wetland treatment systems for the remediation of metal- bearing aqueous discharges. Final report

    SciTech Connect

    Woodis, A.L.

    1995-08-01

    Electric utility activities, such as coal mining, processing, and combustion, often produce aqueous (wastewater) discharges containing metals. Chemical treatment of these discharges to achieve compliance with National Pollution Discharge Elimination System (NPDES) requirements can be costly. Constructed wetland treatment systems offer an inexpensive, natural, low-maintenance, and potentially long-term solution for the treatment of aqueous discharges without chemical additives. At the present time, several electric utilities are using constructed wetland treatment systems to achieve NPDES compliance. Constructed wetland treatment systems take advantage of natural biogeochemical processes to treat utility wastewaters, thus meeting NPDES compliance levels in an environmentally effective manner. This report provides information on the natural science, wastewater treatment, and regulatory/jurisdictional aspects of constructed wetland treatment systems used within the electric utility industry. Included is data from a number of electric utility constructed wetland treatment sites. The principal advantages of using constructed wetland systems to treat wastewater are the low overall cost compared to more conventional chemical treatment methods, the simplicity of operation, and the capacity to provide long-term resource recovery. For example, using a lined constructed wetland treatment system with high retention efficiency for heavy metals provides the option of resource recovery at some future date from a discrete volume of wetland material. Contaminants that can be removed with high efficiency in a number of constructed wetland treatment systems include heavy metals, toxic organics, suspended solids, and nutrients. This report discusses the treatability of specific contaminants as well as metal uptake and translocation processes in constructed wetlands.

  1. 78 FR 27185 - Magnesium Metal From the People's Republic of China: Final Results of Antidumping Duty...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-05-09

    ...: Magnesium Metal From the People's Republic of China, 70 FR 19928 (April 15, 2005), remains dispositive...- 2012, 78 FR 1834 (January 9, 2013) (``Preliminary Results''). DATES: Effective Date: May 9, 2013. FOR... FR 65694 (October 24, 2011). \\4\\ See id. Cash Deposit Requirements The following cash...

  2. CRADA Final Report: Characterization of Failure Modes in Lithium Metal Batteries

    SciTech Connect

    Kerr, John B.

    2005-06-27

    A plan was prepared to investigate the factors that controlled the growth of dendrites in lithium metal polymer batteries. Full agreement on the scope of the work could not be reached due to factors outside the control of the parties. The program was terminated as a result.

  3. Transition metal catalysis in the generation of petroleum and natural gas. Final report

    SciTech Connect

    Mango, F.D.

    1997-01-21

    This project originated on the premise that natural gas could be formed catalytically in the earth rather than thermally as commonly believed. The intention was to test this hypothetical view and to explore generally the role of sedimentary metals in the generation of light hydrocarbons (C1 - C9). We showed the metalliferous source rocks are indeed catalytic in the generation of natural gas. Various metal compounds in the pure state show the same levels of catalytic activity as sedimentary rocks and the products are identical. Nickel is particularly active among the early transition metals and is projected to remain catalytically robust at all stages of catagenesis. Nickel oxide promotes the formation of n-alkanes in addition to natural gas (NG), demonstrating the full scope of the hypothetical catalytic process: The composition of catalytic gas duplicates the entire range of natural gas, from so-called wet gas to dry gas (60 to 95+ wt % methane), while gas generated thermally is consistently depleted in methane (10 to 60 wt % methane). These results support the view that metal catalysis is a major pathway through which natural gas is formed in the earth.

  4. Final Technical Report: Viral Infection of Subsurface Microorganisms and Metal/Radionuclide Transport

    SciTech Connect

    Weber, Karrie A.; Bender, Kelly S.; Li, Yusong

    2013-09-28

    Microbially mediated metabolisms have been identified as a significant factor either directly or indirectly impacting the fate and transport of heavy metal/radionuclide contaminants. To date microorganisms have been isolated from contaminated environments. Examination of annotated finished genome sequences of many of these subsurface isolates from DOE sites, revealed evidence of prior viral infection. To date the role that viruses play influencing microbial mortality and the resulting community structure which directly influences biogeochemical cycling in soils and sedimentary environments remains poorly understood. The objective of this exploratory study was to investigate the role of viral infection of subsurface bacteria and the formation of contaminant-bearing viral particles. This objective was approached by examining the following working hypotheses: (i) subsurface microorganisms are susceptible to viral infections by the indigenous subsurface viral community, and (ii) viral surfaces will adsorb heavy metals and radionuclides. Our results have addressed basic research needed to accomplish the BER Long Term Measure to provide sufficient scientific understanding such that DOE sites would be able to incorporate coupled physical, chemical and biological processes into decision making for environmental remediation or natural attenuation and long-term stewardship by establishing viral-microbial relationships on the subsequent fate and transport of heavy metals and radionuclides. Here we demonstrated that viruses play a significant role in microbial mortality and community structure in terrestrial subsurface sedimentary systems. The production of viral-like particles within subsurface sediments in response to biostimulation with dissolved organic carbon and a terminal electron acceptor resulted in the production of viral-like particles. Organic carbon alone did not result in significant viral production and required the addition of a terminal electron acceptor

  5. Sequestration of Zinc Oxide by Fimbrial Designer Chelators

    PubMed Central

    Kjærgaard, Kristian; Sørensen, Jack K.; Schembri, Mark A.; Klemm, Per

    2000-01-01

    Type 1 fimbriae are surface organelles of Escherichia coli. By engineering a structural component of the fimbriae, FimH, to display a random peptide library, we were able to isolate metal-chelating bacteria. A library consisting of 4 × 107 independent clones was screened for binding to ZnO. Sequences responsible for ZnO adherence were identified, and distinct binding motifs were characterized. The sequences selected exhibited various degrees of affinity and specificity towards ZnO. Competitive binding experiments revealed that the sequences recognized only the oxide form of Zn. Interestingly, one of the inserts exhibited significant homology to a specific sequence in a putative zinc-containing helicase, which suggests that searches such as this one may aid in identifying binding motifs in nature. The zinc-binding bacteria might have a use in detoxification of metal-polluted water. PMID:10618196

  6. Chelation behavior of various flavonols and transfer of flavonol-chelated zinc(II) to alanylaspartic dipeptide: A PCM/DFT investigation

    NASA Astrophysics Data System (ADS)

    Yasarawan, Nuttawisit; Thipyapong, Khajadpai; Ruangpornvisuti, Vithaya

    2016-03-01

    Alanylaspartic dipeptide (AlaAsp) and zinc(II)-flavonol complex could represent a metal-binding site in proteins and a metal-ion releasing agent, respectively. Chelation of zinc(II) by either AlaAsp or flavonol ligands in aqueous solution has been examined using DFT methods with polarizable continuum model (PCM/DFT). Coordination geometry, complexation stoichiometry, coordination bond strength, preferable metal-binding site on ligands and effect of water coordination on the stability of complexes have been addressed. In several cases, the long-range corrected density functional CAM-B3LYP allows the most accurate prediction of both structural and spectroscopic data. The preferential transfer of flavonol-chelated zinc(II) to AlaAsp under solvation is attainable through the ligand-exchange reaction. The energy barrier of such reaction is significantly dependent on the degree of hydrogen bonding within the transition state. In summary, either hydroxylation or methoxylation at particular positions on the 3-hydroxyflavone backbone significantly affects the reactivity of flavonol chelates in the metal-ion transfer.

  7. Superelement methods in high temperature metal matrix composites. Final Report; M.S. Thesis, 1989

    NASA Technical Reports Server (NTRS)

    Trowbridge, Daniel

    1991-01-01

    A study into fiber fracture and debonding in metal matrix composites is conducted using the finite element method. The superelement finite element technique was used to model a metal matrix composite under various loading condition and with varying degrees of fiber debonding. The use of superelement saved many man hours by allowing for alteration of only the primary superelement to manipulate partial bonding for the entire model. The composite's material properties were calculated and the effects of fiber debonding on these properties were noted. The internal stress state of the composite while under various loads was also studied. Special interest was devoted to the change in stress state as a result of increasing fiber debonding.

  8. Influence of thermal debinding on the final properties of Fe-Si soft magnetic alloys for metal injection molding (MIM)

    NASA Astrophysics Data System (ADS)

    Páez-Pavón, A.; Jiménez-Morales, A.; Santos, T. G.; Quintino, L.; Torralba, J. M.

