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Sample records for chelated uranyl antibody

  1. Development of a Recombinant Antibody with Specificity for Chelated Uranyl Ions

    Energy Technology Data Exchange (ETDEWEB)

    X. Li; A.M. Kriegel; T.C. Bishop; R.C. Blake; E. Figueiredo; H. Yu; D.A. Blake

    2005-04-18

    The goal of our project is to continue the development of new techniques for rapid, automated identification of radionuclides, metals, and chelators that may contaminant sur face and groundwater at DOE sites. One of the four specific aims of the present project is to develop new technologies in antibody engineering that will enhance our immunosensor program. Recombinant antibodies have potential advantages over monoclonal antibodies produced by standard hybridoma technology. The cloned genes represent a stable, recoverable source for antibody production. In addition, the recombinant format offers opportunities for protein engineering that enhances antibody performance and for studies that relate antibody sequence to binding activity. In this study, a hybridoma that synthesized an antibody (12F6) that recognized a 1:1 complex between 2,9-dicarboxyl-1,10- phenanthroline (DCP) and UO{sub 2}{sup 2+} was used as a source of RNA for the development of a recombinant (Fab){sub 2} fragment. RNA was isolated from the 12F6 hybridoma and the cDNA encoding the entire {kappa} light chain and the linked VH and C1 portions of the heavy chain were amplified from total RNA. cDNA sequences were verified by comparison with the N-terminal amino acid sequences of the light and heavy chains of the native 12F6 monoclonal antibody. A leader sequence and appropriate restriction sites were added to each chain, and the fragments were ligated into a commercial dicistronic vector (pBudCE4.1, Invitrogen, Inc.). COS-1 cells were transfected with this vector and the culture supernatant was assayed for activity and the (Fab){sub 2} protein. Cells transfected with vector containing 12F6 cDNA synthesized and secreted recombinant (Fab){sub 2} fragments that bound to the UO{sub 2}{sup 2+}-DCP complex with an affinity indistinguishable from that of a (Fab){sub 2} fragment prepared from the native antibody. Molecular models of the heavy and light chain variable domains were constructed according to the

  2. Development of a Recombinant Antibody with Specificity for Chelated Uranyl Ions

    International Nuclear Information System (INIS)

    The goal of our project is to continue the development of new techniques for rapid, automated identification of radionuclides, metals, and chelators that may contaminant sur face and groundwater at DOE sites. One of the four specific aims of the present project is to develop new technologies in antibody engineering that will enhance our immunosensor program. Recombinant antibodies have potential advantages over monoclonal antibodies produced by standard hybridoma technology. The cloned genes represent a stable, recoverable source for antibody production. In addition, the recombinant format offers opportunities for protein engineering that enhances antibody performance and for studies that relate antibody sequence to binding activity. In this study, a hybridoma that synthesized an antibody (12F6) that recognized a 1:1 complex between 2,9-dicarboxyl-1,10- phenanthroline (DCP) and UO22+ was used as a source of RNA for the development of a recombinant (Fab)2 fragment. RNA was isolated from the 12F6 hybridoma and the cDNA encoding the entire κ light chain and the linked VH and C1 portions of the heavy chain were amplified from total RNA. cDNA sequences were verified by comparison with the N-terminal amino acid sequences of the light and heavy chains of the native 12F6 monoclonal antibody. A leader sequence and appropriate restriction sites were added to each chain, and the fragments were ligated into a commercial dicistronic vector (pBudCE4.1, Invitrogen, Inc.). COS-1 cells were transfected with this vector and the culture supernatant was assayed for activity and the (Fab)2 protein. Cells transfected with vector containing 12F6 cDNA synthesized and secreted recombinant (Fab)2 fragments that bound to the UO22+-DCP complex with an affinity indistinguishable from that of a (Fab)2 fragment prepared from the native antibody. Molecular models of the heavy and light chain variable domains were constructed according to the canonical structures method detailed by Morea et al

  3. High-affinity uranyl-specific antibodies suitable for cellular imaging

    International Nuclear Information System (INIS)

    Monoclonal antibodies (mAbs) have proved to be valuable models for the study of protein-metal interactions, and previous reports have described very specific antibodies to chelated metal ions, including uranyl. We raised specific mAbs against UO22+-DCP-BSA (DCP, 1, 10-phenanthroline-2,9-dicarboxylic acid) to generate new sets of antibodies that might cross-react with various complexed forms of uranyl in different environments for further application in the field of toxicology. Using counter-screening with UO22+-DCP-casein, we selected two highly specific mAbs against uranyl-DCP (KD = 10-100 pM): U04S and U08S. Competitive assays in the presence of different metal ions (UO22+, Fe3+, Zn2+, Cu2+, and Ca2+) showed that uranyl in solution can act as a good competitor, suggesting some antibody ability to cross-react with chelating groups other than DCP in the UO22+ equatorial coordination plane. Interestingly, one of the antibodies could be used for revealing uranyl cations in cell samples. Fluorescence activated cell sorting analyses after immuno-labeling revealed the interaction of uranyl with human kidney cells HK2. The intracellular accumulation of uranyl could be directly visualized by metal-immunostaining using fluorescent-labeled mAb. Our results suggest that U04S mAb epitopes mostly include the uranyl fraction and its para-topes can accommodate a wide variety of chelating groups. (authors)

  4. Deciphering the Energy Landscape of the Interaction Uranyl-DCP with Antibodies Using Dynamic Force Spectroscopy

    OpenAIRE

    Teulon, Jean-Marie; Parot, Pierre; Odorico, Michael; Pellequer, Jean-Luc

    2008-01-01

    Previous studies on molecular recognition of uranyl-DCP (dicarboxy-phenanthroline chelator) compound by two distinct monoclonal antibodies (Mabs U04S and U08S) clearly showed the presence of a biphasic shape in Bell-Evans' plots and an accentuated difference in slopes at the high loading rates. To further explore the basis in the slope difference, we have performed complementary experiments using antibody PHE03S, raised against uranyl-DCP but, presenting a strong cross-reactivity toward the D...

  5. Nonionic metal-chelating surfactants mediated solvent-free thermo-induced separation of uranyl

    Energy Technology Data Exchange (ETDEWEB)

    Larpent, Ch.; Prevost, S. [Versailles-St-Quentin Univ., Institut Lavoisier, UMR-CNRS 8180, 78 - Versailles (France); Prevost, S.; Zemb, Th.; Testard, F. [CEA Saclay, Dept. de Recherche sur l' Etat Condense, les Atomes et les Molecules (DSM/DRECAM/SCM/LIONS), 91 - Gif sur Yvette (France); Berthon, L. [CEA Valrho, Site de Marcoule, Dept. Radiochimie et Procedes (DEN/DRCP/SCPS/LCSE), 30 (France)

    2007-08-15

    Thermo-responsive metal-chelating surfactants permit the solvent-free, cloud point extraction of uranyl nitrate and afford a real molecular economy compared to conventional separation techniques. (authors)

  6. Deciphering the energy landscape of the interaction uranyl-DCP with antibodies using dynamic force spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Teulon, J.M.; Parot, P.; Odorico, M.; Pellequer, J.L. [CEA, DSV, Inst Biotechnol et Environm Biol IBEB, F-30207 Bagnols Sur Ceze (France)

    2008-07-01

    Previous studies on molecular recognition of uranyl-DCP (dicarboxy-phenanthroline chelator) compound by two distinct monoclonal antibodies (Mabs U04S and U08S) clearly showed the presence of a biphasic shape in Bell-Evans' plots and an accentuated difference in slopes at the high loading rates. To further explore the basis in the slope difference, we have performed complementary experiments using antibody PHE03S, raised against uranyl-DCP but, presenting a strong cross-reactivity toward the DCP chelator. This work allowed us to obtain a reallocation of the respective contributions of the metal ion itself and that of the chelator. Results led us to propose a 2D schematic model representing two energy barriers observed in the systems Mabs U04S- and U08S-[UO{sub 2}-DCP] where the outer barrier characterizes the interaction between UO{sub 2} and Mab whereas the inner barrier characterizes the interaction between DCP and Mab. Using dynamic force spectroscopy, it is thus possible to dissect molecular interactions during the unbinding between proteins and ligands. (authors)

  7. Deciphering the energy landscape of the interaction uranyl-DCP with antibodies using dynamic force spectroscopy.

    Science.gov (United States)

    Teulon, Jean-Marie; Parot, Pierre; Odorico, Michael; Pellequer, Jean-Luc

    2008-11-15

    Previous studies on molecular recognition of uranyl-DCP (dicarboxy-phenanthroline chelator) compound by two distinct monoclonal antibodies (Mabs U04S and U08S) clearly showed the presence of a biphasic shape in Bell-Evans' plots and an accentuated difference in slopes at the high loading rates. To further explore the basis in the slope difference, we have performed complementary experiments using antibody PHE03S, raised against uranyl-DCP but, presenting a strong cross-reactivity toward the DCP chelator. This work allowed us to obtain a reallocation of the respective contributions of the metal ion itself and that of the chelator. Results led us to propose a 2D schematic model representing two energy barriers observed in the systems Mabs U04S- and U08S-[UO(2)-DCP] where the outer barrier characterizes the interaction between UO(2) and Mab whereas the inner barrier characterizes the interaction between DCP and Mab. Using dynamic force spectroscopy, it is thus possible to dissect molecular interactions during the unbinding between proteins and ligands.

  8. New thermo-sensitive chelating surfactants for selective solvent-free extraction of uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Prevost, S.; Larpent, C.; Testard, F.; Coulombeau, H.; Baczko, K.; Berthon, L.; Desvaux, H.; Madic, C.; Zemb, T

    2004-07-01

    Functional surfactants were synthesised by grafting a chelating group (amino-acid residue) to the tip of a poly-ethoxylated nonionic surfactant chain (C{sub i}E{sub j}: C{sub i}H{sub 2i}+1(OCH{sub 2}CH{sub 2}){sub j}OH)) or in a branched position. C{sub i}E{sub j} nonionic surfactants are known to be thermo-reversible and to exhibit a clouding phenomenon associated to phase separation of micelles. The functional surfactants retain both surface-active properties, characteristic thermo-reversible behaviour and have efficient complexing properties toward uranyl. In the presence of uranyl nitrate, small micelles are formed at ambient temperature and the de-mixing leads to a separation of the target ion trapped by the functional surfactant (cloud point extraction). Those surfactants are more efficient than mixture of classical C{sub i}E{sub j} and complexing agent solubilized in the micelles. This reveals a synergistic effect of the covalent bond between the chelating group and the nonionic surfactant C{sub i}E{sub j}. This paper presents a systematic study of the extraction and aggregation properties and the influence of the nature of the ions. (authors)

  9. Thermo-responsive metal-chelating surfactants. Properties and use in cloud point extraction of uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Prevost, S.; Coulombeau, H. [CEA, IRAMIS, SCM, LIONS, 91 - Gif-sur-Yvette (France); Univ. de Versailles St Quentin en Y. Institut Lavoisier UMR CNRS 8180 (France); Baczko, K.; Larpent, C. [Univ. de Versailles St Quentin en Y. Institut Lavoisier UMR CNRS 8180 (France); Berthon, L.; Zorz, N. [CEA/DEN/DRCP/SCPS/LCSE, 30 - Bagnols sur Ceze (France); Desvaux, H.; Testard, F. [CEA, IRAMIS, SCM, LIONS, 91 - Gif-sur-Yvette (France); Zemb, T. [ICSM, UMR 5257 CEA/CNRS/UM2/ENSCM, 30 - Bagnols sur Ceze (France)

    2009-03-15

    The properties of new thermo-responsive functional surfactants, capable of forming a metal chelate, synthesized by grafting a diamide group (amino-acid residue) to the tip hydrophilic endgroup or in a branched position to polyoxyethylene nonionic surfactants [C{sub i}E{sub j}:C{sub i}H{sub 2i+1}(OCH{sub 2}CH{sub 2}){sub j}OH)], are studied. Their use in cloud point extraction of uranyl nitrate is tested. The reversible temperature-dependent behavior of classical non-ionic surfactants associated to phase separation of micellar solutions known as clouding behavior is exploited for separation based on cation specific binding to the chelating group. The functional surfactants under investigation combine surface-active properties and characteristic thermoreversible behavior with a capacity to bind uranyl cation. The influence of the complexation on the cloud points of functional surfactants is determined. The chelating surfactants are found efficient for the cloud point extraction of uranyl nitrate at low surfactant-to-uranyl ratio. These new thermoresponsive surfactants with chelating properties hold most promise for the development of new solvent free extraction processes.

  10. Thermo-responsive Metal-chelating Surfactants: Properties and Use in Cloud Point Extraction of Uranyl Nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Prevost, S.; Coulombeau, H.; Baczko, K.; Larpent, C. [Univ Versailles St Wuentin Y, Inst Lavoisier, UMR 8180, CNRS, F-78035 Versailles, (France); Prevost, S.; Coulombeau, H.; Desvaux, H.; Testard, F. [CEA, IRAMIS, SCM, LIONS, F-91191 Gif Sur Yvette, (France); Berthon, L.; Zorz, N. [CEA, DEN DRCP SCPS LCSE, F-30207 Bagnols Sur Ceze, (France); Zemb, Th. [ICSM, UMR 5257, CEA CNRS UM2 ENSCM, F-30207 Bagnols Sur Ceze, (France)

    2009-07-01

    The properties of new thermo-responsive functional surfactants, capable of forming a metal chelate, synthesized by grafting a diamide group (amino-acid residue) to the tip hydrophilic end-group or in a branched position to polyoxyethylene nonionic surfactants [CiEj: C{sub i}H{sub 2i+1}(OCH{sub 2}CH{sub 2}){sub j}OH)], are studied. Their use in cloud point extraction of uranyl nitrate is tested. The reversible temperature-dependent behavior of classical non-ionic surfactants associated to phase separation of micellar solutions known as clouding behavior is exploited for separation based on cation specific binding to the chelating group. The functional surfactants under investigation combine surface-active properties and characteristic thermo-reversible behavior with a capacity to bind uranyl cation. The influence of the complexation on the cloud points of functional surfactants is determined. The chelating surfactants are found efficient for the cloud point extraction of uranyl nitrate at low surfactant-to-uranyl ratio. These new thermo-responsive surfactants with chelating properties hold most promise for the development of new solvent free extraction processes. (authors)

  11. Modification of monoclonal antibodies by polymers possessing chelating properties

    Energy Technology Data Exchange (ETDEWEB)

    Torchilin, V.P.; Khaw, B.A.; Klibanov, A.L.; Slinkin, M.A.; Haber, E.; Smirnov, V.N.

    1986-12-01

    This paper describes a basically new approach to obtaining diagnostic antibodies, consisting of a one-point modification of the antibody, without loss of its activity, by a high-molecular-weight synthetic polymer with the ability of effectively chelating ions of heavy metals. As a result of this approach, preparations of active antibodies containing some tens of atoms of the metal per protein molecule can be obtained. The concentration of radioactive metal (/sup 111/In) was determined with a gamma-counter and the Mn and Cd concentrations by spectroscopy. Gel-filtration of polymer-modified antibodies after binding of /sup 111/InCl/sub 3/ is shown. Also, solid-phase radioimmunoassay of antibodies and Fab fragments, native and modified by chelating polymers, is presented.

  12. Tumor targeting of radiolabeled antibodies using HYNIC chelate

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Tae Sup; Chung, Wee Sup; Woo, Kwang Sun; Choi, Tae Hyun; Chung, Hye Kyung; Lee, Myung Jin; Kim, So Yeon; Jung, Jae Ho; Choi, Chang Woon; Lim, Sang Moo [KIRAMS, Seoul (Korea, Republic of); Darwati, Siti [National Nuclear Energy Agency, Tangerang (Indonesia)

    2004-07-01

    There is an increasing interest in the use of labeled antibodies for diagnosis of cancers as well as for therapy. Various radiolabeling methods have been used in order to obtain better tumor specific targeting for detection and therapy. It was generally used to tumor targeted immunotherapy and immunodetection that lym-1, mouse monoclonal antibody, was specific binding to surface antigen of Raji. The 3E8 antibody was produced from humanized anti-TAG-72 monoclonal antibody (AKA) by amino acid change in 95-99 residues of heavy chain complementary determinant regions (HCDRs) 3 using phage displayed library technology. In this study, we are investigating the usefulness of HYNIC chelate as a bifunctional chelating agent in radioimmunodetecton of tumor. Two types of antibodies, Lym-1 and 3E8, were used for the conjugation with HYNIC chelate. Lym-1 and 3E8 are specific antibodies to surface antigen of Non-Hogkin's lymphoma and TAG-72 antigen of colorectal carcinoma, respectively. We prepare HYNIC-antibody conjugates, determine radiolabeling yield with {sup 99m}Tc and evaluate tumor targeting in tumor bearing nude mice model.

  13. Comparison of bifunctional chelates for {sup 64}Cu antibody imaging

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Cara L.; Crisp, Sarah; Bensimon, Corinne [MDS Nordion, Vancouver, BC (Canada); Yapp, Donald T.T.; Ng, Sylvia S.W. [British Columbia Cancer Agency Research Centre, Vancouver, BC (Canada); University of British Columba, The Faculty of Pharmaceutical Sciences, Vancouver, BC (Canada); Sutherland, Brent W. [British Columbia Cancer Agency Research Centre, Vancouver, BC (Canada); Gleave, Martin [Prostate Centre at Vancouver General Hospital, Vancouver, BC (Canada); Jurek, Paul; Kiefer, Garry E. [Macrocyclics Inc., Dallas, TX (United States)

    2010-11-15

    Improved bifunctional chelates (BFCs) are needed to facilitate efficient {sup 64}Cu radiolabeling of monoclonal antibodies (mAbs) under mild conditions and to yield stable, target-specific agents. The utility of two novel BFCs, 1-Oxa-4,7,10-triazacyclododecane-5-S-(4-isothiocyanatobenzyl)-4,7,10-triacetic acid (p-SCN-Bn-Oxo-DO3A) and 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-4-S-(4-isothiocyanatobenzyl)-3,6,9-triacetic acid (p-SCN-Bn-PCTA), for mAb imaging with {sup 64}Cu were compared to the commonly used S-2-(4-isothiocyanatobenzyl)-1,4,7,10-tetraazacyclododecane-tetraacetic acid (p-SCN-Bn-DOTA). The BFCs were conjugated to trastuzumab, which targets the HER2/neu receptor. {sup 64}Cu radiolabeling of the conjugates was optimized. Receptor binding was analyzed using flow cytometry and radioassays. Finally, PET imaging and biodistribution studies were done in mice bearing either HER2/neu-positive or HER2/neu-negative tumors. {sup 64}Cu-Oxo-DO3A- and PCTA-trastuzumab were prepared at room temperature in >95% radiochemical yield (RCY) in <30 min, compared to only 88% RCY after 2 h for the preparation of {sup 64}Cu-DOTA-trastuzumab under the same conditions. Cell studies confirmed that the immunoreactivity of the mAb was retained for each of the bioconjugates. In vivo studies showed that {sup 64}Cu-Oxo-DO3A- and PCTA-trastuzumab had higher uptake than the {sup 64}Cu-DOTA-trastuzumab at 24 h in HER2/neu-positive tumors, resulting in higher tumor to background ratios and better tumor images. By 40 h all three of the {sup 64}Cu-BFC-trastuzumab conjugates allowed for clear visualization of the HER2/neu-positive tumors but not the negative control tumor. The antibody conjugates of PCTA and Oxo-DO3A were shown to have superior {sup 64}Cu radiolabeling efficiency and stability compared to the analogous DOTA conjugate. In addition, {sup 64}Cu-PCTA and Oxo-DO3A antibody conjugates may facilitate earlier imaging with greater target to background ratios than

  14. Chelate chase of radiopharmaceuticals reversibly bound to monoclonal antibodies improves dosimetry

    International Nuclear Information System (INIS)

    One hundred micrograms of monoclonal antibody (MoAb) CHA 255 with a binding constant Kb of 4 x 109 was complexed with indium-111 labeled BLEDTA II, GLEDTA IV, benzyl EDTA, and an EDTA conjugate of Fab. The 24-hour tumor and organ distribution in BALB/c mice bearing KHJJ tumors was studied for each compound alone, the antibody complex, and 3 hours following a chelate chase of the antibody complex. Whole-body biological half-life was measured for 7 days with and without a chelate chase for each antibody complex. The 24-hour whole-body counts dropped 20-60% within 3 hours of administering the chelate chase. Blood concentration fell over 89% within 3 hours of administering the chase and there was a decrease in concentration in all organs, except the kidneys, of 10 to 85%. Theoretical equivalent human doses were calculated from the 24-hour organ concentrations, effective half-life, and MIRD 11 S values (absorbed dose per cumulated activity). Liver and spleen were the target organs, with the dose ranging from 0.50 to 3.91 rads per millicurie. The reduction in organ radiation dose varied up to 95% following the chelate chase. Rapid selective renal clearance of chelate labeled radiopharmaceuticals by competitive inhibition (chelate chase) of their reversible binding to monoclonal antibodies, greatly improves the radiation dosimetry of tumor imaging agents. 28 references, 5 figures, 5 tables

  15. The antibody-linked chelating polymers for nuclear therapy and diagnostics

    Energy Technology Data Exchange (ETDEWEB)

    Torchilin, V.P.; Klibanov, A.L. (USSR Cardiology Research Center, Moscow (USSR))

    1991-01-01

    This review deals with the problem of protein modification with chelating polymers. The main purpose of this approach is the preparation of monoclonal antibodies labeled with heavy metal isotopes ({alpha}-, {beta}-, and {delta}-emitting metals and metals used for NMR-tomography). Traditional binding of metals with proteins via chelating agents directly coupled to protein molecule does not allow binding a high number of metal atoms per single protein molecule and can also alter protein specific properties. At the same time, metal-to-protein binding via intermediate chelating polymer makes possible the binding of several dozen metal atoms per single protein without affecting its specific properties. Moreover, the variations in polymer properties and molecular weight allow controlled modified antibody biodistribution and clearance rate. Modified antibodies can be used successfully for nuclear and NMR diagnostics and for nuclear therapy. The following problems are discussed: the chemistry of the coupling of chelating groups to polymer backbone; the binding of chelating polymers to proteins, including monoclonal antibodies; the ability of chelating polymer-to-protein conjugates to bind heavy metals; the influence of the modification on protein conformation and specific properties; the behavior of metal-containing conjugates in vivo; the practical use of conjugates obtained for radioimmunoimaging, radioimmunotherapy, NMR-tomography, and in vitro immunoassays. Future prospects of the approach are also discussed.101 references.

  16. The antibody-linked chelating polymers for nuclear therapy and diagnostics

    International Nuclear Information System (INIS)

    This review deals with the problem of protein modification with chelating polymers. The main purpose of this approach is the preparation of monoclonal antibodies labeled with heavy metal isotopes (α-, β-, and δ-emitting metals and metals used for NMR-tomography). Traditional binding of metals with proteins via chelating agents directly coupled to protein molecule does not allow binding a high number of metal atoms per single protein molecule and can also alter protein specific properties. At the same time, metal-to-protein binding via intermediate chelating polymer makes possible the binding of several dozen metal atoms per single protein without affecting its specific properties. Moreover, the variations in polymer properties and molecular weight allow controlled modified antibody biodistribution and clearance rate. Modified antibodies can be used successfully for nuclear and NMR diagnostics and for nuclear therapy. The following problems are discussed: the chemistry of the coupling of chelating groups to polymer backbone; the binding of chelating polymers to proteins, including monoclonal antibodies; the ability of chelating polymer-to-protein conjugates to bind heavy metals; the influence of the modification on protein conformation and specific properties; the behavior of metal-containing conjugates in vivo; the practical use of conjugates obtained for radioimmunoimaging, radioimmunotherapy, NMR-tomography, and in vitro immunoassays. Future prospects of the approach are also discussed.101 references

  17. Characterization of Tumor-Avid Antibody Fragments Genetically Engineered for Mono-Specific Radionuclide Chelation

    Energy Technology Data Exchange (ETDEWEB)

    Quinn, T.P.

    2003-12-31

    The successful clinical application of targeted-radiopharmaceuticals depends on the development of molecules that optimize tumor specific radionuclide deposition and minimize non-specific organ irradiation. To this end, this proposal outlines a research effort to identify and evaluate novel antibodies and antibody fragments that bind breast tumors. The tumor-avid antibodies will be investigated for as imaging and therapeutic agents and to gain a better understanding of the pharmacokinetics and metabolism of radiolabeled tumor-avid antibody fragments through the use of site-specifically labeled molecules. Antibodies or antibody fragments, that bind breast carcinoma carbohydrate antigens, will be obtained from hybridoma or bacteriophage library screening. More specifically, antibody fragments that bind the carcinoma-associated Thomsen-Friedenreich (T) antigen will be radiolabeled with {sup 99m}Tc and {sup 188}Re at a natural amino acid chelation site and will be investigated in vivo for their abilities to target human breast tumors. In addition, site-specific radiolabeled antibody fragments will be biosynthesized using misacylated suppressor tRNAs. Homogeneously radiolabeled populations of antibody fragments will be used to investigate the effects of radionuclide location and chelation chemistries on their biodistribution and metabolism. It is hypothesized that site-specifically radiolabeled antibody fragments will possess enhanced tumor imaging and therapeutic properties due to optimal label location and conjugation chemistries. New insights into the factors that govern antibody metabolism in vivo are also expected from this work. Results from these studies should enhance our ability to design and synthesize radiolabeled antibody fragments that have improved pharmacokinetic properties. The studies in this proposal involve basic research into the development of antibody-based radiopharmaceuticals, with the ultimate goal of application in humans. This type of basic

  18. Characterization of Tumor-Avid Antibody Fragments Genetically Engineered for Mono-Specific Radionuclide Chelation

    International Nuclear Information System (INIS)

    The successful clinical application of targeted-radiopharmaceuticals depends on the development of molecules that optimize tumor specific radionuclide deposition and minimize non-specific organ irradiation. To this end, this proposal outlines a research effort to identify and evaluate novel antibodies and antibody fragments that bind breast tumors. The tumor-avid antibodies will be investigated for as imaging and therapeutic agents and to gain a better understanding of the pharmacokinetics and metabolism of radiolabeled tumor-avid antibody fragments through the use of site-specifically labeled molecules. Antibodies or antibody fragments, that bind breast carcinoma carbohydrate antigens, will be obtained from hybridoma or bacteriophage library screening. More specifically, antibody fragments that bind the carcinoma-associated Thomsen-Friedenreich (T) antigen will be radiolabeled with 99mTc and 188Re at a natural amino acid chelation site and will be investigated in vivo for their abilities to target human breast tumors. In addition, site-specific radiolabeled antibody fragments will be biosynthesized using misacylated suppressor tRNAs. Homogeneously radiolabeled populations of antibody fragments will be used to investigate the effects of radionuclide location and chelation chemistries on their biodistribution and metabolism. It is hypothesized that site-specifically radiolabeled antibody fragments will possess enhanced tumor imaging and therapeutic properties due to optimal label location and conjugation chemistries. New insights into the factors that govern antibody metabolism in vivo are also expected from this work. Results from these studies should enhance our ability to design and synthesize radiolabeled antibody fragments that have improved pharmacokinetic properties. The studies in this proposal involve basic research into the development of antibody-based radiopharmaceuticals, with the ultimate goal of application in humans. This type of basic nuclear

  19. Deferoxamine as a chelator for {sup 67}Ga in the preparation of antibody conjugates

    Energy Technology Data Exchange (ETDEWEB)

    Govindan, Serengulam V. [Immunomedics, Inc., Morris Plains, NJ 07950 (United States); Michel, Rosana B. [Center for Molecular Medicine and Immunology, Belleville, NJ 07109 (United States); Griffiths, Gary L. [Immunomedics, Inc., Morris Plains, NJ 07950 (United States); Goldenberg, David M. [Center for Molecular Medicine and Immunology, Belleville, NJ 07109 (United States); Mattes, M. Jules [Center for Molecular Medicine and Immunology, Belleville, NJ 07109 (United States)]. E-mail: mjmattes@gscancer.org

    2005-07-01

    {sup 67}Ga antibodies (Abs) have been shown to be effective agents for single-cell killing due to the Auger electrons emitted, but their specific activities have not been as high as desired. We therefore evaluated deferoxamine (DFO) as a chelator, as opposed to the cyclic chelator NOTA, which was used previously. Use of DFO for Ab conjugation to {sup 67}Ga was reported previously by several laboratories. DFO was conjugated to Abs by two methods, one using Ablysine conjugation and another using mild reduction of Abs to generate thiols in the hinge region. Labeling with {sup 67}Ga was efficient, and the specific activities obtained under nonoptimized conditions were twice as high as those achieved previously. However, analysis of these conjugates revealed two problems that appear to prevent their further development. First, the stability was inadequate for the 3-day half-life of the nuclide. Second, the labels were poorly retained within cells after Ab internalization and catabolism. Also, it was found that stability was significantly affected by the incubation buffer used: buffers lacking physiological concentrations of divalent cations Ca and Mg resulted in much lower stability than buffers including them. In conclusion, DFO does not seem to be a suitable chelator for {sup 67}Ga conjugation for our purposes.

  20. Molecular design of Calix[4]arene derivatives for uranyl ion extraction from aqueous media

    International Nuclear Information System (INIS)

    Uranyl ion extraction is an important part of nuclear waste reprocessing. Use of organic ligands having chelating property with uranyl ions is a promising tool in this area, because of the possibility to improve the selectivity and the affinity of the ligands towards uranyl ions. In this study, Calix[4]arene derivatives containing B, Al, C, Si, N, P, O and S elements in bridging positions were designed and their chelating energetics with uranyl cation are calculated by means of DFT methods.

  1. Engineering an antibody with picomolar affinity to DOTA chelates of multiple radionuclides for pretargeted radioimmunotherapy and imaging

    Energy Technology Data Exchange (ETDEWEB)

    Orcutt, Kelly Davis; Slusarczyk, Adrian L. [Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Cieslewicz, Maryelise [Department of Biological Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Ruiz-Yi, Benjamin [Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Bhushan, Kumar R. [Division of Hematology/Oncology, Beth Israel Deaconess Medical Center, Boston, MA 02215 (United States); Frangioni, John V. [Division of Hematology/Oncology, Beth Israel Deaconess Medical Center, Boston, MA 02215 (United States); Department of Radiology, Beth Israel Deaconess Medical Center, Boston, MA 02215 (United States); Wittrup, K. Dane, E-mail: wittrup@mit.ed [Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Department of Biological Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Koch Institute for Integrative Cancer Research, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

    2011-02-15

    Introduction: In pretargeted radioimmunotherapy (PRIT), a bifunctional antibody is administered and allowed to pre-localize to tumor cells. Subsequently, a chelated radionuclide is administered and captured by cell-bound antibody while unbound hapten clears rapidly from the body. We aim to engineer high-affinity binders to 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelates for use in PRIT applications. Methods: We mathematically modeled antibody and hapten pharmacokinetics to analyze hapten tumor retention as a function of hapten binding affinity. Motivated by model predictions, we used directed evolution and yeast surface display to affinity mature the 2D12.5 antibody to DOTA, reformatted as a single chain variable fragment (scFv). Results: Modeling predicts that for high antigen density and saturating bsAb dose, a hapten-binding affinity of 100 pM is needed for near-maximal hapten retention. We affinity matured 2D12.5 with an initial binding constant of about 10 nM to DOTA-yttrium chelates. Affinity maturation resulted in a 1000-fold affinity improvement to biotinylated DOTA-yttrium, yielding an 8.2{+-}1.9 picomolar binder. The high-affinity scFv binds DOTA complexes of lutetium and gadolinium with similar picomolar affinity and indium chelates with low nanomolar affinity. When engineered into a bispecific antibody construct targeting carcinoembryonic antigen, pretargeted high-affinity scFv results in significantly higher tumor retention of a {sup 111}In-DOTA hapten compared to pretargeted wild-type scFv in a xenograft mouse model. Conclusions: We have engineered a versatile, high-affinity, DOTA-chelate-binding scFv. We anticipate it will prove useful in developing pretargeted imaging and therapy protocols to exploit the potential of a variety of radiometals.

  2. Engineering an antibody with picomolar affinity to DOTA chelates of multiple radionuclides for pretargeted radioimmunotherapy and imaging

    International Nuclear Information System (INIS)

    Introduction: In pretargeted radioimmunotherapy (PRIT), a bifunctional antibody is administered and allowed to pre-localize to tumor cells. Subsequently, a chelated radionuclide is administered and captured by cell-bound antibody while unbound hapten clears rapidly from the body. We aim to engineer high-affinity binders to 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelates for use in PRIT applications. Methods: We mathematically modeled antibody and hapten pharmacokinetics to analyze hapten tumor retention as a function of hapten binding affinity. Motivated by model predictions, we used directed evolution and yeast surface display to affinity mature the 2D12.5 antibody to DOTA, reformatted as a single chain variable fragment (scFv). Results: Modeling predicts that for high antigen density and saturating bsAb dose, a hapten-binding affinity of 100 pM is needed for near-maximal hapten retention. We affinity matured 2D12.5 with an initial binding constant of about 10 nM to DOTA-yttrium chelates. Affinity maturation resulted in a 1000-fold affinity improvement to biotinylated DOTA-yttrium, yielding an 8.2±1.9 picomolar binder. The high-affinity scFv binds DOTA complexes of lutetium and gadolinium with similar picomolar affinity and indium chelates with low nanomolar affinity. When engineered into a bispecific antibody construct targeting carcinoembryonic antigen, pretargeted high-affinity scFv results in significantly higher tumor retention of a 111In-DOTA hapten compared to pretargeted wild-type scFv in a xenograft mouse model. Conclusions: We have engineered a versatile, high-affinity, DOTA-chelate-binding scFv. We anticipate it will prove useful in developing pretargeted imaging and therapy protocols to exploit the potential of a variety of radiometals.

  3. Association of uranyl with the cell wall of Pseudomonas fluorescens inhibits metabolism

    Science.gov (United States)

    Bencheikh-Latmani, Rizlan; Leckie, James O.

    2003-11-01

    Citric acid is found along with uranyl in the subsurface of former nuclear facilities because of its use as a decontamination agent in the nuclear industry. Citrate's metal chelating properties affect the mobility of uranyl in the subsurface and consequently, citrate biodegradation may significantly impact uranyl fate and transport. Under the non-growth conditions considered, low (micromolar) uranyl concentrations inhibit the biodegradation of citrate by Pseudomonas fluorescens, a common subsurface denitrifying bacterium. Additionally, uranyl is found readily associated with the cell envelope of P. fluorescens. The observed inhibition appears to be linked to the binding of uranyl to the cell surface and is reversible by desorbing cell-bound uranyl. This study establishes a link between uranyl association with the cell surface and the observed inhibitory effect of uranyl on cell metabolism.

  4. EVALUATION OF DESFERAL AS A BIFUNCTIONAL CHELATING AGENT FOR LABELING ANTIBODIES WITH ZR-89

    NARCIS (Netherlands)

    MEIJS, WE; HERSCHEID, JDM; Haisma, Hidde; PINEDO, HM

    1992-01-01

    Zirconium-desferal was prepared and analysed by TLC, NMR and u.v.-spectroscopy. The stoichiometry of the complex was found to be 1:1. Chelation of desferal, coupled to resin, with Zr-88 appeared to be fast and almost quantitative in various buffer systems in a broad pH-range (4-7). A high in vitro s

  5. A new bifunctional chelate, BrMe sub 2 HBED: An effective conjugate for radiometals and antibodies

    Energy Technology Data Exchange (ETDEWEB)

    Mathias, C.J.; Connett, J.M.; Philpott, G.W.; Welch, M.J. (Washington Univ. School of Medicine, St. Louis, MO (USA)); Sun, Yizhen; Martell, A.E. (Texas A and M Univ., College Station (USA))

    1990-04-18

    A new bifunctional chelate, N-(2-hydroxy-3,5-dimethylbenzyl)-N{prime}-(2-hydroxy-5-(bromoacetamido)benzyl)ethylenediamine-N,-N{prime}-diacetic acid (BrMe{sub 2}HBED), was designed and synthesized to bind trivalent cationic metals with monoclonal antibodies. The stability constants (log values) for indium complexed with a similar ligand, HBED, were increased over those of more commonly used ligands DTPA and EDTA. Predictably, the increased metal-ligand complex stability would expedite the in vivo clearance from nontarget regions and perhaps enhance the localization of the radiolabeled antibody (Ab). BrMe{sub 2}HBED was conjugated with the Ab (24 h) and then radiolabeled with indium-111 citrate (24 h). Additionally, the Ab was radiolabeled by using conventional methods ({sup 111}In-DTPA and {sup 125}I-lactoperoxidase) and then compared by measuring the in vitro stability, in vitro immunoreactivity(IR), and in vivo distribution and clearance. A 10:1 BrMe{sub 2} HBED:Ab mole ratio resulted in good labeling efficiency with {sup 111}In and more importantly a very high IR. In a hamster tumor model, {sup 111}In-BrMe{sub 2} HBED-labeled monoclonal antibody (1A3) had high uptake in the tumor tissue and preferable blood clearance compared to either of the more conventional radiolabeled 1A3 monoclonal antibodies ({sup 111}In-DTPA or {sup 125}I-lactoperoxidase). 49 refs., 4 figs., 8 tabs.