    2016-10-01

    Metal injection molding (MIM) may be used to produce soft magnetic materials with optimal mechanical and magnetic properties. Unlike other techniques, MIM enables the production of complex and small Fe-Si alloy parts with silicon contents greater than 3% by weight. In MIM process development, it is critical to design a proper debinding cycle not only to ensure complete removal of the binder system but also to obtain improved properties in the final part. This work is a preliminary study on the production of Fe-3.8Si soft magnetic parts by MIM using pre-alloyed powders and a non-industrialized binder. Two different heating rates during thermal debinding were used to study their effect on the final properties of the part. The final properties of the sintered parts are related to thermal debinding. It has been demonstrated that the heating rate during thermal debinding has a strong influence on the final properties of Fe-Si soft magnetic alloys.

  9. Numerical Predictions on the Final Properties of Metal Injection Moulded Components after Sintering Process

    SciTech Connect

    Song, J.; Barriere, T.; Gelin, J. C.

    2007-04-07

    A macroscopic model based on a viscoplastic constitutive law is presented to describe the sintering process of metallic powder components obtained by injection moulding. The model parameters are identified by the gravitational beam-bending tests in sintering and the sintering experiments in dilatometer. The finite element simulations are carried out to predict the shrinkage, density and strength after sintering. The simulation results have been compared to the experimental ones, and a good agreement has been obtained.

  10. Bis-NHC chelate complexes of nickel(0) and platinum(0).

    PubMed

    Brendel, Matthias; Braun, Carolin; Rominger, Frank; Hofmann, Peter

    2014-08-11

    For a long time d(10)-ML2 fragments have been known for their potential to activate unreactive bonds by oxidative addition. In the development of more active species, two approaches have proven successful: the use of strong σ-donating ligands leading to electron-rich metal centers and the employment of chelating ligands resulting in a bent coordination geometry. Combining these two strategies, we synthesized bis-NHC chelate complexes of nickel(0) and platinum(0). Bis(1,5-cyclooctadiene)nickel(0) and -platinum(0) react with bisimidazolium salts, deprotonated in situ at room temperature, to yield tetrahedral or trigonal-planar bis-NHC chelate olefin complexes. The synthesis and characterization of these complexes as well as a first example of C-C bond activation with these systems are reported. Due to the enforced cis arrangement of two NHCs, these compounds should open interesting perspectives for bond-activation chemistry and catalysis.

  11. Oxidation of aqueous sulfur dioxide. 3. The effects of chelating agents and phenolic antioxidants

    SciTech Connect

    Lim, P.K.; Huss, A. Jr.; Eckert, C.A.

    1982-10-14

    The inhibiting effects of chelating agents (1,10-phenanthroline and EDTA) and phenolic antioxidants (phenol, hydroquinone, resorcinol, pyrocatechol, phloroglucinol, and pyrogallol) on the catalyzed oxidations of low- and high-pH aqueous S(IV) solutions were investigated. Both the low-pH Mn(II)- and Fe(II)-catalyzed reactions were inhibited by phenolic antioxidants, with the effect on the Mn(II)-catalyzed reaction being much more pronounced. The chelating agents, on the other hand, had a far greater inhibiting influence on the Fe(II)-catalyzed reaction. The high-pH Cu(II)-catalyzed reaction was markedly inhibited by both chelating agents and antioxidants. The results support our previous conclusion that the previously accepted uncatalyzed oxidations of S(IV) were in fact primarily trace-metal catalyzed. 7 figures.

  12. 75 FR 56989 - Magnesium Metal From the Russian Federation: Final Results of Antidumping Duty Administrative Review

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-09-17

    ... Duty Administrative Review, 75 FR 26922 (May 13, 2010) (Preliminary Results). We invited interested... Magnesium in Granular Form From the People's Republic of China, 66 FR 49345 (September 27, 2001), Notice of Final Determination of Sales at Less Than Fair Value: Pure Magnesium From Israel, 66 FR 49349...

  13. Development of a dipodal Schiff base ligand with N-imine and O-naphtholate donors: A potential chelator towards Cu(II) metal ion established through potentiometric and spectrophotometric studies

    NASA Astrophysics Data System (ADS)

    Baral, Minati; Gupta, Amit; Kanungo, B. K.

    2015-08-01

    A novel hydroxynaphthaldehyde derived Schiff base ligand N,N'-bis-[2-[(2-hydroxy-1-naphthyl)methyleneamino]ethyl]propanediamide (DOTA2HNAP) containing nitrogen and oxygen donor atoms has been developed. The lowest energy molecular structure of DOTA2HNAP and its complexes with Cu (II) metal ion were examined by molecular mechanics using MM+ force which later was re-optimized by semi-empirical method. The theoretical IR and UV spectra of the ligand were obtained using semi empirical/ZINDO/PM3 and were compared with the experimental ones. The coordinating ability of DOTA2HNAP with H+ and Cu(II) ions was investigated in 1:99 (DMSO: water) binary solvent mixture at 25±1°C by potentiometric and spectrophotometric method. The electronic spectra of the ligand show three distinct peaks (253nm, 320nm and 360nm) implicating existence of the Schiff base in quinone form that was well supported by theoretical spectral studies. Out of various complex species forming in solution, all the metal ions show higher stability of complexes when in 1:1 metal-ligand stoichiometry, binding through two N-imine and two O-naphtholate groups.

  14. Development of a dipodal Schiff base ligand with N-imine and O-naphtholate donors: A potential chelator towards Cu(II) metal ion established through potentiometric and spectrophotometric studies

    SciTech Connect

    Baral, Minati Gupta, Amit; Kanungo, B. K.

    2015-08-28

    A novel hydroxynaphthaldehyde derived Schiff base ligand N,N’-bis-[2-[(2-hydroxy-1-naphthyl)methyleneamino]ethyl]propanediamide (DOTA2HNAP) containing nitrogen and oxygen donor atoms has been developed. The lowest energy molecular structure of DOTA2HNAP and its complexes with Cu (II) metal ion were examined by molecular mechanics using MM+ force which later was re-optimized by semi-empirical method. The theoretical IR and UV spectra of the ligand were obtained using semi empirical/ZINDO/PM3 and were compared with the experimental ones. The coordinating ability of DOTA2HNAP with H{sup +} and Cu(II) ions was investigated in 1:99 (DMSO: water) binary solvent mixture at 25±1°C by potentiometric and spectrophotometric method. The electronic spectra of the ligand show three distinct peaks (253nm, 320nm and 360nm) implicating existence of the Schiff base in quinone form that was well supported by theoretical spectral studies. Out of various complex species forming in solution, all the metal ions show higher stability of complexes when in 1:1 metal-ligand stoichiometry, binding through two N-imine and two O-naphtholate groups.

  15. Rational design, synthesis, and evaluation of tetrahydroxamic acid chelators for stable complexation of zirconium(IV).

    PubMed

    Guérard, François; Lee, Yong-Sok; Brechbiel, Martin W

    2014-05-01

    Metals of interest for biomedical applications often need to be complexed and associated in a stable manner with a targeting agent before use. Whereas the fundamentals of most transition-metal complexation processes have been thoroughly studied, the complexation of Zr(IV) has been somewhat neglected. This metal has received growing attention in recent years, especially in nuclear medicine, with the use of (89) Zr, which a β(+) -emitter with near ideal characteristics for cancer imaging. However, the best chelating agent known for this radionuclide is the trishydroxamate desferrioxamine B (DFB), the Zr(IV) complex of which exhibits suboptimal stability, resulting in the progressive release of (89) Zr in vivo. Based on a recent report demonstrating the higher thermodynamic stability of the tetrahydroxamate complexes of Zr(IV) compared with the trishydroxamate complexes analogues to DFB, we designed a series of tetrahydroxamic acids of varying geometries for improved complexation of this metal. Three macrocycles differing in their cavity size (28 to 36-membered rings) were synthesized by using a ring-closing metathesis strategy, as well as their acyclic analogues. A solution study with (89) Zr showed the complexation to be more effective with increasing cavity size. Evaluation of the kinetic inertness of these new complexes in ethylenediaminetetraacetic acid (EDTA) solution showed significantly improved stabilities of the larger chelates compared with (89) Zr-DFB, whereas the smaller complexes suffered from insufficient stabilities. These results were rationalized by a quantum chemical study. The lower stability of the smaller chelates was attributed to ring strain, whereas the better stability of the larger cyclic complexes was explained by the macrocyclic effect and by the structural rigidity. Overall, these new chelating agents open new perspectives for the safe and efficient use of (89) Zr in nuclear imaging, with the best chelators providing dramatically

  16. Reversible adsorption of catalase onto Fe(3+) chelated poly(AAm-GMA)-IDA cryogels.

    PubMed

    Aktaş Uygun, Deniz; Uygun, Murat; Akgöl, Sinan; Denizli, Adil

    2015-05-01

    In this presented study, poly(acrylamide-glycidyl methacrylate) [poly(AAm-GMA)] cryogels were synthesized by cryopolymerization technique at sub-zero temperature. Prepared cryogels were then functionalized with iminodiacetic acid (IDA) and chelated with Fe(3+) ions in order produce the metal chelate affinity matrix. Synthesized cryogels were characterized with FTIR, ESEM and EDX analysis, and it was found that the cryogel had sponge like structure with interconnected pores and their pore diameter was about 200 μm. Fe(3+) chelated poly(AAm-GMA)-IDA cryogels were used for the adsorption of catalase and optimum adsorption conditions were determined by varying the medium pH, initial catalase concentration, temperature and ionic strength. Maximum catalase adsorption onto Fe(3+) chelated poly(AAm-GMA)-IDA cryogel was found to be 12.99 mg/g cryogel at 25 °C, by using pH 5.0 acetate buffer. Adsorbed catalase was removed from the cryogel by using 1.0M of NaCl solution and desorption yield was found to be 96%. Additionally, reusability profile of the Fe(3+) chelated poly(AAm-GMA)-IDA cryogel was also investigated and it was found that, adsorption capacity of the cryogels didn't decrease significantly at the end of the 40 reuses. Catalase activity studies were also tested and it was demonstrated that desorbed catalase retained 70% of its initial activity.