  6. Development and validation of the 57Co assay for determining the ligand to antibody ratio in bifunctional chelate/antibody conjugates for use in radioimmunotherapy

    International Nuclear Information System (INIS)

    Introduction: The ligand to antibody ratio is an important characteristic of a chelate/antibody conjugate. It has been widely reported that if the ratio is too high, there will be detrimental effects on immunoreactivity and biodistribution; conversely, if the ratio is too low, the radionuclide may not bind efficiently, and the stability and the specific activity will be reduced. There are little published data on the accuracy or precision of the 57Co assay. The UK Clinical Trials Regulations state that “systems with procedures that assure the quality of every aspect of the trial should be implemented”. The aims of this study were to assess the reliability and accuracy of the 57Co binding assay and validate it against defined criteria. Method: Thirty-two serial assays were assessed for reliability. Two batches of conjugated antibody were also analysed by matrix-assisted laser desorption/ionisation time of flight (MALDI-TOF) mass spectrometry (MS) to allow the comparison of the functional test with a physical method. Results: Reliability: The coefficient of variation was 0.13. Accuracy: There was 9% variation between the 57Co binding assay and MALDI-TOF MS results. Conclusion: A detailed method for the 57Co ligand to antibody test is described that allows a discrete value to be obtained. The assay was validated as fit for purpose against target values of coefficient of variation <0.20, accuracy±10%, over a permissive range of 0.5–3.0 ligand to antibody ratio.

  7. Uranyl ion coordination

    Science.gov (United States)

    Evans, H.T.

    1963-01-01

    A review of the known crystal structures containing the uranyl ion shows that plane-pentagon coordination is equally as prevalent as plane-square or plane-hexagon. It is suggested that puckered-hexagon configurations of OH - or H2O about the uranyl group will tend to revert to plane-pentagon coordination. The concept of pentagonal coordination is invoked for possible explanations of the complex crystallography of the natural uranyl hydroxides and the unusual behavior of polynuclear ions in hydrolyzed uranyl solutions.

  8. DOTA-Functionalized Polylysine: A High Number of DOTA Chelates Positively Influences the Biodistribution of Enzymatic Conjugated Anti-Tumor Antibody chCE7agl

    OpenAIRE

    Jürgen Grünberg; Simone Jeger; Dikran Sarko; Patrick Dennler; Kurt Zimmermann; Walter Mier; Roger Schibli

    2013-01-01

    Site-specific enzymatic reactions with microbial transglutaminase (mTGase) lead to a homogenous species of immunoconjugates with a defined ligand/antibody ratio. In the present study, we have investigated the influence of different numbers of 1,4,7,10-tetraazacyclododecane-N-N'-N''-N'''-tetraacetic acid (DOTA) chelats coupled to a decalysine backbone on the in vivo behavior of the chimeric monoclonal anti-L1CAM antibody chCE7agl. The enzymatic conjugation of (DOTA)1-decalysine, (DOTA)3-decaly...

  9. Tetraalkylammonium uranyl isothiocyanates.

    Science.gov (United States)

    Rowland, Clare E; Kanatzidis, Mercouri G; Soderholm, L

    2012-11-01

    Three tetraalkylammonium uranyl isothiocyanates, [(CH(3))(4)N](3)UO(2)(NCS)(5) (1), [(C(2)H(5))(4)N](3)UO(2)(NCS)(5) (2), and [(C(3)H(7))(4)N](3)UO(2)(NCS)(5) (3), have been synthesized from aqueous solution and their structures determined by single-crystal X-ray diffraction. All of the compounds consist of the uranyl cation equatorially coordinated to five N-bound thiocyanate ligands, UO(2)(NCS)(5)(3-), and charge-balanced by three tetraalkylammonium cations. Raman spectroscopy data have been collected on compounds 1-3, as well as on solutions of uranyl nitrate with increasing levels of sodium thiocyanate. By tracking the Raman signatures of thiocyanate, the presence of both free and bound thiocyanate is confirmed in solution. The shift in the Raman signal of the uranyl symmetric stretching mode suggests the formation of higher-order uranyl thiocyanate complexes in solution, while the solid-state Raman data support homoleptic isothiocyanate coordination about the uranyl cation. Presented here are the syntheses and crystal structures of 1-3, pertinent Raman spectra, and a discussion regarding the relationship of these isothiocyanates to previously described uranyl halide phases, UO(2)X(4)(2-). PMID:23072277

  10. Imaging cancer using PET - the effect of the bifunctional chelator on the biodistribution of a {sup 64}Cu-labeled antibody

    Energy Technology Data Exchange (ETDEWEB)

    Dearling, Jason L.J., E-mail: jason.dearling@childrens.harvard.ed [Division of Nuclear Medicine and Department of Radiology, Children' s Hospital Boston, 300 Longwood Avenue, Boston, MA 02115 (United States); Harvard Medical School, Boston, MA 02115 (United States); Voss, Stephan D. [Division of Nuclear Medicine and Department of Radiology, Children' s Hospital Boston, 300 Longwood Avenue, Boston, MA 02115 (United States); Harvard Medical School, Boston, MA 02115 (United States); Dunning, Patricia; Snay, Erin [Division of Nuclear Medicine and Department of Radiology, Children' s Hospital Boston, 300 Longwood Avenue, Boston, MA 02115 (United States); Fahey, Frederic [Division of Nuclear Medicine and Department of Radiology, Children' s Hospital Boston, 300 Longwood Avenue, Boston, MA 02115 (United States); Harvard Medical School, Boston, MA 02115 (United States); Smith, Suzanne V. [Australian National Science and Technology Organisation (ANSTO), New Illawarra Road, PMB1, Menai, New South Wales 2234 (Australia); Huston, James S. [EMD Serono Research Center, 45A Middlesex Turnpike, Billerica, MA 01821-3936 (United States); Boston Biomedical Research Institute, Watertown, MA 02472-2899 (United States); Meares, Claude F. [Department of Chemistry, University of California, One Shields Avenue, Davis, CA 95616-5295 (United States); Treves, S. Ted; Packard, Alan B. [Division of Nuclear Medicine and Department of Radiology, Children' s Hospital Boston, 300 Longwood Avenue, Boston, MA 02115 (United States); Harvard Medical School, Boston, MA 02115 (United States)

    2011-01-15

    Introduction: Use of copper radioisotopes in antibody radiolabeling is challenged by reported loss of the radionuclide from the bifunctional chelator used to label the protein. The objective of this study was to investigate the relationship between the thermodynamic stability of the {sup 64}Cu-complexes of five commonly used bifunctional chelators (BFCs) and the biodistribution of an antibody labeled with {sup 64}Cu using these chelators in tumor-bearing mice. Methods: The chelators [S-2-(aminobenzyl)1,4,7-triazacyclononane-1,4,7-triacetic acid (p-NH{sub 2}-Bn-NOTA): 6-[p-(bromoacetamido)benzyl]-1, 4, 8, 11-tetraazacyclotetradecane-N, N', N'', N'''-tetraacetic acid (BAT-6): S-2-(4-aminobenzyl)-1,4,7,10-tetraazacyclododocane tetraacetic acid (p-NH{sub 2}-Bn-DOTA): 1,4,7,10-tetraazacyclododocane-N, N', N', N''-tetraacetic acid (DOTA): and 1-N-(4-aminobenzyl)-3,6,10,13,16,19-hexaazabicyclo[6.6.6]eicosane-1, 8-diamine (SarAr)] were conjugated to the anti-GD2 antibody ch14.18, and the modified antibody was labeled with {sup 64}Cu and injected into mice bearing subcutaneous human melanoma tumors (M21) (n = 3-5 for each study). Biodistribution data were obtained from positron emission tomography images acquired at 1, 24 and 48 hours post-injection, and at 48 hours post-injection a full ex vivo biodistribution study was carried out. Results: The biodistribution, including tumor targeting, was similar for all the radioimmunoconjugates. At 48 h post-injection, the only statistically significant differences in radionuclide uptake (p < 0.05) were between blood, liver, spleen and kidney. For example, liver uptake of [{sup 64}Cu]ch14.18-p-NH{sub 2}-Bn-NOTA was 4.74 {+-} 0.77 per cent of the injected dose per gram of tissue (%ID/g), and for [{sup 64}Cu]ch14.18-SarAr was 8.06 {+-} 0.77 %ID/g. Differences in tumor targeting correlated with variations in tumor size rather than which BFC was used. Conclusions: The results of this

  11. Standardization of methodology to derivatization and radiolabeling of the anti-CD20 monoclonal antibody from bifunctional chelator DOTA-NHS-Ester

    International Nuclear Information System (INIS)

    Lymphomas are cancers of the lymphatic system, being the most common the non-Hodgkin lymphoma (NHL). The Radioimmunotherapy (RIT), that increase the cytotoxic effect of monoclonal antibodies (mAb), therefore labeling these Mab with different radioisotopes. RIT combines the specificity of the antibody and the toxicity of the radionuclides. The mAb anti-CD20 is used for treatment of relapse or refractory NHL. The labeling of anti- CD20 with 177Lu, requires a bifunctional chelating agent that is designed to make a 'connect bridge' between the mAb and the radionuclide. The incorporation of the chelating group in mAb structure is called derivatization. The aim of this work is to study the derivatization of anti-CD20 antibody with DOTA-NHS-ester chelating group and labeling parameters to produce 177Lu-DOTA-Anti CD20. Five milligrams of anti-CD20 were purified by dialysis against phosphate buffer pH 8.0 and derivatized with DOTA-NHS-ester in 1:250, 1:500 and 1:1000 molar ratios. The reaction was conducted for 1 hour in gently mixing at room temperature and remained under refrigeration for 48 hours. The reaction mixture was purified in gel column Sephadex G-50 ; the aliquots that presented greater protein concentration, were mixed and concentrated. The purified antibody conjugated was added to 111-185MBq (3-5mCi) of 177LuCl3 diluted in 0.4 M acetate buffer pH 5.5. Radiochemical purity was less than 95% in all the molar ratios, indicating necessity of the purification after the labeling. The mAb derivatized showed stable when stored for to 1 month to 4 deg C and 4 days at -20 deg C. (author)

  12. Production and Characterization of Desmalonichrome Relative Binding Affinity for Uranyl Ions in Relation to other Siderophores

    Energy Technology Data Exchange (ETDEWEB)

    Mo, Kai-For; Dai, Ziyu; Wunschel, David S.

    2016-05-27

    Siderophores are Fe binding secondary metabolites that have been investigated for their uranium binding properties. Much of the previous work has focused on characterizing hydroxamate types of siderophores, such as desferrioxamine B, for their uranyl binding affinity. Carboxylate forms of these metabolites hold potential to be more efficient chelators of uranyl, yet they have not been widely studied and are more difficult to obtain. Desmalonichrome is a carboxylate siderophore which is not commercially available and so was obtained from the ascomycete fungus Fusarium oxysporum cultivated under Fe depleted conditions. The relative affinity for uranyl binding of desmalonichrome was investigated using a competitive analysis of binding affinities between uranyl acetate and different concentrations of iron(III) chloride using electrospray ionization mass spectrometry (ESI-MS). In addition to desmalonichrome, three other siderophores, including two hydroxamates (desferrioxamine B and desferrichrome) and one carboxylate (desferrichrome A) were studied to understand their relative affinities for the uranyl ion at two pH values. The binding affinities of hydroxymate siderophores to uranyl ion were found to decrease to a greater degree at lower pH as the concentration of Fe (III) ion increases. On the other hand, lowering pH has little impact on the binding affinities between carboxylate siderophores and uranyl ion. Desmalonichrome was shown to have the greatest relative affinity for uranyl at any pH and Fe(III) concentration. These results suggest that acidic functional groups in the ligands are critical for strong chelation with uranium at lower pH.

  13. Specific uranyl binding by macrocyclic ligands attached to resins

    International Nuclear Information System (INIS)

    Macrocyclic polydentates have attracted enormous attention from chemists because of their unique and significant characteristics of the strong and selective binding of a variety of metal ions. The metal binding is governed mostly by the size of the macroring and the nature of heteroatoms involved. The most important role of the macrocyclic structure is, in general, the so-called macrocyclic effect - to increase (making less negative) a large negative entropy change involved in the polydentate chelation. Basic strategy of uranium binding, is to design a ligand of very strong metal binding to take advantage of this macrocyclic effect, where number of chelating heteroatoms and their spatial arrangement is designed to be most appropriate for uranyl (UO22+) binding, since in natural sea water uranium is dissolved mostly in a form of uranyl carbonate. The following macrocylic ligands, hexamine, hexaketone, hexacarboxylic acid, were prepared and tested. The macrocyclic hexacarboxylic ligand was the most promising. The addition of hexacarboxylic acid to a uranyl tricarbonate solution gave a change of visible absorption due to the competitive formation of the uranyl complex. From this competitive binding, a relative formation constant was estimated to be 10-5, giving a log K/sub f/ value of 16.4 at 250C for the uranyl complex. This value is the largest among the hosts ever reported to bind uranyl ion.The selectivity of the macrocyclic hexacarboxylic ligand was also ascertained by testing with other metal cations. Results indicate that uranyl ions can be extracted efficiently from sea water using the hexacarboxylic acid ligands which are attached to a polymer insoluble in water

  14. 8102 and 7601 as antidotes for acute uranyl nitrate intoxication in rats

    International Nuclear Information System (INIS)

    The effect of phenolic chelating agents, 8102 and 7601, as antidotes for acute uranyl nitrate (100-500 mg/kg) intoxication was examined. The results show that after intraperitoneal injection of 50 mg of uranyl nitrate per kg, all the control rats died at 3rd and 4th days and exhibited acute renal tubular necrosis and protein casts. 8102 and 7601 could promote the animals survival and reduce the histologic lesion of kidneys in rats intoxicated with uranyl nitrate (100-350 mg/kg). 8102 is more effective than 7601

  15. DOTA-functionalized polylysine: a high number of DOTA chelates positively influences the biodistribution of enzymatic conjugated anti-tumor antibody chCE7agl.

    Directory of Open Access Journals (Sweden)

    Jürgen Grünberg

    Full Text Available Site-specific enzymatic reactions with microbial transglutaminase (mTGase lead to a homogenous species of immunoconjugates with a defined ligand/antibody ratio. In the present study, we have investigated the influence of different numbers of 1,4,7,10-tetraazacyclododecane-N-N'-N''-N'''-tetraacetic acid (DOTA chelats coupled to a decalysine backbone on the in vivo behavior of the chimeric monoclonal anti-L1CAM antibody chCE7agl. The enzymatic conjugation of (DOTA1-decalysine, (DOTA3-decalysine or (DOTA5-decalysine to the antibody heavy chain (via Gln295/297 gave rise to immunoconjugates containing two, six or ten DOTA moieties respectively. Radiolabeling of the immunoconjugates with (177Lu yielded specific activities of approximately 70 MBq/mg, 400 MBq/mg and 700 MBq/mg with increasing numbers of DOTA chelates. Biodistribution experiments in SKOV3ip human ovarian cancer cell xenografts demonstrated a high and specific accumulation of radioactivity at the tumor site for all antibody derivatives with a maximal tumor accumulation of 43.6±4.3% ID/g at 24 h for chCE7agl-[(DOTA-decalysine]2, 30.6±12.0% ID/g at 24 h for chCE7agl-[(DOTA3-decalysine]2 and 49.9±3.1% ID/g at 48 h for chCE7agl-[(DOTA5-decalysine]2. The rapid elimination from the blood of chCE7agl-[(DOTA-decalysine]2 (1.0±0.1% ID/g at 24 h is associated with a high liver accumulation (23.2±4.6% ID/g at 24 h. This behavior changed depending on the numbers of DOTA moieties coupled to the decalysine peptide with a slower blood clearance (5.1±1.0 (DOTA3 versus 11.7±1.4% ID/g (DOTA5, p<0.005 at 24 h and lower radioactivity levels in the liver (21.4±3.4 (DOTA3 versus 5.8±0.7 (DOTA5, p<0.005 at 24 h. We conclude that the site-specific and stoichiometric uniform conjugation of the highly DOTA-substituted decalysine ((DOTA5-decalysine to an anti-tumor antibody leads to the formation of immunoconjugates with high specific activity and excellent in vivo behavior and is a valuable option for

  16. p-carboxyethyl-phenylglyoxal bis(n-methylthiosemicarbazone) (CE-DTS), a bifunctional chelating agent for Tc-99m labeled monoclonal antibody

    Energy Technology Data Exchange (ETDEWEB)

    Arano, Y.; Yokoyama, A.; Furukawa, T.; Saji, H.; Endo, K.; Torizaka, K.

    1985-05-01

    In the search for bifunctional chelating agents (BCA) with better affinity, selectivity and stability as for Tc-99m, synthesis of a novel BCA containing di-thio-semicarbazone as for Tc-99m chelating site has offered interesting characteristics for the labeling of macromolecules. In the present paper, monoclonal IgG (MoAb) against human thyroglobulin was selected as a model and conditions for coupling, labeling reactions were tested along with immunological reactivity. CE-DTS was coupled to MoAb by the azido method and effect of conjugation on the MoAb immunoreactivity was followed by RIA. When CE-DTS was coupled to MoAb at the molar ratio of 1:1, no loss of its original immunoreactivity was observed. Tc-99m labeling, using the stannous ion reducing method, indicated the reaction pH as being a determinant parameter. The reducing agent prepared in tartrate buffer (pH 3) offered high yield and stable Tc-99m-CE-DTS-MoAb, as evidence by HPLC. In vivo studies in mice indicated percent of injected dose and blood clearance alike the I-131-MoAb. This good labeled state of Tc-99m-CE-DTS-MoAb was also demonstrated by using second antibody reaction in serum of mice. The newly synthesized CE-DTS offered good basis for the Tc-99m labeling of monclonal antibodies with preserved immunological properties, as desirable for the radioimmunodetection. Work with tumor related monoclonal antibodies is under progress.

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

    Science.gov (United States)

    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.

  18. {sup 177}Lu-labeled-VG76e monoclonal antibody in tumor angiogenesis: a comparative study using DOTA and DTPA chelating systems

    Energy Technology Data Exchange (ETDEWEB)

    Fani, M.; Psimadas, D. [Inst. of Radioisotopes and Radiodiagnostic Products, National Centre for Scientific Research ' ' Demokritos' ' , Athens (Greece); Biomedica Life Sciences S.A., Athens (Greece); Bouziotis, P.; Gourni, E.; Varvarigou, A.D. [Inst. of Radioisotopes and Radiodiagnostic Products, National Centre for Scientific Research ' ' Demokritos' ' , Athens (Greece); Harris, A.L. [Weatherall Inst. of Molecular Medicine, Cancer Research U.K., Univ. of Oxford (United Kingdom); Loudos, G. [Biomedical Simulations and Imaging Lab., National Technical Univ. of Athens (Greece); Maecke, H.R. [Div. of Radiological Chemistry, Univ. Hospital Basel (Switzerland)

    2007-07-01

    Vascular endothelial growth factor (VEGF) is one of the molecules which regulate angiogenesis, a phenomenon observed in many diseases, including cancer. VG76e, an anti-VEGF monoclonal antibody, was labeled with {sup 177}Lu via p-SCN-Bz-DOTA and CHX-A''-DTPA chelating systems, in order to investigate its possible therapeutic use. Labeling was performed by a 30 min incubation of {sup 177}LuCl{sub 3} and each immunoconjugate, at 37 C. Radiochemical analysis showed the formation of a single radioactive species, at a yield higher than 98%, for both immunoconjugates. Kits have been formulated for both VG76e-DOTA and VG76e-DTPA. Stability studies, in the presence of a competitor excess, showed that both radiolabeled species remained sufficiently stable (95%) for at least 48 h. Biodistribution results in normal mice were similar for both radioimmunoconjugates, with no significant bone uptake. Gamma camera images of tumor-bearing mice showed satisfactory visualization of the tumor 24 h p.i., while a higher uptake was observed at 48 h p.i. Our findings indicate that both the bifunctional chelating agents p-SCN-Bz-DOTA and CHX-A''-DTPA can be used for the labeling of VG76e with {sup 177}Lu, with high labeling yield and stability. Their in vivo behaviour in normal and tumor-bearing mice looks promising and they can be successfully used for tumor imaging studies. (orig.)

  19. Layered metal uranyl phosphates

    International Nuclear Information System (INIS)

    HUO2PO4·4H2O (HUP) forms a laminar intercalate with butylamine, c = 29.30(5) angstrom, which accepts cationic metals in exchange for the n-butylammonium ions. Hydrated uranyl metal phosphates M(UO2PO4)2·nH2O (M=Mn,Co,Ni,Cu,Zn,Cd) are obtained by ionic exchange and were studied by thermal analysis and X-ray diffraction. The tetragonal structures of all these product compounds are derived from HUP. The diffuse electronic reflectance spectra of every sample show characteristic UO22+ absorption bands. In the spectra of the Co, Ni and Cu phosphates there are other bands in the 500-800 nm zone compatible with their observed aquocation transitions

  20. p-Isothiocyanatobenzyl-desferrioxamine: a new bifunctional chelate for facile radiolabeling of monoclonal antibodies with zirconium-89 for immuno-PET imaging

    Energy Technology Data Exchange (ETDEWEB)

    Perk, Lars R.; Vosjan, Maria J.W.D.; Budde, Marianne [VU University Medical Center, Department of Otolaryngology/Head and Neck Surgery, De Boelelaan 1117, PO Box 7057, MB, Amsterdam (Netherlands); Visser, Gerard W.M. [VU University Medical Center, Nuclear Medicine and PET Research, Amsterdam (Netherlands); Jurek, Paul; Kiefer, Garry E. [Macrocyclics Inc., Dallas, TX (United States); Dongen, Guus A.M.S. van [VU University Medical Center, Department of Otolaryngology/Head and Neck Surgery, De Boelelaan 1117, PO Box 7057, MB, Amsterdam (Netherlands); VU University Medical Center, Nuclear Medicine and PET Research, Amsterdam (Netherlands)

    2010-02-15

    Immuno-PET is an emerging imaging tool for the selection of high potential antibodies (mAbs) for imaging and therapy. The positron emitter zirconium-89 ({sup 89}Zr) has attractive characteristics for immuno-PET with intact mAbs. Previously, we have described a multi-step procedure for stable coupling of {sup 89}Zr to mAbs via the bifunctional chelate (BFC) tetrafluorophenol-N-succinyldesferal (TFP-N-sucDf). To enable widespread use of {sup 89}Zr-immuno-PET, we now introduce the novel BFC p-isothiocyanatobenzyl-desferrioxamine B (Df-Bz-NCS) and compare its performance in {sup 89}Zr-immuno-PET with the reference BFC TFP-N-sucDf. Three mAbs were premodified with Df-Bz-NCS and labeled with {sup 89}Zr at different pHs to assess the reaction kinetics and robustness of the radiolabeling. Stability of both {sup 89}Zr-Df-Bz-NCS- and {sup 89}Zr-N-sucDf-conjugates was evaluated in different buffers and human serum. Comparative biodistribution and PET studies in tumor-bearing mice were undertaken. The selected conjugation conditions resulted in a chelate:mAb substitution ratio of about 1.5:1. Under optimal radiolabeling conditions (pH between 6.8-7.2), the radiochemical yield was >85% after 60 min incubation at room temperature, resulting in radioimmunoconjugates with preserved integrity and immunoreactivity. The new radioimmunoconjugate was very stable in serum for up to 7 days at 37 C, with <5% {sup 89}Zr release, and was equally stable compared to the reference conjugate when stored in the appropriate buffer at 4 C. In biodistribution and imaging experiments, the novel and the reference radioimmunoconjugates showed high and similar accumulation in tumors in nude mice. The novel Df-Bz-NCS BFC allows efficient and easy preparation of optimally performing {sup 89}Zr-labeled mAbs, facilitating further exploration of {sup 89}Zr-immuno-PET as an imaging tool. (orig.)

  1. Uranyl complexes of n-alkanediaminotetra-acetic acids

    International Nuclear Information System (INIS)

    The uranyl complexes of n-propanediaminetetra-acetic acid, n-butanediaminetetra-acetic acid and n-hexanediaminetetra-acetic acid have been studied by potentiometry, with computer evaluation of the titration data by the MINIQUAD program. Stability constants of the 1:1 and 2:1 metal:ligand chelates have been determined as well as the respective hydrolysis and polymerization constants at 25 deg in 0.10M and 1.00M KNO3. The influence of the length of the alkane chain of the ligands on the complexes formed is discussed. (author)

  2. Novel enterobactin analogues as potential therapeutic chelating agents: Synthesis, thermodynamic and antioxidant studies

    Science.gov (United States)

    Zhang, Qingchun; Jin, Bo; Shi, Zhaotao; Wang, Xiaofang; Liu, Qiangqiang; Lei, Shan; Peng, Rufang

    2016-09-01

    A series of novel hexadentate enterobactin analogues, which contain three catechol chelating moieties attached to different molecular scaffolds with flexible alkyl chain lengths, were prepared. The solution thermodynamic stabilities of the complexes with uranyl, ferric(III), and zinc(II) ions were then investigated. The hexadentate ligands demonstrate effective binding ability to uranyl ion, and the average uranyl affinities are two orders of magnitude higher than 2,3-dihydroxy-N1,N4-bis[(1,2-hydroxypyridinone-6-carboxamide)ethyl]terephthalamide [TMA(2Li-1,2-HOPO)2] ligand with similar denticity. The high affinity of hexadentate ligands could be due to the presence of the flexible scaffold, which favors the geometric agreement between the ligand and the uranyl coordination preference. The hexadentate ligands also exhibit higher antiradical efficiency than butylated hydroxyanisole (BHA). These results provide a basis for further studies on the potential applications of hexadentate ligands as therapeutic chelating agents.

  3. Role of chelates in treatment of cancer

    Directory of Open Access Journals (Sweden)

    Tripathi Laxmi

    2007-01-01

    Full Text Available Chelates are used in cancer as cytotoxic agent, as radioactive agent in imaging studies and in radioimmunotherapy. Various chelates based on ruthenium, copper, zinc, organocobalt, gold, platinum, palladium, cobalt, nickel and iron are reported as cytotoxic agent. Monoclonal antibodies labeled with radioactive metals such as yttrium-90, indium-111 and iodine-131 are used in radioimmunotherapy. This review is an attempt to compile the use of chelates as cytotoxic drugs and in radioimmunotherapy.

  4. Evaluation of 177Lu-DOTA-labeled aglycosylated monoclonal anti-L1-CAM antibody chCE7: influence of the number of chelators on the in vitro and in vivo properties

    International Nuclear Information System (INIS)

    Introduction: In this study, we optimized the 1,4,7,10-tetraazacyclododecane-N-N'-N''-N''''-tetraacetic acid (DOTA) chelator-to-antibody (c/a) ratio for the aglycosylated variant of the anti-L1-CAM antibody chCE7 (chCE7agl), providing high specific activity and low liver uptake in 177Lu-labeled form. Methods: chCE7agl was substituted with increasing molar excess of DOTA-NCS. The number of chelators coupled to the antibody and the binding affinities to target tumor cells (IC5 values) of the resulting immunoconjugates were determined. The different immunoconjugates were labeled with 177Lu; specific activity was measured, and metabolic stability was analyzed in human plasma. The effect of different c/a ratios on blood clearance and liver uptake was tested in nude mice. Changes of the protein backbone structure were analyzed by circular dichroism spectroscopy. Results: chCE7agl was substituted with 7, 12 or 15 DOTA ligands. The IC5 concentrations displacing radioiodinated chCE7 antibody increased with the number of chelators (1.5-fold with 7 ligands, 2.5-fold with 12 ligands and a 5-fold increase with 15 ligands). The highest specific activity for 177Lu-DOTA-chCE7agl was obtained with a c/a ratio of 12 (106 MBq/mg). Radioimmunoconjugates were stable in human plasma for at least 24 h. Blood clearance and liver uptake were measured after 24 h (c/a ratios of 12 and 15) or 48 h (c/a ratio of 7). The liver-to-blood ratios were 0.35±0.14 (7 ligands), 0.77±0.19 (12 ligands) and 17.85±3.44 (15 ligands). Conclusions: DOTA-chCE7agl conjugates with a c/a ratio of 12 combined high specific activity with good in vitro and in vivo properties. The rapid elimination rate from the blood and the high uptake in the liver of chCE7agl substituted with 15 DOTA ligands were found not to be due to conformational changes of the antibody backbone structure

  5. Bis-phosphonate sequestering agents. Synthesis and preliminary evaluation for in vitro and in vivo uranium(VI) chelation

    Energy Technology Data Exchange (ETDEWEB)

    Sawicki, M.; Lecercle, D.; Taran, F. [CEA Saclay, IBiTecS, Serv Chim Bioorgan et Marquage, F-91191 Gif Sur Yvette (France); Grillon, G.; Le Gall, B.; Serandour, A.L.; Poncy, J.L. [CEA, DSV, DRR, Lab Radiotoxicol, F-91680 Bruyeres Le Chatel (France); Bailly, T.; Burgada, R.; Lecouvey, M.; Challeix, V. [CNRS, Lab Chim Struct Biomol, UMR 7033, F-93017 Bobigny (France); Leydier, A.; Pellet-Rostaing, S. [Univ Lyon 1, ICBMS, UMR 5246, Lab Catalyse et Synth Organ, F-69622 Villeurbanne (France); Ansoborlo, E. [CEA, DEN, DRCP, CETAMA, VRH Marcoule, F-30207 Bagnols Sur Ceze (France)

    2008-07-01

    A library of bis-phosphonate-based ligands was prepared using solution-phase parallel synthesis and tested for its uranium-binding properties. With the help of a screening method, based on a chromo-phoric complex displacement procedure, 23 dipodal and tripodal chelates bearing bis-phosphonate chelating functions were found to display very high affinity for the uranyl ion and were selected for evaluation of their in vivo uranyl-removal efficacy. Among them, 11 ligands induced a huge modification of the uranyl biodistribution by deviating the metal from kidney and bones to liver. Among the other ligands, the most potent was the dipodal bis-phosphonate 3C which reduced the retention of uranyl and increased its excretion by around 10% of the injected metal. (authors)

  6. Synthesis, structure, and spectroscopic characterization of three uranyl phosphates with unique structural units

    International Nuclear Information System (INIS)

    Single crystals of Zn4(OH)2[(UO2)(PO4)2(OH)2(H2O)] (UZnP), Cs[(UO2)(HPO4)NO3] (UCsP), and In3[(UO2)2(PO4)4OH(H2O)6].2H2O (UInP) were obtained from hydrothermal reactions and have been structurally and chemically characterized. UZnP crystallizes in space group Pbcn, a=8.8817(7), b=6.6109(5), c=19.569(1) Å; UCsP crystallizes in P−1, a=7.015(2), b=7.441(1), c=9.393(2) Å, α=72.974(2), β=74.261(2), γ=79.498(2); and UInP crystallizes in P−1, a=7.9856(5), b=9.159(1), c=9.2398(6) Å α=101.289(1), β=114.642(1), γ=99.203(2). The U6+ cations are present as (UO2)2+ uranyl ions coordinated by five O atoms to give pentagonal bipyramids. The structural unit in UZnP is a finite cluster containing a uranyl pentagonal bipyramid that shares corners with two phosphate tetrahedra. The structural unit in UCsP is composed of uranyl pentagonal bipyramids with one chelating nitrate group that are linked into chains by three bridging hydrogen phosphate tetrahedra. In UInP, the structural unit contains pairs of edge-sharing uranyl pentagonal bipyramids with two chelating phosphate tetrahedra that are linked into chains through two bridging phosphate tetrahedra. Indium octahedra link these uranyl phosphate chains into a 3-dimensional framework. All three compounds exhibit unique structural units that deviate from the typical layered structures observed in uranyl phosphate solid-state chemistry. - Graphical abstract: Three new uranyl phosphates with unique structural units are reported. ▪ Highlights: ► Three new uranyl phosphates have been synthesized hydrothermally. ► Single crystal analyses reveal unique structural units. ► The dimensionality of these compounds deviate from typical U6+ layered structures

  7. Uranyl fluoride luminescence in acidic aqueous solutions

    International Nuclear Information System (INIS)

    Luminescence emission spectra and decay rates are reported for uranyl species in acidic aqueous solutions containing HF or added NaF. The longest luminescence lifetime, 0.269 ± 0.006 ms, was observed from uranyl in 1 M HF + 1 M HClO4 at 296 K and decreased with increasing temperature. Based on a luminescence dynamics model that assumes equilibrium among electronically excited uranyl fluoride species and free fluoride ion, this long lived uranyl luminescence in aqueous solution is attributed primarily to UO2F2. Studies on the effect of added LiNO3 or Na2WO4·2H2O showed relatively weak quenching of uranyl fluoride luminescence which suggests that high sensitivity determination of the UF6 content of WF6 gas should be feasible via uranyl luminescence analysis of hydrolyzed gas samples of impure WF6

  8. Optical apparatus and method for sensing uranyl

    Science.gov (United States)

    Baylor, L.C.; Buchanan, B.R.

    1994-01-01

    An optical sensing device for uranyl and other substances, a method for making an optical sensing device and a method for chemically binding uranyl and other indicators to glass, quartz, cellulose and similar substrates. The indicator, such as arsenazo III, is immobilized on the substrate using a chemical binding process. The immobilized arsenazo III causes uranyl from a fluid sample to bind irreversibly to the substrate at its active sites, thus causing absorption of a portion of light transmitted through the substrate. Determination of the amount of light absorbed, using conventional means, yields the concentration of uranyl present in the sample fluid. The binding of uranyl on the substrate can be reversed by subsequent exposure of the substrate to a solution of 2,6-pyridinedicarboxylic acid. The chemical binding process is suitable for similarly binding other indicators, such as bromocresol green.

  9. Uranyl ion complexation by citric and citramalic acids in the presence of di-amines

    International Nuclear Information System (INIS)

    Uranyl nitrate reacts with citric (H4cit) or D-(-)-citramalic (H3citml) acids under mild hydrothermal conditions and in the presence of di-amines to give different complexes which are all characterized by the presence of 2:2 uranyl/poly-carboxylate di-anionic dimers or of polymeric chains based on the same dimeric motif. Each uranium ion is chelated by the two ligands through the alkoxide and the α- or β-carboxylate groups, the second β-carboxylic group in citrate being uncoordinated. The uranium coordination sphere is completed by either a water molecule or the β-carboxylate group of a neighboring unit, thus giving zero- or one-dimensional assemblages, respectively. The evidence for [UO2(Hcit)]2 dimers in the solid state confirms previous results from potentiometric and EXAFS measurements on solutions. Depending on the diamine used (DABCO, 2,2'- and 4,4'-bipyridine, [2.2.2]cryptand) and its ability to form divergent hydrogen bonds or not, different uranyl/poly-carboxylate topologies are obtained, thus evidencing template effects, and extended hydrogen bonding gives two- or three-dimensional assemblages. These results, together with those previously obtained with NaOH as a base, add to the knowledge of the uranyl/citrate system, which is much investigated for its environmental relevance. (author)

  10. Thermodynamic properties of uranyl metaborate

    International Nuclear Information System (INIS)

    The standard enthalpy of formation of crystalline UO2(BO2)2 (-2542.5 ± 3.5 kJ/mol) at 298.15 K was determined by reaction calorimetry. The heat capacity of this compound was measured over the temperature range 6-302 K by adiabatic vacuum calorimetry. The thermodynamic functions were calculated, including the standard entropy (502.8 ± 2.1 J/(mol K)) and Gibbs function of formation (-2392.5 ± 4.0 kJ/mol) at 298.15 K. The standard thermodynamic functions of reactions with the participation of uranyl metaborate were calculated and analyzed

  11. Preparation and near-quantitative Y-90 labelings of monoclonal antibody-macrocylic chelator (MAb-DOTA) conjugates for radioimmunotherapy (RAIT)

    Energy Technology Data Exchange (ETDEWEB)

    Govindan, S.V.; Griffiths, G.L.; Losman, M.J. [Immunomedics, Inc., Morris Plains, NJ (United States)] [and others

    1996-05-01

    The importance of kinetically inert Y-90-DOTA chelate for RAIT is well recognized. The aim of this study was to adapt a published procedure to overcome long-standing problems related to practical preparation of DOTA-MAb conjugates and poor Y-90 incorporation, and further improve upon labeling efficiencies. Using monoactivated DOTA, we have prepared conjugates of a CEA MAb (MN-14), a lymphoma MAb (LL2), their humanized versions (hMN-14 and hLL2), and the respective divalent fragments, and systematically examined the Y-90-labeling parameters. The DOTA/Mab ratios in conjugates were in the 3.0-6.8 range. In competitive CEA-binding assays, unmodified MN-14, MN-14-DOTA (6.8 chelators) and hMN-14-DOTA (4.4 chelators) exhibited very similar binding patterns. Y-90 labeling yields of >90% were obtained using a labeling time of 2 h at 40-45{degrees}C, pH {approximately}5.5, and DOTA/MAb ratio >3. Incorporations (specific activities):>99%for hMN-14-DOTA (103-170 MBa/mg), 94-97% for hLL2-DOTA (107-185 MBa/mg), 93-98%for hLL2F(ab`){sub 2}-DOTA (111 MBa/mg), and >90% for MN14-DOTA (37-185 MBq/mg). Aggregate content was usually less than 5%. Observed high incorporations are due both to the higher temperature used and DOTA/Y-90 molar ratios which readily exceeded a threshold requirement of three. Labeling efficiencies also depended upon the level of trace metal contaminants in the Y-90 shipment. Incubations of Y-90 labeled DOTA conjugates of hMN-14 and hLL2 in serum and in 1 mM DTPA at 37{degrees}C showed no detectable loss of metal over a 10-day period. These results should allow us to routinely use Y-90-DOTA-MAb conjugates in future preclinical and clinical RAIT studies.

  12. Monoclonal antibody modification with chelate-linked high-molecular-weight polymers: major increases in polyvalent cation binding without loss of antigen binding

    Energy Technology Data Exchange (ETDEWEB)

    Torchilin, V.P.; Klibanov, A.L.; Nossiff, N.D.; Slinkin, M.A.; Strauss, H.W.; Haber, E.; Smirnov, V.N.; Khaw, B.A.

    1987-06-01

    Polyethyleneimine or polylysines of differing molecular sizes were substituted with either EDTA or DTPA and then with succinic acid groups. These polymers were then reacted with the amino groups on myosin-specific monoclonal antibody or its Fab using a water soluble carbodiimide. The polymer-antibody complexes were capable of binding up to 150 di- or trivalent ions per mole (Mn++, Gd , or /sup 111/In ) without attendant loss of antigen binding. The polylysine derivatives of the intact antibody were rapidly cleared and sequestered in the liver, whereas the polylysine 14-kilodalton (kd) derivative of Fab was cleared from the circulation with minimal hepatic and kidney sequestration. This differed from the biodistribution of intact antimyosin or its Fab labeled with /sup 111/In via direct attachment of DTPA to the epsilon amino group of the lysyl residues. Applications in magnetic resonance and nuclear imaging are envisioned.

  13. Antibodies conjugated with new highly luminescent Eu3+ and Tb3+ chelates as markers for time resolved immunoassays. Application to simultaneous determination of clenbuterol and free cortisol in horse urine.

    Science.gov (United States)

    Bacigalupo, M A; Meroni, G; Secundo, F; Scalera, C; Quici, S

    2009-12-15

    Highly luminescent Eu(3+) and Tb(3+) complexes of 10-[4-(3-isothiocyanatopropoxy)benzoylmethyl]-1,4,7,10-tetraazacyclododecane-1,4,7 triacetic acid Eu(3+) is a subset of 1 and Tb(3+) is a subset of 1 were conjugated with a goat anti-rabbit IgG and a rabbit anti-mouse IgG, respectively, and applied as markers in a time resolved immunoassay for simultaneous quantitative determination of anabolic compounds clenbuterol (CL) and hydrocortisone (HC). The assay was performed in horse urine, using a monoclonal antibody specific to CL and a rabbit polyclonal antibody specific to the free HC. These lanthanide chelates are very stable and highly luminescent in aqueous solution and allowed to reach 10 microg L(-1) and 40 microg L(-1) sensitivities for CL and for HC, respectively. Application to the horse urine, that is a very complex matrix, has a considerable interest in the control of illegal use of these compounds. PMID:19836578

  14. A propeller-like uranyl metallomesogen

    OpenAIRE

    Cardinaels, Thomas; Ramaekers, Jan; Guillon, Daniel; Donnio, Bertrand; Binnemans, Koen

    2005-01-01

    Uranyl triflate forms with three imidazo[4,5-f]-1,10-phenanthroline ligands a propeller-like complex that exhibits a hexagonal columnar phase. The ligand is not liquid-crystalline, but a mesophase is induced upon complex formation with the uranyl salt. The thermal behavior has been investigated by polarizing optical microscopy and by high-temperature X-ray diffraction. A model of the stacking of the molecules in the mesophase is proposed.

  15. Denitration of Uranyl Nitrate Using Tridodecyl Amine

    International Nuclear Information System (INIS)

    Nitrate extraction from uranyl nitrate using extractant tridodecyl amine and paraffin has been carried out. The aim of this research was to prepare uranyl nitrate with low nitrate content (acid deficiency uranyl nitrate/ADUN). ADUN is a raw material for making kernels uranium oxide in a spherical from which cannot easily be broken/cracked. This ADUN was prepared by extracting nitric acid in uranyl nitrate solution with tridodecyl amine (TDA) and paraffin. Nitric acid in uranyl nitrate solution moved into organic phase due to the complex formation with TDA. The aqueous phase was ADUN, it was than analyzed its nitric and uranium contents using titration method. Tree variables were observed, i.e. uranium contents (80-125 g/l), process temperature (50-100 oC) and TDA/Nitrate molar ratio (0.5-1). Experiment results showed that optimum condition accurate at uranium content of 100 g/l, temperature extraction 60-70 oC and TDA to Nitrate molar ratio 0.75-0.80 with an efficiency of 77 %. (author)

  16. Thermochemical investigations on uranyl phosphates and arsenates

    International Nuclear Information System (INIS)

    The results are described of a study of the thermochemical stability of anhydrous uranyl phosphates and arsenates. A number of aspects of chemical technological importance are indicated in detail. The synthesized anhydrous uranyl phosphates and arsenates were very hygroscopic, so that experiments on these compounds had to be carried out under moisture-free conditions. Further characterisation of these compounds are given, including a study of their thermal stabilities and phase relations. The uranyl phosphates reduced reversibly at temperatures of the order of 1100 to 16000C. This makes it possible to express their relative stabilities quantitatively, in terms of the oxygen pressures of the reduction reactions. The thermal decomposition of uranyl arsenates did not occur by reduction, as for the phosphates, but by giving off arsenic oxide vapour. The results of measurements of enthalpies of solution led to the determination of the enthalpies of formation, heat capacity and the standard entropies of the uranyl arsenates. The thermochemical functions at high-temperatures could consequently be calculated. Attention is paid to the possible formation of uranium arsenates, whose uranium has a valency lower than six, hitherto not reported in literature. It was not possible to prepare arsenates of tetravalent uranium. However, three new compounds were observed, one of these, UAsO5, was studied in some detail. (Auth.)

  17. Chelation in Metal Intoxication

    Directory of Open Access Journals (Sweden)

    Swaran J.S. Flora

    2010-06-01

    Full Text Available 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.

  18. Uranyl Sequestration: Synthesis and Structural Characterization of Uranyl Complexes with a Tetradentate Methylterephthalamide Ligand

    Energy Technology Data Exchange (ETDEWEB)

    Ni, Chengbao; Shuh, David; Raymond, Kenneth

    2011-03-07

    Uranyl complexes of a bis(methylterephthalamide) ligand (LH{sub 4}) have been synthesized and characterized by X-ray crystallography. The structure is an unexpected [Me{sub 4}N]{sub 8}[L(UO{sub 2})]{sub 4} tetramer, formed via coordination of the two MeTAM units of L to two uranyl moieties. Addition of KOH to the tetramer gave the corresponding monomeric uranyl methoxide species [Me{sub 4}N]K{sub 2}[LUO{sub 2}(OMe)].

  19. Macrocyclic bifunctional chelating agents

    Science.gov (United States)

    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.

  20. Syntheses and structures of uranyl ethylenediphosphonates: from layers to elliptical nanochannels.

    Science.gov (United States)

    Tian, Tao; Yang, Weiting; Wang, Hao; Dang, Song; Pan, Qing-Jiang; Sun, Zhong-Ming

    2013-06-17

    A family of uranium diphosphonates have been hydrothermally synthesized through the reaction of ethylenediphosphonic acid (EDP, H4L) and uranyl nitrate/zinc uranyl acetate in the presence of organic templates, such as tetraethyl ammonium (NEt4(+)), 4,4'-bipyridine (bipy), and 1,10-phenanthroline (phen). The UO2(2+) in UO2(H2O)(H2L)(EDP-U1) is equatorially five-coordinated by four phosphonate groups and one aqua ligand, forming a pentagonal bipyramid. Each EDP ligand is doubly protonated and chelates three UO2(2+), resulting in a layered structure. Compounds (NEt4)2(UO2)3(HL)2(H2L)·4H2O (EDP-U2) and (H2bipy)UO2L (EDP-U3) have the same layered structure in which NEt4(+) and protonated bipy fill in the uranyl-phosphonate interlayers, respectively, and play a role to balance the negative charges. Different from that in EDP-U1, the UO2(2+) exists in the form of a UO6 tetragonal bipyramid and is surrounded by four different EDP ligands in EDP-U2 and EDP-U3. (Hphen)2(UO2)2(H2L)3 (EDP-U4) features a three-dimensional framework structure with large elliptical channels along the c axis (1.3 × 1.1 nm(2)). Monoprotonated phen molecules fill in these channels and hold together through strong π···π interactions. All of the four compounds have been characterized by IR and photoluminescent spectroscopy. Their characteristic emissions have been attributed as transition properties of uranyl cations. The ion-exchange study indicates that [Co(en)3](3+) could partially replace the protonated phen molecules.

  1. The Chelate Effect Redefined.

    Science.gov (United States)

    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)

  2. The Influence of Linker Geometry on Uranyl Complexation by Rigidly-Linked Bis(3-hydroxy-N-methyl-pyridin-2-one)

    Energy Technology Data Exchange (ETDEWEB)

    Szigethy, Geza; Raymond, Kenneth

    2010-04-22

    A series of bis(3-hydroxy-N-methyl-pyridin-2-one) ligands was synthesized, and their respective uranyl complexes were characterized by single crystal X-ray diffraction analyses. These structures were inspected for high-energy conformations and evaluated using a series of metrics to measure co-planarity of chelating moieties with each other and the uranyl coordination plane, as well as to measure coordinative crowding about the uranyl dication. Both very short (ethyl, 3,4-thiophene and o-phenylene) and very long ({alpha},{alpha}{prime}-m-xylene and 1,8-fluorene) linkers provide optimal ligand geometries about the uranyl cation, resulting in planar, unstrained molecular arrangements. The planarity of the rigid linkers also suggests there is a degree of pre-organization for a planar coordination mode that is ideal for uranyl-selective ligand design. Comparison of intramolecular N{sub amide}-O{sub phenolate} distances and {sup 1}H NMR chemical shifts of amide protons supports earlier results that short linkers provide the optimal geometry for intramolecular hydrogen bonding.

  3. Physico-chemical study of new functionalized surfactants having thermo sensitive de-mixing behaviour: use in extraction of uranyl nitrate

    International Nuclear Information System (INIS)

    New thermo-sensitive functionalized surfactants with metal-chelating properties have been developed and their physical-chemistry studied. They associate a polyethoxylated nonionic surfactant (CiEj) block and a amino-acid residue as a chelating group. Functionalization preserves both properties of the thermo-sensitive surfactant moiety and the chelating group, a diamide closed to uranyl ionophore.The complexing group participates to the polar head group of the surfactant, increasing the area per molecule. As a result, functionalized surfactants form spherical micelles when diluted in water, and the concentrated part of their phase diagrams exhibits structures having higher curvatures than the nonionic precursor CiEj. The structure of the uranyl - diamide complex has been elucidated by NMR and ESI-MS and is of the type UO2(NO3)2.L; the associated complexation constant, which is very low, has been evaluated by 1H NMR.A nitrate salt, LiNO3, is added at high concentration to improve complexation. The effect of this salt has been analyzed, and was found to be rather similar to the effect on classical CiEj. When uranyl nitrate complexation occurs, the cloud point decreases dramatically, together with the reduction of the area per head group at micelle/solution interface. This effect can be minimized by using a nonionic precursor having a larger polar head group. The functionalized surfactants have been tested in the cloud point extraction of uranyl nitrate, and have proved their efficiency. Those results demonstrate the viability of the functionalized surfactants design, with a covalent link between a thermo-sensitive surfactant block and a chelating group. (author)

  4. Chelation in metal intoxication

    DEFF Research Database (Denmark)

    Aaseth, Jan; Skaug, Marit Aralt; Cao, yang;

    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...

  5. Ferrocene base metal chelates

    International Nuclear Information System (INIS)

    Review of the works, devoted to different types of ferrocene metal chelates and to a possibility of ferrocene-containing ligand modification by means of complexing, is presented. Structure, properties and spectral characteristics of transitional metal, rare earth element, Cd2+, UO22+, Th4+ etc. complexes with ferrocene diketones, ferrocene acyl derivatives based on thiosemicarbazones and hydrazones and other heterometal ferrocene-containing metal chelates, are considered. 134 refs., 1 tab

  6. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor

    2015-01-22

    The present application offers a solution to the current problems associated with recovery and recycling of precious metals from scrap material, discard articles, and other items comprising one or more precious metals. The solution is premised on a microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  7. The bare uranyl(2+) ion, UO22+

    International Nuclear Information System (INIS)

    Ion-molecule reactions between U2+ and oxygen donors or charge-stripping collisions between singly charged UO22 ions and O2 collision partners generate uranyl(2+) ions in the gas phase. These do not readily dissociate into singly charged fragments. The standard enthalpy of formation for UO22+ is estimated to be 371±60 kcal mol-1, in accord with the results of ab initio calculations. (orig.)

  8. Thermochemical investigations on uranyl phosphates and arsenates

    International Nuclear Information System (INIS)

    Results are described of a study of the thermochemical stability of anhydrous phosphates and arsenates. The results of phase studies deal with compound formation and characterization, coexisting phases and limiting physical or chemical properties. The uranyl phosphates evolve oxygen at higher temperatures and the arsenates lose arsenic oxide vapour. These phenomena give the possibility to describe their thermodynamic stabilities. Thus oxygen pressures of uranyl phosphates have been measured using a static, non-isothermal method. Having made available the pure anhydrous compounds in the course of this investigation, molar thermodynamic quantities have been measured as well. These include standard enthalpies of formation from solution calorimetry and high-temperature heat-capacity functions derived from enthalpy increments measured. Some attention is given to compounds with uranium in valencies lower than six which have been met during the investigation. An evaluation is made of the thermodynamics of the compounds studied, to result in tabulized high-temperature thermodynamic functions. Relative stabilities within the systems are discussed and comparisons of the uranyl phosphates and the arsenates are made. (Auth.)

  9. Computer simulation of uranyl uptake by the rough lipopolysaccharide membrane of Pseudomonas aeruginosa.

    Science.gov (United States)

    Lins, Roberto D; Vorpagel, Erich R; Guglielmi, Matteo; Straatsma, T P

    2008-01-01

    Heavy metal environmental contaminants cannot be destroyed but require containment, preferably in concentrated form, in a solid or immobile form for recycling or final disposal. Microorganisms are able to take up and deposit high levels of contaminant metals, including radioactive metals such as uranium and plutonium, into their cell wall. Consequently, these microbial systems are of great interest as the basis for potential environmental bioremediation technologies. The outer membranes of Gram-negative microbes are highly nonsymmetric and exhibit a significant electrostatic potential gradient across the membrane. This gradient has a significant effect on the uptake and transport of charged and dipolar compounds. However, the effectiveness of microbial systems for environmental remediation will depend strongly on specific properties that determine the uptake of targeted contaminants by a particular cell wall. To aid in the design of microbial remediation technologies, knowledge of the factors that determine the affinity of a particular bacterial outer membrane for the most common ionic species found in contaminated soils and groundwater is of great importance. Using our previously developed model for the lipopolysaccharide (LPS) membrane of Pseudomonas aeruginosa, this work presents the potentials of mean force as the estimate of the free energy profile for uptake of sodium, calcium, chloride, uranyl ions, and a water molecule by the bacterial LPS membrane. A compatible classical parameter set for uranyl has been developed and validated. Results show that the uptake of uranyl is energetically a favorable process relative to the other ions studied. At neutral pH, this nuclide is shown to be retained on the surface of the LPS membrane through chelation with the carboxyl and hydroxyl groups located in the outer core.

  10. Computer simulation of uranyl uptake by the rough lipopolysaccharide membrane of Pseudomonas aeruginosa.

    Science.gov (United States)

    Lins, Roberto D; Vorpagel, Erich R; Guglielmi, Matteo; Straatsma, T P

    2008-01-01

    Heavy metal environmental contaminants cannot be destroyed but require containment, preferably in concentrated form, in a solid or immobile form for recycling or final disposal. Microorganisms are able to take up and deposit high levels of contaminant metals, including radioactive metals such as uranium and plutonium, into their cell wall. Consequently, these microbial systems are of great interest as the basis for potential environmental bioremediation technologies. The outer membranes of Gram-negative microbes are highly nonsymmetric and exhibit a significant electrostatic potential gradient across the membrane. This gradient has a significant effect on the uptake and transport of charged and dipolar compounds. However, the effectiveness of microbial systems for environmental remediation will depend strongly on specific properties that determine the uptake of targeted contaminants by a particular cell wall. To aid in the design of microbial remediation technologies, knowledge of the factors that determine the affinity of a particular bacterial outer membrane for the most common ionic species found in contaminated soils and groundwater is of great importance. Using our previously developed model for the lipopolysaccharide (LPS) membrane of Pseudomonas aeruginosa, this work presents the potentials of mean force as the estimate of the free energy profile for uptake of sodium, calcium, chloride, uranyl ions, and a water molecule by the bacterial LPS membrane. A compatible classical parameter set for uranyl has been developed and validated. Results show that the uptake of uranyl is energetically a favorable process relative to the other ions studied. At neutral pH, this nuclide is shown to be retained on the surface of the LPS membrane through chelation with the carboxyl and hydroxyl groups located in the outer core. PMID:18067253

  11. Chelation Therapy for Mercury Poisoning

    Directory of Open Access Journals (Sweden)

    Rong Guan

    2009-01-01

    Full Text Available Chelation therapy has been the major treatment for heavy metal poisoning. Various chelating agents have been developed and tested for treatment of heavy metal intoxications, including mercury poisoning. It has been clearly shown that chelating agents could rescue the toxicity caused by heavy metal intoxication, but the potential preventive role of chelating agents against heavy metal poisoning has not been explored much. Recent paper by Siddiqi and colleagues has suggested a protective role of chelating agents against mercury poisoning, which provides a promising research direction for broader application of chelation therapy in prevention and treatment of mercury poisoning.

  12. Pro-oxidative, genotoxic and cytotoxic properties of uranyl ions

    International Nuclear Information System (INIS)

    It is demonstrated that hydroxyl radicals and hydrogen peroxide are formed under the action of uranyl ions in aqueous solutions containing no reducing agents. In the presence of uranyl ions, formation of 8-oxoguanine in DNA and long-lived protein radicals are observed in vitro. It is shown that the pro-oxidant properties of uranyl at micromolar concentrations mostly result from the physico-chemical nature of the compound rather than its radioactive decay. Uranyl ions lead to damage in DNA and proteins causing death of HEp-2 cells by necrotic pathway. It is revealed that the uranyl ions enhance radiation-induced oxidative stress and significantly increase a death rate of mice exposed to sublethal doses of X-rays

  13. Biomineralization of uraninite and uranyl phosphate controlled by organic acids

    International Nuclear Information System (INIS)

    Biomineralization of uraninite (UO2) and uranyl phosphate minerals are both able to decrease the mobility of uranium in the environment. We examined biomineralization of UO2 and uranyl phosphate by Shewanella putrefaciens in the basic medium containing lactate as an electron donor, β- glycerolphosphate as a phosphorous source, and uranyl nitrate in the absence and presence of weak or strong complexing organic acids (WCOA or SCOA) under an anaerobic condition. In the basic medium, only biomineralization of UO2 was observed because of rapid reduction of U(VI). Biomineralization of UO2 and uranyl phosphate occurred in the media with WCOA, however the no biomineralization was occurred in the presence of SCOA. It is thought that formation of stable U(VI)-, and U(IV)- organic complexes prevents the biomineralization. These finding suggest that coexisting organic acids control the biomineralization of UO2 and uranyl phosphate minerals by microorganisms. (author)

  14. Uranyl photofootprinting of triple helical DNA.

    OpenAIRE

    Nielsen, P E

    1992-01-01

    Two triple helix structures (15-mers containing only T.A-T triplets or containing mixed T.A-T and C.G-C triplets) have been studied by uranyl mediated DNA photocleavage to probe the accessibility of the phosphates of the DNA backbone. Whereas the phosphates of the pyrimidine strand are at least as accessible as in double stranded DNA, in the phosphates of the purine strand are partly shielded and more so at the 5'-end of the strand. With the homo A/T target increased cleavage is observed towa...

  15. Chelation Therapy for Mercury Poisoning

    OpenAIRE

    Rong Guan; Han Dai

    2009-01-01

    Chelation therapy has been the major treatment for heavy metal poisoning. Various chelating agents have been developed and tested for treatment of heavy metal intoxications, including mercury poisoning. It has been clearly shown that chelating agents could rescue the toxicity caused by heavy metal intoxication, but the potential preventive role of chelating agents against heavy metal poisoning has not been explored much. Recent paper by Siddiqi and colleagues has suggested a protective role o...

  16. Surface Plasmon Resonance for Rapid Screening of Uranyl Affine Proteins

    International Nuclear Information System (INIS)

    A sensitive immunoassay based on SPR analysis was developed to measure uranyl cation (UO22+) affinity for any protein in a free state under physiological conditions. The technique involves immobilization of a specific monoclonal antibody (mAb) raised against UO22+ and 1, 10-phenanthroline-2, 9-dicarboxylic acid (DCP) used as a probe of UO22+ captured by the mAb. Calibration curves were established for accurate determination of UO22+ concentrations with a detection limit of 7 nM. The remaining free UO22+ could be accurately quantified from the different protein-metal equilibrium and a dose-response curve established for KD determination. This generic method was applied not only to proteins such as transferrin and albumin but also to small phosphonated ligands. Its robustness allows the fast UO22+ KD determination of any kind of macromolecules and small ligands using very few amount of compounds, thus opening new prospects in the field of uranium toxicity. (authors)

  17. Cement encapsulation of uranyl nitrate waste

    International Nuclear Information System (INIS)

    During decontamination of the former nuclear fuel reprocessing plant at West Valley, New York, low-level radioactive waste streams are being identified which require disposal in an environmentally acceptable manner. One such waste stream, consisting essentially of uranyl nitrate, has been located in one of the processing cells. A study was conducted on this waste stream to determine if it could be stably encapsulated in cement. First, a recipe was developed for cement-encapsulating this highly acidic waste. Samples were then made to perform waste qualification testing as described in the NRC Branch Technical Position-Waste Form to determine the stability of this waste form. The testing showed that the waste form had a compressive strength much greater than the 345 kPA (50 psi) minimum guideline after room-temperature cure, irradiation, thermal cycling, immersion, and biodegradation. In addition, the encapsulated waste had uranium and cerium leachability index values greater than six, which is the minimum recommended by the NRC position paper. The cement-encapsulated uranyl nitrate waste thus met the NRC stability guidelines for the disposal of Class B and Class C radioactive wastes

  18. Structure and spectroscopy of uranyl salicylaldiminate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Tamasi, A.L.; Barnes, C.L.; Walensky, J.R. [Missouri Univ., Columbia, MO (United States). Dept. of Chemistry

    2013-07-01

    The synthesis of uranyl complexes coordinated to tridentate, monoanionic salicylaldiminate (Schiff base) ligands was achieved by the reaction of UO{sub 2}Cl{sub 2}(THF){sub 3}, 1, with one equivalent of the corresponding sodium salicylaldiminate salts affording [(C{sub 9}H{sub 6}N)N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 2, [(NC{sub 5}H{sub 4})N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 3, and [(C{sub 6}H{sub 4}SCH{sub 3})N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 4. These are uncommon examples of uranyl complexes with a monoanionic ancillary ligand to stabilize the coordination sphere and one chloride ligand. Compounds 2-4 have been characterized by {sup 1}H and {sup 13}C NMR spectroscopy as well as IR and UVVis spectroscopy and their structures determined by X-ray crystallography. (orig.)

  19. Preparation and characterization of a volatile uranyl compound, Bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)dioxouranium-tetrahydrofuran

    International Nuclear Information System (INIS)

    A volatile uranyl compound UO2[(CF3CO)2CH]2.THF with a vapor pressure of 0.7 torr at 1000C has been prepared. The compound has high thermal stability and is suitable for studies of laser-induced isotope separation. The compound has been characterized by its IR, UV, NMR, fluorescence, and mass spectra and other physical and chemical properties including an X-ray structural determination. The molecule contains a linear uranyl ion equatorially surrounded by a pentagon of oxygen atoms. The chelating anions are tilted slightly in a boatlike configuration from this plane. The crystals are monoclinic,P2/sub 1/c, with a = 8.540 (3) A, b = 9.110 (4) A, c = 28.884 (11) A, β = 94.26 (3)0, and Z = 4

  20. Catalytic hydrogenation of uranyl nitrate - engineering scale studies

    International Nuclear Information System (INIS)

    Uranous nitrate is employed as partitioning agent for the separation of plutonium from uranium in PUREX process, the conventional process for the reprocessing of spent nuclear fuel. It is currently produced from uranyl nitrate solution by the electrochemical route. Since the conversion is only 50%, an innovative method based on catalytic hydrogenation has been developed. Parametric studies have been carried out on 5 L scale using natural uranyl nitrate solution as fed. Based on these studies, number of runs were carried out on engineering scale using contaminated uranyl nitrate solution. More than 100 kg of uranous nitrate has been made. Performance of the reduction process is described in detail. (author)

  1. METHOD OF INHIBITING CORROSION IN URANYL SULFATE SOLUTIONS

    Science.gov (United States)

    Bohlmann, E.G.; Griess, J.C. Jr.

    1960-08-23

    A method is given for treating a uranyl sulfate solution to inhibit the corrosiveness of the solution and elevate the phase separation temperature of the solution. Lithium sulfate is added to the solution in an amount ranging from 0.25 to 1.3 times the uranyl sulfate concentration. The corrosiveness of the solution with respect to stainless steel is substantially decreased by this means. This treatment also serves to raise the phase separation temperature of the solution (above 250 deg C), at which time the uranyl sulfate solution separates into two liquid phases of unequal uranium concentration and thus becomes unsuitable as nuclear reactor fuel.

  2. Thermal decomposition of ammonium diuranate, uranyl nitrate hexahydrate and uranyl peroxide

    International Nuclear Information System (INIS)

    The behaviors of three types of starting powder had been investigated during their thermal decomposition processes in nitrogen, air, and hydrogen. The powder types were the products of uranyl nitrate precipitation, i.e. ADU (ammonium diuranate), UNH (uranyl nitrate hexahydrate), and UPO (uranyl peroxide). The objective of the investigation was to find out the best atmosphere that would result in good quality powder in a thermal decomposition process with the lowest temperature and the shortest period of time in order to reduce the cost of UO2 powder preparation. Before the thermal decomposition process was initiated, all powder types were characterized for their crystal structures. The investigation was conducted by TG-DTA instrument at temperature up to 800°C and the heating rate of 10°C/minute. The crystal structures were identified by X-Ray Diffractometer with Cu-Ka radiation. The specific surface area of the powder was also observed using BET method, especially for the powder that underwent the process in hydrogen heated up to 800°C. The Results showed that the process took place faster in hydrogen, and UNH required lower thermal decomposition temperature in relations with other types of powder. (author)

  3. Recycling of uranyl from contaminated water

    International Nuclear Information System (INIS)

    Many separation processes are related to the behavior of ions close to charged surfaces. In this work, we examine uranyl ions, which can be considered as rod-like molecular ions with a spatially distributed charge, embedded in a system of like charged surfaces. The analysis of the system is based on an approximate field theory which is accurate from the weak to the strong electrostatic coupling regimes. The numerical results show that close to the charged surface the ions are oriented parallel to the surface, whereas at distances greater than half of the ion length, they are randomly oriented. Due to the restriction of the orientational degrees of freedom, the density of ions at the charged surface decreases to zero. For large surface charge densities, the force between like charged surfaces becomes attractive, as a result of charge correlations. The theoretical results are in good agreement with Monte Carlo simulation results. (authors)

  4. Adsorption isotherm of uranyl ions by fish scales of corvina

    International Nuclear Information System (INIS)

    Fish scale is by-product of fishery. The scales are mainly formed by hydroxyapatite and collagen forming a kind of natural composite with a large specific surface area that intensifies the adsorption process. In this paper the potential of adsorption of scales of Corvina fish for uranyl ions from nitric solutions was studied. The scales were washed several times with faucet water, sun-dried, triturated and sieved. Equilibrium and kinetic studies in adsorption of uranyl ions in batch systems were carried out at room temperature. Equilibrium time was reached at 5 min for 0.1 g L-1 uranyl solution with removal efficiency over 82%, and at 1 min of contact was observed about 60% of removal. The equilibrium isotherm was obtained and the Langmuir model fitted best. These preliminary results are very promising, showing great perspectives of application of the fish scales as biosorbent for uranyl ions in radioactive wastewater treatment processes with a sustainable technology. (author)

  5. Radiolysis studies of uranyl nitrate solution in nitric acid medium

    International Nuclear Information System (INIS)

    The radiolysis of acidic uranyl nitrate solutions was investigated using Co-60 gamma radiation. Hydrogen peroxide was determined as a function of increasing dose. The UV-vis absorption spectra of the irradiated solutions were measured and the spectral changes were analyzed. The increasing dose increases the absorbance intensities, possibly by an increment in nitrate concentration produced by radiolysis, which can originate the formation of different uranyl complexes in solution. (author)

  6. Chelated minerals for poultry

    Directory of Open Access Journals (Sweden)

    SL Vieira

    2008-06-01

    Full Text Available Organic minerals have been subject of an increasing number of investigations recently. These compounds can be considered the most significant event regarding commercial forms of minerals targeting animal supplementation in the last decades. Minerals, especially metals, are usually supplemented in poultry feeds using cheap saline sources and have never required a lot of attention in terms of quality. On the other hand, definitions of organic minerals are very broad and frequently lead to confusion when decision-making becomes necessary. Organic minerals include any mineral bound to organic compounds, regardless of the type of existing bond between mineral and organic molecules. Proteins and carbohydrates are the most frequent candidates in organic mineral combinations. Organic fraction size and bond type are not limitations in organic mineral definition; however, essential metals (Cu, Fe, Zn, and Mn can form coordinated bonds, which are stable in intestinal lumen. Metals bound to organic ligands by coordinated bonds can dissociate within animal metabolism whereas real covalent bonds cannot. Chelated minerals are molecules that have a metal bound to an organic ligand through coordinated bonds; but many organic minerals are not chelates or are not even bound through coordinated bonds. Utilization of organic minerals is largely dependent on the ligand; therefore, amino acids and other small molecules with facilitated access to the enterocyte are supposed to be better utilized by animals. Organic minerals with ligands presenting long chains may require digestion prior to absorption. After absorption, organic minerals may present physiological effects, which improve specific metabolic responses, such as the immune response. Many studies have demonstrated the benefits of metal-amino acid chelates on animal metabolism, but the detection positive effects on live performance is less consistent.

  7. EXAFS Study of Uranyl Complexation at Pseudomonas fluorescens Cell Surfaces

    Science.gov (United States)

    Bencheikh, R.; Bargar, J. R.; Tebo, B. M.

    2002-12-01

    Little is known about the roles of microbial biomass as a sink and source for uranium in contaminated aquifers, nor of the impact of bacterial biochemistry on uranium speciation in the subsurface. A significant role is implied by the high affinities of both Gram positive and Gram negative cells for binding uranyl (UO2{ 2+}). In the present study, Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy was used to identify membrane functional groups involved in uranyl binding to the Gram negative bacterium Pseudomonas fluorescens from pH 3 to pH 8. Throughout this pH-range, EXAFS spectra can be described primarily in terms of coordination of carboxylic groups to uranyl. U-C distances characteristic of 4-, 5- and 8- membered rings were observed, as well as the possibility of phosphato groups. Both shell-by-shell fits and principle component analyses indicate that the functional groups involved in binding of uranyl to the cell surface do not vary systematically across the pH range investigated. This result contrasts with EXAFS results of uranyl sorbed to Gram positive bacteria, and suggests an important role for long-chain carboxylate-terminated membrane functional groups in binding uranyl.

  8. Efficacy of chelating agents for treatment of acute uranium intoxication in rats

    International Nuclear Information System (INIS)

    Chelating agents (8102, 7601, 811, 7603, 8307, DTPA) were tested for treatment of acute uranium intoxication in rats. All phenolic chelating agents distinctively increased removal of uranium when they were injected immediately after intoxication of uranyl nitrate. 8102 was the best of them on removing uranium. After a single i.m. injection of 8102 at dose of 500 mg/kg, the excretion of uranium in the urine was 2.9 times higher than that for control, and the retention of uranium in kidneys was their 29%. When 8102 was administered 1 h before and up to 4 h after intoxication, it markedly increased the removal of uranium. When 8102 was administered to rats 1 h before intoxication, the histological lesion in kidneys was only a slight hydropic degeneration of the tubule epithelial cells. On the contrary, there wa a severe necrosis of the tubule epithelial cells in kidneys for controls

  9. Modulation of the Structure and Properties of Uranyl Ion Coordination Polymers Derived from 1,3,5-Benzenetriacetate by Incorporation of Ag(I) or Pb(II).

    Science.gov (United States)

    Thuéry, Pierre; Harrowfield, Jack

    2016-07-01

    Reaction of uranyl nitrate with 1,3,5-benzenetriacetic acid (H3BTA) in the presence of additional species, either organic bases or their conjugate acids or metal cations, has provided 12 new crystalline complexes, all but one obtained under solvo-hydrothermal conditions. The complexes [C(NH2)3][UO2(BTA)]·H2O (1) and [H2NMe2][UO2(BTA)] (2) crystallize as one- or two-dimensional (1D or 2D) assemblies, respectively, both with uranyl tris-chelation by carboxylate groups and hydrogen-bonded counterions but different ligand conformations. One of the bound carboxylate units is replaced by chelating 1,10-phenanthroline (phen) or 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4phen) in the complexes [(UO2)3(BTA)2(phen)3]·4H2O (3) and [(UO2)3(BTA)2(Me4phen)3]·NMP·3H2O (4) (NMP = N-methyl-2-pyrrolidone), which are a 2D network with honeycomb topology and a 1D polymer, respectively. With silver(I) cations, [UO2Ag(BTA)] (5), a three-dimensional (3D) framework in which the ligand assumes various chelating/bridging coordination modes, and the aromatic ring is involved in Ag(I) bonding, is obtained. A series of seven heterometallic complexes results when lead(II) cations and N-chelating molecules are both present. The complexes [UO2Pb(BTA)(NO3)(bipy)] (6) and [UO2Pb2(BTA)2(bipy)2]·3H2O (7), where bipy is 2,2'-bipyridine, crystallize from the one solution, as 1D and 2D assemblies, respectively. The two 1D coordination polymers [UO2Pb(BTA)(HCOO)(phen)] (8 and 9), again obtained from the one synthesis, provide an example of coordination isomerism, with the formate anion bound either to lead(II) or to uranyl cations. Another 2D architecture is found in [(UO2)2Pb2(BTA)2(HBTA)(H2O)2(phen)2]·2H2O (10), which provides a possible example of a Pb-oxo(uranyl) "cation-cation" interaction. While [UO2Pb(BTA)(HCOO)0.5(NO3)0.5(Me2phen)] (11), where Me2phen is 5,6-dimethyl-1,10-phenanthroline, is a 1D assembly close to those in 6 and 8, [UO2Pb2(BTA)2(Me4phen)2] (12), obtained together with

  10. Solid state and aqueous behavior of uranyl peroxide cage clusters

    Science.gov (United States)

    Pellegrini, Kristi Lynn

    Uranyl peroxide cage clusters include a large family of more than 50 published clusters of a variety of sizes, which can incorporate various ligands including pyrophosphate and oxalate. Previous studies have reported that uranyl clusters can be used as a method to separate uranium from a solid matrix, with potential applications in reprocessing of irradiated nuclear fuel. Because of the potential applications of these novel structures in an advanced nuclear fuel cycle and their likely presence in areas of contamination, it is important to understand their behavior in both solid state and aqueous systems, including complex environments where other ions are present. In this thesis, I examine the aqueous behavior of U24Pp 12, as well as aqueous cluster systems with added mono-, di-, and trivalent cations. The resulting solutions were analyzed using dynamic light scattering and ultra-small angle X-ray scattering to evaluate the species in solution. Precipitates of these systems were analyzed using powder X-ray diffraction, X-ray fluorescence spectrometry, and Raman spectroscopy. The results of these analyses demonstrate the importance of cation size, charge, and concentration of added cations on the aqueous behavior of uranium macroions. Specifically, aggregates of various sizes and shapes form rapidly upon addition of cations, and in some cases these aggregates appear to precipitate into an X-ray amorphous material that still contains U24Pp12 clusters. In addition, I probe aggregation of U24Pp12 and U60, another uranyl peroxide cage cluster, in mixed solvent water-alcohol systems. The aggregation of uranyl clusters in water-alcohol systems is a result of hydrogen bonding with polar organic molecules and the reduction of the dielectric constant of the system. Studies of aggregation of uranyl clusters also allow for comparison between the newer uranyl polyoxometalate family and century-old transition metal polyoxometalates. To complement the solution studies of uranyl

  11. Evaluation of renal function following administration of ethane-1-hydroxy-1,1-biphosphonate (EHBP) in animals submitted to oral intoxication with uranyl nitrate

    International Nuclear Information System (INIS)

    Workers involved in the processes of extraction, purification and manufacture of uranium of nuclear plants are occupationally exposed to both natural and enriched uranium. Several chelating agents (TIRON, EDTA, BAI, etc.) have been tested in terms of their capacity to sequester uranium before it reaches its target organs. Our laboratory has studied a first generation biphosphonate, ethane-1-hydroxy-1,1-biphosphonate (EHBP). We have shown that treatment with EHBP induces survival rates of 75% and 100% in adult and suckling rats respectively intoxicated with an intraperitoneal injection of uranyl nitrate. There are no data available to date on the renal function following treatment with EBHP to counteract the toxic effects of an oral lethal dose of uranyl nitrate. The aim of the present study was to assay creatininemia and uremia as end-points to assess renal function. The results obtained reveal that the alterations in renal function induced by oral uranyl nitrate intoxication can be reduced at 48 hours and reverted at 14 days by subcutaneous or oral administration of EHBP. (author)

  12. The catalytic role of uranyl in formation of polycatechol complexes

    Directory of Open Access Journals (Sweden)

    Halada Gary P

    2011-03-01

    Full Text Available Abstract To better understand the association of contaminant uranium with natural organic matter (NOM and the fate of uranium in ground water, spectroscopic studies of uranium complexation with catechol were conducted. Catechol provides a model for ubiquitous functional groups present in NOM. Liquid samples were analyzed using Raman, FTIR, and UV-Vis spectroscopy. Catechol was found to polymerize in presence of uranyl ions. Polymerization in presence of uranyl was compared to reactions in the presence of molybdate, another oxyion, and self polymerization of catechol at high pH. The effect of time and dissolved oxygen were also studied. It was found that oxygen was required for self-polymerization at elevated pH. The potential formation of phenoxy radicals as well as quinones was monitored. The benzene ring was found to be intact after polymerization. No evidence for formation of ether bonds was found, suggesting polymerization was due to formation of C-C bonds between catechol ligands. Uranyl was found to form outer sphere complexes with catechol at initial stages but over time (six months polycatechol complexes were formed and precipitated from solution (forming humic-like material while uranyl ions remained in solution. Our studies show that uranyl acts as a catalyst in catechol-polymerization.