  17. [Extraction of Cd by ramie from soils as affected by applications of chelators and peat].

    PubMed

    Shen, Li-Ping; Zong, Liang-Gang; Jiang, Pei; Liu, Wei-Xing; Jiang, Bo; Chen, Ya-Hua

    2009-09-15

    Pot experiments were performed to study the effectiveness of chelators (EDTA, citric acid) and peat in enhancing phyremediation of heavy metal Cd by ramie. The results showed that peat increased the ramie's biomass by improving soil's physical and chemical properties, and the relative yields of peat alone, chelators(EDTA, citric acid) combined with peat were 1.23, 1.13 and 1.41 respectively. So the combination of citric acid and peat was more useful for growth of the ramie. As far as improving Cd uptake was concerned, it seemed that the combination of chelators with peat significantly promoted Cd uptake by the plant, and the percent of changeable Cd in soil were 61.6% and 58.3% . In addition, it had better bioaccumulation effects to combine with chelators and peat, of which Cd bioaccumulation coefficients were 1.33 and 1.32, compared to 1.11, 1.11 and 1.05 in application of peat, EDTA and citric acid respectively. What's more, cadmium removal rates in soil were up to 1.13% and 1.22% respectively in applications of two kinds of chleators (EDTA, citric acid) combined with peat. Therefore, it had better effects of phytoremediation to accumulate more cadmium amounts by combining with citric acid and peat because of more biomass. In conclusion, the phytoremediation by ramie can be more effective when chelators and peat were combined and added to soils.

  18. Controlling lipid oxidation via a biomimetic iron chelating active packaging material.

    PubMed

    Tian, Fang; Decker, Eric A; Goddard, Julie M

    2013-12-18

    Previously, a siderophore-mimetic metal chelating active packaging film was developed by grafting poly(hydroxamic acid) (PHA) from the surface of polypropylene (PP) films. The objective of the current work was to demonstrate the potential applicability of this PP-g-PHA film to control iron-promoted lipid oxidation in food emulsions. The iron chelating activity of this film was investigated, and the surface chemistry and color intensity of films were also analyzed after iron chelation. In comparison to the iron chelating activity in the free Fe(3+) solution, the PP-g-PHA film retained approximately 50 and 30% of its activity in nitrilotriacetic acid (NTA)/Fe(3+) and citric acid/Fe(3+) solutions, respectively (pH 5.0), indicating a strong chelating strength for iron. The ability of PP-g-PHA films to control lipid oxidation was demonstrated in a model emulsion system (pH 3.0). PP-g-PHA films performed even better than ethylenediaminetetraacetic acid (EDTA) in preventing the formation of volatile oxidation products. The particle size and ζ potential results of emulsions indicated that PP-g-PHA films had no adverse effects on the stability of the emulsion system. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) analysis suggested a non-migratory nature of the PP-g-PHA film surface. These results suggest that such biomimetic, non-migratory metal chelating active packaging films have commercial potential in protecting foods against iron-promoted lipid oxidation. PMID:24313833

  19. MOD silver metallization for photovoltaics. Final technical report, December 1, 1983-May 31, 1985

    SciTech Connect

    Vest, G.M.; Vest, R.W.

    1985-07-01

    This was a study to investigate the feasibility of utilizing metallo-organic decomposition (MOD) silver inks for front contact metallization of solar cells. Generic synthesis procedures were developed for all metallo-organic compounds investigated. Silver neodecanoate was found to be the most suitable silver metallo-organic compound for use in thick film inks. Benzene was the most suitable solvent investigated for silver neodecanoate, and tetrahydrofuran was a less desirable alternative. A combination of neodecanoic acid and butyl carbitol acetate imparted suitable rheology to silver MOD inks for screen printing. A permanent binding agent was found to be necessary to obtain reproducible, long term adhesion. Bismuth 2-ethylhexanoate, which decomposes to bismuth oxide upon firing, was shown to be suitable for this purpose. Both platinum 2-ethylhexanoate and bismuth 2-ethylhexanoate, which respectively decompose to platinum and bismuth oxide, were suitable for imparting solder leach resistance to the silver films. Ink SC-10Y, which produces fired films of theoretical metallic composition 99 w/o Ag-1 w/o Bi, was the most suitable of all inks developed for solar cell front contact metallization. The contacts fabricated with it exhibited long term adhesion, excellent solderability and solder leach resistance, and a dense microstructure. The preferred firing sequence for ink SC-10Y involves a 70 minute cycle with a maximum temperature of 292/sup 0/C. The combination of HF cleaning and the preferred firing sequence produced a high resistance back contact with certain lots of solar cells. This observation requires that changes be made either in the metallurgy of the back contact or in the processing of the MOD inks.

  20. Feasibility study for the recycling of nickel metal hydride electric vehicle batteries. Final report

    SciTech Connect

    Sabatini, J.C.; Field, E.L.; Wu, I.C.; Cox, M.R.; Barnett, B.M.; Coleman, J.T.

    1994-01-01

    This feasibility study examined three possible recycling processes for two compositions (AB{sub 2} and AB{sub 5}) of nickel metal hydride electric vehicle batteries to determine possible rotes for recovering battery materials. Analysts examined the processes, estimated the costs for capital equipment and operation, and estimated the value of the reclaimed material. They examined the following three processes: (1) a chemical process that leached battery powders using hydrochloric acid, (2) a pyrometallurical process, and (3) a physical separation/chemical process. The economic analysis revealed that the physical separation/chemical process generated the most revenue.

  1. Development of filler metals for welding of iron aluminide alloys. Final report

    SciTech Connect

    Goodwin, G.M.; Scott, J.L.

    1995-06-29

    Attempts were made to develop a coating formulation for shielded metal arc (SMA) welding electrodes for iron aluminide alloys. Core wires of various compositions were produced by aspiration casting at ORNL and coating formulation development was conducted by Devasco, Inc. It was found that, except for weld deposit compositions containing less than 10 weight % aluminum, all weld deposits exhibited extensive cold cracking and/or porosity. It was concluded that current coating formulation technology limits successful iron aluminide deposits to less than 10 weight % aluminum.

  2. Final Report for "Stabilization of resistive wall modes using moving metal walls"

    SciTech Connect

    Forest, Cary B.

    2014-02-05

    The UW experiment used a linear pinch experiment to study the stabilization of MHD by moving metal walls. The methodology of the experiment had three steps. (1) Identify and understand the no-wall MHD instability limits and character, (2) identify and understand the thin-wall MHD instabilities (re- sistive wall mode), and then (3) add the spinning wall and understand its impact on stability properties. During the duration of the grant we accomplished all 3 of these goals, discovered new physics, and completed the experiment as proposed.

  3. Bifunctional Gallium-68 Chelators: Past, Present, and Future.

    PubMed

    Spang, Philipp; Herrmann, Christian; Roesch, Frank

    2016-09-01

    This article reviews the development of bifunctional chelates for synthesising (68)Ga radiopharmaceuticals. It structures the chelates into groups of macrocycles, nonmacrocycles, and chimeric derivatives. The most relevant bifunctional chelates are discussed in chelate structure, parameters of (68)Ga-labeling, and stability of the (68)Ga-chelate complexes. Furthermore those derivatives are included, where (67)Ga was applied instead of (68)Ga. A particular feature discussed is the ability of certain bifunctional chelate structures to function in kit-type preparation of the (68)Ga radiopharmaceuticals. Currently, nonmacrocyclic and chimeric derivates attract particular attention such as THP-derivates and DATA-derivates. PMID:27553464

  4. Method of encapsulating polyaminopolycarboxylic acid chelating agents in liposomes

    DOEpatents

    Rahman, Yueh Erh

    1977-11-10

    A method is provided for transferring a polyaminopolycarboxylic acid chelating agent across a cellular membrane by encapsulating the charged chelating agent within liposomes, which liposomes will be taken up by the cells, thereby transferring the chelating agent across the cellular membrane. The chelating agent is encapsulated within liposomes by drying a lipid mixture to form a thin film and wetting the lipid film with a solution containing the chelating agent. Mixing then results in the formation of a suspension of liposomes encapsulating the chelating agent, which liposomes can then be separated.

  5. Chemistry of carcinogenic metals.

    PubMed Central

    Martell, A E

    1981-01-01

    The periodic distribution of known and suspected carcinogenic metal ions is described, and the chemical behavior of various types of metal ions is explained in terms of the general theory of hard and soft acids and bases. The chelate effect is elucidated, and the relatively high stability of metal chelates in very dilute solutions is discussed. The concepts employed for the chelate effect are extended to explain the high stabilities of macrocyclic and cryptate complexes. Procedures for the use of equilibrium data to determine the speciation of metal ions and complexes under varying solution conditions are described. Methods for assessing the interferences by hydrogen ion, competing metal ions, hydrolysis, and precipitation are explained, and are applied to systems containing iron(III) chelates of fourteen chelating agents designed for effective binding of the ferric ion. The donor groups available for the building up of multidentate ligands are presented, and the ways in which they may be combined to achieve high affinity and selectivity for certain types of metal ions are explained. PMID:6791915

  6. Silicon halide-alkali metal flames as a source of solar grade silicon. Final report

    SciTech Connect

    Olson, D.B.; Miller, W.J.; Gould, R.K.

    1980-01-01

    The object of this program was to determine the feasibility of using continuous high-temperature reactions of alkali metals and silicon halides to produce silicon in large quantities and of suitable purity for use in the production of photovoltaic solar cells. Equilibrium calculations showed that a range of conditions were available where silicon was produced as a condensed phase but the byproduct alkali metal salt was a vapor. A process was proposed using the vapor phase reaction of Na with SiCl/sub 4/. Low pressure experiments were performed demonstrating that free silicon was produced and providing experience with the construction of reactant vapor generators. Further experiments at higher reagent flow rates were performed in a low temperature flow tube configuration with co-axial injection of reagents. Relatively pure silicon was produced in these experiments. A high temperature graphite flow tube was built and continuous separation of Si from NaCl was demonstrated. A larger-scaled well-stirred reactor was built. Experiments were performed to investigate the compatibility of graphite-based reactor materials of construction with sodium. At 1100 to 1200 K none of these materials were found to be suitable. At 1700 K the graphites performed well with little damage except to coatings of pyrolytic graphite and silicon carbide which were damaged.

  7. Kinetics and Mechanism of Metal Retention/Release in Geochemical Processes in Soil - Final Report

    SciTech Connect

    Taylor, Robert W.

    2000-12-29

    Effective, remediation of soils contaminated with heavy metals requires a better understanding of the mechanisms by which the metals are retained/released in soils over a long period of time. Studies on reaction of Cr(VI) with iron-rich clays indicated that structural iron (II) in these surfaces is capable of reducing chromate to chromium (III). We found that iron (II) either found naturally or produced by treatment of clay with sodium dithionite, effectively reduced Cr (VI) to Cr (III). Thus, in situ remediation of chromium combines reduction of Cr (VI) to Cr (III) and immobilization of chromium on mineral surfaces. During this study, lead sorption on a kaolin surface was found to be a rapid and a pH dependant process in which lead sorption significantly increased with the amount of phosphate on the clay surface. This study verifies that methylmercury cation remains intact when it binds to humic acids, forming a monodentate complex with some sub-population of humic thiol ligands .

  8. Final Report Theoretical Studies of Surface Reactions on Metals and Electronic Materials

    SciTech Connect

    Jerry L. Whitten

    2012-04-23

    This proposal describes the proposed renewal of a theoretical research program on the structure and reactivity of molecules adsorbed on transition metal surfaces. A new direction of the work extends investigations to interfaces between solid surfaces, adsorbates and aqueous solutions and includes fundamental work on photoinduced electron transport into chemisorbed species and into solution. The goal is to discover practical ways to reduce water to hydrogen and oxygen using radiation comparable to that available in the solar spectrum. The work relates to two broad subject areas: photocatalytic processes and production of hydrogen from water. The objective is to obtain high quality solutions of the electronic structure of adsorbate-metal-surface-solution systems so as to allow activation barriers to be calculated and reaction mechanisms to be determined. An ab initio embedding formalism provides a route to the required accuracy. New theoretical methods developed during the previous grant period will be implemented in order to solve the large systems involved in this work. Included is the formulation of a correlation operator that is used to treat localized electron distributions such as ionic or regionally localized distributions. The correlation operator which is expressed as a two-particle projector is used in conjunction with configuration interaction.

  9. Temperature dependent nonlinear metal matrix laminae behavior. Final technical report, December 1984-November 1985

    SciTech Connect

    Barrett, D.J.; Buesking, K.W.

    1986-09-01

    An analytical method is described for computing the nonlinear thermal and mechanical response of laminated plates. The material model focuses upon the behavior of metal matrix materials by relating the nonlinear composite response to plasticity effects in the matrix. The foundation of the analysis is the unidirectional material model which is used to compute the instantaneous properties of the lamina based upon the properties of the fibers and matrix. The unidirectional model assumes that the fibers properties are constant with temperature and assumes that the matrix can be modelled as a temperature dependent, bilinear, kinematically hardening material. An incremental approach is used to compute average stresses in the fibers and matrix caused by arbitrary mechanical and thermal loads. The layer model is incorporated in an incremental laminated plate theory to compute the nonlinear response of laminated metal matrix composites of general orientation and stacking sequence. The report includes comparisons of the method with other analytical approaches and compares theoretical calculations with measured experimental material behavior. A section is included which describes the limitations of the material model.

  10. Microbial recovery of metals from spent coal liquefaction catalysts. Final report

    SciTech Connect

    Sperl, P.L.; Sperl, G.T.

    1995-07-01

    This project was initiated on October 1, 1989, for the purpose of recovering metals from spent coal liquefaction catalysts. Two catalyst types were the subject of the contract. The first was a Ni-No catalyst support on alumina (Shell 324), the catalyst used in a pilot scale coal liquefaction facility at Wilsonville, Alabama. The second material was an unsupported ammonium molybdate catalyst used in a pilot process by the Department of Energy at the Pittsburgh Energy Technology Center. This material was obtained in late February 1990 but has not been pursued since the Mo content of this particular sample was too low for the current studies and the studies at the Pittsburgh Energy Technology Center have been discontinued. The object of the contract was to treat these spent catalysts with microorganisms, especially Thiobacillus ferrooxidans , but also other Thiobacillus spp. and possibly Sulfolobus and other potential microorganisms, to leach and remove the metals (Ni and Mo) from the spent catalysts into a form which could be readily recovered by conventional techniques.

  11. CaNa2EDTA chelation attenuates cell damage in workers exposed to lead--a pilot study.

    PubMed

    Čabarkapa, A; Borozan, S; Živković, L; Stojanović, S; Milanović-Čabarkapa, M; Bajić, V; Spremo-Potparević, B

    2015-12-01

    Lead induced oxidative cellular damage and long-term persistence of associated adverse effects increases risk of late-onset diseases. CaNa2EDTA chelation is known to remove contaminating metals and to reduce free radical production. The objective was to investigate the impact of chelation therapy on modulation of lead induced cellular damage, restoration of altered enzyme activities and lipid homeostasis in peripheral blood of workers exposed to lead, by comparing the selected biomarkers obtained prior and after five-day CaNa2EDTA chelation intervention. The group of smelting factory workers diagnosed with lead intoxication and current lead exposure 5.8 ± 1.2 years were administered five-day CaNa2EDTA chelation. Elevated baseline activity of antioxidant enzymes Cu, Zn-SOD and CAT as well as depleted thiols and increased protein degradation products-carbonyl groups and nitrites, pointing to Pb induced oxidative damage, were restored toward normal values following the treatment. Lead showed inhibitor potency on both RBC AChE and BChE in exposed workers, and chelation re-established the activity of BChE, while RBC AChE remained unaffected. Also, genotoxic effect of lead detected in peripheral blood lymphocytes was significantly decreased after therapy, exhibiting 18.9% DNA damage reduction. Administration of chelation reversed the depressed activity of serum PON 1 and significantly decreased lipid peroxidation detected by the post-chelation reduction of MDA levels. Lactate dehydrogenase LDH1-5 isoenzymes levels showed evident but no significant trend of restoring toward normal control values following chelation. CaNa2EDTA chelation ameliorates the alterations linked with Pb mediated oxidative stress, indicating possible benefits in reducing health risks associated with increased oxidative damage in lead exposed populations.