  13. Some thermodynamic characteristics of uranyl benzenesulfonate and uranyl p-toluenesulfonate

    International Nuclear Information System (INIS)

    The enthalpy of dissolution of the anhydrous and hydrated salts in 4 M hydrochloric acid was determined. Based on experimental and published data, the enthalpy of water addition to the anhydrous salts and lowest hydrates of uranyl p-toluenesulfonate (UPTS) was evaluated. The enthalpy of addition of a water molecule to UPTS monohydrate was found to be approximately two times lower than in the case of UPTS trihydrate. This is in a good agreement with published data on formation of fairly stable coarse crystals of UPTS pentahydrate in slow crystallization in air. We did not find any published data on the standard enthalpy of formation of the sulfonate ions. However, according to the presented thermo-chemical cycles, from the experimental data we can evaluated the enthalpies of formation of sulfonates from the components, i.e. from amorphous uranium trioxide and aqueous solutions of benzenesulfonic and p-toluenesulfonic acids. It was shown that considering all approximations used in the evaluation, the enthalpy of formation of UPTS is by approximately 20 kJ.mole-1 more negative than in the case of uranyl benzenesulfonate. Along with thermochemical characteristics of hydrates, this allows us to conclude that electron-donor power of p-toluenesulfonate ion is noticeably greater than that of the benzenesulfonate ion, which is responsible for the differences in the characteristics of these salts

  14. Hydrothermal Phase Relations Among Uranyl Minerals at the Nopal I Analog Site

    International Nuclear Information System (INIS)

    Uranyl mineral paragenesis at Nopal I is an analog of spent fuel alteration at Yucca Mountain. Petrographic studies suggest a variety of possible hydrothermal conditions for uranium mineralization at Nopal I. Calculated equilibrium phase relations among uranyl minerals show uranophane stability over a broad range of realistic conditions and indicate that uranyl mineral variety reflects persistent chemical potential heterogeneity. (author)

  15. The polarographic electroreduction of uranyl ion in arsenic acid solution

    International Nuclear Information System (INIS)

    The electroreduction of uranyl ion in arsenic acid studied by d.c. polarography shows one reduction wave at all the used arsenic acid concentrations corresponding to one electron reduction mechanism. At low arsenic acid concentration (0,1 - 0,3 M)UO2(ClO4)2 is reduced to HUO2AsO4. At higher acid concentration (0,6 M) the HUO2AsO4 molecules are reduced to UO2+ (pentavalent uranium). It is also reliable to study polarographic behaviour of uranyl ions in arsenic acid solutions up to pH 3,01. It is also possible to apply this method for the analytical determination of uranyl ion concentrations up to 2 mM. (Author)

  16. Production of chelating agents by Pseudomonas aeruginosa grown in the presence of thorium and uranium

    International Nuclear Information System (INIS)

    Chelating agents produced by microorganisms enhance the dissolution of iron increasing the mobility and bioavailability of the metal. Since some similarities exist in the biological behavior of ferric, thorium and uranyl ions, microorganisms resistant to these metals and which grow in their presence may produce sequestering agents of Th and U, and other metals in a manner similar to the complexation of iron by siderophores. The ability of P. aeruginosa to elaborate sequestering agents in medium containing thorium or uranium salts was tested. Uranium has a stronger inhibitory effect on growth of the organism than thorium at similar concentrations. Analyses of the culture media have shown, that relative to the control, and under the experimental conditions used, the microorganisms have produced several new chelating agents for thorium and uranium. Extracts containing these chelating agents have been tested for their decorporation potential. In vitro mouse liver bioassay and in vivo mouse toxicity tests indicate that their efficiency is comparable to DTPA and DFOA and that they are virtually non-toxic to mice. The bacterially produced compounds resemble, but are not identical to the known iron chelating siderophores isolated from microorganisms. Some of their chemical properties are also discussed. (author)

  17. Optimization of a uranyl nitrate passive neutron counter

    Energy Technology Data Exchange (ETDEWEB)

    Rauch, Eric Benton [Los Alamos National Laboratory; Bracken, David [Los Alamos National Laboratory; West, James [Los Alamos National Laboratory; Freeman, Corey [Los Alamos National Laboratory; Newell, Matthew R [Los Alamos National Laboratory; Bourret, Steven C [Los Alamos National Laboratory; Rothrock, Richard B [Los Alamos National Laboratory; Ladd - Lively, Jennifer L [ORNL; Schuh, Denise [ORNL

    2010-01-01

    Safeguarding natural uranium as it enters the fuel cycle has become a priority for the safeguards community in recent years. Uranyl nitrate is a material of interest in this endeavor because it is normally a step in the process from converting uranium ores to more concentrated forms like UO{sub 2} and U{sub 3}O{sub 8}. This paper will detail the improvements and design optimizations made for a uranyl nitrate neutron detector. The original design of the detector was based on standard neutron counter designs and featured 2 rings of He-3 tubes fully moderated and shielded from background. Several areas for enhancement were identified after months of testing in three different locations. An operating uranyl nitrate facility was included as one of the test locations. Three significant upgrades to the counter addressed in the redesign were: real time background detection, counter reliability improvements, and optimization of the detector design for the detection of neutrons emitted by the uranyl nitrate flowing through the monitored process pipe. The optimized detector design includes significant electronics upgrades, the ability to detect neutrons (background and signal) with 36 degree spatial resolution around the process pipe for signal and 45 degree spatial resolution for background, inner and outer rings of He-3 tubes for real time background corrections, and notably more reliable cabling. Monte Carlo N-Particle (MCNP) modeling was used to optimize the signal (neutrons from uranyl nitrate in the monitored process pipe) to noise (background neutrons from all sources) ratio of the inner ring of He-3 tubes. Additionally, MCNP modeling maximized noise to signal on the outer ring of He-3 tubes. Details of the detector optimization as well as all the additional detector enhancements will be discussed. The neutron counter will be field tested on the Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory (ORNL).

  18. Complex formation reactions of uranyl(VI) with neutral N-donors in dimethyl sulfoxide. Influence of small amounts of water

    International Nuclear Information System (INIS)

    Quantitative information about the existence and thermodynamic stability of uranyl(VI) ion complexes based solely upon nitrogen coordination has been obtained in the solvent dimethyl sulfoxide. Calorimetric, potentiometric, and FT-IR investigations, under controlled anhydrous conditions, show that the uranyl(VI) ion can form both mono and bis chelates with the ethylenediamine ligand and only a mono chelate of rather low stability with propylenediamine. With the monodentate ligand n-butylamine only a very weak metal-ligand interaction has been detected. The stability constants and the enthalpy and entropy changes have been calculated for the identified coordinated species. All data refer to 25.0 degree C and a tetraethylammonium perchlorate medium of ionic strength 0.1 M. All the complexes are enthalpy stabilized whereas the entropy contributions oppose the complex formation. Calorimetric and FT-IR measurements carried out to investigate the effects of small amounts of water present show that a very low water concentration, comparable to that of the coordinating metal ion, can give rise to hydrolysis reactions that may compete with complex formation. This is due to the combined action of different factors that are discussed. 39 refs., 6 figs., 1 tab

  19. Production and Characterization of Desmalonichrome Relative Binding Affinity for Uranyl Ions in Relation to Other Siderophores.

    Science.gov (United States)

    Mo, Kai-For; Dai, Ziyu; Wunschel, David S

    2016-06-24

    Siderophores are iron (Fe)-binding secondary metabolites that have been investigated for their uranium-binding properties. Previous work has focused on characterizing hydroxamate types of siderophores, such as desferrioxamine B, for their uranyl (UO2)-binding affinity. Carboxylate forms of these metabolites hold potential to be more efficient chelators of UO2, yet they have not been widely studied. Desmalonichrome is a carboxylate siderophore that is not commercially available and so was obtained from the fungus Fusarium oxysporum cultivated under Fe-depleted conditions. The relative affinity for UO2 binding of desmalonichrome was investigated using a competitive analysis of binding affinities between UO2 acetate and different concentrations of Fe(III) chloride using electrospray ionization mass spectrometry. In addition to desmalonichrome, three other siderophores, including two hydroxamates (desferrioxamine B and desferrichrome) and one carboxylate (desferrichrome A), were studied to understand their relative affinities for the UO2(2+) ion at two pH values. The binding affinities of hydroxamate siderophores to UO2(2+) ions were observed to decrease with increasing Fe(III)Cl3 concentration at the lower pH. On the other hand, decreasing the pH has a smaller impact on the binding affinities between carboxylate siderophores and the UO2(2+) ion. Desmalonichrome in particular was shown to have the greatest relative affinity for UO2 at all pH and Fe(III) concentrations examined. These results suggest that acidic functional groups in the ligands are important for strong chelation with UO2 at lower pH. PMID:27232848

  20. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns

    2005-05-11

    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

  1. Uranyl salophenes as ionophores for phosphate-selective electrodes

    NARCIS (Netherlands)

    Wroblewski, Wojciech; Wojciechowski, Kamil; Dybko, Artur; Brzozka, Zbigniew; Egberink, Richard J.M.; Snellink-Ruel, Bianca H.M.; Reinhoudt, David N.

    2000-01-01

    Anion selectivities of poly(vinylchloride) (PVC) plasticized membranes containing uranyl salophene derivatives were presented. The influence of the membrane components (i.e. ionophore structure, dielectric constant and structure of plasticizer, the amount of incorporated ammonium salt) on its phosph

  2. Durable phosphate-selective electrodes based on uranyl salophenes

    NARCIS (Netherlands)

    Wroblewski, Wojciech; Wojciechowski, Kamil; Dybko, Artur; Brzozka, Zbigniew; Egberink, Richard J.M.; Snellink-Ruel, Bianca H.M.; Reinhoudt, David N.

    2001-01-01

    Lipophilic uranyl salophenes derivatives were used as ionophores in durable phosphate-selective electrodes. The influence of the ionophore structure and membrane composition (polarity of plasticizer, the amount of incorporated ionic sites) on the electrode selectivity and long-term stability were st

  3. First principles NEXAFS simulations of N-donor Uranyl complexes

    Science.gov (United States)

    Pemmaraju, C. D.; Duan, R.; Copping, R.; Jeon, B.; Teat, S. J.; Janousch, M.; Tyliszczak, T.; Canning, A.; Grønbech-Jensen, N.; Shuh, D. K.; Prendergast, D.

    2013-03-01

    The synthesis and study of soft-donor uranyl complexes can provide new insights into the coordination chemistry of non-aqueous [UO]2+ Recently, the tunable N-donor ligand 2,6-Bis(2-benzimidazyl)pyridine (BBP) was employed to produce novel uranyl complexes in which the [UO]2+ cation is ligated by anionic and covalent groups with discrete chemical differences. In this work we investigate the electronic structure of the three such uranyl-BBP complexes via near-edge X-ray absorption fine structure (NEXAFS) experiments and simulations using the eXcited electron and Core-Hole (XCH) approach. The evolution of the structural as well as electronic properties across the three complexes is studied systematically. Computed N K-edge and O K-edge NEXAFS spectra are compared with experiment and spectral features assigned to specific electronic transitions in these complexes. Studying the variations in spectral features arising from N K-edge absorption provides a clear picture of ligand-uranyl bonding in these systems.

  4. Colorimetric peroxidase mimetic assay for uranyl detection in sea water

    KAUST Repository

    Zhang, Dingyuan

    2015-03-04

    Uranyl (UO2 2+) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently reported uranyl-specific DNAzymes systems. However, to the best of our knowledge, few efficient detection methods have been reported for uranyl sensing in seawater. Herein, gold nanoclusters (AuNCs) are employed in an efficient spectroscopic method to detect uranyl ion (UO2 2+) with a detection limit of 1.86 ÎM. In the absence of UO2 2+, the BSA-stabilized AuNCs (BSA-AuNCs) showed an intrinsic peroxidase-like activity. In the presence of UO2 2+, this activity can be efficiently restrained. The preliminary quenching mechanism and selectivity of UO2 2+ was also investigated and compared with other ions. This design strategy could be useful in understanding the binding affinity of protein-stabilized AuNCs to UO2 2+ and consequently prompt the recycling of UO2 2+ from seawater.

  5. Preparation of pure uranyl chloride from crude yellow cake

    International Nuclear Information System (INIS)

    A process is described for the preparation of pure uranyl chloride solution from crude yellow cake. The process involves dissolution of the latter in hydrochloric acid followed by uranium extraction using TBP-kerosene mixture. A series of experiments were carried out in order to determine the optimum conditions for both the dissolution and the extraction steps

  6. Polaron effects in the protonic conductor hydrogen uranyl phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Lupu, D. (Inst. of Isotopic and Molecular Technology, Cluj-Napoca (Romania)); Grecu, R. (Inst. of Chemistry, Cluj-Napoca (Romania)); Biris, A.R. (Inst. of Isotopic and Molecular Technology, Cluj-Napoca (Romania))

    1993-08-01

    The isotope effects on the conductivity of hydrogen uranyl phosphate reveal ionic polaron effects in this solid protonic conductor, in agreement with the small polaron theory. An absorption band is observed at 0.67 eV, which can be correlated with the conduction mechanism consisting in both tunnelling and over-barrier hopping processes. (orig.)

  7. Density functional study of uranyl (Ⅵ) amidoxime complexes

    Institute of Scientific and Technical Information of China (English)

    Chi Fang-Ting; Li Peng; Xiong Jie; Hu Sheng; Gao Tao; Xia Xiu-Long; Wang Xiao-Lin

    2012-01-01

    Uranyl (Ⅵ) amidoxime complexes are investigated using relativistic density functional theory.The equilibrium structures,bond orders,and Mulliken populations of the complexes have been systematically investigated under a generalized gradient approximation (GGA).Comparison of (acet) uranyl amidoxime complexes ([UO2(AO)n]2-n,1≤n ≤4) with available experimental data shows an excellent agreement.In addition,the U-O(1),U-O(3),C(1)-N(2),and C(3)-N(4) bond lengths of [UO2(CH3AO)4]2- are longer than experimental data by about 0.088,0.05,0.1,and 0.056(A).The angles of N(3)-O(3)-U,O(2)-N(1)-C(1),N(3)-C(3)-N(4),N(4)-C(3)-C(4),and C(4)-C(3)-N(3) are different from each other,which is due to existing interaction between oxygen in uranyl and hydrogen in amino group.This interaction is found to be intra-molecular hydrogen bond.Studies on the bond orders,Mulliken charges,and Mulliken populations demonstrate that uranyl oxo group functions as hydrogen-bond acceptors and H atoms in ligands act as hydrogen-bond donors forming hydrogen bonds within the complex.

  8. Dynamic interplay between uranyl phosphate precipitation, sorption, and phase evolution

    International Nuclear Information System (INIS)

    Highlights: • In all experiments, final concentrations of uranium were lower than U.S. EPA standards. • U–P minerals more stable than chernikovite were slow to develop without sorption. • Heterogeneous nucleation was not observed. • U sorbs much more readily to the goethite than mica in the absence of phosphate. • Nucleation-growth-sorption cycles occur over weeks, not hours, at room temperature. - Abstract: Natural examples demonstrate uranyl-phosphate minerals can maintain extremely low levels of aqueous uranium in groundwaters due to their low solubility. Therefore, greater understanding of the geochemical factors leading to uranyl phosphate precipitation may lead to successful application of phosphate-based remediation methods. However, the solubility of uranyl phosphate phases varies over >3 orders of magnitude, with the most soluble phases typically observed in lab experiments. To understand the role of common soil/sediment mineral surfaces in the nucleation and transformation of uranyl phosphate minerals under environmentally relevant conditions, batch experiments were carried out with goethite and mica at pH 6 in mixed electrolyte solutions ranging from 1–800 μM U and 1–800 μM P. All experiments ended with uranium concentrations below the USEPA MCL for U, but with 2–3 orders of magnitude difference in uranium concentrations. Despite the presence of many cations that are well known to incorporate into less soluble autunite-group minerals, chernikovite rapidly precipitated in all experiments containing U and P, except for solutions with 1 μM U and 1 μM P that were calculated to be undersaturated. Textures of uranyl phosphates observed by AFM and TEM indicate that nucleation was homogenous and independent of the initial mineral content. Comparison of time-course U and P concentrations from the experiments with thermodynamic modeling of solution equilibria demonstrated that aqueous uranium concentrations in the experimental systems evolved

  9. Overview of current chelation practices

    Directory of Open Access Journals (Sweden)

    Y. Aydinok

    2011-12-01

    Full Text Available Deferoxamine (DFO is reference standard therapy for transfusional iron overload since the 1980s. Although it is a highly effective iron chelator, the compliance problem to subcutaneous administration of DFO remains as the major problem. The oral chelator Deferiprone (DFP has no marketing licence in North America, however, it has been licensed in India since 1994 and the European Union (EU granted marketing approval for DFP in 1999, specifically for patients with thalassemia major when DFO is inadequate, intolerable or unacceptable. There are still limited data available on the use of DFP in children between 6 and 10 years of age, and no data on DFP use in children under 6 years of age. Subsequently the oral chelator Deferasirox (DFX was approved by FDA and EMA for the treatment of patients with transfusional iron overload -older than 2 years of age- as first line therapy, in 2005 and 2006 respectively. The primary objective of iron chelation is to maintain body iron at safe levels at all times but once iron is accumulated, the objective of iron chelation is to reduce tissue iron to safe levels which is a slow process. The chelation regimen, dose and frequency of administration, of the chelator(s are mainly determined based on body iron burden, presence of myocardial iron and the transfusional iron loading rate. A proper monitoring of chelation is of importance for measuring the response rate to a particular regimen and providing dose adjustments to enhance chelation efficacy and to avoid toxicity. Efficacy of a chelation regimen may exhibit individual variability resulting from factors such as absorbtion and metabolism of the chelator. Tolerability and compliance are also individual variables effecting the response to chelation. Understanding of advantages and limitations of chelators, accurately determining chelation needs of patients with iron overload and designing individualized chelation regimens with less toxicity but optimum efficacy

  10. Residual biomass for removal of uranyl ions;Biomassa residual para remocao de ions uranilo

    Energy Technology Data Exchange (ETDEWEB)

    Boniolo, Milena Rodrigues [Universidade Federal de Sao Carlos (UFScar), SP (Brazil). Dept. de Biogeoquimica Ambiental; Yamaura, Mitiko; Monteiro, Raquel Almeida, E-mail: milenaboniolo@usp.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Quimica e Meio Ambiente

    2010-07-01

    Activities related to nuclear industry, production of phosphoric acid and hospitals have generated considerable volumes of radioactive waste containing uranyl ions. Banana pith was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy and was investigated as a biosorbent for uranyl ions from nitric solutions by batch experiments. Influences of adsorbent size, kinetics and equilibrium adsorption were studied. The biosorption of the uranyl ions followed pseudo-second-order kinetics. The adsorption isotherm data were closely fitted to the Freundlich equation. (author)

  11. Structural determination of some uranyl compounds by vibrational spectroscopy

    International Nuclear Information System (INIS)

    The vibrational spectra of different uranyl compounds has been studied and of it spectral information has been used the fundamental asymmetric vibrational frequency, to determine the length and constant bond force U=O by means of the combination of the concept of absorbed energy and the mathematical expression of Badger modified by Jones. It is intended a factor that simplifies the mathematical treatment and the results are compared with the values obtained for other methods. (Author)

  12. Aggregation-induced emission active tetraphenylethene-based sensor for uranyl ion detection.

    Science.gov (United States)

    Wen, Jun; Huang, Zeng; Hu, Sheng; Li, Shuo; Li, Weiyi; Wang, Xiaolin

    2016-11-15

    A novel tetraphenylethene-based fluorescent sensor, TPE-T, was developed for the detection of uranyl ions. The selective binding of TPE-T to uranyl ions resulted in a detectable signal owing to the quenching of its aggregation-induced emission. The developed sensor could be used to visually distinguish UO2(2+) from lanthanides, transition metals, and alkali metals under UV light; the presence of other metal ions did not interfere with the detection of uranyl ions. In addition, TPE-T was successfully used for the detection of uranyl ions in river water, illustrating its potential applications in environmental systems. PMID:27439180

  13. Structure and bonding in crystalline cesium uranyl tetrachloride under pressure.

    Science.gov (United States)

    Osman, Hussien H; Pertierra, Pilar; Salvadó, Miguel A; Izquierdo-Ruiz, F; Recio, J M

    2016-07-21

    A thorough investigation of pressure effects on the structural properties of crystalline cesium uranyl chloride was performed by means of first-principles calculations within the density functional theory framework. Total energies, equilibrium geometries and vibrational frequencies were computed at selected pressures up to 50 GPa. Zero pressure results present good agreement with available experimental and theoretical data. Our calculated equation of state parameters reveal that Cs2UO2Cl4 is a high compressible material, similar to other ionic compounds with cesium cations, and displays a structural anisotropic behavior guided by the uranyl moiety. An unexpected variation of the U-O bond length, dUO, is detected as pressure is applied. It leads to a dUO-stretching frequency relationship that cannot be described by the traditional Badger's rule. Interestingly enough, it can be explained in terms of a change in the main factor controlling dUO. At low pressure, the charge transferred to the uranyl cation induces an increase of the bond length and a red shift of the stretching frequencies, whereas it is the mechanical effect of the applied pressure above 10 GPa that is the dominant factor that leads to a shortening of dUO and a blue shift of the stretching frequencies. PMID:27340008

  14. Structure and bonding in crystalline cesium uranyl tetrachloride under pressure.

    Science.gov (United States)

    Osman, Hussien H; Pertierra, Pilar; Salvadó, Miguel A; Izquierdo-Ruiz, F; Recio, J M

    2016-07-21

    A thorough investigation of pressure effects on the structural properties of crystalline cesium uranyl chloride was performed by means of first-principles calculations within the density functional theory framework. Total energies, equilibrium geometries and vibrational frequencies were computed at selected pressures up to 50 GPa. Zero pressure results present good agreement with available experimental and theoretical data. Our calculated equation of state parameters reveal that Cs2UO2Cl4 is a high compressible material, similar to other ionic compounds with cesium cations, and displays a structural anisotropic behavior guided by the uranyl moiety. An unexpected variation of the U-O bond length, dUO, is detected as pressure is applied. It leads to a dUO-stretching frequency relationship that cannot be described by the traditional Badger's rule. Interestingly enough, it can be explained in terms of a change in the main factor controlling dUO. At low pressure, the charge transferred to the uranyl cation induces an increase of the bond length and a red shift of the stretching frequencies, whereas it is the mechanical effect of the applied pressure above 10 GPa that is the dominant factor that leads to a shortening of dUO and a blue shift of the stretching frequencies.

  15. Design of one evaporation system for uranyl nitrate solution

    International Nuclear Information System (INIS)

    The authors propose an instant evaporation system with recirculation of the concentrated solution to raise the concentration from 50 to 1500 g of uranium per litre of solution. The capacity of the plant is to be 14.1 kg of uranium per hour. The main equipment used in the system is as follows: 1. Ring-type heat exchanger, for increasing the temperature of the mixture of fresh and recirculated solution from 80 to 1150C; 2. Separation tank, in which instant evaporation is carried out. The absolute pressure inside the tank will be 500 mmHg, with steam separation from a concentrated (78.5 wt.%) uranyl nitrate solution; 3. Desuperheater-condenser of horizontal tubular type for condensing water vapour and recovering any uranyl nitrate that may have been entrained; 4. Storage tank for the concentrate, with a capacity for one day's normal operation, and a heating coil to prevent crystallization of the concentrated solution; 5. Two storage tanks for feed and condensate with capacity for one day's normal operation; 6. Supporting structure for the above components. Virtually all equipment in contact with the uranyl nitrate solution will be made of 304 stainless steel. Saturated steam at 143.30C will be required. The cost of the proposed system is $543 030.00. (author)

  16. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates.

    Science.gov (United States)

    Miskowiec, Andrew; Kirkegaard, Marie C; Huq, Ashfia; Mamontov, Eugene; Herwig, Kenneth W; Trowbridge, Lee; Rondinone, Adam; Anderson, Brian

    2015-12-10

    We report a novel production method for uranium oxyfluoride [(UO2)7F14(H2O)7]·4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl fluoride, UO2F2, through the gas phase at ambient temperatures followed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7]·4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous structure), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielastic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform restricted motion on a length scale commensurate with the O-H bond (r = 0.92 Å). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps(-1)) than their hydrogen-bonded partners (Dr = 28.7 ps(-1)). PMID:26575434

  17. Serum stability of 67Cu chelates: comparison with 111In and 57Co

    International Nuclear Information System (INIS)

    Simple chelates and chelate conjugated monoclonal antibodies labeled with 111In, 57Co and 67Cu demonstrate marked differences in stability when exposed to a serum environment. Among these radiometals, on DTPA, the order of stability is 111In > 57Co >> 67Cu. On benzyl-EDTA, the order of stability is 111In approx. 57Co >> 67Cu. Among those investigated, the only serum stable 67Cu chelate found was 67>Cu-TETA. The order of stability observed for 57Co vs 67Cu is contrary to published equilibrium constants. These in vitro studies suggest that the in vivo behavior of metal chelates exposed to a complex molecular environment may not be predicted by classically determined equilibrium constants. (author)

  18. Iron mobilization using chelation and phlebotomy

    DEFF Research Database (Denmark)

    Flaten, T. P.; Aaseth, J.; Andersen, Ole;

    2012-01-01

    are phlebotomy and chelation. Phlebotomy is the initial treatment of choice in haemochromatosis, while chelation is a mainstay in the treatment of transfusional siderosis. The classical iron chelator is deferoxamine (Desferal), but due to poor gastrointestinal absorption it has to be administered intravenously...... or subcutaneously, mostly on a daily basis. Thus, there is an obvious need to find and develop new effective iron chelators for oral use. In later years, particularly two such oral iron chelators have shown promise and have been approved for clinical use, namely deferiprone (Ferriprox) and deferasirox (Exjade...

  19. Enhanced environmental detection of uranyl compounds based on luminescence characterization

    Science.gov (United States)

    Nelson, Jean Dennis

    Uranium (U) contamination can be introduced to the environment as a result of mining and manufacturing activities related to nuclear power, detonation of U-containing munitions (DoD), or nuclear weapons production/processing (DOE facilities). In oxidizing environments such as surface soils, U predominantly exists as U(VI), which is highly water soluble and very mobile in soils. U(VI) compounds typically contain the UO22+ group (uranyl compounds). The uniquely structured and long-lived green luminescence (fluorescence) of the uranyl ion (under UV radiation) has been studied and remained a strong topic of interest for two centuries. The presented research is distinct in its objective of improving capabilities for remotely sensing U contamination by understanding what environmental conditions are ideal for detection and need to be taken into consideration. Specific focuses include: (1) the accumulation and fluorescence enhancement of uranyl compounds at soil surfaces using distributed silica gel, and (2) environmental factors capable of influencing the luminescence response, directly or indirectly. In a complex environmental system, matrix effects co-exist from key soil parameters including moisture content (affected by evaporation, temperature and humidity), soil texture, pH, CEC, organic matter and iron content. Chapter 1 is a review of pertinent background information and provides justification for the selected key environmental parameters. Chapter 2 presents empirical investigations related to the fluorescence detection and characterization of uranyl compounds in soil and aqueous samples. An integrative experimental design was employed, testing different soils, generating steady-state fluorescence spectra, and building a comprehensive dataset which was then utilized to simultaneously test three hypotheses: The fluorescence detection of uranyl compounds is dependent upon (1) the key soil parameters, (2) the concentration of U contamination, and (3) time of analysis

  20. Luminescent lanthanide chelates and methods of use

    Energy Technology Data Exchange (ETDEWEB)

    Selvin, Paul R. (Berkeley, CA); Hearst, John (Berkeley, CA)

    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.

  1. Chelators for investigating zinc metalloneurochemistry.

    Science.gov (United States)

    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.

  2. Combination therapies in iron chelation

    Directory of Open Access Journals (Sweden)

    Raffaella Origa

    2014-12-01

    Full Text Available The availability of oral iron chelators and new non-invasive methods for early detection and treatment of iron overload, have significantly improved the life expectancy and quality of life of patients with b thalassemia major. However, monotherapy is not effective in all patients for a variety of reasons. We analyzed the most relevant reports recently published on alternating or combined chelation therapies in thalassemia major with special attention to safety aspects and to their effects in terms of reduction of iron overload in different organs, improvement of complications, and survival. When adverse effects, such as gastrointestinal upset with deferasirox or infusional site reactions with deferoxamine are not tolerable and organ iron is in an acceptable range, alternating use of two chelators (drugs taken sequentially on different days, but not taken on the same day together may be a winning choice. The association deferiprone and deferoxamine should be the first choice in case of heart failure and when dangerously high levels of cardiac iron exist. Further research regarding the safety and efficacy of the most appealing combination treatment, deferiprone and deferasirox, is needed before recommendations for routine clinical practice can be made.

  3. Uranyl-organic assemblies with acetate-bearing phenyl- and cyclohexyl-based ligands

    International Nuclear Information System (INIS)

    Six novel complexes formed under hydrothermal conditions by uranyl ions with three ligands comprising a rigid phenyl- or cyclohexyl-containing platform, and two to four acetate arms have been obtained. 1,3,5-Benzene-triacetic acid (H3BTA) yielded the complex [NMe4][UO2(BTA)].H2O (1), in which the structure-directing counter-ion induces a two-dimensional, bilayer-type structure different from that previously reported, with both the tris-chelating ligand and the metal ion as trigonal nodes. Two complexes were obtained with 1,2-phenylenedioxy-diacetic acid (H2PDDA), [UO2(PDDA)(H2O)] (2) and [H2DABCO][(UO2)2(PDDA)3].1.5H2O (3). Complex 2 is a simple, ribbon-like, one-dimensional polymer, while 3 is a nano-tubular assembly built around the hydrogen-bonded, structure-directing counterions. Three complexes were obtained with trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid (H4DCTA), a polyamino-poly-carboxylic acid, with different bases, [UO2(H2DCTA)(H2O)2].H2O (4), [UO2(H2DCTA)(H2O)].1.5H2O (5), and [UO2Na(HDCTA)(H2O)] (6). The nitrogen atoms are not coordinated, both of them (4) or only one (5 and 6) being protonated, and the carboxylic/ate groups are monodentate, except for one chelating in 6 and one nonbonding in 4. These differences in bonding result in various assemblies, one-dimensional in 4 and two-dimensional in 5 and 6. The layers in 5 are strongly corrugated, with the cyclohexyl groups pointing on either side, and their packing displays oval-shaped channels, while the layers in 6 are planar, with the cyclohexyl groups located on one side, and further assembled into dimeric units by the disordered sodium ions. These are the first crystal structures of actinide ion complexes with both H2PDDA and H4DCTA. (authors)

  4. Copper(II) and uranyl(II) complexes with acylthiosemicarbazide: synthesis, characterization, antibacterial activity and effects on the growth of promyelocytic leukemia cells HL-60.

    Science.gov (United States)

    Angelusiu, Madalina Veronica; Almajan, Gabriela Laura; Rosu, Tudor; Negoiu, Maria; Almajan, Eva-Ruxandra; Roy, Jenny

    2009-08-01

    New chelates of N(1)-[4-(4-X-phenylsulfonyl)benzoyl]-N(4)-butyl-thiosemicarbazide (X=H, Cl, Br) with Cu(2+) and UO(2)(2+) have been prepared and characterized by analytical and physico-chemical techniques such as magnetic susceptibility measurements, elemental and thermal analyses, electronic, ESR and IR spectral studies. Room temperature ESR spectra of Cu(II) complexes yield {g} values characteristic of distorted octahedral and pseudo-tetrahedral geometry. Infrared spectra indicate that complexes contain six-coordinate uranium atom with the ligand atoms arranged in an equatorial plane around the linear uranyl group. Effects of these complexes on the growth of human promyelocytic leukemia cells HL-60 and their antibacterial activity (against Staphylococcus epidermidis ATCC 14990, Bacillus subtilis ATCC 6633, Bacillus cereus ATCC 14579, Pseudomonas aeruginosa ATCC 9027 and Escherichia coli ATCC 11775 strains) were studied comparatively with that of free ligands. PMID:19356828

  5. SERS detection of uranyl using functionalized gold nanostars promoted by nanoparticle shape and size.

    Science.gov (United States)

    Lu, Grace; Forbes, Tori Z; Haes, Amanda J

    2016-08-15

    The radius of curvature of gold (Au) nanostar tips but not the overall particle dimensions can be used for understanding the large and quantitative surface-enhanced Raman scattering (SERS) signal of the uranyl (UO2)(2+) moiety. The engineered roughness of the Au nanostar architecture and the distance between the gold surface and uranyl cations are promoted using carboxylic acid terminated alkanethiols containing 2, 5, and 10 methylene groups. By systematically varying the self-assembled monolayer (SAM) thickness with these molecules, the localized surface plasmon resonance (LSPR) spectral properties are used to quantify the SAM layer thickness and to promote uranyl coordination to the Au nanostars in neutral aqueous solutions. Successful uranyl detection is demonstrated for all three functionalized Au nanostar samples as indicated by enhanced signals and red-shifts in the symmetric U(vi)-O stretch. Quantitative uranyl detection is achieved by evaluating the integrated area of these bands in the uranyl fingerprint window. By varying the concentration of uranyl, similar free energies of adsorption are observed for the three carboxylic acid terminated functionalized Au nanostar samples indicating similar coordination to uranyl, but the SERS signals scale inversely with the alkanethiol layer thickness. This distance dependence follows previously established models assuming that roughness features associated with the radius of curvature of the tips are considered. These results indicate that SERS signals using functionalized Au nanostar substrates can provide quantitative detection of small molecules and that the tip architecture plays an important role in understanding the resulting SERS intensities. PMID:27326897

  6. A protein engineered to bind uranyl selectively and with femtomolar affinity

    Science.gov (United States)

    Zhou, Lu; Bosscher, Mike; Zhang, Changsheng; Özçubukçu, Salih; Zhang, Liang; Zhang, Wen; Li, Charles J.; Liu, Jianzhao; Jensen, Mark P.; Lai, Luhua; He, Chuan

    2014-03-01

    Uranyl (UO22+), the predominant aerobic form of uranium, is present in the ocean at a concentration of ~3.2 parts per 109 (13.7 nM) however, the successful enrichment of uranyl from this vast resource has been limited by the high concentrations of metal ions of similar size and charge, which makes it difficult to design a binding motif that is selective for uranyl. Here we report the design and rational development of a uranyl-binding protein using a computational screening process in the initial search for potential uranyl-binding sites. The engineered protein is thermally stable and offers very high affinity and selectivity for uranyl with a Kd of 7.4 femtomolar (fM) and >10,000-fold selectivity over other metal ions. We also demonstrated that the uranyl-binding protein can repeatedly sequester 30-60% of the uranyl in synthetic sea water. The chemical strategy employed here may be applied to engineer other selective metal-binding proteins for biotechnology and remediation applications.

  7. Exploring the uranyl organometallic chemistry: from single to double uranium carbon bonds

    International Nuclear Information System (INIS)

    Uranyl organometallic complexes featuring uranium(VI) carbon single and double bonds have been obtained from uranyl UO2X2 precursors by avoiding reduction of the metal center. X-ray diffraction and density functional theory analyses of these complexes showed that the UC and UdC bonds are polarized toward the nucleophilic carbon. (authors)

  8. Spectroscopic studies on uranyl complexes with tri-n-butyl phosphate (TBP) in ionic liquids

    International Nuclear Information System (INIS)

    The complexes formed from uranyl salts and tri-n-butyl phosphate (TBP) in ionic liquids (ILs) were studied by spectroscopic methods. [UO2(TBP)4]2+ is formed from UO2(ClO4)2· xH2O with excess of TBP in ILs. The coordination number of uranyl in [UO2(TBP)4]2+ is determined as 4 by ATR-FTIR study. In [Bmim][NTf2], though TBP cannot replace the NO3- coordinated to uranyl, TBP/[Bmim][NTf2] can extract 'nitrate-free' uranyl complex from diluted HNO3 medium and the extracted complex is converted into [UO2(TBP)4]2+ after drying. The formation of [UO2(TBP)4]2+ provides spectroscopic evidence for the cation-exchange mechanism of uranyl extraction by TBP/[Bmim][NTf2] from diluted HNO3 medium. (author)

  9. Quantification of uranyl in presence of citric acid; Cuantificacion de uranilo en presencia de acido citrico

    Energy Technology Data Exchange (ETDEWEB)

    Garcia G, N.; Barrera D, C.E. [UAEM, Facultad de Quimica, 50000 Toluca, Estado de Mexico (Mexico); Ordonez R, E. [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)]. e-mail: nidgg@yahoo.com.mx

    2007-07-01

    To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

  10. Acute toxicity of uranium hexafluoride, uranyl fluoride and hydrogen fluoride

    International Nuclear Information System (INIS)

    Uranium hexafluoride (UF6) released into the atmosphere will react rapidly with moisture in the air to form the hydrolysis products uranyl fluoride (UO2F2) and hydrogen fluoride (HF). Uranium compounds such as UF6 and UO2F2 exhibit both chemical toxicity and radiological effects, while HF exhibits only chemical toxicity. This paper describes the development of a methodology for assessing the human health consequences of a known acute exposure to a mixture of UF6, UO2F2, and HF. 4 refs., 2 figs., 5 tabs

  11. Biosolubilization of uranyl ions in uranium ores by hydrophyte plants

    International Nuclear Information System (INIS)

    This paper investigated the bioleaching of uranyl ions from uranium ores, in aqueous medium by hydrophyte plants: Lemna minor, Azolla caroliniana and Elodea canadensis under different experimental conditions. The oxidation of U(IV) to U(VI) species was done by the atomic oxygen generated in the photosynthesis process by the aquatic plants in the solution above uranium ores. Under identical experimental conditions, the capacity of bioleaching of uranium ores decreases according to the following series: Lemna minor > Elodea canadensis > Azolla caroliniana. The results of IR spectra suggest the possible use of Lemna minor and Elodea canadensis as a biological decontaminant of uranium containing wastewaters. (author)

  12. Thyroid Antibodies

    Science.gov (United States)

    ... be limited. Home Visit Global Sites Search Help? Thyroid Antibodies Share this page: Was this page helpful? Also known as: Thyroid Autoantibodies; Antithyroid Antibodies; Antimicrosomal Antibody; Thyroid Microsomal Antibody; ...

  13. Enhanced Adsorption and Recovery of Uranyl Ions by NikR Mutant-Displaying Yeast

    Directory of Open Access Journals (Sweden)

    Kouichi Kuroda

    2014-04-01

    Full Text Available Uranium is one of the most important metal resources, and the technology for the recovery of uranyl ions (UO22+ from aqueous solutions is required to ensure a semi-permanent supply of uranium. The NikR protein is a Ni2+-dependent transcriptional repressor of the nickel-ion uptake system in Escherichia coli, but its mutant protein (NikRm is able to selectively bind uranyl ions in the interface of the two monomers. In this study, NikRm protein with ability to adsorb uranyl ions was displayed on the cell surface of Saccharomyces cerevisiae. To perform the binding of metal ions in the interface of the two monomers, two metal-binding domains (MBDs of NikRm were tandemly fused via linker peptides and displayed on the yeast cell surface by fusion with the cell wall-anchoring domain of yeast α-agglutinin. The NikRm-MBD-displaying yeast cells with particular linker lengths showed the enhanced adsorption of uranyl ions in comparison to the control strain. By treating cells with citrate buffer (pH 4.3, the uranyl ions adsorbed on the cell surface were recovered. Our results indicate that the adsorption system by yeast cells displaying tandemly fused MBDs of NikRm is effective for simple and concentrated recovery of uranyl ions, as well as adsorption of uranyl ions.

  14. Understanding the bonding nature of uranyl ion and functionalized graphene: a theoretical study.

    Science.gov (United States)

    Wu, Qun-Yan; Lan, Jian-Hui; Wang, Cong-Zhi; Xiao, Cheng-Liang; Zhao, Yu-Liang; Wei, Yue-Zhou; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-03-20

    Studying the bonding nature of uranyl ion and graphene oxide (GO) is very important for understanding the mechanism of the removal of uranium from radioactive wastewater with GO-based materials. We have optimized 22 complexes between uranyl ion and GO applying density functional theory (DFT) combined with quasi-relativistic small-core pseudopotentials. The studied oxygen-containing functional groups include hydroxyl, carboxyl, amido, and dimethylformamide. It is observed that the distances between uranium atoms and oxygen atoms of GO (U-OG) are shorter in the anionic GO complexes (uranyl/GO(-/2-)) compared to the neutral GO ones (uranyl/GO). The formation of hydrogen bonds in the uranyl/GO(-/2-) complexes can enhance the binding ability of anionic GO toward uranyl ions. Furthermore, the thermodynamic calculations show that the changes of the Gibbs free energies in solution are relatively more negative for complexation reactions concerning the hydroxyl and carboxyl functionalized anionic GO complexes. Therefore, both the geometries and thermodynamic energies indicate that the binding abilities of uranyl ions toward GO modified by hydroxyl and carboxyl groups are much stronger compared to those by amido and dimethylformamide groups. This study can provide insights for designing new nanomaterials that can efficiently remove radionuclides from radioactive wastewater.

  15. Escherichia coli response to uranyl exposure at low pH and associated protein regulations.

    Directory of Open Access Journals (Sweden)

    Arbia Khemiri

    Full Text Available Better understanding of uranyl toxicity in bacteria is necessary to optimize strains for bioremediation purposes or for using bacteria as biodetectors for bioavailable uranyl. In this study, after different steps of optimization, Escherichia coli cells were exposed to uranyl at low pH to minimize uranyl precipitation and to increase its bioavailability. Bacteria were adapted to mid acidic pH before exposure to 50 or 80 µM uranyl acetate for two hours at pH≈3. To evaluate the impact of uranium, growth in these conditions were compared and the same rates of cells survival were observed in control and uranyl exposed cultures. Additionally, this impact was analyzed by two-dimensional differential gel electrophoresis proteomics to discover protein actors specifically present or accumulated in contact with uranium.Exposure to uranium resulted in differential accumulation of proteins associated with oxidative stress and in the accumulation of the NADH/quinone oxidoreductase WrbA. This FMN dependent protein performs obligate two-electron reduction of quinones, and may be involved in cells response to oxidative stress. Interestingly, this WrbA protein presents similarities with the chromate reductase from E. coli, which was shown to reduce uranyl in vitro.

  16. Effect of organic solvent properties on enthalpies of their mixing with uranyl nitrate

    International Nuclear Information System (INIS)

    Results of studying dissolution enthalpies of anhydrons uranyl nitrate and its hexahydrate in different organic solvents and water are generalized. Analysis of different solvation effects during uranyl nitrate and its hexahydrate dissolution in 26 solvents shows that the main contribution to dissolution enthalpy is made by acidic-basic interaction of uranyl-nitrates with donor lone electron pairs. The obtained equations permit to predict with acceptable accuracy the values of dissolution enthalpies of the mentioned compounds in other midea on the basis of their physico-chemical properties

  17. Metal ions, Alzheimer's disease and chelation therapy.

    Science.gov (United States)

    Budimir, Ana

    2011-03-01

    In the last few years, various studies have been providing evidence that metal ions are critically involved in the pathogenesis of major neurological diseases (Alzheimer, Parkinson). Metal ion chelators have been suggested as potential therapies for diseases involving metal ion imbalance. Neurodegeneration is an excellent target for exploiting the metal chelator approach to therapeutics. In contrast to the direct chelation approach in metal ion overload disorders, in neurodegeneration the goal seems to be a better and subtle modulation of metal ion homeostasis, aimed at restoring ionic balance. Thus, moderate chelators able to coordinate deleterious metals without disturbing metal homeostasis are needed. To date, several chelating agents have been investigated for their potential to treat neurodegeneration, and a series of 8-hydroxyquinoline analogues showed the greatest potential for the treatment of neurodegenerative diseases.

  18. Metal ions, Alzheimer's disease and chelation therapy.

    Science.gov (United States)

    Budimir, Ana

    2011-03-01

    In the last few years, various studies have been providing evidence that metal ions are critically involved in the pathogenesis of major neurological diseases (Alzheimer, Parkinson). Metal ion chelators have been suggested as potential therapies for diseases involving metal ion imbalance. Neurodegeneration is an excellent target for exploiting the metal chelator approach to therapeutics. In contrast to the direct chelation approach in metal ion overload disorders, in neurodegeneration the goal seems to be a better and subtle modulation of metal ion homeostasis, aimed at restoring ionic balance. Thus, moderate chelators able to coordinate deleterious metals without disturbing metal homeostasis are needed. To date, several chelating agents have been investigated for their potential to treat neurodegeneration, and a series of 8-hydroxyquinoline analogues showed the greatest potential for the treatment of neurodegenerative diseases. PMID:21406339

  19. Radioimmunotherapy with engineered antibody fragments

    International Nuclear Information System (INIS)

    Authors have developed and begun evaluating radiometal-chelated (213Bi) engineered antibody fragments as radioimmunotherapy agents that target the HER2/neu (c-erbB-2) antigen. The diabody format was found to have 40-fold greater affinity for HER2/neu and to be associated with significantly greater tumor localization than is achieved with scFv molecule. It is shown that short-lived isotopes like 213Bi would be most effective when used in conjunction with antibodies that targeted diffuse malignancies (leukemia or lymphoma) or when used for very rapid pretargeted radioimmunotherapy application in which the radioisotope is conjugated to a very small ligand

  20. Evaluation of lanthanide salts as alternative stains to uranyl acetate.

    Science.gov (United States)

    Hosogi, Naoki; Nishioka, Hideo; Nakakoshi, Masamichi

    2015-12-01

    Uranyl acetate (UAc) has been generally used not only as a superb staining reagent for ultrathin sections of plastic-embedded biological materials, but also as high-contrast negative stains for biological macromolecules such as particles of protein or virus. However, the use and purchase of radioactive UAc have been restricted. In this study, we determine the performance of ytterbium triacetate, lutetium triacetate, samarium triacetate and gadolinium triacetate as new staining reagents for biological electron microscopy. We observed chemically fixed spinach (Spinacia oleracea) leaves stained with these reagents. Ultrathin sections were stained with these reagents. Some of them were counterstained with lead citrate. The transmission electron microscopy contrast of spinach organelles was evaluated in sections exposed to the conventional stain and new stains. We show acetate salts of samarium, gadolinium, ytterbium and lutetium could be excellent substitutes for UAc for thin section staining and for negative staining. In addition, each reagent showed appreciable negative-staining effects. PMID:26374081

  1. First Synthesis of Uranyl Aluminate nano-particles

    Energy Technology Data Exchange (ETDEWEB)

    Chave, T.; Nikitenko, S. I. [UMII, ICSM, CEA, CNRS, ENSCM, Ctr Marcoule, UMR 5257, F-30207 Bagnols Sur Ceze (France); Scheinost, A. C. [European Synchrotron Radiat Facil, Rossendorf Beamline CRG BM20, F-38043 Grenoble (France); Scheinost, A. C. [FZD, Inst Radiochem, D-01314 Dresden (Germany); Berthon, C.; Arab-Chapelet, B.; Moisy, Ph. [CEA Marcoule, DEN, DRCP, Ctr Marcoule, F-30207 Bagnols Sur Ceze (France)

    2010-07-01

    This paper describes, for the first time, a simple method for the synthesis of uranyl aluminate (URAL) nano-particles. URAL was prepared by U(VI) hydrolytic precipitation with ammonia at pH = 11 in the presence of meso-porous alumina MSU-X under 20 kHz of sonication followed by annealing of the obtained solids at 800 C. TEM, XAFS, powder XRD, and {sup 27}Al MAS NMR studies revealed that the speciation of uranium in this system strongly depends on uranium concentration. The sample with 5 wt % of uranium yields air-stable nano-particles (similar to 5 nm) of URAL. Presumably, UO{sub 2}{sup 2+} cations in this compound are coordinated with bidentate AlO{sub 2}{sup -} groups. The increase of uranium concentration to 30 wt % causes mostly formation of U{sub 3}O{sub 8} fine particles (similar to 50 nm) and small amounts of URAL. (authors)

  2. Complex formation between uranyl and various thiosemicarbazide derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Chuguryan, D.G.; Dzyubenko, V.I.

    1987-01-01

    Complex formation between hexavalent uranium and salicylaldehyde thiosemicarbazone (H/sub 2/L), salicylaldehyde S-methyl-isothiosemicarbazone (H/sub 2/Q), S-methyl-N/sub 1/,N/sub 4/-bis(salicylidene)isothiosemicarbazide(H/sub 2/Z), and thiosemicarbazidodiacetic acid (H/sub 2/R) has been studied spectrophotometrically in solution. Stability constants for complexes having the composition UO/sub 2/A have been calculated. Solid uranyl derivatives having the composition UO/sub 2/L x 2H/sub 2/O, UO/sub 2/Q x 2H/sub 2/O, UO/sub 2/Z x 2H/sub 2/O, and UO/sub 2/R x 2H/sub 2/O have been obtained. These derivatives were isolated and their IR spectroscopic behavior and thermal properties were investigated.

  3. Reaction of gallocyanine methyl ester with uranyl ions

    Energy Technology Data Exchange (ETDEWEB)

    Kotoucek, M.; Hrbkova, M. (Palackeho Univ., Olomouc (Czechoslovakia). Prirodovedecka Fakulta)

    1984-09-01

    The reaction of gallocyanine methyl ester with uranyl ions was studied spectrophotometrically in slightly acid or neutral solutions of 40% (m/m) ethanol. A violet complex of UO/sub 2/L/sub 2/ is formed at pH>5. The conditional stability constants of the complex in the pH range 6-7.4 and the equilibrium constants of the coordination reaction were derived from the concentration curves and the continuous variations curves. The optimum conditions were sought for the spectrophotometric determination of uranium based on the occurrence of the UO/sub 2/L/sub 2/ complex. The relative standard deviation obtained for a uranium concentration of 106 ..mu..g.l/sup -1/ was ssub(r)=2.13%.

  4. Decontamination of metal surface contaminated by uranyl solution

    International Nuclear Information System (INIS)

    Decontamination degrees was measured for the metallic equipments in the uranium conversion plant by a chemical decontamination and contamination degrees also measured. Most equipments was made of stainless steel and contacted with uranium(VI) and nitric acid solution. So, metallic surfaces was contaminated with uranium(VI) materials. And decontamination degrees can be expressed by alpha activity measurements. For the alpha activity measurements, metallic specimens were selected in the three representative processes, dissolution process, solvent extraction, and Ammonium Uranyl Carbonate(AUC) precipitation and were prepared to rectangular parallelepipeds with 18mm width and 18mm length and 5mm height. The metallic surfaces can be decontaminated under 10 Bq/cm2 alpha activity due to uranium by only water decontamination, and under 0.04 Bq/cm2 alpha activity by 10% nitric acid decontamination that is ground activity level

  5. On thermal decomposition of double manganese and uranyl sulfates

    International Nuclear Information System (INIS)

    Thermal decomposition of MnUO2(SO4)2x5H2O was studied by differential thermal, thermogravimetric, and X-ray phase analysis. The parameters of rhombic unit cells of α-MnU3O10 a=6.563, b=3.790, c=8.273 A, Z=1; β-MnU3O10 - a=6.564, b=7.581, c=16.54 A, Z=4; (U,Mn)3O8 - a=6.389, b=11.32, c=8.262 A, Z=4; and MnUO4 - a=6.645, b=6.747, c=6.980 A, Z=4; space group Imam were determined. The interplane distances for anhydrous manganese sulphate and uranyl are given

  6. Investigation into uranyl sulfate crystallohydrate interaction with pyridine

    International Nuclear Information System (INIS)

    The product of UO2SO4x2.5H2O interaction with pyridine is investigated. It is detected that as a result of interaction one of the aqueous molecules of band hydrate of uranyl sulfate is subjected to intramolecular dissociation with the formation of hydroxy compound and transfer of proton to pyridine. Protonated amine is kept in the structure of the compound investigated in the interlayer space by means of hydrogen bonds. The (PyH((UO2SO4xOHH2O) formula is prescribed to the complex prepared. The substance is characterized by the methods of chemical, X-ray phase, spectral and thermal analyses. Decomposition of the sulfate group is established to begin about 450 deg C with separation of pyridinium sulfate to the gaseous phase. Change in pyridinium and water molecule removal in thermal decomposition of the complex is discussed

  7. Investigation of the Uranyl(II)-3-Hydroxyflavone complex

    International Nuclear Information System (INIS)

    By the application of suitable spectrophotometric methods and pH-metric measurements it has been established that uranyl ion and 3-hydroxyflavone from a [UO2(C15H9O3)]+ complex. The concentration stability constant of the complex was determined by Bent-French's (β1 = 8,59 at pH = 3,5) and Bjerrum's (from 8,68 at pH = 4 to 6,14 at pH = 7) methods. Conditions are given for the spectrophotometric determination of 3-hydroxyflavone by means of the complex. The regression equation is calculated and the accuracy of the method is determined. All investigations were carried out with 80 % ethanolic solutions at room temperature (20 %), the spectrophotometric measurements being performed at a constant pH (3,5) and a constant ionic strength (0,01 M). (Authors)

  8. First Synthesis of Uranyl Aluminate nano-particles

    International Nuclear Information System (INIS)

    This paper describes, for the first time, a simple method for the synthesis of uranyl aluminate (URAL) nano-particles. URAL was prepared by U(VI) hydrolytic precipitation with ammonia at pH = 11 in the presence of meso-porous alumina MSU-X under 20 kHz of sonication followed by annealing of the obtained solids at 800 C. TEM, XAFS, powder XRD, and 27Al MAS NMR studies revealed that the speciation of uranium in this system strongly depends on uranium concentration. The sample with 5 wt % of uranium yields air-stable nano-particles (similar to 5 nm) of URAL. Presumably, UO22+ cations in this compound are coordinated with bidentate AlO2- groups. The increase of uranium concentration to 30 wt % causes mostly formation of U3O8 fine particles (similar to 50 nm) and small amounts of URAL. (authors)

  9. Reaction of gallocyanine methyl ester with uranyl ions

    International Nuclear Information System (INIS)

    The reaction of gallocyanine methyl ester with uranyl ions was studied spectrophotometrically in slightly acid or neutral solutions of 40% (m/m) ethanol. A violet complex of UO2L2 is formed at pH>5. The conditional stability constants of the complex in the pH range 6-7.4 and the equilibrium constants of the coordination reaction were derived from the concentration curves and the continuous variations curves. The optimum conditions were sought for the spectrophotometric determination of uranium based on the occurrence of the UO2L2 complex. The relative standard deviation obtained for a uranium concentration of 106 μg.l-1 was ssub(r)=2.13%. (author)

  10. The uranyl influence on a mutation process in germ and somatic cells of mice

    International Nuclear Information System (INIS)

    The mutagenic effect of uranyl was revealed by the chromosome rearrangement test in germ and somatic cells of mice. The effect value depended on duration of substance administration into organism. (authors)

  11. Adsorption of uranyl species on hydroxylated titanium carbide nanosheet: A first-principles study.

    Science.gov (United States)

    Zhang, Yu-Juan; Lan, Jian-Hui; Wang, Lin; Wu, Qun-Yan; Wang, Cong-Zhi; Bo, Tao; Chai, Zhi-Fang; Shi, Wei-Qun

    2016-05-01

    In this work, hydroxylated titanium carbide Ti3C2(OH)2, a representative of the two-dimensional transition metal carbides, has been predicted to be an effective adsorbent for uranyl ions in aqueous environments for the first time using density functional theory simulations. The calculations revealed that the uranyl ion can strongly bind with Ti3C2(OH)2 nanosheet in aqueous solution regardless of the presence of anionic ligands such as OH(-), Cl(-) and NO3(-). The bidentate coordination of uranyl to the surface is energetically more favorable than other adsorption configurations, and the uranyl ion prefers to bind with the deprotonated O adsorption site rather than the protonated one on the hydroxylated surface. During the adsorption process, the chemical adsorption as well as the formation of hydrogen bonds is the dominant factor.

  12. Uranyl determination using pyridylazoresorcinol as complexing active by adsorb voltametry technique with cathodic redissolution

    International Nuclear Information System (INIS)

    The development method for uranyl ion determination by the optimization of chemical reaction and instrumental parameters is shown. This method is based on preconcentration stage, where in adsorptive accumulation of metallic complex in a static electrode is presented. (author)

  13. Studies of crystalline water at low temperatures by selective laser excitation of impurity uranyl ion fluorescence

    International Nuclear Information System (INIS)

    Fine-structure fluorescence spectrum of uranyl aqueous solution is obtained for the first time at low temperatures. It is established that the uranyl local surrounding in crystals of ice is characterized by low ordering, more typical for glasses. Temperature dependence of the width of the fluorescence resonance 0-0 line is measured. This dependence at temperatures above 20 K is described by interaction with phonons within the frames of the Debye model

  14. Hydrothermal syntheses and characterization of uranyl tungstates with electro-neutral structural units

    Energy Technology Data Exchange (ETDEWEB)

    Balboni, Enrica; Burns, Peter C. [Univ. of Notre Dame, IN (United States). Dept. of Civil and Enviromental Engineering and Earth Sciences; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry

    2015-11-01

    Two uranyl tungstates, (UO{sub 2})(W{sub 2}O{sub 7})(H{sub 2}O){sub 3} (1) and (UO{sub 2}){sub 3}(W{sub 2}O{sub 8})F{sub 2}(H{sub 2}O){sub 3} (2), were synthesized under hydrothermal conditions at 220 C and were structurally, chemically, and spectroscopically characterized. 1 Crystallizes in space group Pbcm, a = 6.673(5) Aa, b = 12.601(11) Aa, c = 11.552 Aa; 2 is in C2/m, a = 13.648(1) Aa, b = 16.852(1) Aa, c = 9.832(1) Aa, β = 125.980(1) {sup circle}. In 1 the U(VI) cations are present as (UO{sub 2}){sup 2+} uranyl ions that are coordinated by five oxygen atoms to give pentagonal bipyramids. These share two edges with two tungstate octahedra and single vertices with four additional octahedra, resulting in a sheet with the iriginite-type anion topology. Only water molecules are located in the interlayer. The structural units of 2 consist of (UO{sub 2}){sup 2+} uranyl oxy-fluoride pentagonal bipyramids present as either [UO{sub 2}F{sub 2}O{sub 3}]{sup -6} or [UO{sub 2}FO{sub 4}]{sup -5}, and strongly distorted tungstate octahedra. The linkage of uranyl pentagonal bipyramids and tungstate octahedra gives a unique sheet anion topology consisting of pentagons, squares and triangles. In 2, the uranyl tungstates sheets are connected into a novel electro-neutral three-dimensional framework through dimers of uranyl pentagonal bipyramids. These dimers connecting the sheets share an edge defined by F anions. 2 is the first example of a uranyl tungstate oxy-fluoride, and 1 and 2 are rare examples of uranyl compounds containing electro-neutral structural units.

  15. Chelating agents in pharmacology, toxicology and therapeutics

    International Nuclear Information System (INIS)

    The proceedings contain 71 abstracts of papers. Fourteen abstracts were inputted in INIS. The topics covered include: the effects of chelating agents on the retention of 63Ni, 109Cd, 203Hg, 144Ce, 95Nb and the excretion of 210Po, 63Ni, 48V, 239Pu, 241Am, 54Mn; the applications of tracer techniques for studies of the efficacy of chelation therapy in patients with heart and brain disorders; and the treatment of metal poisoning with chelating agents. (J.P.)

  16. Control of oxo-group functionalization and reduction of the uranyl ion.

    Science.gov (United States)

    Arnold, Polly L; Pécharman, Anne-Frédérique; Lord, Rianne M; Jones, Guy M; Hollis, Emmalina; Nichol, Gary S; Maron, Laurent; Fang, Jian; Davin, Thomas; Love, Jason B

    2015-04-01

    Uranyl complexes of a large, compartmental N8-macrocycle adopt a rigid, "Pacman" geometry that stabilizes the U(V) oxidation state and promotes chemistry at a single uranyl oxo-group. We present here new and straightforward routes to singly reduced and oxo-silylated uranyl Pacman complexes and propose mechanisms that account for the product formation, and the byproduct distributions that are formed using alternative reagents. Uranyl(VI) Pacman complexes in which one oxo-group is functionalized by a single metal cation are activated toward single-electron reduction. As such, the addition of a second equivalent of a Lewis acidic metal complex such as MgN″2 (N″ = N(SiMe3)2) forms a uranyl(V) complex in which both oxo-groups are Mg functionalized as a result of Mg-N bond homolysis. In contrast, reactions with the less Lewis acidic complex [Zn(N″)Cl] favor the formation of weaker U-O-Zn dative interactions, leading to reductive silylation of the uranyl oxo-group in preference to metalation. Spectroscopic, crystallographic, and computational analysis of these reactions and of oxo-metalated products isolated by other routes have allowed us to propose mechanisms that account for pathways to metalation or silylation of the exo-oxo-group.

  17. Hydrothermal Crystallization of Uranyl Coordination Polymers Involving an Imidazolium Dicarboxylate Ligand: Effect of pH on the Nuclearity of Uranyl-Centered Subunits.

    Science.gov (United States)

    Martin, Nicolas P; Falaise, Clément; Volkringer, Christophe; Henry, Natacha; Farger, Pierre; Falk, Camille; Delahaye, Emilie; Rabu, Pierre; Loiseau, Thierry

    2016-09-01

    Four uranyl-bearing coordination polymers (1-4) have been hydrothermally synthesized in the presence of the zwitterionic 1,3-bis(carboxymethyl)imidazolium (= imdc) anion as organic linkers after reaction at 150 °C. At low pH (0.8-3.1), the form 1 ((UO2)2(imdc)2(ox)·3H2O; ox stands for oxalate group) has been identified. Its crystal structure (XRD analysis) consists of the 8-fold-coordinated uranyl centers linked to each other through the imdc ligand together with oxalate species coming from the partial decomposition of the imdc molecule. The resulting structure is based on one-dimensional infinite ribbons intercalated by free water molecules. By adding NaOH solution, a second form 2 is observed for pH 1.9-3.9 but in a mixture with phase 1. The pure phase of 2 is obtained after a hydrothermal treatment at 120 °C. It corresponds to a double-layered network (UO2(imdc)2) composed of 7-fold-coordinated uranyl cations linked via the imdc ligands. In the same pH range, a third phase ((UO2)3O2(H2O)(imdc)·H2O, 3) is formed: it is composed of hexanuclear units of 7-fold- and 8-fold-coordinated uranyl cations, connected via the imdc molecules in a layered assembly. At higher pH, the chain-like solid (UO2)3O(OH)3(imdc)·2H2O (4) is observed and composed of the infinite edge-sharing uranyl-centered pentagonal bipyramidal polyhedra. As a function of pH, uranyl nuclearity increases from discrete 8- or 7-fold uranyl centers (1, 2) to hexanuclear bricks (3) and then infinite chains in 4 (built up from the hexameric fragments found in 3). This observation emphasized the influence of the hydrolysis reaction occurring between uranyl centers. The compounds have been further characterized by thermogravimetric analysis, infrared, and luminescence spectroscopy. PMID:27509393

  18. Synthesis of a Functional Metal-Chelating Polymer and Steps towards Quantitative Mass Cytometry Bioassays

    OpenAIRE

    Majonis, Daniel; Herrera, Isaac; Ornatsky, Olga; Schulze, Maren; Lou, Xudong; Soleimani, Mohsen; Nitz, Mark; Mitchell A. Winnik

    2010-01-01

    We describe the synthesis and characterization of metal-chelating polymers with a degree of polymerization of 67 and 79, high DTPA functionality, Mw/Mn ≤ 1.17, and a maleimide as an orthogonal functional group for conjugation to antibodies. The polymeric disulfide form of the DPn = 79 DTPA polymer was analyzed by thermogravimetric analysis to determine moisture and sodium-ion content, and by isothermal titration calorimetry (ITC) to determine the Gd3+ binding capacity. These results showed ea...

  19. SYNTHESIS AND APPLICATION OF IMINOCARBOXYLIC CHELATING FIBERS

    Institute of Scientific and Technical Information of China (English)

    LiHangqiu; ZhouShaoji

    1997-01-01

    In this paper,fibrous chelating exchangers with-N(CH2COOH)2 group have been prepared for the first time by a weakly basic anion exchange fiber (aminated fiber)as the starting materials.The fibers were quite effective for the adsorption of heavy metal ion such as Cu2+.In addition,IR spectrum of the structure of fibers confirms that it is feasible to prepare iminocarboxylic chelating fiber through direct carboxylation reaction.

  20. Characterization of the Aqueous Uranyl-Silicate Complex Using X-Ray Absorption Spectroscopy and Ab Initio Modeling

    Science.gov (United States)

    Vu, M.; Massey, M.; Huang, P.

    2015-12-01

    The speciation of aqueous uranium ions is an important factor in predicting its mobility and fate in the environment. Two major controls on speciation are pH and the presence of complexing ligands. For the case of aqueous uranyl, UO22+(aq), some common complexes include uranyl-hydroxy, uranyl-carbonato, and uranyl-calcium-carbonato complexes, all of which differ in chemical reactivity and mobility. Uranyl-silicate complexes are also known but remain poorly characterized. In this work, we studied uranyl speciation in a series of aqueous solutions of 0.1 mM uranyl and 2 mM silicate with pH ranging from 4 to 7. Extended X-Ray Absorption Fine Structure (EXAFS) spectra of these samples were recorded at the Stanford Synchrotron Radiation Lightsource (SLAC National Accelerator Laboratory). Of particular note are the uranyl and silicate concentrations employed in our experiments, which are lower than conditions in previously reported EXAFS studies and approach conditions in natural groundwater systems. Preliminary analyses of EXAFS data indicate that uranyl speciation changes across the pH range, consistent with published thermodynamic data that suggest uranyl-silicate complexes may be important for pH ~ 5 and below, while uranyl-carbonato complexes become dominant at circumneutral pH. To guide the interpretation of the EXAFS data, molecular-scale simulations were carried out using density functional theory. We considered two classes of models: (i) hydrated clusters, and (ii) ab initio molecular dynamics simulations of 3D-periodic models involving uranyl and silicate in water. These calculations reveal that at pH ~ 5, the uranyl speciation is the [UO2(H2O)4H3SiO4]+ complex formed by the substitution of an equatorial uranyl water with a monodentate silicate ligand. The evidence from experiments and simulations provide a consistent picture for the uranyl-silicate complex, which may be important in the transport of uranyl in acidic, silicate-rich waters.

  1. Uranium (VI) chemistry at the interface solution/minerals (quartz and aluminium hydroxide): experiments and spectroscopic investigations of the uranyl surface species

    International Nuclear Information System (INIS)

    This study deals with the understanding of the uranyl chemistry at the 0.1 M NaNO3 solution/mineral (quartz and aluminium hydroxide) interface. The aims are:(i) to identify and to characterize the different uranyl surface species (mononuclear, polynuclear complexes and/or precipitates...), i.e. the coordination environments of sorbed/precipitated uranyl ions, by using X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and time-resolved laser-induced fluorescence spectroscopy (TRLFS), and;(ii) to investigate the influence of pH, initial uranyl aqueous concentration and hydroxyl ligand concentration on the uranyl surface speciation. Our study on the speciation of uranyl ions at the quartz surface (i) confirms the formation of uranyl polynuclear/oligomers on quartz from moderate (1 μmol/m2) to high (26 μmol/m2) uranyl surface concentrations and (ii) show that theses polynuclear species coexist with uranyl mononuclear surface species over a pH range ≅ 5-8.5 and a wide range of initial uranyl concentration o f the solutions (10-100 μM). The uranyl concentration of these surface species depends on pH and on the initial uranyl aqueous concentration. Hydrate (surface-) precipitates and/or adsorbed polynuclear species and monomeric uranyl surface complexes are formed on aluminium hydroxide. Uranyl mononuclear complexes are predominant at acidic pH, as well as uranyl in solution or on the surface. Besides mononuclear species, precipitates and/or adsorbed polynuclear species are predominantly formed at neutral pH values on aluminium hydroxide. A main contribution of our investigations is that precipitation and/or adsorption of polynuclear species seem to occur at low uranyl surface concentrations (0.01-0.4 μmol/m2). The uranyl surface speciation is mainly dependent on the pH and the aluminol ligand concentration. (author)

  2. Fluid extraction using carbon dioxide and organophosphorus chelating agents

    Science.gov (United States)

    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.

  3. Removal of uranyl ions from aqueous solutions using barium titanate

    International Nuclear Information System (INIS)

    Remediation of water sources contaminated with radioactive waste products is a major environmental issue that demands new and more efficient technologies. For this purpose, we report a highly efficient ion-exchange material for the removal of radioactive nuclides from aqueous solutions. The kinetic characteristics of adsorption of uranyl ions on the surface of barium titanate were investigated using a spectrophotometric method under a wide range of conditions. By controlling the pH it was possible to exert fine control over the speciation of uranium, and by optimizing the temperature and grain size of the exchanger, almost total removal was achieved in a matter of just hours. The highest efficiency (>90 % removal) was realized at high temperature (80 deg C). Moreover, the effect of competitive ion adsorption from a range of different cations and anions was quantified. Adsorption was found to follow first-order kinetics and both Freundlich and Langmuir isotherms could be applied to this system. The results of a mathematical treatment of the kinetic data combined with the observation that adsorption was independent of stirring speed and dependent on the ion-exchanger grain size, indicate that the dominant mechanism influencing adsorption is particle spreading. The adsorption behavior was not influenced by exposure to high-intensity gamma radiation, indicating potential for use of this ion-exchanger in systems containing radioactive material. These results will be of use in the development of uranium extraction systems for contaminated water sources. (author)

  4. Ultrastructural and metabolic changes in osteoblasts exposed to uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Tasat, D.R. [Universidad Nacional de San Martin, Escuela de Ciencia y Tecnologia, Pcia de Bs.As. (Argentina); Universidad de Buenos Aires, Catedra de Histologia y Embriologia, Facultad de Odontologia, Buenos Aires (Argentina); Orona, N.S. [Universidad Nacional de San Martin, Escuela de Ciencia y Tecnologia, Pcia de Bs.As. (Argentina); Mandalunis, P.M. [Universidad de Buenos Aires, Catedra de Histologia y Embriologia, Facultad de Odontologia, Buenos Aires (Argentina); Cabrini, R.L. [Comision Nacional de Energia Atomica, Departamento de Radiobiologia, Buenos Aires (Argentina); Ubios, A.M. [Comision Nacional de Energia Atomica, Departamento de Radiobiologia, Buenos Aires (Argentina); Universidad de Buenos Aires, Catedra de Histologia y Embriologia, Facultad de Odontologia, Buenos Aires (Argentina)

    2007-05-15

    Exposure to uranium is an occupational hazard to workers who continually handle uranium and an environmental risk to the population at large. Since the cellular and molecular pathways of uranium toxicity in osteoblast cells are still unknown, the aim of the present work was to evaluate the adverse effects of uranyl nitrate (UN) on osteoblasts both in vivo and in vitro. Herein we studied the osteoblastic ultrastructural changes induced by UN in vivo and analyzed cell proliferation, generation of reactive oxygen species (ROS), apoptosis, and alkaline phosphatase (APh) activity in osteoblasts exposed to various UN concentrations (0.1, 1, 10, and 100 {mu}M) in vitro. Cell proliferation was quantified by means of the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, ROS was determined using the nitro blue tetrazolium test, apoptosis was morphologically determined using Hoechst 3332 and APh activity was assayed spectrophotometrically. Electron microscopy revealed that the ultrastructure of active and inactive osteoblasts exposed to uranium presented cytoplasmic and nuclear alterations. In vitro, 1-100 {mu}M UN failed to modify cell proliferation ratio and to induce apoptosis. ROS generation increased in a dose-dependent manner in all tested doses. APh activity was found to decrease in 1-100 {mu}M UN-treated cells vs. controls. Our results show that UN modifies osteoblast cell metabolism by increasing ROS generation and reducing APh activity, suggesting that ROS may play a more complex role in cell physiology than simply causing oxidative damage. (orig.)

  5. Status Update: Uranyl Nitrate Calibration Loop Equipment (UNCLE) at ORNL

    International Nuclear Information System (INIS)

    The successful completion of a field trial of safeguards monitoring equipment at a natural uranium conversion plant (NUCP) demonstrated the need for a facility in which to perform full-scale equipment testing under controlled conditions prior to field deployment of safeguards systems at additional plants. Oak Ridge National Laboratory has developed a Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility to simulate the full-scale operating conditions for a purified uranium-bearing aqueous stream exiting the solvent extraction process conducted in an NUCP. In addition to calibrating instruments such as the neutron detector developed at Los Alamos National Laboratory, UNCLE will be used to test other in-line instruments (mass and volumetric flowmeters, spectrophotometers, etc.). UNCLE will be able to test commercially available equipment, such as the Endress+Hauser Promass 83F Coriolis meter that was used in the field test and other equipment that is presently under development. UNCLE is designed to accommodate different pipe sizes, flow rates, solution concentrations, and other variables of interest. Construction is expected to be completed by the end of September 2008 with initial testing beginning later that year. The design and current status of UNCLE will be presented, along with the capabilities of the facility and the proposed test plans.

  6. Ultrastructural and metabolic changes in osteoblasts exposed to uranyl nitrate

    International Nuclear Information System (INIS)

    Exposure to uranium is an occupational hazard to workers who continually handle uranium and an environmental risk to the population at large. Since the cellular and molecular pathways of uranium toxicity in osteoblast cells are still unknown, the aim of the present work was to evaluate the adverse effects of uranyl nitrate (UN) on osteoblasts both in vivo and in vitro. Herein we studied the osteoblastic ultrastructural changes induced by UN in vivo and analyzed cell proliferation, generation of reactive oxygen species (ROS), apoptosis, and alkaline phosphatase (APh) activity in osteoblasts exposed to various UN concentrations (0.1, 1, 10, and 100 μM) in vitro. Cell proliferation was quantified by means of the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, ROS was determined using the nitro blue tetrazolium test, apoptosis was morphologically determined using Hoechst 3332 and APh activity was assayed spectrophotometrically. Electron microscopy revealed that the ultrastructure of active and inactive osteoblasts exposed to uranium presented cytoplasmic and nuclear alterations. In vitro, 1-100 μM UN failed to modify cell proliferation ratio and to induce apoptosis. ROS generation increased in a dose-dependent manner in all tested doses. APh activity was found to decrease in 1-100 μM UN-treated cells vs. controls. Our results show that UN modifies osteoblast cell metabolism by increasing ROS generation and reducing APh activity, suggesting that ROS may play a more complex role in cell physiology than simply causing oxidative damage. (orig.)

  7. Dehydration of Uranyl Nitrate Hexahydrate to Uranyl Nitrate Trihydrate under Ambient Conditions as Observed via Dynamic Infrared Reflectance Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.; Mausolf, Edward J.; Kim, Eunja; Weck, Philippe F.; Buck, Edgar C.; McNamara, Bruce K.