  12. Thermal Conductivity and Thermopower near the 2D Metal-Insulator transition, Final Technical Report

    SciTech Connect

    SARACHIK, MYRIAM P

    2015-02-20

    STUDIES OF STRONGLY-INTERACTING 2D ELECTRON SYSTEMS – There is a great deal of current interest in the properties of systems in which the interaction between electrons (their potential energy) is large compared to their kinetic energy. We have investigated an apparent, unexpected metal-insulator transition inferred from the behavior of the temperature-dependence of the resistivity; moreover, detailed analysis of the behavior of the magnetoresistance suggests that the electrons’ effective mass diverges, supporting this scenario. Whether this is a true phase transition or crossover behavior has been strenuously debated over the past 20 years. Our measurements have now shown that the thermoelectric power of these 2D materials diverges at a finite density, providing clear evidence that this is, in fact, a phase transition to a new low-density phase which may be a precursor or a direct transition to the long sought-after electronic crystal predicted by Eugene Wigner in 1934.

  13. Dimensional, microstructural and compositional stability of metal fuels. Final performance report

    SciTech Connect

    Solomon, A.A.; Dayananda, M.A.

    1993-03-15

    The projects undertaken were to address two areas of concern for metal-fueled fast reactors: metallurgical compatibility of fuel and its fission products with the stainless steel cladding, and effects of porosity development in the fuel on fuel/cladding interactions and on sodium penetration in fuel. The following studies are reported on extensively in appendices: hot isostatic pressing of U-10Zr by coupled boundary diffusion/power law creep cavitation, liquid Na intrusion into porous U-10Zr fuel alloy by differential capillarity, interdiffusion between U-Zr fuel and selected Fe-Ni-Cr alloys, interdiffusion between U-Zr fuel vs selected cladding steels, and interdiffusion of Ce in Fe-base alloys with Ni or Cr.

  14. Electron Microscopy Characterization of Tc-Bearing Metallic Waste Forms- Final Report FY10

    SciTech Connect

    Buck, Edgar C.; Neiner, Doinita

    2010-09-30

    The DOE Fuel Cycle Research & Development (FCR&D) Program is developing aqueous and electrochemical approaches to the processing of used nuclear fuel that will generate technetium-bearing waste streams. This final report presents Pacific Northwest National Laboratory (PNNL) research in FY10 to evaluate an iron-based alloy waste form for Tc that provides high waste loading within waste form processing limitations, meets waste form performance requirements for durability and the long-term retention of radionuclides and can be produced with consistent physical, chemical, and radiological properties that meet regulatory acceptance requirements for disposal.

  15. Metal hydride/chemical heat-pump development project. Phase I. Final report

    SciTech Connect

    Argabright, T.A.

    1982-02-01

    The metal hydride/chemical heat pump (MHHP) is a chemical heat pump containing two hydrides for the storage and/or recovery of thermal energy. It utilizes the heat of reaction of hydrogen with specific metal alloys. The MHHP design can be tailored to provide heating and/or cooling or temperature upgrading over a wide range of input and ambient temperatures. The system can thus be used with a variety of heat sources including waste heat, solar energy or a fossil fuel. The conceptual design of the MHHP was developed. A national market survey including a study of applications and market sectors was conducted. The technical tasks including conceptual development, thermal and mechanical design, laboratory verification of design and material performance, cost analysis and the detailed design of the Engineering Development Test Unit (EDTU) were performed. As a result of the market study, the temperature upgrade cycle of the MHHP was chosen for development. Operating temperature ranges for the upgrader were selected to be from 70 to 110/sup 0/C (160 to 230/sup 0/F) for the source heat and 140 to 190/sup 0/C (280 to 375/sup 0/F) for the product heat. These ranges are applicable to many processes in industries such as food, textile, paper and pulp, and chemical. The hydride pair well suited for these temperatures is LaNi/sub 5//LaNi/sub 4/ /sub 5/Al/sub 0/ /sub 5/. The EDTU was designed for the upgrade cycle. It is a compact finned tube arrangement enclosed in a pressure vessel. This design incorporates high heat transfer and low thermal mass in a system which maximizes the coefficient of performance (COP). It will be constructed in Phase II. Continuation of this effort is recommended.

  16. Chemical vapor deposition of metal nitrides, phosphides and arsenides. Final report

    SciTech Connect

    Hoffman, D.M.

    1994-03-01

    The author recently reported that dialkylamido complexes are promising precursors to nitride thin films. On this basis it was reasoned that transition metal and main group disilazide complexes in which the silicon has dialkylamido substituents are potential precursors to ternary silicon nitride films. Bulky disilazide ligands are known to stabilize main group and transition metal complexes with low coordination numbers. Reaction of dimethylamine with Cl{sub 3}SiN(H)SiMe{sub 3} in hexane solution at 25{degrees}C gave the bulky disilazane [(Me{sub 2}N){sub 3}Si]N(h)SiMe{sub 3} (1) in 73% yield. Reaction of (1) with n-butyl lithium in benzene at 0{degrees}C produced [(Me{sub 2}N){sub 3}Si]N(Li)SiMe{sub 3} in 82% yield. LiN[Si(NMe{sub 2}){sub 3}]{sub 2} was chemically prepared in 92% yield and was converted to the amine with 83% yield. The author examined the use of amido precursors for main group oxide thin films. Sn(NMe{sub 2}){sub 4} and Si(NMe{sub 2}){sub 4} react with oxygen in an atmospheric pressure chemical vapor deposition reactor to give SnO{sub 2} and SiO{sub 2} films, respectively. The films were deposited on quartz, silicon, and glass at substrate temperatures of 250--400 {degrees}C. The results of the characterizations of the films and compounds are presented in this report.

  17. Alternative granular media for the metal casting industry. Final report, September 30, 1994

    SciTech Connect

    Guichelaar, P.J.; Ramrattan, S.N.; Tieder, R.E.

    1995-09-01

    Silica sand for foundry use is inexpensive to purchase, readily transported and widely available. As a result, it is universally used. However, three factors are becoming increasingly significant as more environmental regulations are promulgated. First, the disposal of waste foundry sand has become an excessively burdensome cost. Second, the phase changes which occur in the silica structure on heating and cooling cause thermal breakdown of the sand into smaller unusable fractions. Third, silica is a relatively weak mineral. Alternatives to silica sand which can withstand the rigors of repetitive reuse must be seriously evaluated as a way to control production costs of the domestic metal casting industry. Chromite sands, olivine sands and carbon sands have each been successfully used to solve operating problems and thus have developed their specific niches in the foundry materials inventory. However, there are several other materials that are candidates for replacing silica sand, such as fused alumina, sintered bauxite and sintered oil well proppants. These media, and others that are generically similar, are manufactured for specific purposes. Compositions and shapes could be readily tailored for used in a metal casting environment of total recycling and materials conservation. This study examines materials that are readily available as alternatives to silica sand from a functionality perspective and a cost perspective. Some of the alternative materials are natural and others are synthetic and thus referring to them as ``sands`` has the potential to cause confusion; the generic term ``granular medium`` is used in this study to mean any material that could functionally substitute for silica sand in the foundry process.

  18. Evaluation of Durable Metallic Supports for Catalytic Combustors, CRADA Final Report ORNL 00-0570

    SciTech Connect

    Pint, B. A.; Wright, I. G.; Lara-Curzio, E.; McCarty, J.; Barnes, J.

    2003-10-01

    In 2000, a Cooperative Research and Development Agreement (CRADA) was undertaken between the Oak Ridge National Laboratory (ORNL) and Catalytica Energy Systems Incorporated (CESI) to determine the properties of current metallic catalyst supports and examine new candidate alloys for this application. A team was established at ORNL to examine oxidation-limited lifetime of these thin-walled metallic components using standard lifetime models and to measure the mechanical properties of the foils (40-200:m in thickness) which can differ substantially from bulk properties. Oxidation experiments were conducted on foil specimens at 700/-1100/C in laboratory air and in air with 10 vol.% water vapor to better simulate the combustor environment. At the higher test temperatures, time to oxidation-induced (i.e. breakaway oxidation) failure was determined in 1h cycles in order to verify predictions from a standard reservoir-type oxidation lifetime model. Selected specimens were run for >10,000h in 100 or 500h cycles at lower test temperatures in order to determine the oxidation kinetics for the model. The creep properties of selected foils were measured for 4,000-8,000h at operation-relevant stresses and temperatures. None of the new candidate alloys significantly out-performed currently used alloys in laboratory testing, particularly in oxidation lifetime testing. Therefore, engine testing was not performed on any of the new candidate alloys. Both the oxidation- and creep-resistance of FeCrAl alloys was greater than expected and the results of the CRADA allowed CESI to extend life or increase operating temperatures for these lower cost substrate alloys in the next generation of catalyst modules.