    2015-05-22

    the hexahydrate [UO2(NO3)2(H2O)6] (UNH) and the trihydrate [UO2(NO3)2(H2O)3] (UNT) forms. Their stabilities depend on both relative humidity and temperature. Both phases have previously been studied by infrared transmission spectroscopy, but the data were limited by both instrumental resolution and the ability to prepare the samples as pellets without desiccating them. We report time-resolved infrared (IR) measurements using an integrating sphere that allow us to observe the transformation from the hexahydrate to the trihydrate simply by flowing dry nitrogen gas over the sample. Hexahydrate samples were prepared and confirmed via known XRD patterns, then measured in reflectance mode. The hexahydrate has a distinct uranyl asymmetric stretch band at 949.0 cm-1 that shifts to shorter wavelengths and broadens as the sample dehydrates and recrystallizes to the trihydrate, first as a blue edge shoulder but ultimately resulting in a doublet band with reflectance peaks at 966 and 957 cm-1. The data are consistent with transformation from UNH to UNT since UNT has two non-equivalent UO22+ sites. The dehydration of UO2(NO3)2(H2O)6 to UO2(NO3)2(H2O)3 is both a morphological and structural change that has the lustrous lime green crystals changing to the dull greenish yellow of the trihydrate. Crystal structures and phase transformation were confirmed theoretically using DFT calculations and experimentally via microscopy methods. Both methods showed a transformation with two distinct sites for the uranyl cation in the trihydrate, as opposed to a single crystallographic site in the hexahydrate.

  8. Structure and Reactivity of X-ray Amorphous Uranyl Peroxide, U2O7.

    Science.gov (United States)

    Odoh, Samuel O; Shamblin, Jacob; Colla, Christopher A; Hickam, Sarah; Lobeck, Haylie L; Lopez, Rachel A K; Olds, Travis; Szymanowski, Jennifer E S; Sigmon, Ginger E; Neuefeind, Joerg; Casey, William H; Lang, Maik; Gagliardi, Laura; Burns, Peter C

    2016-04-01

    Recent accidents resulting in worker injury and radioactive contamination occurred due to pressurization of uranium yellowcake drums produced in the western U.S.A. The drums contained an X-ray amorphous reactive form of uranium oxide that may have contributed to the pressurization. Heating hydrated uranyl peroxides produced during in situ mining can produce an amorphous compound, as shown by X-ray powder diffraction of material from impacted drums. Subsequently, studtite, [(UO2)(O2)(H2O)2](H2O)2, was heated in the laboratory. Its thermal decomposition produced a hygroscopic anhydrous uranyl peroxide that reacts with water to release O2 gas and form metaschoepite, a uranyl-oxide hydrate. Quantum chemical calculations indicate that the most stable U2O7 conformer consists of two bent (UO2)(2+) uranyl ions bridged by a peroxide group bidentate and parallel to each uranyl ion, and a μ2-O atom, resulting in charge neutrality. A pair distribution function from neutron total scattering supports this structural model, as do (1)H- and (17)O-nuclear magnetic resonance spectra. The reactivity of U2O7 in water and with water in air is higher than that of other uranium oxides, and this can be both hazardous and potentially advantageous in the nuclear fuel cycle. PMID:26974702

  9. Electron microscopy studies of natural and synthetic zeolites impregnated with uranyl dioxide

    International Nuclear Information System (INIS)

    Full text. The use of Y zeolite and erionite to remove uranyl dioxide ions from aqueous solution is focussed on catalysis and energy transfer problems but it can be oriented to recovery uranyl dioxide ions, among other radioactive compounds. The samples impregnated with uranyl dioxide at several concentrations and contact times were studied using conventional, high resolution and scanning electron microscopy in order to detect changes as consequence of contact with a radioactive material and to verify mechanical stability of zeolites. Also X ray diffraction, thermal analysis, neutron activation were used to characterize the samples at several steps of treatment. The crystallinity of zeolites was maintained only when using dilute uranyl nitrate solution (up to 0.0100 N for y zeolite and 0.0300 N for erionite). The samples impregnated with highest nitrate concentrations partially lost their crystallinity. From selected area electron diffraction pattern, lattice parameter variations were detected and from high resolution electron microscopy localization of uranyl ions in and on zeolite structure was determined. Surface modification in zeolites was observed by scanning electron microscopy just for samples with long contact time with radioactive solutions. (author)

  10. Preparation of thin {alpha}-particle sources using poly-pyrrole films functionalized by a chelating agent; Preparation de sources minces d'emetteurs alpha a l'aide de films de polypyrrole fonctionnalises par un ligand chelatant

    Energy Technology Data Exchange (ETDEWEB)

    Mariet, C. [CEA Saclay, INSTN, Institut National des Sciences et Techniques Nucleaires, 91 - Gif-sur-Yvette (France); Universite Pierre et Marie Curie, 75 - Paris (France)

    2000-07-01

    This work takes place in the scope of analysis of the {alpha}-particle emitting elements U, Pu and Am present in compound environmental matrix like sols and sediments. The samples diversity and above all the {alpha}-ray characteristics require the analyst to implement a sequence of chemical steps in which the more restricting is the actinides concentration in a uniform and thin layer en allowing an accurately measure of alpha activity. On this account, we studied a new technique for radioactive sources preparation based on tow steps: preparation of a thin film as source support; incorporation of radioactive elements by a chelating extraction mechanism. The thin films were obtained through electro-polymerization of pyrrole monomer functionalized by an chelating ligand able to extract actinides from concentrated acidic solutions. Polymerization conditions of this monomer were perfected, then obtained films were characterized from a physico-chemical point of view. We point out their extracting properties were comparable to (retention capacity, distribution coefficient) to those of usual ion-exchange resins. The underscore of uranyl and americium nitrate complexes formed in the thin layer allowed to calculate the extraction constants in case acid extraction is negligible. Thanks to this results, the values of the coefficients distribution D{sub U} and D{sub Am} could be provided for all nitric solutions in which acid extraction is negligible. Optimal actinides retention conditions in the polymer were defined and used to settle a protocol for plutonium analysis in environmental samples. (author)

  11. Trypanotoxic activity of thiosemicarbazone iron chelators.

    Science.gov (United States)

    Ellis, Samuel; Sexton, Darren W; Steverding, Dietmar

    2015-03-01

    Only a few drugs are available for treating sleeping sickness and nagana disease; parasitic infections caused by protozoans of the genus Trypanosoma in sub-Saharan Africa. There is an urgent need for the development of new medicines for chemotherapy of these devastating diseases. In this study, three newly designed thiosemicarbazone iron chelators, TSC24, Dp44mT and 3-AP, were tested for in vitro activity against bloodstream forms of Trypanosoma brucei and human leukaemia HL-60 cells. In addition to their iron chelating properties, TSC24 and Dp44mT inhibit topoisomerase IIα while 3-AP inactivates ribonucleotide reductase. All three compounds exhibited anti-trypanosomal activity, with minimum inhibitory concentration (MIC) values ranging between 1 and 100 µM and 50% growth inhibition (GI50) values of around 250 nM. Although the compounds did not kill HL-60 cells (MIC values >100 µM), TSC24 and Dp44mT displayed considerable cytotoxicity based on their GI50 values. Iron supplementation partly reversed the trypanotoxic and cytotoxic activity of TSC24 and Dp44mT but not of 3-AP. This finding suggests possible synergy between the iron chelating and topoisomerase IIα inhibiting activity of the compounds. However, further investigation using separate agents, the iron chelator deferoxamine and the topoisomerase II inhibitor epirubicin, did not support any synergy for the interaction of iron chelation and topoisomerase II inhibition. Furthermore, TSC24 was shown to induce DNA degradation in bloodstream forms of T. brucei indicating that the mechanism of trypanotoxic activity of the compound is topoisomerase II independent. In conclusion, the data support further investigation of thiosemicarbazone iron chelators with dual activity as lead compounds for anti-trypanosomal drug development. PMID:25595343

  12. Car-Parrinello molecular dynamics study of the uranyl behaviour at the gibbsite/water interface

    Science.gov (United States)

    Lectez, Sébastien; Roques, Jérôme; Salanne, Mathieu; Simoni, Eric

    2012-10-01

    The uranyl cation UO22+ adsorption on the basal face of gibbsite is studied via Car-Parrinello molecular dynamics. In a first step, we study the water sorption on a gibbsite surface. Three different sorption modes are observed and their hydrogen bond patterns are, respectively, characterized. Then we investigate the sorption properties of an uranyl cation, in the presence of water. In order to take into account the protonation state of the (001) gibbsite face, both a neutral (001) face and a locally deprotonated (001) face are modeled. In the first case, three adsorbed uranyl complexes (1 outer sphere and 2 inner spheres) with similar stabilities are identified. In the second case, when the gibbsite face is locally deprotonated, two adsorbed complexes (1 inner sphere and 1 outer one) are characterized. The inner sphere complex appears to be the most strongly linked to the gibbsite face.

  13. Molecular simulation of the diffusion of uranyl carbonate species in aqueous solution

    Science.gov (United States)

    Kerisit, Sebastien; Liu, Chongxuan

    2010-09-01

    Potential-based molecular dynamics simulations of aqueous uranyl carbonate species (M xUO 2(CO 3) y2+2x-2y with M = Mg, Ca, or Sr) were carried out to gain molecular-level insight into the hydration properties of these species. The simulation results were used to estimate the self-diffusion coefficients of these uranyl carbonate species, which often dominate uranyl speciation in groundwater systems. The diffusion coefficients obtained for the monoatomic alkaline-earth cations and polyatomic ions (uranyl, carbonate, and uranyl tri-carbonate) were compared with those calculated from the Stokes-Einstein (SE) equation and its variant formulation by Impey et al. (1983). Our results show that the equation of Impey et al. (1983), originally formulated for monovalent monoatomic ions, can be extended to divalent monoatomic ions, with some success in reproducing the absolute values and the overall trend determined from the molecular dynamics simulations, but not to polyatomic ions, for which the hydration shell is not spherically symmetrical. Despite the quantitative failure of both SE formulations, a plot of the diffusion coefficients of the uranyl carbonate complexes as a function of the inverse of the equivalent spherical radius showed that a general linear dependence is observed for these complexes as expected from the SE equation. The nature of the alkaline-earth cation in the uranyl carbonate complexes was not found to have a significant effect on the ion's diffusion coefficient, which suggests that the use of a single diffusion coefficient for different alkaline-earth uranyl carbonate complexes in microscopic diffusion models is appropriate. The potential model reproduced well published quantum mechanical and experimental data of UO(CO)32x-4 and of the individual constituent ions, and therefore is expected to offer reliable predictions of the structure of magnesium and strontium uranyl carbonate aqueous species, for which there is no structural data available to date

  14. Copper(I) and copper(II) uranyl heterometallic hybrid materials.

    Science.gov (United States)

    Weng, Zhehui; Zhang, Zhi-hui; Olds, Travis; Sterniczuk, Marcin; Burns, Peter C

    2014-08-01

    Two copper-uranium heterometallic compounds, [(UO2)3Cu(II)O2(C6NO2)5] (1) and [(UO2)Cu(I)(C6NO2)3] (2), have been synthesized by the reaction of uranyl acetate with copper salts in the presence of isonicotinic acid. Both compounds have been characterized by single-crystal X-ray diffraction, IR, Raman, and UV-vis spectroscopy. In compound 1, interactions between copper and uranium centers occur and result in a three-dimensional pillar layered structure. Compound 1 is also the first example of a heterometallic uranyl organic framework with a trinuclear U3O18 building block. Compound 2 is the first uranyl organic framework that contains monovalent copper, which arises from the reaction of Cu(II) chloride and is assumed to be due to the oxidation of chloride at low pH. PMID:25029287

  15. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Univ. of California, Berkeley, CA (United States)

    2015-01-21

    The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  16. Bonding and charge transfer in nitrogen-donor uranyl complexes: insights from NEXAFS spectra.

    Science.gov (United States)

    Pemmaraju, C D; Copping, Roy; Wang, Shuao; Janousch, Markus; Teat, Simon J; Tyliszcak, Tolek; Canning, Andrew; Shuh, David K; Prendergast, David

    2014-11-01

    We investigate the electronic structure of three newly synthesized nitrogen-donor uranyl complexes [(UO2)(H2bbp)Cl2], [(UO)2(Hbbp)(Py)Cl], and [(UO2)(bbp)(Py)2] using a combination of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy experiments and simulations. The complexes studied feature derivatives of the tunable tridentate N-donor ligand 2,6-bis(2-benzimidazyl)pyridine (bbp) and exhibit discrete chemical differences in uranyl coordination. The sensitivity of the N K-edge X-ray absorption spectrum to local bonding and charge transfer is exploited to systematically investigate the evolution of structural as well as electronic properties across the three complexes. A thorough interpretation of the measured experimental spectra is achieved via ab initio NEXAFS simulations based on the eXcited electron and Core-Hole (XCH) approach and enables the assignment of spectral features to electronic transitions on specific absorbing sites. We find that ligand-uranyl bonding leads to a signature blue shift in the N K-edge absorption onset, resulting from charge displacement toward the uranyl, while changes in the equatorial coordination shell of the uranyl lead to more subtle modulations in the spectral features. Theoretical simulations show that the flexible local chemistry at the nonbinding imidazole-N sites of the bbp ligand is also reflected in the NEXAFS spectra and highlights potential synthesis strategies to improve selectivity. In particular, we find that interactions of the bbp ligand with solvent molecules can lead to changes in ligand-uranyl binding geometry while also modulating the K-edge absorption. Our results suggest that NEXAFS spectroscopy combined with first-principles interpretation can offer insights into the coordination chemistry of analogous functionalized conjugated ligands. PMID:25330350

  17. Development of a new radiolabel (lead-203) and new chelating agents for labeling monoclonal anntibodies for imaging

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, S.C.; Mease, R.C.; Meinken, G.E.; Mausner, L.F.; Steplewski, Z.

    1988-01-01

    High liver uptake and slow body clearance presently limit the usefulness of /sup 111/In labeled antibodies for tumor imaging. We have investigated /sup 203/Pb as an alternate and better antibody label. The DTPA and cyclohexyl EDTA (CDTA) conjugates of an anticolon carcinoma antibody, 17-1A were labeled (bicyclic anhydride method) with /sup 203/Pb and /sup 111/In with 60 and 90% labeling yields, respectively. The biodistribution of /sup 203/Pb-17-1A conjugates was compared with the corresponding /sup 111/In-labeled preparations and with /sup 203/Pb-DTPA, /sup 203/Pb-nitrate and nonrelevant antibody controls in normal and human tumor (SW948) xenografted nude mice at 24, and 96 hr. Lead-203-labeled CDTA and DTPA antibody conjugates gave similar in vivo distributions. Even though the lead bound to these chelate-antibody conjugates was more labile in serum and in vivo, compared to indium, it cleared much faster from the liver and the whole body. A new series of chelating agents based on the incorporation of a trans-1,2- diaminocyclohexane moiety into the carbon backbone of polyaminocarboxylates is being synthesized. These are expected to provide stronger complexing ability for lead and produce greater in vivo stability. These ligands are also expected to be superior to EDTA and DTPA for labeling antibodies with other radiometals, including indium. 32 refs., 3 tabs.

  18. Characterization of osteopontin-uranyl interaction: role of multiple phosphorylations

    International Nuclear Information System (INIS)

    While some metals are essential for Life, other ones are only toxicants for living organisms, tolerated below well-definite concentrations. This is the case for uranium, a natural element which has no known biological function. It is a low α emitter and its chemical toxicity rather than its radiological toxicity is a subject of concern. Once in the body, this metal reaches the blood and accumulates in the bones under the action of unknown mechanisms. Uranium mainly exists in form of uranyl ion (UO22+) in aqueous media and particularly reacts with carboxylates, phenolates and phosphates of the proteins. Previous studies have highlighted that UO22+ modulates the SPP1 expression, a gene which codes for osteopontin (OPN). This highly phosphorylated glycoprotein plays an important role in bone homeostasis. This role and its biochemical properties led us to hypothesize that OPN might be a potential target of UO22+ and involved in its accumulation in bones. A simple and original purification process was optimized to produce very highly purified OPN starting from human and bovine milk. Various biophysical approaches were set up and confirmed that both bovine and human OPN display very high affinity for UO22+. Moreover, the formation of stable UO2-protein complexes originating from structural changes was evidenced. The major role of phosphorylations, both on the OPN's affinity for UO22+ and the stability of the UO2-protein complexes, was confirmed. These results demonstrate that OPN presents all the characteristics to be a major UO22+ binding-protein in vitro, and they open new insights in the understanding of the UO22+ mineralization process mechanisms. (author)

  19. Removal of uranyl ions by p-hexasulfonated calyx[6]arene acid

    Energy Technology Data Exchange (ETDEWEB)

    Popescu, Ioana-Carmen [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Petru, Filip [“C.D. Nenitescu” Institute of Organic Chemistry, Splaiul Independentei 202B, Sector 6, Bucharest 71141 (Romania); Humelnicu, Ionel [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania); Mateescu, Marina [National R and D Institute for Chemistry and Petrochemistry, Splaiul Independenţei No. 202, Bucharest 060021 (Romania); Militaru, Ecaterina [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Humelnicu, Doina, E-mail: doinah@uaic.ro [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania)

    2014-10-15

    Radioactive pollution is a significant threat for the people’s health. Therefore highly effective radioactive decontamination methods are required. Ion exchange, biotechnologies and phytoremediation in constructed wetlands have been used as radioactive decontamination technologies for uranium contaminated soil and water remediation. Recently, beside those classical methods the calix[n]arenic derivatives’ utilization as radioactive decontaminators has jogged attention. The present work aims to present the preliminary research results of uranyl ion sorption studies on the p-hexasulfonated calyx[6]arenic acid. The effect of temperature, contact time, sorbent amount and uranyl concentration variation on sorption efficiency was investigated. Isotherm models revealed that the sorption process fit better Langmuir isotherm.

  20. Structure and vibrational spectra of uranyl dinitrate complexes with water and DMSO

    International Nuclear Information System (INIS)

    Structural models were designed and spectral characteristics were computed based on DFT calculations for uranyl dinitrate complexes with H2O and DMSO [UO2(NO3)2×2DMSO, UO2(NO3)2×2H2O×2DMSO, UO2(NO3)2×2H2O×4DMSO]. Vibrational IR and Raman spectra of UO2(NO3)2×2DMSO were interpreted using models for bidentate and monodentate coordination of nitrate ions to uranyl. Several spectral signatures that characterized DMSO complexation in the second coordination sphere were identified and had analytical significance. (authors)

  1. Removal of uranyl ions by p-hexasulfonated calyx[6]arene acid

    Science.gov (United States)

    Popescu (Hoştuc), Ioana-Carmen; Petru, Filip; Humelnicu, Ionel; Mateescu, Marina; Militaru, Ecaterina; Humelnicu, Doina

    2014-10-01

    Radioactive pollution is a significant threat for the people’s health. Therefore highly effective radioactive decontamination methods are required. Ion exchange, biotechnologies and phytoremediation in constructed wetlands have been used as radioactive decontamination technologies for uranium contaminated soil and water remediation. Recently, beside those classical methods the calix[n]arenic derivatives’ utilization as radioactive decontaminators has jogged attention. The present work aims to present the preliminary research results of uranyl ion sorption studies on the p-hexasulfonated calyx[6]arenic acid. The effect of temperature, contact time, sorbent amount and uranyl concentration variation on sorption efficiency was investigated. Isotherm models revealed that the sorption process fit better Langmuir isotherm.

  2. K8(K5F)U6Si8O40: An Intergrowth Uranyl Silicate.

    Science.gov (United States)

    Morrison, Gregory; Tran, T Thao; Halasyamani, P Shiv; Zur Loye, Hans-Conrad

    2016-04-01

    Single crystals of K8(K5F)U6Si8O40 were grown from a mixed alkali halide flux. K8(K5F)U6Si8O40 is the first intergrowth uranyl silicate, being composed of alternating slabs related to two previously reported uranyl silicates: Cs2USiO6 and [Na9F2][(UO2)(UO2)2(Si2O7)2]. It exhibits intense luminescence, which is influenced by the [(UO2)2O] dimers present in the structure. PMID:26974872

  3. Strongly coupled binuclear uranium-oxo complexes from uranyl oxo rearrangement and reductive silylation

    OpenAIRE

    Arnold, Polly L.; Jones, Guy M.; Odoh, Samuel O.; Schreckenbach, Georg; Magnani, Nicola; Love, Jason B.

    2012-01-01

    The most common motif in uranium chemistry is the d(0)f(0) uranyl ion [UO(2)](2+) in which the oxo groups are rigorously linear and inert. Alternative geometries, such as the cis-uranyl, have been identified theoretically and implicated in oxo-atom transfer reactions that are relevant to environmental speciation and nuclear waste remediation. Single electron reduction is now known to impart greater oxo-group reactivity, but with retention of the linear OUO motif, and reactions of the oxo grou...

  4. an investigation of the ammonium poly uranate precipitation via uranyl nitrate solution

    International Nuclear Information System (INIS)

    a series of experiments were made concerning the interaction of uranyl nitrate with ammonium hydroxide solution, with the aim of preparing ammonium poly uranate (APU) as an intermediate product during nuclear reactors fuel fabrication. the particle size and final product characteristics of the uranium oxide depend greatly on the ways of preparation of the APU , in the present work, the kinetics of deposition and the composition of the formed products upon adding increasing amounts of ammonium hydroxide to uranyl nitrate solution have been followed in a trial to understand the prevailing mechanisms

  5. Complexation of uranyl ion by polyvinylimidazole. Electrochemical preparation and leaching tests investigations

    International Nuclear Information System (INIS)

    In this work, we intend to check the claims of an U.S. Patent (Westinghouse E.C.) which describes an original treatment for low level activity radioactive wastes. The process deals with electrochemical preparation of polyvinylimidazole (PVI) which is a polymer capable of complexing uranyl ions. We confirm the complexation of uranyl ions by PVI in various media by FT-IR and UV-Visible analysis but all these complexes were found to be soluble in water so we put forward new complexes with an additional polymer to shape out insoluble complex. Leaching tests demonstrate the efficiency of our process. (author)

  6. Complexation of uranyl ion by three polyacrylamide type polymers. Electrochemical preparation and leaching tests investigations

    International Nuclear Information System (INIS)

    An original process for the treatment of low level activity radioactive liquid waste is described. Electrochemical preparation of three polyacrylate polymers: polyacrylamide (PAam), polyacrylamidoglycolic acid (PAAG), polyacrylamidomethylpropanesulfonic acid (PAMPS) which are capable of complexing uranyl ions is delt with. Complexation of uranyl is demonstrated by FT-IR and UV-Visible spectroscopy. All these complexes are soluble in water and we insolubilize in turn the complexes by crosslinking or by neutralization of positively charged complexes by the addition of polyanions to the medium. Dynamic and static leaching tests on these insoluble complexes were then done. (author)

  7. Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene; Synthese et proprietes complexantes vis-a-vis de l'ion uranyle de derives carboxyliques du p-tert-butyl-calix[6]arene

    Energy Technology Data Exchange (ETDEWEB)

    Souane, R

    2005-03-15

    In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO{sub 2}{sup 2+} form in the various installations, have many varied physico-chemical forms and there is a risk of exposure and internal contamination in the nuclear industry. It is necessary to exert a medical control to ensure the protection of the health of the workers. This medical control is done by dosing uranyl cation in the urine of the exposed people. This work forms part of this context. Indeed, we prepared a ligand able to complex the ion uranyl and which is also to be grafted on a solid support. In the family of calixarenes, the calix[6]arenes functionalized by three or four carboxylic functions were selected like chelating molecules of the ion uranyl. The properties of complexation of these calixarenes were studied by potentiometry in methanol, under these conditions balances of protonation and complexation were determined and the constant partners were obtained using the Hyperquad program. We synthesized tri-carboxylic calix[6]arenes comprising of the groupings nitro (NO{sub 2}) in para position of phenol in order to see the influence of a substitution in para position on the complexation. We also synthesized calix[6]arenes tetra-carboxylic in order to show the role of an additional carboxylic acid grouping. The potentiometric study determined thermodynamic parameters of protonation and complexation of carboxylic calix[6]arenes. The results of the complexation highlighted which complex UO{sub 2}L corresponding to the ligand para-tert-butyl-calix[6]arene tetra-acid is more stable than that corresponding to the ligand mono-nitro calix[6]arene tri-acid ({delta}log{beta}110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO{sub 2}{sup 2+}. This makes it possible to consider as possible the grafting of the calix[6]arenes which one knows the behaviour of trapping. To this end we synthesized the ligand 23

  8. Development of an upconverting chelate assay

    Science.gov (United States)

    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.

  9. Questions and Answers on Unapproved Chelation Products

    Science.gov (United States)

    ... it Email Print The U.S. Food and Drug Administration (FDA) advises consumers to be wary of so-called “chelation” products that are marketed over-the-counter (OTC) to prevent or treat diseases. Companies are marketing unapproved OTC chelation therapy products to ...

  10. Study of the extraction mechanisms by TBP saturated by uranyl nitrate; Etude des mecanismes d'extraction du TBP sature par le nitrate d'uranyle

    Energy Technology Data Exchange (ETDEWEB)

    Meze, F

    2004-02-15

    This work deals with a particular phenomenon likely to occur in the nuclear waste reprocessing process PUREX. It was shown earlier by Russian works that the extractant molecule, tributyl phosphate (TBP), saturated by uranyl nitrate keeps its extraction capacities for nitric acid and tetravalent actinides. This study is composed of three parts. Firstly, some liquid-liquid extraction experiments were conducted to verify the ability of TBP saturated by uranyl nitrate to conserve its extraction capacities for nitric acid. Then, during these experiments, the UV and infrared spectra of both phases were recorded to obtain the organic phase speciation. At last, the informations gathered during the experimental part were used to build a general species distribution model of the H{sub 2}O/HNO{sub 3}/UO{sub 2}(NO{sub 3}){sub 2}/TBP system. (author)

  11. Overview of chelation recommendations for thalassaemia and sickle cell disease

    Directory of Open Access Journals (Sweden)

    Banu Kaya

    2014-12-01

    Full Text Available The long term consequences of iron toxicity are mostly reversible with effective iron chelation therapy. Recommendations for use of chelation therapy in transfusion dependent thalassaemia (TDT, sickle cell disease (SCD and non transfusion dependent thalassaemia (NTDT continue to evolve as our knowledge and clinical experience increases. Improved chelation options including drug combinations and a better understanding of condition specific factors may help to improve efficiency of chelation regimens and meet the needs of patients more effectively.

  12. The system uranyl nitrate-dietyl ether-water. Extraction by water in spray and packed columns from uranyl nitrate-either solutions

    International Nuclear Information System (INIS)

    This paper is a continuation of the one published in Chemical Engineering Progress. Symposium Series, 50, n. 12, 127 (1954). New runs for spray columns, are given and other concentrations in uranyl nitrate for the packed columns. New correlations for the overall H.T.U. are also given. The individual H.T.U. have been grapycally calculated and show that the film resistances have similar values, being independent of the concentration of the ether phase. (Author) 24 refs

  13. Standard test method for isotopic analysis of hydrolyzed uranium hexafluoride and uranyl nitrate solutions by thermal ionization mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2005-01-01

    1.1 This method applies to the determination of isotopic composition in hydrolyzed nuclear grade uranium hexafluoride. It covers isotopic abundance of 235U between 0.1 and 5.0 % mass fraction, abundance of 234U between 0.0055 and 0.05 % mass fraction, and abundance of 236U between 0.0003 and 0.5 % mass fraction. This test method may be applicable to other isotopic abundance providing that corresponding standards are available. 1.2 This test method can apply to uranyl nitrate solutions. This can be achieved either by transforming the uranyl nitrate solution to a uranyl fluoride solution prior to the deposition on the filaments or directly by depositing the uranyl nitrate solution on the filaments. In the latter case, a calibration with uranyl nitrate standards must be performed. 1.3 This test method can also apply to other nuclear grade matrices (for example, uranium oxides) by providing a chemical transformation to uranyl fluoride or uranyl nitrate solution. 1.4 This standard does not purport to address al...

  14. Quenching of the luminescent state of the uranyl ion (UO22+) by metal ions

    International Nuclear Information System (INIS)

    The quenching of the luminescence of the uranyl ion by other metal ions has been studied in aqueous solution. The quenching is shown to be a dynamic process, and the correlation of the logarithm of the quenching rate with the metal ion ionization potential suggests that intermolecular electron transfer is the predominant mechanism. Evidence that this involves complete electron transfer comes from flash photolysis of solutions of UO2+2 and manganese (11), where a broad absorption lambdasub(max) = 505 nm) is observed which is assigned to Mn3+. Consideration of the energetics of the quenching process suggests that in the quenching of uranyl by silver(1), the products (U0+2 and Ag2+) are produced in their electronic ground states. Studies of the effect of temperature on the quenching suggest that if an intermediate complex (exciplex) is involved in the quenching then this must involve only very weak binding. With silver(I), the quenching is sensitive to the ionic strength of the solution. Further studies suggest that the lifetime of the luminescent state of the uranyl ion in aqueous solution varies with both temperature and uranyl ion concentration. (author)

  15. Nucleobase assemblies supported by uranyl cation coordination and other non-covalent interactions

    Indian Academy of Sciences (India)

    Jitendra Kumar; Sandeep Verma

    2011-11-01

    We describe synthesis and solid state structural description of uranyl complexes of carboxylate functionalized adenine and uracil derivatives. The metal coordination through carboxylate pendant leads to the formation of dimeric assemblies, whereas the directional nature of hydrogen bonding interaction supported by nucleobases and aqua ligands, result in the generation of complex 3-D architectures containing embedded nucleobase ribbons.

  16. Application of the NICADonnan model for proton, copper and uranyl binding to humic acid

    NARCIS (Netherlands)

    Saito, T.; Nagasaki, S.; Tanaka, S.; Koopal, L.K.

    2004-01-01

    Humic acids are natural organic materials that play an important role in the migration of heavy metal and actinide ions in aquatic and soil systems. In the present study, the binding of protons, copper ions and uranyl ions to the purified Aldrich humic acid (PAHA) is investigated and the results are

  17. On the bonding and the electric field gradient of the uranyl ion

    NARCIS (Netherlands)

    de Jong, WA; Visscher, L; Nieuwpoort, WC

    1999-01-01

    Molecular properties of the uranyl ion ([UO2](2+)) are studied using both a non-relativistic and a relativistic method. Inclusion of relativity leads to a bond length expansion and makes the electric field gradient (EFG) at the uranium nucleus strongly dependent on the U-O bond distance, The non-rel

  18. Removal of uranyl ions from residual waters using some algae types

    NARCIS (Netherlands)

    Cecal, A; Palamaru, [No Value; Humelnicu, D; Popa, K; Salaru, VV; Rudic, [No Value; Gulea, A

    1999-01-01

    This paper deals with a study on the bioaccumulation of uranyl ions resulted from residual effluents by means of some microbiological collectors: Scenedesmus quadricauda, Anabaena karakumica, Calothrix brevissima, Penicillinium sp, as well as the Glucide extract of Porphyridium cruentum, under vario

  19. On the retention of uranyl and thorium ions from radioactive solution on peat moss

    Energy Technology Data Exchange (ETDEWEB)

    Humelnicu, Doina, E-mail: doinah@uaic.ro [' Al.I. Cuza' University of Iasi, Faculty of Chemistry, Bd. 11 Carol I Boulevard, 700506 Iasi (Romania); Bulgariu, Laura; Macoveanu, Matei [Technical University ' Gh. Asachi' of Iasi, Faculty of Chemical Engineering and Environmental Protection, Department of Environmental Engineering and Management, Bd. D. Mangeron, 71A, 700050 Iasi (Romania)

    2010-02-15

    The efficiency of the radioactive uranyl and thorium ions on the peat moss from aqueous solutions has been investigated under different experimental conditions. The sorption and desorption of uranyl and thorium ions on three types (unmodified peat moss, peat moss treated with HNO{sub 3} and peat moss treated with NaOH) of peat moss were studied by the static method. Peat moss was selected as it is available in nature, in any amount, as a cheap and accessible sorbent. Study on desorption of such ions led to the conclusion that the most favourable desorptive reagent for the uranyl ions is Na{sub 2}CO{sub 3} 1 M while, for the thorium ions is HCl 1 M. The results obtained show that the parameters here under investigation exercise a significant effect on the sorption process of the two ions. Also, the investigations performed recommend the peat moss treated with a base as a potential sorbent for the uranyl and thorium ions from a radioactive aqueous solution.

  20. Identification of Uranyl Minerals Using Oxygen K-Edge X Ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.; Smith, Steven C.; McNamara, Bruce K.; Buck, Edgar C.; Eiden, Gregory C.; Duffin, Andrew M.

    2016-03-01

    Uranium analysis is consistently needed throughout the fuel cycle, from mining to fuel fabrication to environmental monitoring. Although most of the world’s uranium is immobilized as pitchblende or uraninite, there exists a plethora of secondary uranium minerals, nearly all of which contain the uranyl cation. Analysis of uranyl compounds can provide clues as to a sample’s facility of origin and chemical history. X-ray absorption spectroscopy is one technique that could enhance our ability to identify uranium minerals. Although there is limited chemical information to be gained from the uranium X-ray absorption edges, recent studies have successfully used ligand NEXAFS to study the physical chemistry of various uranium compounds. This study extends the use of ligand NEXAFS to analyze a suite of uranium minerals. We find that major classes of uranyl compounds (carbonate, oxyhydroxide, silicate, and phosphate) exhibit characteristic lineshapes in the oxygen K-edge absorption spectra. As a result, this work establishes a library of reference spectra that can be used to classify unknown uranyl minerals.

  1. Vibrational spectra of monouranates and uranium hydroxides as reaction products of alkali with uranyl nitrate

    International Nuclear Information System (INIS)

    Vibrational (IR absorption and Raman scattering) spectra for the reaction products of uranyl nitrate hexahydrate with NaOH and KOH have been studied. As a result of exchange reactions, the uranyl-ion coordinated nitrate groups are completely replaced by hydroxyl ions and various uranium and uranyl oxides or hydrates are formed. An analysis of the vibrations has been performed in terms of the frequencies of a free or coordinated nitrate group; comparison with the vibrations of the well-known uranium oxides and of the uranyl group UO22+ has been carried out. Vibrational spectra of a free nitrate group are characterized by four vibrational frequencies 1050, 724, 850, and 1380 cm-1, among which the frequencies at 724 and 1380 cm-1 are doubly degenerate and attributed to E’ symmetry of the point group D3h. When this group is uranium coordinated, its symmetry level is lowered to C2v, all vibrations of this group being active both in Raman and IR spectra. The doubly degenerate vibrations are exhibited as two bands and a frequency of the out-of-plane vibration is lowered to 815 cm-1. (authors)

  2. Influence of Chelating Agents on Chromium Fate in Sediment

    Institute of Scientific and Technical Information of China (English)

    WANGXIAOCHANG; SUNJINHE; 等

    1996-01-01

    A laboratory investigation on reaction between chelating agents and chromium was conducted to evaluate the effect of chelating agents on the adsorption and desorption of chromium in sediment.The amount of adsorbed chromium(VI) in sediment decreased slightly by 5%-10% because of addition of chelating agents.Chelating agents inhibited the removal of Cr(Ⅲ)by sediment from solutions and the inhibiting effect was in the order:citric acid>tartaric acid>EDTA,Salicylic acid.No effect of chelating agents on desorption of chromium in sediment was observed.

  3. Pentaarylcyclopentadiene und chirale Ruthenium-Chelat-Komplexe

    OpenAIRE

    Kanthak, Matthias

    2010-01-01

    Die Synthese von mono-ortho-funktionalisierten Pentaphenylcyclopentadienen gelang durch eine Abwandlung der klassischen Tetracyclon-Route. Durch die Umsetzung der funktionalisierten Cyclopentadiene mit Ru3(CO)12 als Metallquelle konnten entsprechende Ruthenium-Komplexe erhalten werden. Die geeignete Wahl der Substituenten an der Phenylgruppe erlaubte die Bildung von Chelat-Komplexen mit chirotopem Metallzentrum. Enantiomerenreine Oxazolin-Seitenarme führten zu diastereomerenreinen...

  4. Federal regulation of unapproved chelation products.

    Science.gov (United States)

    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.

  5. Acute iron poisoning. Rescue with macromolecular chelators.

    OpenAIRE

    Mahoney, J R; Hallaway, P E; Hedlund, B E; Eaton, J. W.

    1989-01-01

    Acute iron intoxication is a frequent, sometimes life-threatening, form of poisoning. Present therapy, in severe cases, includes oral and intravenous administration of the potent iron chelator, deferoxamine. Unfortunately, high dose intravenous deferoxamine causes acute hypotension additive with that engendered by the iron poisoning itself. To obviate this problem, we have covalently attached deferoxamine to high molecular weight carbohydrates such as dextran and hydroxyethyl starch. These ma...

  6. IRON CHELATION THERAPY IN THALASSEMIA SYNDROMES

    Directory of Open Access Journals (Sweden)

    Paolo Cianciulli

    2009-06-01

    Full Text Available Transfusional hemosiderosis is a frequent complication in patients with transfusion dependent chronic diseases such as  thalassemias and severe type of sickle cell diseases. As there are no physiological mechanisms to excrete the iron contained in transfused red cells (1 unit of blood contains approximately 200 mg of iron the excess of iron is stored in various organs. Cardiomyopathy is the most severe complication covering more than 70% of the causes of death of thalassemic patients. Although the current reference standard iron chelator deferoxamine (DFO has been used clinically for over four decades, its effectiveness is limited by a demanding therapeutic regimen that leads to poor compliance. Despite poor compliance, because of the inconvenience of subcutaneous infusion, DFO improved considerably the survival and quality of life of patients with thalassemia. Deferiprone since 1998 and Deferasirox since 2005 were licensed for clinical use. The oral chelators have a better compliance because of oral use, a comparable efficacy to DFO in iron excretion and probably a better penetration to myocardial cells. Considerable increase in iron excretion was documented with combination therapy of DFO and Deferiprone. The proper use of the three chelators will improve the prevention and treatment of iron overload, it will reduce  complications, and improve survival and quality of life of transfused patients

  7. Increasing the Net Negative Charge by Replacement of DOTA Chelator with DOTAGA Improves the Biodistribution of Radiolabeled Second-Generation Synthetic Affibody Molecules.

    Science.gov (United States)

    Westerlund, Kristina; Honarvar, Hadis; Norrström, Emily; Strand, Joanna; Mitran, Bogdan; Orlova, Anna; Eriksson Karlström, Amelie; Tolmachev, Vladimir

    2016-05-01

    A promising strategy to enable patient stratification for targeted therapies is to monitor the target expression in a tumor by radionuclide molecular imaging. Affibody molecules (7 kDa) are nonimmunoglobulin scaffold proteins with a 25-fold smaller size than intact antibodies. They have shown an apparent potential as molecular imaging probes both in preclinical and clinical studies. Earlier, we found that hepatic uptake can be reduced by the incorporation of negatively charged purification tags at the N-terminus of Affibody molecules. We hypothesized that liver uptake might similarly be reduced by positioning the chelator at the N-terminus, where the chelator-radionuclide complex will provide negative charges. To test this hypothesis, a second generation synthetic anti-HER2 ZHER2:2891 Affibody molecule was synthesized and labeled with (111)In and (68)Ga using DOTAGA and DOTA chelators. The chelators were manually coupled to the N-terminus of ZHER2:2891 forming an amide bond. Labeling DOTAGA-ZHER2:2891 and DOTA-ZHER2:2891 with (68)Ga and (111)In resulted in stable radioconjugates. The tumor-targeting and biodistribution properties of the (111)In- and (68)Ga-labeled conjugates were compared in SKOV-3 tumor-bearing nude mice at 2 h postinjection. The HER2-specific binding of the radioconjugates was verified both in vitro and in vivo. Using the DOTAGA chelator gave significantly lower radioactivity in liver and blood for both radionuclides. The (111)In-labeled conjugates showed more rapid blood clearance than the (68)Ga-labeled conjugates. The most pronounced influence of the chelators was found when they were labeled with (68)Ga. The DOTAGA chelator gave significantly higher tumor-to-blood (61 ± 6 vs 23 ± 5, p DOTA chelator. This study demonstrated that chelators may be used to alter the uptake of Affibody molecules, and most likely other scaffold-based imaging probes, for improvement of imaging contrast. PMID:27010700

  8. Investigation of the effect of the uranyl ion on proton-spin-relaxation times in aqueous solutions

    International Nuclear Information System (INIS)

    The purpose of this project was to determine the effect of the uranyl ion on the spin-lattice relaxation time of protons in aqueous solutions. A flowmeter using nuclear magnetic resonance (NMR) techniques is being designed for monitoring the flow rate of aqueous solutions which are acidic, contain plutonium and uranium ions, chemical waste, and radioactive waste materials. The spin-lattice relaxation time is critical to the design of a flowmeter using nuclear magnetic resonance techniques. Experimental studies showed that spin-lattice relaxation time did not change for different molar concentrations of sample solutions of uranyl nitrate and uranyl acetate prepared from pure laboratory chemicals dissolved in distilled water. Therefore, it was concluded that the uranyl ion does not contribute to the relaxation process for protons in water

  9. Uranyl adsorption at solvated edge surfaces of 2 : 1 smectites. A density functional study.

    Science.gov (United States)

    Kremleva, Alena; Krüger, Sven; Rösch, Notker

    2015-05-28

    We systematically studied the adsorption of uranyl(vi) on two common edge surfaces, (010) and (110), of 2 : 1 smectite clay minerals, using standard periodic DFT models. To describe various types of permanently charged clay minerals, we introduced charged defects into the initially neutral layer of pyrophyllite, cation substitutions in tetrahedral (beidellitic) and octahedral (montmorillonitic) sheets. Comparing uranyl(vi) species at various sites of these two types of surfaces, we found that structural parameters of such adsorption complexes are essentially determined by the surface chemical groups forming the adsorption site, not by the type of the clay mineral. Even for sites involving a substituted cation we noticed only a weak effect of the substitution on the geometric parameters. Geometry optimization resulted in adsorbed uranyl or uranyl hydroxide, with coordination numbers of 4 or 5. However, in most cases the same species was determined on the same type of site, independent of the substitutions. Optimization of adsorbed uranyl leads to hydrolysis at sites close to a AlOH(-1/2) surface group, resulting in uranyl monohydroxide as adsorbate and protonation of the AlOH(-1/2) group. While most species are equatorially five-coordinated, coordination 4 is preferred when uranyl adsorbs on mixed AlO(H)-SiO(H) sites. Calculated formation energies of surface complexes do not single out a preferred species or site, but point to an equilibrium of several species. Comparison to experiment and consideration of pH conditions suggests AlOHOH and AlOH-SiO sites of (010) surfaces and AlOmOH, SiOOm, and AlOH-SiO sites of (110) surfaces as most probable for uranyl adsorption. PMID:25941904

  10. Density functional studies of uranyl ion sorption on TiO{sub 2} (110) surface

    Energy Technology Data Exchange (ETDEWEB)

    Perron, H. [Universite Paris XI, Institut de Physique Nucleaire, Batiment 100, 91406 Orsay cedex (France)]|[EDF-R et D, Departement Materiaux et Mecanique des Composants, Les Renardieres, Ecuelles, 77818 Moret sur loing Cedex (France); Domain, C.; Catalette, H. [EDF-R et D, Departement Materiaux et Mecanique des Composants, Les Renardieres, Ecuelles, 77818 Moret sur loing Cedex (France); Roques, J.; Vandenborre, J.; Drot, R.; Simoni, E. [Universite Paris XI, Institut de Physique Nucleaire, Batiment 100, 91406 Orsay cedex (France)

    2005-07-01

    Full text of publication follows: One of the most important processes affecting safety during the storage of nuclear waste in underground disposal is the migration of radio-toxic elements through the geosphere. The major factor involved in the retention of these elements, in the case of water infiltration, would be their sorption at the water/mineral interface. In order to predict if a disposal will be safe, retardation process must be correctly understood. Among the radionuclides of interest, an experimental team of our laboratory is studying the interaction between uranyl ions (UO{sub 2}{sup 2+}) and the TiO{sub 2} (110) surface. Under experimental conditions, using XPS and TRLFS measurements two uranyl surface complexes were identified on the TiO{sub 2} (110) surface and it was shown that only the free aquo uranyl ion reacts with the surface sites. The relative intensities of these two structures change with the surface coverage indicating two different stabilities. The purpose of this work is to provide a theoretical support to the experimental investigation. With this aim in view, we report first principles density functional calculations on the adsorption of water and uranyl ions on the TiO{sub 2} (110) surface. Two different approaches were used. First, TiO{sub 2} (110) surface was modeled with periodic slabs in order to investigate clean surface relaxations, water adsorption, and finally interaction of uranyl ions with the mineral surface. The goal of this first step was to identify the most probable UO{sub 2}{sup 2+} adsorption sites and to establish their relative energy stabilities as a function of the surface coverage. Then, starting from the previous TiO{sub 2} (110) relaxed structure, (TiO{sub 2}){sub n} clusters were used to simulate the (110) rutile surface. This second step was done in order to study, from a local point of view, the interaction of one uranyl ion with the TiO{sub 2} (110) surface for the different possible adsorption sites. Each

  11. Studies on the preparation and characterisation of ammonium uranyl carbonate (AUC)

    International Nuclear Information System (INIS)

    Studies have been carried out in the laboratory on the preparation of ammonium uranyl carbonate (AUC), using concentrated solution of uranyl nitrate. The precipitation of AUC has been done by addition of (NH4)2CO3 solution and injecting gaseous ammonia and carbon dioxide. The precipitates obtained under varying parameter have been characterised by chemical and XRD analysis and the precipitate obtained under ideal conditions have been found to have the formula [(NH4)4UO2(CO3)3]. Though the studies were mainly aimed at standardising the procedures for the identification of precipitates, some of the AUC samples have been tested to see their suitability for conversion to ceramic grade UO2 powder and its pelletisation and sintering properties of the pellets. The data collected during these studies is presented. (author). 15 refs., 3 figs., 2 tabs

  12. Determination of uranyl nitrate diffusion coefficients in organic and aqueous media using the porous diaphragm method

    International Nuclear Information System (INIS)

    The diffusion coefficient is one of the parameters necessary for the obtention of the extraction exponential coefficients, that are contained within the H.T.U. (height of transfer unity) calculation expression, when operating with continuous organic phase. The organic phase used was tri-n-butyl-phosphate (TBP) and varsol in the 35% and 65% proportions respectively. After each experiment, the uranium content present in each compartment was spectrophotometrically determined and the quantities contained in the aqueous phases were determined by means of volumetric titration. It was found out that the uranyl ion diffusion coefficient is two and one half times less in organic phase, this just being attributed to the greater interactions of the uranyl ions in organic than in aqueous medium

  13. Interaction of uranyl ions with snake venom proteins from Lachesis muta muta

    International Nuclear Information System (INIS)

    The reaction product of uranyl nitrate with whole-protein Bushmaster snake venom in nitrate buffer at pH 3.5 has been studied. The maximum uptake of uranium was 291 μmol U x g-1 of venom. The infrared spectrum of the product showed an asymmetric O-U-O vibration at 921 cm-1 typical of complex formation with the uranyl ion. Stability measurements with the UO22+-protein complex in neutral medium indicated moderate hydrolytic stability, with 14% dissociation after 16 hours at 0 deg C. Neutron irradiation and desorption studies with a 235U-labelled complex showed that generated fission products such as lanthanides and barium were readily lixiviated at pH 7, whereas Ru and Zr were highly retained by the protein substrate. (author)

  14. Heating efficiency of microwave heating direct denitration of a mixture of uranyl nitrate and plutonium nitrate

    International Nuclear Information System (INIS)

    A mixture of plutonium nitrate and uranyl nitrate is co-converted to MOX powder by the microwave heating method developed by JAEA. The heating efficiency is very important for improving the energy-saving performance in this conversion process. In this study, the heating efficiency was measured using both experimental and engineering-scale microwave ovens in water, nitric acid and a mixture of plutonium nitrate and uranyl nitrate as a function of distance between the specimen and the base of the oven. In addition, the distribution of electromagnetic field strength and its absorption concentration in the solution were numerically evaluated by an electromagnetic field analysis code, MWS 2009. The experimental results could almost be explained by the numerical analysis results. When the distance of the specimen and the base of the oven was beyond 1/4 wavelength, the efficiency became constant because the influence disappeared. (author)

  15. Chelation therapy in intoxications with mercury, lead and copper

    DEFF Research Database (Denmark)

    Cao, yang; Skaug, Marit Aralt; Andersen, Ole;

    2015-01-01

    In the present review we provide an update of the appropriate use of chelating agents in the treatment of intoxications with compounds of mercury, lead and copper. The relatively new chelators meso-2,3-dimercaptosuccinic acid (DMSA) and 2,3-dimercapto-propanesulphonate (DMPS) can effectively...... or tetrathiomolybdate may be more suitable alternatives today. In copper-toxicity, a free radical scavenger might be recommended as adjuvant to the chelator therapy...

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

    Science.gov (United States)

    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

  17. Trypanotoxic activity of thiosemicarbazone iron chelators

    OpenAIRE

    Ellis, Samuel; Sexton, Darren; Steverding, Dietmar

    2015-01-01

    Only a few drugs are available for treating sleeping sickness and nagana disease; parasitic infections caused by protozoans of the genus Trypanosoma in sub-Saharan Africa. There is an urgent need for the development of new medicines for chemotherapy of these devastating diseases. In this study, three newly designed thiosemicarbazone iron chelators, TSC24, Dp44mT and 3-AP, were tested for in vitro activity against bloodstream forms of T. brucei and human leukaemia HL-60 cells. In addition to t...

  18. Novel Terbium Chelate Doped Fluorescent Silica Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    Ning Qiaoyu; Meng Jianxin; Wang Haiming; Liu Yingliang; Man Shiqing

    2006-01-01

    Novel terbium chelate doped silica fluorescent nanoparticles were prepared and characterized.The preparation was carried out in water-in-oil (W/O) microemulsion containing monomer precursor (pAB-DTPAA-APTEOS), Triton X-100, n-hexanol, and cyclohexane by controlling copolymerization of tetraethyl orthosilicate and 3-aminopropyl-triethyloxysilane.The nanoparticles are spherical and uniform in size, about 30 nm in diameter, strongly fluorescent, and highly stable.The amino groups directly introduced to the surface of the nanoparticles using APTEOS during preparation made the surface modification and bioconjugation of the nanoparticles easier.The nanoparticles are expected as an efficient time-resolved luminescence biological label.

  19. Heavy metal chelation in neurotoxic exposures.

    Science.gov (United States)

    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

  20. Synthesis, characterization and photo luminescence studies of uranyl doped SrBPO5

    International Nuclear Information System (INIS)

    SrBPO5: UO22+ was synthesized using solid state reaction method and characterized using powder X-ray diffraction. PXRD data showed the formation of single phase confirming successful doping of UO22+. Photo luminescence investigation informed stabilization of Uranium as Uranyl (UO22+) in SrBPO5 matrix. Luminescence decay time data suggested two possible environments for UO22+ with two different life time values

  1. Uranyl Solvation by a Three-Dimensional Reference Interaction Site Model.

    Science.gov (United States)

    Matveev, Alexei; Li, Bo; Rösch, Notker

    2015-08-13

    We report an implementation of the three-dimensional reference interaction site model (3D RISM) that in particular addresses the treatment of the long-range Coulomb field of charged species, represented by point charges and/or a distributed charge density. A comparison of 1D and 3D results for atomic ions demonstrates a reasonable accuracy, even for a moderate size of the unit cell and a moderate grid resolution. In an application to uranyl complexes with 4-6 explicit aqua ligands and an implicit bulk solvent modeled by RISM, we show that the 3D technique is not susceptible to the deficiencies of the 1D technique exposed in our previous work [Li, Matveev, Krüger, Rösch, Comp. Theor. Chem. 2015, 1051, 151]. The 3D method eliminates the artificial superposition of explicit aqua ligands and the RISM medium and predicts essentially the same values for uranyl and uranyl-water bond lengths as a state-of-the-art polarizable continuum model. With the first solvation shell treated explicitly, the observables are nearly independent of the order of the closure relationship used when solving the set of integral equations for the various distribution functions. Furthermore, we calculated the activation barrier of water exchange with a hybrid approach that combines the 3D RISM model for the bulk aqueous solvent and a quantum mechanical description (at the level of electronic density functional theory) of uranyl interacting with explicitly represented water molecules. The calculated result agrees very well with experiment and the best theoretical estimates. PMID:26167741

  2. Preparation of low-temperature sintered UO2 nanomaterials by radiolytic reduction of ammonium uranyl tricarbonate

    Science.gov (United States)

    Wang, Yongming; Chen, Qingde; Shen, Xinghai

    2016-10-01

    UO2 nanoparticles were successfully obtained from ammonium uranyl tricarbonate with high efficiency by γ-irradiation. More importantly, the as-prepared nanoparticles were stable in the irradiated mother solution exposed to air atmosphere. The purified UO2 powders could be sintered at 450-600 °C, much lower than the reported values (above 1700 °C) of bulk UO2. These advantages made this method promising in the production of UO2 nuclear fuels.

  3. Complex formation of uranyl acetate with tetracycline and its utilization for their microdetermination

    International Nuclear Information System (INIS)

    Conductometric and spectrophotometric (covering the visible, uv, and ir ranges) studies as well as microanalyses of uranyl complexes with tetracycline revealed the existence of the 1:1 complex species. The mean stability constant of the 1:1 complex, as determined spectrophotometrically, amounted to 1.2 x 105. This finding permits the use of the procedure for the microdetermination of tetracycline using UO2+2 ion or vice versa. (U.S.)

  4. A bibliographical review on the radiolysis of uranyl nitrate solutions in nitric acid medium

    International Nuclear Information System (INIS)

    A bibliographical study on the effects of ionizing radiation on uranyl nitrate solutions in nitric acid medium was performed, and the state of knowledge on this subject is presented. The main experimental and theoretical results on water, nitric acid and uranium solutions radiolysis are reviewed and critically evaluated. This paper provides a collection of references as an aid to the development of practical applications, and to stimulate new research on fundamental processes in these systems. (author)

  5. The Uranyl Cation as a Visible-Light Photocatalyst for C(sp(3) )-H Fluorination.

    Science.gov (United States)

    West, Julian G; Bedell, T Aaron; Sorensen, Erik J

    2016-07-25

    The fluorination of unactivated C(sp(3) )-H bonds remains a desirable and challenging transformation for pharmaceutical, agricultural, and materials scientists. Previous methods for this transformation have used bench-stable fluorine atom sources; however, many still rely on the use of UV-active photocatalysts for the requisite high-energy hydrogen atom abstraction event. Uranyl nitrate hexahydrate is described as a convenient, hydrogen atom abstraction catalyst that can mediate fluorinations of certain alkanes upon activation with visible light. PMID:27320442

  6. Photosensitized decomposition of hydrogen peroxide by the uranyl ion, production of hydroperoxide radicals

    International Nuclear Information System (INIS)

    The photosensitized decomposition of hydrogen peroxide by the uranyl ion in sulfuric acid media has been demonstrated and the kinetics of oxygen evolution have been measured as a function of the initial concentrations. The HO2 radical stabilized by complexation with UO22+ is an intermediate in this decomposition. This reaction can be employed in the photoassisted oxidation of diverse organic molecules using UO22+ as the sensitizer

  7. Method and apparatus for producing uranyl peroxide (U0/sub 4/ . 2H/sub 2/O) from uranium and uranium alloy pieces

    International Nuclear Information System (INIS)

    A method of producing uranyl peroxide (UO/sub 4/ . 2H/sub 2/O) from uranium-bearing metal pieces comprising: dissolving the uranium-bearing metal pieces in a first aqueous solution containing nitric acid and at least 0.5% but no greater than 5.0% fluoboric acid to provide a second aqueous solution which includes uranyl ions (UO/sub 2//sup +2/) and nitric and fluoboric acids; adding hydrogen peroxide to the second aqueous solution to precipitate uranyl peroxide out of the second solution and provide a third aqueous solution containing nitric and fluoboric acids; and separating the uranyl peroxide from the third aqueous solution

  8. Progress on Study of Luminescence of Rare Earth Organic Chelates

    Institute of Scientific and Technical Information of China (English)

    杨燕生; 安保礼; 龚孟濂; 史华红; 雷衡毅; 孟建新

    2002-01-01

    Based on the investigation of the luminescence of a series of rare earth organic chelates, some relationships between luminescence and the structure of the chelates were proposed: the intensity of sensitized luminescence of central lanthanide ions(Ln3+) in a rare earth organic chelate depends on (1)the suitability of the energy gap between the excited triplet energy level of the ligands and the lowest excited energy level of Ln3+ ions; (2)the rigidity and planarity of the structure of the chelate molecule; (3)the existence of a suitable secondary ligand which may increase rigidity and the stability of the chelate molecule; and (4) the existence of a suitable π-conjugated system in the chelate molecule. According to the above relationships, 25 novel organic ligands were designed and synthesized, and their lanthanide chelates were prepared. Investigation of the photoluminescence for the new chelates shows that some of the chelates are strongly luminescent, and are applied to fluoroimmunoassay for determination of human immunoglobulin(IgG), to preparation of fluorescent plastics, and to determination of growth hormone for plants. Two novel spectroscopy-probe techniques for structure of coordination compounds and biological molecules were proposed and developed based on vibronic spectroscopy of Tb3+ complexes and fluorescence of Ce3+.

  9. Plutonium-237: comparative uptake in chelated and non-chelated form by channel catfish (Ictalurus punctatus)

    International Nuclear Information System (INIS)

    Chelation can either enhance or reduce the uptake of ingested plutonium relative to PuOH (monomer) in channel catfish. Reduced uptake of 237Pu-fulvate is due either to the molecular weight of the complex or its stability in metabolic systems. Increased uptake of 237Pu-citrate is attributable to instability of the complex in metabolic systems. (author)

  10. Determination of parameters dissolution of yellow-cake. Production of uranyl nitrate - Gas precipitation of AUC

    International Nuclear Information System (INIS)

    The different stages of the purification cycle of yellow-cakes have been studied thoroughly in order to obtain an ammonium uranyl carbonate (AUC) as an intermediate product of uranium dioxide (UO2). The optimal parameters of yellow-cake dissolution, filtration, extraction by solvent, scrubbing and stripping were determined. An original program of thermodynamic calculation was developed for the determination of the free energies of yellow-cake dissolution reactions. Different numerical methods were used to determine the kinetic constant, the reaction order and correlation equations of uranyl nitrate density as a function of U and H+ concentrations, before and after the extraction cycle. For the first time, Algerian filteraids were used for the filtration of uranyl nitrate solutions with satisfactory results. A laboratory designed installation enabled the precipitation of AUC by injection of ammonia and carbon dioxide gases. Interesting results have been obtained and further investigations should be carried out in order to optimize all the paremeters of the gas precipitation of AUC

  11. Selective colorimetric and fluorescent quenching determination of uranyl ion via its complexation with curcumin

    Science.gov (United States)

    Zhu, Jing-Hui; Zhao, Xin; Yang, Jidong; Tan, Yu-Ting; Zhang, Lei; Liu, Shao-Pu; Liu, Zhong-Fang; Hu, Xiao-Li

    2016-04-01

    Under pH 4.0 HAc-NaAc buffer medium, curcumin alone possesses extraordinary weak fluorescence emission. Nevertheless, the introduction of Triton X-100 micelles can largely enhance the fluorescence intensity of curcumin. Uranyl ions can complex with micelles-capped curcumin, along with the slight red shift of curcumin fluorescence (about 1-7 nm), a clear decrement of absorbance (424 nm) and fluorescence (507 nm) intensities, and a distinct color change from bright yellow to orange. The fluorescence decrements (ΔF, 507 nm) are positively correlated to the amount of uranyl ions in the concentration range of 3.7 × 10- 6-1.4 × 10- 5 mol L- 1. The detection limit of this fluorescence quenching methods is 3.7 × 10- 6 mol L- 1, which is nearly 9000 times lower than the maximum allowable level in drinking water proposed by World Health Organization. Good selectivity is achieved because of a majority of co-existing substances (such as Ce4 +, La3 +, and Th4 +) do not affect the detection. The content of uranyl ions in tap water samples was determined by the proposed method with satisfactory results.

  12. Gas-phase reactions of molecular oxygen with uranyl(V) anionic complexes-synthesis and characterization of new superoxides of uranyl(VI).

    Science.gov (United States)

    Lucena, Ana F; Carretas, José M; Marçalo, Joaquim; Michelini, Maria C; Gong, Yu; Gibson, John K

    2015-04-16

    Gas-phase complexes of uranyl(V) ligated to anions X(-) (X = F, Cl, Br, I, OH, NO3, ClO4, HCO2, CH3CO2, CF3CO2, CH3COS, NCS, N3), [UO2X2](-), were produced by electrospray ionization and reacted with O2 in a quadrupole ion trap mass spectrometer to form uranyl(VI) anionic complexes, [UO2X2(O2)](-), comprising a superoxo ligand. The comparative rates for the oxidation reactions were measured, ranging from relatively fast [UO2(OH)2](-) to slow [UO2I2](-). The reaction rates of [UO2X2](-) ions containing polyatomic ligands were significantly faster than those containing the monatomic halogens, which can be attributed to the greater number of vibrational degrees of freedom in the polyatomic ligands to dissipate the energy of the initial O2-association complexes. The effect of the basicity of the X(-) ligands was also apparent in the relative rates for O2 addition, with a general correlation between increasing ligand basicity and O2-addition efficiency for polyatomic ligands. Collision-induced dissociation of the superoxo complexes showed in all cases loss of O2 to form the [UO2X2](-) anions, indicating weaker binding of the O2(-) ligand compared to the X(-) ligands. Density functional theory computations of the structures and energetics of selected species are in accord with the experimental observations.

  13. Chemical treatment of chelated metal finishing wastes.

    Science.gov (United States)

    McFarland, Michael J; Glarborg, Christen; Ross, Mark A

    2012-12-01

    This study evaluated two chemical approaches for treatment of commingled cadmium-cyanide (Cd-CN) and zinc-nickel (Zn-Ni) wastewaters. The first approach, which involved application of sodium hypochlorite (NaOCl), focused on elimination of chelating substances. The second approach evaluated the use of sodium dimethyldithiocarbamate (DMDTC) to specifically target and precipitate regulated heavy metals. Results demonstrated that by maintaining a pH of 10.0 and an oxidation-reduction potential (ORP) value of +600 mV, NaOCl treatment was effective in eliminating all chelating substances. Cadmium, chromium, nickel, and zinc solution concentrations were reduced from 0.27, 4.44, 0.06, and 0.10 ppm to 0.16, 0.17, 0.03, and 0.06 ppm, respectively. Similarly, a 1% DMDTC solution reduced these same metal concentrations in commingled wastewater to 0.009, 1.142, 0.036, and 0.320 ppm. Increasing the DMDTC concentration to 2% improved the removal of all regulated heavy metals except zinc, the removal of which at high pH values is limited by its amphotericity. PMID:23342939

  14. Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF α mediators

    International Nuclear Information System (INIS)

    Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO3 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO3. We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O2−). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O2− may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O2− may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through all the range of doses tested.

  15. Structural evolution of a uranyl peroxide nano-cage fullerene: U60, at elevated pressures

    Science.gov (United States)

    Turner, K. M.; Lin, Y.; Zhang, F.; McGrail, B.; Burns, P. C.; Mao, W. L.; Ewing, R. C.

    2015-12-01

    U60 is a uranyl peroxide nano-cage that adopts a highly symmetric fullerene topology; it is topologically identical to C60. Several studies on the aqueous-phase of U60 clusters, [UO2(O2)(OH)]6060-, have shown its persistence in complex solutions and over lengthy time scales. Peroxide enhances corrosion of nuclear fuel in a reactor accident-uranyl peroxides often form near contaminated sites. U60 (Fm-3) crystallizes with approximate formula: Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310. Here, we have used the diamond anvil cell (DAC) to examine U60 to understand the stability of this cluster at high pressures. We used a symmetric DAC with 300 μm culet diamonds and two different pressure-transmitting media: a mixture of methanol+ethanol and silicone oil. Using a combination of in situ Raman spectroscopy and synchrotron XRD, and electrospray ionization mass spectroscopy (ESI-MS) ex situ, we have determined the pressure-induced evolution of U60. Crystalline U60 undergoes an irreversible phase transition to a tetragonal structure at 4.1 GPa, and irreversibly amorphizes at 13 GPa. The amorphous phase likely consists of clusters of U60. Above 15 GPa, the U60 cluster is irreversibly destroyed. ESI-MS shows that this phase consists of species that likely have between 10-20 uranium atoms. Raman spectroscopy complements the diffraction measurements. U60 shows two dominant vibrational modes: a symmetric stretch of the uranyl U-O triple bond (810 cm-1), and a symmetric stretch of the U-O2-U peroxide bond (820 cm-1). As pressure is increased, these modes shift to higher wavenumbers, and overlap at 4 GPa. At 15 GPa, their intensity decreases below detection. These experiments reveal several novel behaviors including a new phase of U60. Notably, the amorphization of U60 occurs before the collapse of its cluster topology. This is different from the behavior of solvated C60 at high pressure, which maintains a hcp structure up to 30 GPa, while the clusters disorder. These results suggest

  16. Potentials and drawbacks of chelate-enhanced phytoremediation of soils

    NARCIS (Netherlands)

    Römkens, P.F.A.M.; Bouwman, L.A.; Japenga, J.; Draaisma, C.

    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 lysi

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

    Science.gov (United States)

    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. Macrocyclic Chelator Assembled RGD Multimers for Tumor Targeting

    OpenAIRE

    Zhang, Xiaofen; Liu, Hongguang; Miao, Zheng; Kimura, Richard; Fan, Feiyue; Cheng, Zhen

    2011-01-01

    Macrocyclic chelators have been extensively used for complexation of metal ions. A widely used chelator, DOTA, has been explored as a molecular platform to assemble multiple bioactive peptides in this paper. The multivalent DOTA-peptide bioconjugates demonstrate promising tumor targeting ability.

  19. Inapplicability of high pressure spray injection for chelate administration

    International Nuclear Information System (INIS)

    A high-pressure spray injector was tested for use in injecting chelating agents around radionuclides in wounds. It was difficult to employ because of the force required for proper injection, and it did not improve the effectiveness of the injected chelate in removing intramuscularly injected 238Pu. (U.S.)

  20. Adsorptive separation of rare earths by using chelating chitosan

    International Nuclear Information System (INIS)

    Two kinds of chelating chitosan were prepared by chemically modifying chitosan with functional groups of EDTA or DTPA, abbreviated as EDTA- and DTPA-chitosan hereafter, respectively, to investigate the adsorption behaviour for rare earths the mutual separation of which is the most difficult among metal ions on these chelating chitosan from dilute hydrochloric or sulfuric acid solution. The plots of the distribution ratio of a series of rare earths against equilibrium pH lay on different straight lines with slope of 3 corresponding to each earth for both of two chelating chitosan, suggesting that 3 hydrogen ions are released for the adsorption of unit ion of each rare earth by chelate formation with the functional group of EDTA or DTPA and that mutual adsorptive separation between adjacent rare earth is possible with these chelating chitosan. Apparent equilibrium constants of the adsorption were evaluated from the intercepts of these straight lines with the ordinate for each rare earth and for both chelating chitosan. It was found that the equilibrium constants of adsorption on EDTA- or DTPA-chitosan are quite analogous to those of chelate formation with EDTA or DTPA themselves, suggesting that chelating characteristics of these complexones is still maintained after their immobilization on polymer matrices of chitosan. (author)

  1. Luminescence of a conjugated polymer containing europium (III) chelate

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Hao; Xie, Fang, E-mail: xiefang4498@126.com

    2013-12-15

    A europium (III) chelate has been incorporated in a conjugated polymer, poly-[2,2′-bipyridine-5,5′-diyl-(2,5-dihexyl-1,4-phenylene)]. From the absorbance and emission spectra measurement and using the Judd–Ofelt theory, an efficient energy transfer between the conjugated polymer and the europium (III) chelate has been confirmed. The luminescence lifetime of Eu{sup 3+} ion in the conjugated polymer is 0.352 ms and the emission cross section of this material is 3.11×10{sup −21} cm{sup 2}. -- Highlights: • A europium chelate has been incorporated in a conjugated polymer. • Energy transfer in the conjugated polymer containing europium chelate is efficient. • The conjugated polymer containing europium chelate is a promising optical material.

  2. Quantitative measurement of metal chelation by fourier transform infrared spectroscopy

    Directory of Open Access Journals (Sweden)

    Monika E. Miller

    2015-12-01

    Full Text Available Nutritionally important minerals are more readily absorbed by living systems when complexed with organic acids, resulting in higher consumer demand and premium prices for these products. These chelated metals are produced by reaction of metal oxides and acids in aqueous solution. However, unreacted dry blends are sometimes misrepresented as metal chelates, when in reality they are only simple mixtures of the reactants typically used to synthesize them. This practice has increased interest in developing analytical methods that are capable of measuring the extent of metal chelation for quality control and regulatory compliance. We describe a novel method to rapidly measure the percent chelation of citric and malic acids with calcium, magnesium, and zinc. Utilization of attenuated total reflectance (FTIR-ATR provides for the direct, rapid measurement of solid samples. The inclusion of an internal standard allows independent determination of either free or chelated acids from integrated areas in a single spectrum.

  3. Treating Lead Toxicity: Possibilities beyond Synthetic Chelation

    Directory of Open Access Journals (Sweden)

    Shambhavi Tannir

    2013-01-01

    Full Text Available Lead, a ubiquitous metal, is one of the most abundant elements present on earth. Its easy availability and cost effectiveness made it an extremely popular component in the industrial revolution. However, its hazardous health effects were not considered at the time. Over the last few decades, with the adverse effects of lead coming to the forefront, nations across the world have started to recognize and treat lead toxicity. The most reliable and used method until now has been chelation therapy. Recent research has suggested the use of natural products and sources to treat lead poisoning with minimal or no side effects. This review has tried to summarize a few of the natural products/sources being investigated by various groups.

  4. Relationship between conformational flexibility and chelate cooperativity.

    Science.gov (United States)

    Misuraca, M Cristina; Grecu, Tudor; Freixa, Zoraida; Garavini, Valentina; Hunter, Christopher A; van Leeuwen, Piet W N M; Segarra-Maset, M Dolores; Turega, Simon M

    2011-04-15

    A family of four biscarbamates (AA) and four bisphenols (DD) were synthesized, and H-bonding interactions between all AA•DD combinations were characterized using (1)H NMR titrations in carbon tetrachloride. A chemical double mutant cycle analysis shows that there are no secondary electrostatic interactions or allosteric cooperativity in these systems, and the system therefore provides an ideal platform for investigating the relationship between chemical structure and chelate cooperativity. Effective molarities (EMs) were measured for 12 different systems, where the number of rotors in the chains connecting the two H-bond sites was varied from 5 to 20. The association constants vary by less than an order of magnitude for all 12 complexes, and the variation in EM is remarkably small (0.1-0.9 M). The results provide a relationship between EM and the number of rotors in the connecting chains (r): EM ≈ 10r(-3/2). The value of 10 M is the upper limit for the value of EM for a noncovalent intramolecular interaction. Introduction of rotors reduces the value of EM from this maximum in accord with a random walk analysis of the encounter probability of the chain ends (r(-3/2)). Noncovalent EMs never reach the very high values observed for covalent processes, which places limitations on the magnitudes of the effects that one is likely to achieve through the use of chelate cooperativity in supramolecular assembly and catalysis. On the other hand, the decrease in EM due to the introduction of conformational flexibility is less dramatic than one might expect based on the behavior of covalent systems, which limits the losses in binding affinity caused by poor preorganization of the interaction sites.

  5. Fixation kinetics of chelated and non-chelated zinc in semi-arid alkaline soils: application to zinc management

    Science.gov (United States)

    Udeigwe, Theophilus K.; Eichmann, Madeleine; Menkiti, Matthew C.

    2016-07-01

    This study was designed to examine the fixation pattern and kinetics of zinc (Zn) in chelated (ethylenediaminetetraacetic acid, EDTA) and non-chelated mixed micronutrient systems of semi-arid alkaline soils from the Southern High Plains, USA. Soils were characterized for a suite of chemical and physical properties and data obtained from extraction experiments fitted to various kinetic models. About 30 % more plant-available Zn was fixed in the non-chelated system within the first 14 days with only about 18 % difference observed between the two systems by day 90, suggesting that the effectiveness of the chelated compounds tended to decrease over time. The strengths of the relationships of change in available Zn with respect to other micronutrients (copper, iron, and manganese) were higher and more significant in the non-chelated system (average R2 of 0.83), compared to the chelated (average R2 of 0.42). Fixation of plant-available Zn was best described by the power-function model (R2 = 0.94, SE = 0.076) in the non-chelated system, and was poorly described by all the models examined in the chelated system. Reaction rate constants and relationships generated from this study can serve as important tools for micronutrient management and for future micronutrient modeling studies on these soils and other semi-arid regions of the world.

  6. Chelating impact assessment of biological ad chemical chelates on metal extraction from contaminated soils

    International Nuclear Information System (INIS)

    Soil contamination is the result of uncontrolled waste dumping and poor practices by humans. Of all the pollutants heavy metals are of particular concern due to their atmospheric deposition, leaching capacity and non-biodegradability. Heavy metal containing effluent is discharged into the agricultural fields and water bodies. This results in the accumulation of heavy metals in soil and the crops grown on that soil. Studies have revealed detrimental impacts on soil fertility and the poor health of animals and humans. Phytoextraction is widely researched for remediation of heavy metal contaminated soil. To enhance the effect of phytoextraction heavy metals have to be available to the plants in soluble form. In this study the potential of different chelating agents was assessed in solubilizing the heavy metals making easy for plants to uptake them. For this purpose efficient chemical and biological chelating agent had to be identified. Along with that an optimum dose and application time for chemical chelating agent was determined. Ethylenediamine tetraacetic acid (EDTA), Diethylene triamine pentaacetic acid (DTPA), Nitriloacetic acid (NTA) were applied to the soil, containing Pb, Cr, Cu and Cd, at different concentrations and application time. Aspergillus niger and Aspergillus flavus were incubated in soil for different time periods. In correspondence with findings of the study, Pb and Cr were best solubilized by 5mM EDTA. For Cd and Cu 5mM DTPA carried out efficient chelation. NTA showed relatively inadequate solubilisation, although for Cr it performed equal to EDTA. A. niger and A. flavus instead of solubilizing adsorbed the metals in their biomass. Adsorption was mainly carried out by A. niger. (author)

  7. Screening wheat genotypes in response to ordinary chelate and nano-iron chelate fertilizers in nutrient solution

    Directory of Open Access Journals (Sweden)

    S. Omidi Nargesi

    2015-11-01

    Full Text Available Recently, attentions have been taken on the investigations regarding the use of nano-sized compounds in different fields including agricultural sector. Due to the importance of evaluating the fate and operation of nano-particles in plant systems, in this survey, responses of 13 wheat genotypes to the effect of nano-iron chelate fertilizer in the Hoagland solution under the conditions of ordinary iron chelate and nano-iron chelate, with concentration of 22.5 mg/L, was studied. This experiment was carried out in Research Greenhouse of Soilless Culture Research Center, Isfahan University of Technology, Iran, in the spring of 2013. Results showed that there were considerable positive and negative variations among wheat genotypes in response to application of nano-sized iron chelate fertilizer. Under the application of iron chelate, among the different measured traits, number of tillers and root/shoot ratio had the highest coefficient of variations, and the lowest values were observed for chlorophyll flourescence and green leaf surface. Under the application of nano-iron chelate, number of tillers and root/shoot ratio had the highest coefficient of variations, and the lowest value was observed for chlorophyll flourescence content. Nano-iron chelate fertilizer caused reduction of average dry matter yield of shoots, leaf area and root volume by 14.1, 9.5 and 8.9 percent, respectively, and increased root/shoot ratio by 13.7% for some wheat varieties, in comparison with the ordinary iron chelate. In response to nano-iron chelate fertilizer, compared to ordinary iron chelate, Line-9-shoory produced the highest total dry matter (14.49% increase and Star variety had the lowest total dry matter (-51.82%.