  19. Multivalent chelators for spatially and temporally controlled protein functionalization.

    PubMed

    You, Changjiang; Piehler, Jacob

    2014-05-01

    Site-specific protein modification-e.g. for immobilization or labelling-is a key prerequisite for numerous bioanalytical applications. Although modification by use of short peptide tags is particularly attractive, efficient and bio-orthogonal systems are still lacking. Here, we review the application of multivalent chelators (MCH) for high-affinity yet reversible recognition of oligohistidine (His)-tagged proteins. MCH are based on multiple nitrilotriacetic acid (NTA) moieties grafted on to molecular scaffolds suitable for conjugation to surfaces, probes or other biomolecules. Reversible interaction with the His-tag is mediated via transition metal ions chelated by the NTA moieties. The small size and biochemical compatibility of these recognition units and the possibility of rapid dissociation of the interaction with His-tagged proteins despite sub-nanomolar binding affinity, enable distinct and versatile handling and modification of recombinant proteins. In this review, we briefly introduce the key principles and features of MCH-His-tag interactions and recapitulate the broad spectrum of bioanalytical applications with a focus on quantitative protein interaction analysis on micro or nano-patterned solid surfaces and specific protein labelling in living cells. PMID:24770786

  20. Synthesis, XAFS and X-ray structural studies of mono- and binuclear metal-chelates of N,O,O(N,O,S) tridentate Schiff base pyrazole derived ligands

    NASA Astrophysics Data System (ADS)

    Burlov, Anatolii S.; Uraev, Ali I.; Garnovskii, Dmitrii A.; Lyssenko, Konstantin A.; Vlasenko, Valery G.; Zubavichus, Yan V.; Murzin, Vadim Yu.; Korshunova, Eugenie V.; Borodkin, Gennadii S.; Levchenkov, Sergey I.; Vasilchenko, Igor S.; Minkin, Vladimir I.

    2014-05-01

    The syntheses of a series of novel N,O,O and N,O,S donor tridentate Schiff base ligands H2L1 and H2L2via the condensation of 1-phenyl-3-methyl-4-formylpyrazol-5-ol(thiol) with 2-hydroxymethylaniline and their Co(II), Ni(II), Cu(II), Fe(III), and Mn(II) complexes are reported. The compounds are characterized by the C, H, N, S, metal elemental analysis, IR spectroscopy; 1H NMR data for ligands, low-temperature magnetic measurements, X-ray absorption spectroscopy. The crystal structures for Ni(II) and Cu(II) coordination compounds with the compositions NiL21 and CuL21 are established by X-ray crystallography.

  1. Spectroscopic and structural studies of new mononucleating tetradentate Schiff base metal chelates derived from 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione and 1,3-diaminopropane

    NASA Astrophysics Data System (ADS)

    Adly, Omima M. I.; Taha, Ali; Fahmy, Shery A.

    2015-08-01

    Metal complexes with the general formula Some newly transition metal complexes, [ML(H2O)x(NO3)y], x = 1-2 and y = 0-1, [M = Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Ce(III), Cd(II), Zn(II) or UO2(VI)], L= of the Schiff base (H2L) derived from the reaction of 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione with 1,3-diaminopropane have been prepared and characterized by physical, spectral and analytical data. The structure of the Schiff - base acts as dibasic tetradentate N2O2 for the complexation reaction with Cr(III), Fe(III), Co(II), Cu(II), Ni(II), Ce(III), Cd(II), and UO2(II) ions via phenolates oxygen and nitrogen of azomethine groups. Based on spectral data and magnetic moments, an octahedral geometry may be proposed for the synthesized complexes except cerium(III) complex which has pentagonal bipyramidal arrangement. The low values of the molar conductance indicate non-electrolyte nature of complexes, while 1:1 electrolyte for cerium(III)- and chromium(III)-complexes. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. All the synthesized compounds were tested for in vitro antibacterial activity against some Gram-positive and Gram-negative bacteria, yeast and fungus. Molecular structure of the Schiff base ligand and its complexes were optimized for the proposed structures on the basis of semiempirical PM3 method.

  2. Biodegradable chelating agents for industrial, domestic, and agricultural applications--a review.

    PubMed

    Pinto, Isabel S S; Neto, Isabel F F; Soares, Helena M V M

    2014-10-01

    Aminopolycarboxylates, like ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), are chelating agents widely used in several industrial, agricultural, and domestic applications. However, the fact that they are not biodegradable leads to the presence of considerable amounts in aquatic systems, with serious environmental consequences. The replacement of these compounds by biodegradable alternatives has been the object of study in the last three decades. This paper reviews the most relevant studies towards the use of environmentally friendly chelating agents in a large number of applications: oxidative bleaching, detergents and cleaning compositions, scale prevention and reduction, remediation of soils, agriculture, electroplating, waste treatment, and biocides. Nitrilotriacetic acid (NTA), ethylenediaminedisuccinic acid (EDDS), and iminodisuccinic acid (IDS) are the most commonly suggested to replace the nonbiodegradable chelating agents. Depending on the application, the requirements for metal complexation might differ. Metal chelation ability of the most promising compounds [NTA, EDDS, IDS, methylglycinediacetic acid (MGDA), L-glutamic acid N,N-diacetic acid (GLDA), ethylenediamine-N,N'-diglutaric acid (EDDG), ethylenediamine-N,N'-dimalonic acid (EDDM), 3-hydroxy-2,2-iminodisuccinic acid (HIDS), 2-hydroxyethyliminodiacetic acid (HEIDA), pyridine-2,6-dicarboxylic acid (PDA)] with Fe, Mn, Cu, Pb, Cd, Zn, Ca, and Mg was simulated by computer calculations. The advantages or disadvantages of each compound for the most important applications were discussed.

  3. The Metal-Lax method of stress reduction in welds. Final report

    SciTech Connect

    Not Available

    1991-12-31

    The preliminary project to evaluate the possibility of replacing or reducing thermal stress relief and preheat with sub-resonant vibration has been completed. Bonal Technologies manufactures the Meta-Lax system of sub-resonant vibration for use in industry and has met with success on many occasions. The uses are varied and cross into many industries, including fabrication, foundries, and marine construction. However, the specific engineering or scientific basis for the successes has proven to be very elusive. The purpose of this preliminary evaluation of the Meta-Lax system was to try and determine what is happening when sub-resonant vibration is introduced during and/or after welding operations. The final goal is to determine if this process can replace or reduce thermal stress relief and preheat now required on many welded assemblies. The potential savings could be enormous.

  4. Current approach to iron chelation in children.

    PubMed

    Aydinok, Yesim; Kattamis, Antonis; Viprakasit, Vip

    2014-06-01

    Transfusion-dependent children, mostly with thalassaemia major, but also and occasionally to a more significant degree, with inherited bone marrow failures, can develop severe iron overload in early life. Moreover, chronic conditions associated with ineffective erythropoiesis, such as non-transfusion-dependent thalassaemia (NTDT), may lead to iron overload through increased gut absorption of iron starting in childhood. Currently, the goal of iron chelation has shifted from treating iron overload to preventing iron accumulation and iron-induced end-organ complications, in order to achieve a normal pattern of complication-free survival and of quality of life. New chelation options increase the likelihood of achieving these goals. Timely initiation, close monitoring and continuous adjustment are the cornerstones of optimal chelation therapy in children, who have a higher transfusional requirements compared to adults in order to reach haemoglobin levels adequate for normal growth and development. Despite increased knowledge, there are still uncertainties about the level of body iron at which iron chelation therapy should be started and about the appropriate degree of iron stores' depletion.

  5. Thermal Stability of Chelated Indium Activable Tracers

    SciTech Connect

    Chrysikopoulos, Costas; Kruger, Paul

    1986-01-21

    The thermal stability of indium tracer chelated with organic ligands ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) was measured for reservoir temperatures of 150, 200, and 240 C. Measurements of the soluble indium concentration was made as a function of time by neutron activation analysis. From the data, approximate thermal decomposition rates were estimated. At 150 C, both chelated tracers were stable over the experimental period of 20 days. At 200 C, the InEDTA concentration remained constant for 16 days, after which the thermal decomposition occurred at a measured rate constant of k = 0.09 d{sup -1}. The thermal decomposition of InNTA at 200 C showed a first order reaction with a measured rate constant of k = 0.16 d{sup -1}. At 240 C, both indium chelated tracers showed rapid decomposition with rate constants greater than 1.8 d{sup -1}. The data indicate that for geothermal reservoir with temperatures up to about 200 C, indium chelated tracers can be used effectively for transit times of at least 20 days. These experiments were run without reservoir rock media, and do not account for concomitant loss of indium tracer by adsorption processes.

  6. Development of an upconverting chelate assay

    NASA Astrophysics Data System (ADS)

    Xiao, Xudong; Haushalter, Jeanne P.; Kotz, Kenneth T.; Faris, Gregory W.

    2005-04-01

    We report progress on performing a cell-based assay for the detection of EGFR on cell surfaces by using upconverting chelates. An upconversion microscope has been developed for performing assays and testing optical response. A431 cells are labeled with europium DOTA and imaged using this upconverting microscope.

  7. Vadose zone microbial community structure and activity in metal/radionuclide contaminated sediments. Final technical report

    SciTech Connect

    Balkwill, David L.

    2002-08-17

    This final technical report describes the research carried out during the final two months of the no-cost extension ending 11/14/01. The primary goals of the project were (1) to determine the potential for transformation of Cr(VI) (oxidized, mobile) to Cr(III) (reduced, immobile) under unsaturated conditions as a function of different levels and combinations of (a) chromium, (b) nitrate (co-disposed with Cr), and (c) molasses (inexpensive bioremediation substrate), and (2) to determine population structure and activity in experimental treatments by characterization of the microbial community by signature biomarker analysis and by RT-PCR and terminal restriction fragment length polymorphism (T-RFLP) and 16S ribosomal RNA genes. It was determined early in the one-year no-cost extension period that the T-RFLP approach was problematic in regard to providing information on the identities of microorganisms in the samples examined. As a result, it could not provide the detailed information on microbial community structure that was needed to assess the effects of treatments with chromium, nitrate, and/or molasses. Therefore, we decided to obtain the desired information by amplifying (using TR-PCR, with the same primers used for T-RFLP) and cloning 16S rRNA gene sequences from the same RNA extracts that were used for T-RFLP analysis. We also decided to use a restriction enzyme digest procedure (fingerprinting procedure) to place the clones into types. The primary focus of the research carried out during this report period was twofold: (a) to complete the sequencing of the clones, and (b) to analyze the clone sequences phylogenetically in order to determine the relatedness of the bacteria detected in the samples to each other and to previously described genera and species.

  8. Hydrogasification of carbon adsorbed on sulfur-poisoned dispersed metal catalysts. Final report

    SciTech Connect

    McCarty, J.G.; Wood, B.J.

    1993-12-01

    The temperature programmed reaction of 1- to 10-atom hydrogen (TPRH) with carbon deposited on alumina supported Ni, Ru, and Co and on fused Fe catalysts has been developed to examine the effect of sulfur poisoning on coking rates and the nature of the deposited carbon. A new procedure, passivation by carbon deposition on clean reduced metals and low temperature (20--50 C) exposure to recirculate dilute H{sub 2}S with moderate 0.1 atm partial pressure of CO{sub 2} was used to slow the rate of sulfur chemisorption. This method facilitated slow uniform sulfur chemisorption to fractional saturation coverages. Fractional sulfur poisoning generally blocked sites of active surface carbon (or hydrocarbon fragments) while suppressing rates of hydrogasification as shown by the increasing temperatures in the TPRH hydrogasification rate versus temperature spectra. Fractional sulfur poisoning (e.g., half saturation) appears to inhibit H{sub 2} gasification with surface carbon surprisingly without strongly affecting catalytic activity. Sulfur poisoning to saturation levels (defined here as {approximately}1 ppm H{sub 2}S in 1-atm H{sub 2} at 500 C) always results in complete loss of activity and is also marked by the growth of a very unreactive form of carbon.

  9. Interaction of highly vibrationally excited molecules with clean metal surfaces. Final technical report

    SciTech Connect

    Wodtke, A.M.; Auerbach, D.J.

    1998-11-01

    The authors present results from a grant funded under the Department of Energy Office of Basic Energy Sciences. A collaboration between Prof. Alec Wodtke of the Department of Chemistry at UCSB and Daniel J. Auerbach of IBM Almaden Research Labs has allowed new experiments on the dynamics of surface chemical reactivity to be successfully executed. High quality data has been generated which provides an excellent test of theoretical models of surface reactivity, a topic of importance to catalysis. The authors have obtained the first experimental measurements on the influence of reactant velocity on the steric effect in a chemical reaction: the dissociative adsorption of hydrogen on copper. They have also designed and built a molecular beam scattering apparatus for the study of highly vibrationally excited molecules and their interactions with clean and oxidized metal surfaces. With this apparatus they have observed the vibrational energy exchange of highly vibrationally excited NO with an oxidized copper surface. Multi-quantum vibrational relaxation was found ({Delta}v = 1-5). Such remarkably strong and efficient vibrational energy transfer represents a qualitatively new phenomenon and is representative of the exciting new behavior that they had hoped might be observable in this project. Evidence of chemical reactivity of vibrationally excited NO on a clean copper surface was also found.

  10. Metal hydride preheater for the M2 diesel burner. Final report, September 1992--October 1997

    SciTech Connect

    Gerstmann, J.; Golben, M.

    1999-03-01

    This report describes the results of a Phase 1 Small Business Innovative Research (SBIR) project to demonstrate the feasibility of preheating the catalytic generator of the M2 diesel burner using a metal hydride preheater. Preliminary testing of an electrically heated generator showed that the originally proposed concept of preheating the catalytic generator of the burner would have resulted in excessive weight for the hydride system. An alternate approach of preheating only the 'superheater,' and using it to vaporize the fuel at start-up, was implemented instead. This resulted in an extremely compact and lightweight burner system that ignited cleanly an rapidly. The Phase 1 results indicate that the 'hydride superheater' is an effective means of obtaining clean ignition of a diesel cook stove burner. Furthermore, the resulting burner is considerably smaller and lighter than the M2 burner. Additional work is required to optimize the designs of the preheater and the superheater, to scale-up the capacity of the burner and to develop practical burner controls.

  11. High-aspect-ratio silicon-cell metallization technical status report. Final report

    SciTech Connect

    Not Available

    1982-01-01

    Two features of the silicon concentrator solar cell are addressed which affect output at high concentration levels. The first is the development of narrow but high electroplated grid lines with improved conductivity. The object is a reduction in cell series resistance without increase in shadowing. This goal is accomplished by electroplating through a thick photo resist mask to produce lines .7 mil wide by .7 mil high. Advance pulse plating techniques are combined with pure silver plating baths to produce a deposit conductivity equal to the bulk silver conductivity (a 1.5 to 2 X improvement over conventional silver plating). The second feature is a double diffused selectively textured front surface. This development employs a deep diffusion in the silicon under the grid lines. Only the non grid line open area is selectively texture etched removing the deep junction. This open textured area is then given a second shallow diffusion for optimum cell efficiency. This selective procedure maintains the original highly polished wafer surface under the grid lines so that high resolution narrow grid lines are possible. The double diffusion protects the junction from metal diffusion while enabling the optimum shallow junction in the illuminated regions. Combining these two features has produced a large area concentrator cells (8 cm/sup 2/) with peak efficiency above 16% and exhibiting a broad peak efficiency extending from 50 to 175 suns above 15%.

  12. Feasibility of synthesizing oxide films on ceramic and metal substrates. Final report, August 1994--May 1995

    SciTech Connect

    Brown, I.G.

    1995-07-01

    Feasibility of synthesizing highly adherent alumina and chromia films on SiC and FeAl substrates using plasma methods was studied. A magnetically filtered, cathodic-arc-produced, metal plasma (Al or Cr) is deposited on the substrate in presence of low pressure oxygen while the substrate is repetitively pulse biased for control of incident ion energy. In the early stages, the ion energy is held in the keV range to produce atomic mixing at the film-substate interface (ion stitching); in the latter stages, the energy is reduced to about 200 eV (IBAD, or ion beam assisted deposition, range) to control the film structure and morphology. Near-stoichiometric films of alumina and chromia were formed on small SiC and FeAl substrates and characterized by RBS, XRD, adhesion, and temperature cycling. The aluminia films were 0.2 to 1.5 {mu} thick, were amorphous prior to heat treatment, and showed an {alpha}-alumina phase after heat treating at 1000 C for up to 16 h. Film substrate adhesion was typically greater than 70 MPa prior to heating, and the thinner films maintained their adhesion even after repetitive cycling in temperature between ambient and 1000 C. It is concluded that the plasma and ion beam techniques developed provide important tools for forming highly adherent and thermally tolerant ceramic films.

  13. Using optical pyrometry to measure gas turbine blade metal temperatures: Final report

    SciTech Connect

    Lindsey, O.L.

    1988-12-01

    This report presents the experience gained by field testing an infrared optical pyrometer as a Turbine Blade Temperature Measurement System (TBTMS). This system was designed, built, and tested to make diagnostic measurements on an operating gas turbine at the T.H. Wharton Station of Houston Lighting and Power. The TBTMS is comprised of a probe assembly, an optical conduit, a detector, and a signal processor. The system senses thermal radiation from the turbine blades and transforms that signal into a real time value indicating the blade metal surface temperature. The information supplied by the TBTMS was recorded by a data acquisition system that also gathered information about the operation and performance of the engine. The information from the TBTMS was correlated with the critical operating parameters of the engine over a span of approximately 7000 hours. Initial performance of the TBTMS was satisfactory, and the configuration proved reasonably durable, demonstrating the value of such a probe for diagnosing engine conditions. Most notably, the pyrometer detected several blades that were consistently hotter than adjacent blades; such conditions could lead to shorter blade life. The report discusses blade temperature profiles and math models for predicting the durability of the blades. Recommendations were included which addressed design improvements for future TBTMS. 56 figs.

  14. Shortened forms of provocative lead chelation

    SciTech Connect

    Sokas, R.K.; Atleson, J.; Keogh, J.P.

    1988-05-01

    Shortened urinary lead collections following provocative chelation have been standardized for pediatric patients, but have not been considered adequate for adults. This study compared shortened urine collections for lead excretion post chelation with standard 24-hour collections. Thirty-five patients without known current lead exposure and with serum creatinine measurements less than 2 mg/dL were hospitalized and had provocative chelation performed as follows: One gram of CaNa2-ethylenediaminetetraacetic acid (EDTA) was administered in 250 mL of a 5% dextrose in water solution intravenously over one hour; the same dose was repeated 12 hours later. A 24-hour urine collection for lead excretion was begun at the time of initiation of the first dose. At three hours and six hours from start of first dose, each patient was instructed to void, total volume to that point was recorded, and a 10-mL aliquot was withdrawn for lead measurement. Both three-hour and six-hour urinary lead excretion following a single dose of EDTA correlated linearly with 24-hour lead excretion post chelation (r = .89 and .94, respectively). When a 24-hour level of 600 micrograms was defined as true positive the three-hour collection had a sensitivity of 76% and specificity of 95% and six-hour urinary lead excretion had 82% sensitivity and 100% specificity. Mild renal insufficiency (reflected by serum creatinine levels between 1.5 and 2.1 mg/dL) did not significantly alter the correlation between three-, six-, and 24-hour urinary post-chelation lead excretion.

  15. Chelation in metal intoxication. XIII. Polyaminocarboxylic acids as chelators in lead poisoning

    SciTech Connect

    Tandon, S.K.; Behari, J.R.; Singh, S.

    1983-01-01

    Diethylene-triaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA) and hydroxyethylene-diaminetriacetic acid (HEDTA) were investigated for their ability to reduce Pb body burden and to restore altered urinary and blood parameters in Pb-poisoned rats.

  16. Integrated superhard and metallic coatings for MEMS : LDRD 57300 final report.

    SciTech Connect

    de Boer, Maarten Pieter; Maboudian, Roya

    2004-12-01

    positive. The tribology of poly-SiC was also investigated. Much improved release stiction and in-use stiction performance relative to polysilicon MEMS was found. Furthermore, wear of poly-SiC-coated MEMS was much reduced relative to uncoated polysilicon MEMS. A prototype baseline process flow now exists to produce poly-SiC in the Berkeley Sensor and Actuator (BSAC) facility. In the second project, galvanic deposition of metals onto polysilicon surfaces has been developed. The possible applications include reflective and optical coatings for optical MEMS, microswitches and microrelays for radio frequency MEMS and catalytic surfaces for microchemical reactors. In contrast to electroless deposition, galvanic displacement deposition requires no prior activation of the surface and is truly selective to silicon surfaces. This approach was used to deposit copper, gold and rhodium onto polysilicon MEMS. A method to study the adhesion of these metals to polysilicon was developed. It was also shown that the surfaces could be rendered hydrophobic by applying thiol-based self-assembled monolayers. This procedure also lowered their surface energy to {approx}3 {micro}J/m{sup 2}, consistent with monolayer-coated polysilicon MEMS.

  17. Flow through luminescence for heavy metal analysis in seawater

    NASA Astrophysics Data System (ADS)

    San Vicente De la Riva, Blanca; Costa Fernandez, Jose M.; Pereiro Garcia, Rosario; Sanz-Medel, Alfredo

    1999-12-01

    The toxicity of heavy metals is well documented today and legislation for their control in seawater continuously becomes more and more restrictive. In order to control and ensure the marine environment quality it is demanded an effort to develop new analytical tools, which allow the analysis of trace levels of heavy metals in seawater. The measurement of luminescence (phosphorescence and fluorescence) gives rise to high sensitive, selective and innovative approaches which could be used to develop new trace metal sensing methods. In this way, we have observed that the metal-chelates formed between different sulphonic-hydroxyquinolines with heavy metals, such as lead, or the metal-chelates between mercury and purines exhibit strong room temperature phosphorescence and fluorescence, respectively. Based on the formation of such quelates, two luminescence methods are investigated for sensing of lead and mercury in seawater. Optimum experimental conditions and the analytical performance characteristics of the methods are discussed. Relative standard deviations in the order of 4% are typical at 100 ng mL-1 of Pb(II) and Hg (II). The detection limits are 0.1 and 1.4 ng mL-1 for lead and mercury, respectively. Possible interferences present in seawater, including sea water cations and anions are evaluated in detail. Finally, the methods are applied to the determination de mercury and lead in seawater samples.

  18. Water-soluble chelating polymers for removal of actinides from watewater

    SciTech Connect

    Jarvinen, G.

    1996-10-01

    Polymer filtration is a technology being developed to recover valuable or regulated metal ions selectively from process or wastewaters. Water-soluble chelating polymers are specially designed to bind selectively with metal ions in aqueous solutions. The polymers molecular weight is large enough so 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.

  19. Spectrophotometric determination and removal of unchelated europium ions from solutions containing Eu-diethylenetriaminepentaacetic acid chelate-peptide conjugates.

    PubMed

    Elshan, N G R Dayan; Patek, Renata; Vagner, Josef; Mash, Eugene A

    2014-11-01

    Europium chelates conjugated with peptide ligands are routinely used as probes for conducting in vitro binding experiments. The presence of unchelated Eu ions in these formulations gives high background luminescence and can lead to poor results in binding assays. In our experience, the reported methods for purification of these probes do not achieve adequate removal of unchelated metal ions in a reliable manner. In this work, a xylenol orange-based assay for the quantification of unchelated metal ions was streamlined and used to determine levels of metal ion contamination as well as the success of metal ion removal on attempted purification. We compared the use of Empore chelating disks and Chelex 100 resin for the selective removal of unchelated Eu ions from several Eu-diethylenetriaminepentaacetic acid chelate-peptide conjugates. Both purification methods gave complete and selective removal of the contaminant metal ions. However, Empore chelating disks were found to give much higher recoveries of the probes under the conditions used. Related to the issue of probe recovery, we also describe a significantly more efficient method for the synthesis of one such probe using Rink amide AM resin in place of Tentagel S resin.

  20. Electronic interactions in metal complexed photoconducting polymers : a ZINDO study.

    SciTech Connect

    Manas, E. S.; Chen, L. X.; Chemistry; Univ. of Pennsylvania School of Medicine

    2000-12-01

    Semi-empirical (INDO/s) calculations have been conducted on molecular fragments with zero to three phenylenevinylene (PV) units attached to 4 and 4{prime} positions of a 2,2{prime}-bipyridine (bpy) group, with and without chelated metal ions, mimicking metal-free and metal-chelated photoconducting polymers 1 and 2 [Chen et al., J. Phys. Chem. B 104 (2000) 1950]. The calculations suggest that: (1) a global lowering of the molecular orbital energy levels due to metal-chelation is responsible for the observed red-shift in the lowest energy transitions; and (2) metal chelation attenuates {pi}-electron delocalization. The relevance of these effects to photoluminescence of metal-chelated polymers is also discussed.