  8. Selective recognition of uranyl ions from bulk of thorium(iv) and lanthanide(iii) ions by tetraalkyl urea: a combined experimental and quantum chemical study.

    Science.gov (United States)

    Vats, Bal Govind; Das, Debasish; Sadhu, Biswajit; Kannan, S; Pius, I C; Noronha, D M; Sundararajan, Mahesh; Kumar, Mukesh

    2016-06-21

    The selective separation of uranyl ions from an aqueous solution is one of the most important criteria for sustainable nuclear energy production. We report herein a known, but unexplored extractant, tetraalkyl urea, which shows supreme selectivity for uranium in the presence of interfering thorium and other lanthanide ions from a nitric acid medium. The structural characterization of the uranyl complex (UO2X2·2L, where X = NO3(-), Cl(-) and Br(-)) by IR, NMR and single crystal X-ray diffraction provides insight into the strong interaction between the uranyl ion and the ligand. The origin of this supreme selectivity for uranyl ions is further supported by electronic structure calculations. Uranyl binding with the extractant is thermodynamically more favourable when compared to thorium and the selectivity is achieved through a combination of electronic and steric effects.

  9. FY-15 Progress Report on Cleanup of irradiated SHINE Target Solutions Containing 140g-U/L Uranyl Sulfate

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, Megan E. [Argonne National Lab. (ANL), Argonne, IL (United States); Bowers, Delbert L. [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2015-09-01

    During FY 2012 and 2013, a process was developed to convert the SHINE Target Solution (STS) of irradiated uranyl sulfate (140 g U/L) to uranyl nitrate. This process is necessary so that the uranium solution can be processed by the UREX (Uranium Extraction) separation process, which will remove impurities from the uranium so that it can be recycled. The uranyl sulfate solution must contain <0.02 M SO42- so that the uranium will be extractable into the UREXsolvent. In addition, it is desired that the barium content be below 0.0007 M, as this is the limit in the Resource Conservation and Recovery Act (RCRA).

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  12. Chelation: Harnessing and Enhancing Heavy Metal Detoxification—A Review

    Directory of Open Access Journals (Sweden)

    Margaret E. Sears

    2013-01-01

    Full Text Available 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.

  13. Nanoparticle and other metal chelation therapeutics in Alzheimer disease.

    Science.gov (United States)

    Liu, Gang; Garrett, Matthew R; Men, Ping; Zhu, Xiongwei; Perry, George; Smith, Mark A

    2005-09-25

    Current therapies for Alzheimer disease (AD) such as the anticholinesterase inhibitors and the latest NMDA receptor inhibitor, Namenda, provide moderate symptomatic delay at various stages of disease, but do not arrest disease progression or supply meaningful remission. As such, new approaches to 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 desferioxamine, 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. In this review, we propose a novel system of chelation therapy through the use of nanoparticles. Nanoparticles conjugated to chelators show a 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 prove to be a safe and effective means of reducing the metal load in neural tissue thus staving off the harmful effects of oxidative damage and its sequelae.

  14. Synthesis and structures of new uranyl malonate complexes with carbamide derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Serezhkina, L. B., E-mail: Lserezh@samsu.ru [Samara State University (Russian Federation); Grigor’ev, M. S. [Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry (Russian Federation); Medvedkov, Ya. A.; Serezhkin, V. N. [Samara State University (Russian Federation)

    2015-09-15

    Crystals of new malonate-containing uranyl complexes [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Imon)(H{sub 2}O)] (I) and [UO{sub 2}(C{sub 3}H{sub 2}O4)(Meur){sub 3}] (II), where Imon is imidazolidin-2-one (ethylenecarbamide) and Meur is methyl-carbamide, have been synthesized and studied by X-ray diffraction. Both compounds crystallize in the monoclinic system with the following unit-cell parameters (at 100 K): a = 11.1147(10) Å, b = 6.9900(6) Å, c = 14.4934(12) Å, β = 92.042(2)°, V = 1125.30(17) Å{sup 3}, sp. gr. P2{sub 1}/n, Z = 4, R{sub 1} = 0.0398 (I); a = 16.6613(5) Å, b = 9.5635(3) Å, c = 22.9773(6) Å, β = 103.669(2)°, V = 3557.51(18) Å{sup 3}, sp. gr. C2/c, Z = 8, R{sub 1} = 0.0207 (II). The crystals are composed of electroneutral chains [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Imon)(H{sub 2}O)] and mononuclear groups [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Meur){sub 3}] as the structural units belonging to the crystal-chemical groups AT{sup 11}M{sub 2}{sup 1} and AB{sup 01}M{sub 3}{sup 1} (A =UO{sub 2}{sup 2+}, T{sup 11} and B{sup 01} = C{sub 3}H{sub 2}, M{sup 1} = Imon, H{sub 2}O, or Meur), respectively, of uranyl complexes. The packing modes of the uranyl-containing complexes were analyzed by the method of molecular Voronoi—Dirichlet polyhedra.

  15. Minimal role of metallothionein in decreased chelator efficacy for cadmium.

    Science.gov (United States)

    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.

  16. Cyclic voltammetric reduction studies of uranyl-di-potassium oxalate (DPO) in acetate buffered solution

    International Nuclear Information System (INIS)

    The eletrochemical reduction of uranyl perchlorate -DPO (Di-potassium oxalate) complex was studied cyclic voltammetrically in the pH range of 1 to 6.5, by using supporting electrolyte 0.1 M KNO3. The cyclic voltammograms were recorded at different voltage scan rates, so as to understand the diffusion controlled nature of the electrode reaction as well as the reversibility of the electrode reaction. Kinetic parameters like current -potential data, transfer coefficients (αn a) and Ksh were calculated for all the pH values studied. (author)

  17. Study on the transport behavior of uranyl nitrate in aqueous and non-aqueous systems

    International Nuclear Information System (INIS)

    The analytical ultracentrifuge has proven itself through diffusion measurements to be well suited for studying radioactive compounds. In the framework of this paper the extent to which the UV and schlieren optics of an analytical ultracentrifuge can be used for extraction-kinetic tests was tested. With this method there is also the possibility of determining the distribution coefficients right at the phase boundary. The results show the good possibility of application of the absorption and schlieren optics to the study of the transport behavior of uranyl nitrate in practice oriented solutions. (orig.)

  18. Thermal Analysis of the Decomposition of Ammonium Uranyl Carbonate (AUC) in Different Atmospheres

    DEFF Research Database (Denmark)

    Hälldahl, L.; Sørensen, Ole Toft

    1979-01-01

    The intermediate products formed during thermal decomposition of ammonium uranyl carbonate (AUC) in different atmospheres, (air, helium and hydrogen) have been determined by thermal analysis, (TG, and DTA) and X-ray analysis. The endproducts observed are U3O8 and UO2 in air/He and hydrogen......, respectively. The following intermediate products were observed in all atmospheres: http://www.sciencedirect.com.globalproxy.cvt.dk/cache/MiamiImageURL/B6THV-44K80TV-FB-1/0?wchp=dGLzVlz-zSkWW X-ray diffraction analysis showed that these phases were amorphous....

  19. Development of fluidized-bed furnace for thermal treatment of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    At present the ammonium uranyl carbonate (AUC) route is developed at a scale of 10 kg/day of UO2. This UO2 is directly compactible and sinterable to densities of 10.55-10.65 gm/cc. The equipment developed include precipitation tank with filtration and methanol washing and fluidized bed furnaces for thermal treatment of AUC and U3O8. During the design and development of these furnaces many experiments were conducted to study fluidization of AUC powder. In this paper the findings of these studies are presented. (author)

  20. Investigation of uranyl sulfate complexes with N-methyl substituted amides

    International Nuclear Information System (INIS)

    Methods of IR spectroscopy, thermal and X-ray analyses were used for physicochemical investigation into UO2SO4·2L (L-N,N-dimethylformamide; N,N-dimethylacetamide or N,N,N',N'-tetramethylcarbamide). Belonging of compounds to AT11M1/2 crystallochemical group of uranyl complexes with trans-position of neutral ligands and tridentate bridge-cyclic (T11) type of sulfate-group coordination was established. Crystallographic characteristics of compounds were obtained. Spectroscopic criterion of distinguishing types of sulfate-ion coordination (T3 or T11) was suggested

  1. New complexes of heteroaromatic N-oxides with europium, uranyl and zinc ions

    Institute of Scientific and Technical Information of China (English)

    Zbigniew Hnatejko

    2012-01-01

    New solid complexes of europium,uranyl and zinc ions with N-oxides of 4-chloro-2,6-dimethylpyridine,quinoline and 4-methoxyquinaldinic acid in presence different anions were obtained and characterized by elemental and TG analyses,IR and luminescence spectra.The compounds are crystalline,hydrated or anhydrous salts with colours typical of metal ions.Thermal studies showed that in hydrated salts lattice or coordination water molecules are present.A role of different anions in the formation of various types of the complexes is presented.

  2. The Complexes of Bisphosphonate and Magnetite Nanoparticles to Remove Uranyl Ions from Aqueous Phase

    International Nuclear Information System (INIS)

    Using tetraethyl-3-amino-propane-1,1-bisphosphonate (BP) as the functional molecule, we functionalized Fe3O4 magnetic nanoparticles via dopamine (DA) linkage to create a system with an Fe3O4-DA-BP nanostructure, which possesses high specificity for removing uranyl ions from water or blood. This work demonstrates that magnetic nanoparticles, combined with specific receptor-ligand interactions, promise a sensitive and rapid platform for the detection, recovery, and decorporation of radioactive metal toxins from biological environment

  3. Recovery of uranium from uranyl nitrate raffinate. Contributed Paper PE-06

    International Nuclear Information System (INIS)

    At New Uranium Oxide Fuel Plant, NUOFP(O) of Nuclear Fuel Complex (NFC), the Uranyl Nitrate Raffinate (UNR) generated during solvent extraction process is washed with Treated Lean Solvent(TLS) to recover residual U. Earlier this UNR consisting of 0.5-1 gm/l and 2.5 FA was neutralised with vapour ammonia. The slurry was then filtered over pre coat drum filter and the resultant Uranyl Nitrate Raffinate cake (UNRC) was stored in polyethylene lined MS drums. The valuable U was thus being locked up in UNRC. Also, the storage of UNRC drums required lot of floor space which have to be repacked frequently to contain the radioactivity. Hence the need has come to avoid the generation of UNRC and the recovery of U from the already generated UNRC. The generation of UNRC was avoided by developing alternate process of UNR treatment with Treated Lean Solvent for the removal of residual U and the resulting Acidic Raffinate Slurry (ARS) is disposed. The Uranium recovery from UNRC is done by dissolving the cake in Uranyl Nitrate Raffinate solution to leach the hexavalent Uranium by utilizing the free acidity in UNR. The leaching time is about six hours and the uranium forms uranyl nitrate. The resulting leach solutions are relatively dilute but complex acidic nitrate solutions containing wide variety of ions. Metallic ions commonly present include uranium, iron, magnesium, aluminium, sodium, calcium etc. The uranium concentration is normally 1-1.5 g/L. This uranium is separated by solvent extraction. The active agent in solvent extraction is Tri Butyl Phosphate in kerosene that can selectively extract uranium into an organic complex which is insoluble in aqueous. The organic used for extraction is Treated Lean Solvent in the quality of freshly prepared solvent and the resulting Acidic Raffinate Slurry is disposed by sale. The leaching of Uranium from UNRC was done in plant scale and about 1200 kgs of UNRC was successfully processed in trial batch. The paper deals with details of

  4. Luminescent properties of [UO2(TFA)2(DMSO)3], a promising material for sensing and monitoring the uranyl ion

    International Nuclear Information System (INIS)

    An uranyl complex [UO2(TFA)2(DMSO)3] (TFA=deprotonated trifluoroacetic acid; DMSO=dimethyl sulfoxide) has been successfully synthesized by reacting UO2(CH3COO)2 ·H2 O with one equivalent of (CF3 CO)2 O and DMSO. The complex has been characterized by single-crystal X-ray diffraction, X-ray powder diffraction, elemental analysis, FTIR spectroscopy, thermal analysis and absorption and emission spectroscopies. The spectroscopic properties of the material make it suitable for its application in the sensing and monitoring of uranyl in the PUREX process. (author)

  5. Synergistic cytotoxicity and DNA strand breaks in cells and plasmid DNA exposed to uranyl acetate and ultraviolet radiation

    OpenAIRE

    Wilson, Janice; Zuniga, Mary C.; Yazzie, Filbert; Stearns, Diane M.

    2014-01-01

    Depleted uranium (DU) has a chemical toxicity that is independent of its radioactivity. The purpose of this study was to explore the photoactivation of uranyl ion by ultraviolet (UV) radiation as a chemical mechanism of uranium genotoxicity. The ability of UVB (302 nm) and UVA (368 nm) radiation to photoactivate uranyl ion to produce single strand breaks was measured in pBR322 plasmid DNA, and the presence of adducts and apurinic/apyrimidinic sites that could be converted to single strand bre...

  6. STUDY ON THERMAL DECOMPOSITION KINETICS OF URUSHIOL METAL CHELATE POLYMERS

    Institute of Scientific and Technical Information of China (English)

    HU Binghuan; CHEN Riyao; LIN Jinhuo; CHEN Wending

    1994-01-01

    The thermal decomposition kinetics of urushiol-Cu, urushiol-Nd and urushiol-Ti chelate polymers has been studied by non-isothermal thermogravimetry. The results suggest that the thermal decomposition kinetics of three chelate polymers are all of first order. Their average activation energy values of the thermal decomposition calculated by Ozawa-(Ⅰ) method are 110.79,136.98 and 163.64 kJ mol-1respectively,which increase linearly with the metal valence of the metal chelate polymers

  7. Screening wheat genotypes in response to ordinary chelate and nano-iron chelate fertilizers in nutrient solution

    OpenAIRE

    S. Omidi Nargesi; Zahedi, M; H.R. Eshghizadeh; A.H. Khoshgoftarmanesh

    2015-01-01

    Recently, attentions have been taken on the investigations regarding the use of nano-sized compounds in different fields including agricultural sector. Due to the importance of evaluating the fate and operation of nano-particles in plant systems, in this survey, responses of 13 wheat genotypes to the effect of nano-iron chelate fertilizer in the Hoagland solution under the conditions of ordinary iron chelate and nano-iron chelate, with concentration of 22.5 mg/L, was studied. This experiment ...

  8. A Brief Review of Chelators for Radiolabeling Oligomers

    Directory of Open Access Journals (Sweden)

    Yuxia Liu

    2010-05-01

    Full Text Available The chemical modification of oligomers such as DNA, PNA, MORF, LNA to attach radionuclides for nuclear imaging and radiotherapy applications has become a field rich in innovation as older methods are improved and new methods are introduced. This review intends to provide a brief overview of several chelators currently in use for the labeling of oligomers with metallic radionuclides such as 99mTc, 111In and 188Re. While DNA and its analogs have been radiolabeled with important radionuclides of nonmetals such as 32P, 35S, 14C, 18F and 125I, the labeling methods for these isotopes involve covalent chemistry that is quite distinct from the coordinate-covalent chelation chemistry described herein. In this review, we provide a summary of the several chelators that have been covalently conjugated to oligomers for the purpose of radiolabeling with metallic radionuclides by chelation and including details on the conjugation, the choice of radionuclides and labeling methods.

  9. Metal chelate process to remove pollutants from fluids

    Science.gov (United States)

    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.

  10. Effects of macromolecular chelators on intestinal cadmium absorption in mice

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, O.; Nielsen, J.B.; Bulman, R.A.

    1989-01-01

    Suppression of absorption by macromolecular chelators have been sucessful with several metals. In this paper a series of immobilized chelators ranging from DTPA to S-containing soft bases have been synthetized and investigated for ability to suppress intestinal uptake of /sup 109/Cd/sup 2+/ in mice. Dextran-O-ethyl-mercaptan, xanthates derived from polysaccharides and polyvinyl alcohol, dithiocarbamates of polyethylene imine and aminoethyl cellulose, and DTPA immobilized on aminopropyl silica were all ineffective. DTPA immobilized on aminoethyl cellulose even enhanced the intestinal uptake. The macromolecular chelators were without extensive effect on organ distribution of absorbed cadmium, except for dithiocarbamate immobilized on polyethylene imine, which enhanced the deposition of cadmium in several organs including the brain. Although the results are discouragign, they indicate that desing and synthesis of immobilized vicinal dithio compounds may represent an avenue for development of non-absorbable chelators with high affinity for cadmium.

  11. Mixed-chelate therapy of intratracheally deposited cadmium oxide

    International Nuclear Information System (INIS)

    Mixed-chelate treatment with EDTA and salicylic acid was no more effective in accelerating the removal of intratracheally instilled 109CdO, or in protecting against CdO-induced mortality, than was EDTA given alone

  12. Development of Multi-Functional Chelators Based on Sarcophagine Cages

    Directory of Open Access Journals (Sweden)

    Shuanglong Liu

    2014-04-01

    Full Text Available A new class of multifunctionalized sarcophagine derivatives was synthesized for 64Cu chelation. The platform developed in this study could have broad applications in 64Cu-radiopharmaceuticals.

  13. Field-Portable Immunoassay Instruments and Reagents to Measure Chelators and Mobile Forms of Uranium

    Energy Technology Data Exchange (ETDEWEB)

    Blake, Diane A.

    2006-01-23

    Progress Report Date: 01/23/06 (report delayed due to Hurricane Katrina) Report of results to date: The goals of this 3-year project are to: (1) update and successfully deploy our present immunosensors at DOE sites; (2) devise immunosensor-based assays for Pb(II), Hg(II), chelators, and/or Cr(III) in surface and groundwater; and (3) develop new technologies in antibody engineering that will enhance this immunosensor program. Note: Work on this project was temporarily disrupted when Hurricane Katrina shut down the University on August 29, 2005. While most of the reagents stored in our refrigerators and freezers were destroyed, all of our hybridoma cell lines were saved because they had been stored in liquid nitrogen. We set up new tissue culture reactors with the hybridomas that synthesize the anti-uranium antibodies, and are purifying new monoclonal antibodies from these culture supernatants. Both the in-line and the field-portable sensor were rescued from our labs in New Orleans in early October, and we continued experiments with these sensors in the temporary laboratory we set up in Hammond, LA at Southeastern Louisiana University.

  14. Alternative process to produce UF{sub 4} using the effluent from ammonium uranyl carbonate route

    Energy Technology Data Exchange (ETDEWEB)

    Silva Neto, Joao B.; Garcia, Rafael Henrique Lazzari; Dal Vechio, Edvaldo, E-mail: jbsneto@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), SP (Brazil); Riella, Humberto G., E-mail: riella@enq.ufsc.br [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil); Instituto Nacional de Ciencias e Tecnologia de Reatores Nucleares Inovadores (INCT/CNPq) (Brazil); Carvalho, Elita F. Urano de; Durazzo, Michelangelo [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), SP (Brazil); Instituto Nacional de Ciencias e Tecnologia de Reatores Nucleares Inovadores (INCT/CNPq) (Brazil)

    2011-07-01

    The Nuclear Fuel Centre of IPEN / CNEN - SP develops and manufactures dispersion fuel with high uranium concentration. It meets the demand of the IEA-R1 reactor and future research reactors to be constructed in Brazil. The fuel uses uranium silicide (U{sub 3}Si{sub 2}) dispersed in aluminum. For producing the fuel, the process of uranium hexafluoride (UF{sub 6}) conversion consist in obtaining U{sub 3}Si{sub 2} and / or U{sub 3}O{sub 8} through the preparation of intermediate compounds, among them ammonium uranyl carbonate - AUC, ammonium diuranate - DUA and uranium tetrafluoride - UF{sub 4}. This work describes a procedure for preparing uranium tetrafluoride via a dry route, using as raw material the filtrate generated when ammonium uranyl carbonate is routinely produced. The filtrate consists mainly of a solution containing high concentrations of ammonium (NH{sup 4+}), fluoride (F{sup -}), carbonate (CO{sup 3-}) and low concentrations of uranium. The procedure consists in recovering NH{sup 4F} and uranium, as UF{sub 4}, through the crystallization of ammonium bifluoride (NH{sub 4}HF{sub 2}) and, in a later step, the addition of UO{sub 2}, occurring fluoridation and decomposition. The UF{sub 4} obtained is further diluted in the UF{sub 4} produced routinely at IPEN / CNEN-SP by a wet route process. (author)

  15. Removal of uranyl ions in aquatic mediums by using a new material: gallocyanine grafted hydrogel.

    Science.gov (United States)

    Ulusoy, Halil İbrahim; Simşek, Selçuk

    2013-06-15

    A new material containing gallocyanine (GC) grafted polyacyril amide (PAA) was synthesized and its adsorption ability was examined for the removal of uranyl ions from aqueous media. The new developed adsorbent was characterized by FTIR, SEM, and PZC analysis. Adsorption of UO₂(2+) ions from aqueous solution as a function of ion concentration, pH, ionic strength, temperature, and reusability of adsorbent was investigated in detail. The adsorption data were analyzed by using the Langmuir, Freundlich and Dubinin-Radushkevich (DR) models. The adsorption of UO₂(2+) increased with pH and reached a plateau value in the pH range 5-6. The adsorption of UO₂(2+) ions were not affected by increasing ionic strength. The adsorption mechanism followed an endothermic and spontaneous process with increased disorderliness at adsorbate/adsorbent interface. The adsorption process followed a pseudo-second-order kinetics. The new developed material is a potential adsorbent for effective removal of uranyl ions from aquatic solutions. PMID:23669652

  16. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

  17. Synthesis and Crystal Structure of Bis(nitrate)bis(dipiperidin-1-yl-methanone)uranyl(II)

    Institute of Scientific and Technical Information of China (English)

    朱利明; 何雪雁; 周俊慧; 于正风; 李宝龙; 张勇

    2004-01-01

    The new uranyl complex UO2(NO3)2[C5H10NC(O)NH10C5]2 has been synthesized and its structure was determined by single-crystal X-ray diffraction. Crystal data: C22H40N6O10U, monoclinic, space group P21/c, a = 11.151(3), b = 13.907(3), c = 10.067(2)A,β= 115.602(4)0,V = 1408.0(5) A3, Mr = 786.63, Z = 2, Dc = 1.855 g/cm3, F(000) = 772,μ = 5.827 mm-1, R = 0.0465 and wR = 0.1065 for 2916 observed reflections (I > 2σ(I)). The central uranyl ion is coordinated by six oxygen atoms, of which two are from the carbonyl groups of di-piperidin-1-yl-methanone molecules and the other four from two nitrate groups.

  18. Structural elucidation and physicochemical properties of mononuclear Uranyl(VI) complexes incorporating dianionic units

    Science.gov (United States)

    Azam, Mohammad; Velmurugan, Gunasekaran; Wabaidur, Saikh Mohammad; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Al-Resayes, Saud I.; Al-Othman, Zeid A.; Venuvanalingam, Ponnambalam

    2016-01-01

    Two derivatives of organouranyl mononuclear complexes [UO2(L)THF] (1) and [UO2(L)Alc] (2), where L = (2,2′-(1E,1′E)-(2,2-dimethylpropane-1,3-dyl)bis(azanylylidene, THF = Tetrahydrofuran, Alc = Alcohol), have been prepared. These complexes have been determined by elemental analyses, single crystal X-ray crystallography and various spectroscopic studies. Moreover, the structure of these complexes have also been studied by DFT and time dependent DFT measurements showing that both the complexes have distorted pentagonal bipyramidal environment around uranyl ion. TD-DFT results indicate that the complex 1 displays an intense band at 458.7 nm which is mainly associated to the uranyl centered LMCT, where complex 2 shows a band at 461.8 nm that have significant LMCT character. The bonding has been further analyzed by EDA and NBO. The photocatalytic activity of complexes 1 and 2 for the degradation of rhodamine-B (RhB) and methylene blue (MB) under the irradiation of 500W Xe lamp has been explored, and found more efficient in presence of complex 1 than complex 2 for both dyes. In addition, dye adsorption and photoluminescence properties have also been discussed for both complexes. PMID:27595801

  19. X-ray diffraction study of uranyl sulfate complexes with acetamide

    International Nuclear Information System (INIS)

    X-ray diffraction study of UO2SO4xLx2H2O (1), UO2SO4x2Lx2H2O (2) and UO2SO4x3LxH2O (3) (L-acetamide) complexes, which crystals were prepared by slow evaporation at room temperature uranyl sulfate and acetamide aqueous solutions with a definite molar ratio, is carried out. The lattice parameters for (1) are: a=17.520; b=6.917; c=8.759 A; β=104.40 deg sp.gr. s2/mC2 or Cm; for (2): a=7.248; b=9.451; c=10.623 A; α=109.15; β=107.79; γ=74.55 deg; sp.gr. P1-bar; for (3): a=8.494; b=10.170; c=10.606 A; α=118.81; β=102.92; γ=90.10 deg; sp.gr. P1-bar. Peculiarities of crystal-structure transformations in acetamide and carbamide uranyl sulfate complexes with change of UO2SO4:L ratio (L-acetamide or carbamide) are discussed

  20. Rapid dissolution of soluble uranyl phases in arid, mine-impacted catchments near Church Rock, NM.

    Science.gov (United States)

    deLemos, Jamie L; Bostick, Benjamin C; Quicksall, Andrew N; Landis, Joshua D; George, Christine C; Slagowski, Naomi L; Rock, Tommy; Brugge, Doug; Lewis, Johnnye; Durant, John L

    2008-06-01

    We tested the hypothesis that runoff of uranium-bearing particles from mining waste disposal areas was a significant mechanism for redistribution of uranium in the northeastern part of the Upper Puerco River watershed (New Mexico). However, our results were not consistent with this hypothesis. Analysis of > 100 sediment and suspended sediment samples collected adjacent to and downstream from uranium source areas indicated that uranium levels in the majority of the samples were not elevated above background. Samples collected within 50 m of a known waste disposal site were subjected to detailed geochemical characterization. Uranium in these samples was found to be highly soluble; treatment with synthetic pore water for 24 h caused dissolution of 10--50% of total uranium in the samples. Equilibrium uranium concentrations in pore water were > 4.0 mg/L and were sustained in repeated wetting events, effectively depleting soluble uranium from the solid phase. The dissolution rate of uranium appeared to be controlled by solid-phase diffusion of uranium from within uranium-bearing mineral particles. X-ray adsorption spectroscopy indicated the presence of a soluble uranyl silicate, and possibly a uranyl phosphate. These phases were exhausted in transported sediment suggesting that uranium was readily mobilized from sediments in the Upper Puerco watershed and transported in the dissolved load. These results could have significance for uranium risk assessment as well as mining waste management and cleanup efforts.

  1. Strongly coupled binuclear uranium-oxo complexes from uranyl oxo rearrangement and reductive silylation

    Science.gov (United States)

    Arnold, Polly L.; Jones, Guy M.; Odoh, Samuel O.; Schreckenbach, Georg; Magnani, Nicola; Love, Jason B.

    2012-03-01

    The most common motif in uranium chemistry is the d0f0 uranyl ion [UO2]2+ in which the oxo groups are rigorously linear and inert. Alternative geometries, such as the cis-uranyl, have been identified theoretically and implicated in oxo-atom transfer reactions that are relevant to environmental speciation and nuclear waste remediation. Single electron reduction is now known to impart greater oxo-group reactivity, but with retention of the linear OUO motif, and reactions of the oxo groups to form new covalent bonds remain rare. Here, we describe the synthesis, structure, reactivity and magnetic properties of a binuclear uranium-oxo complex. Formed through a combination of reduction and oxo-silylation and migration from a trans to a cis position, the new butterfly-shaped Si-OUO2UO-Si molecule shows remarkably strong UV-UV coupling and chemical inertness, suggesting that this rearranged uranium oxo motif might exist for other actinide species in the environment, and have relevance to the aggregation of actinide oxide clusters.

  2. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    International Nuclear Information System (INIS)

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660±0.092 at 25 C, and extraction enthalpy is -5. 46±0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 x 106±3.56 x 104 at 25 C; reaction enthalpy was -9.610±0.594 kcal/mol. Nitration complexation constant is 8.412±0.579, with an enthalpy of -10.72±1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured

  3. Uranyl ion transport across tri-n-butyl phosphate/n-dodecane liquid membranes

    International Nuclear Information System (INIS)

    Carrier-facilitated transport of uranium (VI) against its concentration gradient from aqueous nitrate acidic solutions across organic bulk liquid membranes (BLM) and supported liquid membranes (SLM) containing TBP as the mobile carrier and n-dodecane as the membrane solvent was investigated. Extremely dilute uranyl nitrate solutions in about 2.5 M nitric acid generally constituted as the source phase. Uranyl transport appreciably increased with both stirring of the receiving phase and the carrier concentration in the organic membrane, while enhanced acidity of the strip side adversely affected the partioning of the cation into this phase. Among the several reagents tested, diluted ammonium carbonate (∼1M) solutions served efficiently as the stripant. Besides Accurel polypropylene (PP) film as the solid support for SLM, some silicon flat-sheet membranes with different inorganic fillers like silica, calcium silicate, calcium carbonate, chromium oxide, zinc oxide etc. and teflon membranes transported about 70% of uranium in nearly 7-8 hr employing 1 M ammonium carbonate as the strippant. Specifically, 30% TBP supported on Accurel flat-sheet supports transfered better than 70% of uranium from moderate acid feeds (2.5M) under similar conditions. Membranes supporting Aliquat-336, TLA, TOPO etc. yielded somewhat poor uranium recoveries. The feed : strip volume ratio showed an inverse relationship to the fraction of cation transported. (author). 9 refs., 2 tab s

  4. Uranyl-Lanthanide Hetero-metallic Complexes with Cucurbit[6]uril and Perrhenate Ligands

    International Nuclear Information System (INIS)

    The reaction of uranyl and lanthanide nitrates with cucurbit[6]uril (CB6) in the presence of perrhenic acid and under hydrothermal conditions yields the novel hetero-metallic uranyl-lanthanide molecular complexes [UO2Ln(CB6)(ReO4)2(NO3)(H2O)7](ReO4)2 (Ln = Sm, Eu, Gd, Lu). Both metal cations are bound to carbonyl groups of the same CB6 portal, one for UO22+ and two for Ln3+. The uranium atom is also bound to one monodentate perrhenate ion and three aquo ligands, while the lanthanide is bound to one monodentate perrhenate and one nitrate ions, and four aquo ligands. Not only are these complexes rare examples of ReO4- bonding to f element ions, but the perrhenate bound to Ln is included in the CB6 cavity, thus providing the first case of inclusion of a tetrahedral oxo-anion in this macrocycle. (author)

  5. Structural elucidation and physicochemical properties of mononuclear Uranyl(VI) complexes incorporating dianionic units.

    Science.gov (United States)

    Azam, Mohammad; Velmurugan, Gunasekaran; Wabaidur, Saikh Mohammad; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Al-Resayes, Saud I; Al-Othman, Zeid A; Venuvanalingam, Ponnambalam

    2016-01-01

    Two derivatives of organouranyl mononuclear complexes [UO2(L)THF] (1) and [UO2(L)Alc] (2), where L = (2,2'-(1E,1'E)-(2,2-dimethylpropane-1,3-dyl)bis(azanylylidene, THF = Tetrahydrofuran, Alc = Alcohol), have been prepared. These complexes have been determined by elemental analyses, single crystal X-ray crystallography and various spectroscopic studies. Moreover, the structure of these complexes have also been studied by DFT and time dependent DFT measurements showing that both the complexes have distorted pentagonal bipyramidal environment around uranyl ion. TD-DFT results indicate that the complex 1 displays an intense band at 458.7 nm which is mainly associated to the uranyl centered LMCT, where complex 2 shows a band at 461.8 nm that have significant LMCT character. The bonding has been further analyzed by EDA and NBO. The photocatalytic activity of complexes 1 and 2 for the degradation of rhodamine-B (RhB) and methylene blue (MB) under the irradiation of 500W Xe lamp has been explored, and found more efficient in presence of complex 1 than complex 2 for both dyes. In addition, dye adsorption and photoluminescence properties have also been discussed for both complexes. PMID:27595801

  6. Uranyl complexation with acetate studied by means of affinity capillary electrophoresis.

    Science.gov (United States)

    Sladkov, Vladimir

    2013-05-10

    The interaction of uranyl with acetate is studied by affinity capillary electrophoresis in aqueous acid solutions at the pH values 2.0 and 2.5. The use of data on metal ion mobilities at different pHs allows to establish the ligand species interacting with metal ion and complex species formed. The formation of two complex species UO2CH3COO(+) and UO2(CH3COO)2 is observed (acetic acid concentration is up to 0.8M). In the case of uranyl-acetic acid system, the viscosity of solution is significantly changed with an increase of acid concentration. For calculation of ion mobilities the viscosity changes are taken into account. The stability constants are calculated at the ionic strengths 0.02 and 0.05 mol L(-1). The logarithms of the thermodynamic stability constants (β°) calculated with Davies equation for the activity coefficients of the ions are log β1(°)=2.94±0.08 and log β2(°)=5.50±0.15 at 25 °C. Obtained values are compared with literature data. PMID:23570853

  7. Chelated Ruthenium Catalysts for Z-Selective Olefin Metathesis

    OpenAIRE

    Endo, Koji; Grubbs, Robert H.

    2011-01-01

    We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands which catalyze highly Z-selective olefin metathesis. A very simple and convenient synthetic procedure of such a catalyst has been developed. An intramolecular C-H bond activation of the NHC ligand, which is promoted by anion ligand substitution, forms the appropriate chelate for stereo- controlled olefin metathesis.

  8. Chelated Ruthenium Catalysts for Z-Selective Olefin Metathesis

    Science.gov (United States)

    Endo, Koji; Grubbs, Robert H.

    2011-01-01

    We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands which catalyze highly Z-selective olefin metathesis. A very simple and convenient synthetic procedure of such a catalyst has been developed. An intramolecular C-H bond activation of the NHC ligand, which is promoted by anion ligand substitution, forms the appropriate chelate for stereo- controlled olefin metathesis. PMID:21563826

  9. Antioxidant, Free Radical Scavenging and Metal Chelating Characteristics of Propolis

    OpenAIRE

    Hikmet Geckil; Burhan Ates; Gokhan Durmaz; Selim Erdogan; Ismet Yilmaz

    2005-01-01

    This study was undertaken to determine the reducing characteristics, metal chelating capability, anti-lipid peroxidative and antiradical properties of propolis compared to two widely used artificial antioxidants, Butylated Hydroxyanisole (BHA) and Butylated Hydroxytoluene (BHT). The water and ethanol extracts of propolis showed significantly a different degree of metal chelating, radical scavenging activity and reducing power. In general, ethanol extracts of propolis showed higher activity re...

  10. Antibody Conjugates: From Heterogeneous Populations to Defined Reagents

    Directory of Open Access Journals (Sweden)

    Patrick Dennler

    2015-08-01

    Full Text Available Monoclonal antibodies (mAbs and their derivatives are currently the fastest growing class of therapeutics. Even if naked antibodies have proven their value as successful biopharmaceuticals, they suffer from some limitations. To overcome suboptimal therapeutic efficacy, immunoglobulins are conjugated with toxic payloads to form antibody drug conjugates (ADCs and with chelating systems bearing therapeutic radioisotopes to form radioimmunoconjugates (RICs. Besides their therapeutic applications, antibody conjugates are also extensively used for many in vitro assays. A broad variety of methods to functionalize antibodies with various payloads are currently available. The decision as to which conjugation method to use strongly depends on the final purpose of the antibody conjugate. Classical conjugation via amino acid residues is still the most common method to produce antibody conjugates and is suitable for most in vitro applications. In recent years, however, it has become evident that antibody conjugates, which are generated via site-specific conjugation techniques, possess distinct advantages with regard to in vivo properties. Here, we give a comprehensive overview on existing and emerging strategies for the production of covalent and non-covalent antibody conjugates.

  11. Eu-Chelate Construct Ultrasensitive Time-Resolved Fluoroimmunoassay-Assay of Pepsinogen I

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Eu-chelate were used to construct a two-site sandwich-type assay for pepsinogen I (PGI) with time-resolved fluoroimmunoassay (TRFIA) as a detection technique. On the noncompetitive assay, captured monoclonal antibodies (McAbs) coated on wells were directed against a specific antigenic site on the PGI. Another McAbs, called as labeling McAbs, were prepared with the Eu-chelate of N-(p-isothiocyanatobenzyl)-diethylenetriamine-N, N, N, N-tetraacetic acid and directed against a different antigenic site on the PGI. The fluorescence counts of bound Eu3 +-McAbs were measured with the auto DELFIA1235 system. The PGI in sera from healthy volunteers were determined by PGI-TRFIA. The within-run and between-run CVs of the PGI-TRFIA were 1.9% and 4.7%, respectively, and the recovery rate was 102.65%. The cross-reacting rate with pepsinogen Ⅱ was negligible. The linear correlation of PGI-TRFIA and radioimmunassay measurePGI. The availability of a highly sensitive, reliable, and convenient method for quantifying PGI will allow investigations into the possible diagnostic value of this analyte in various clinical conditions, including gastric carcinoma, duodenal ulcer, gastritis and severe atrophic gastritis.

  12. Site-specific conjugation of bifunctional chelator BAT to mouse IgG1 Fab' fragment

    Institute of Scientific and Technical Information of China (English)

    Jun LI; Xue-hao WANG; Xiao-ming WANG; Zhao-lai CHEN

    2006-01-01

    Aim: To perform a site-specific conjugation of Fab' fragments of a mouse monoclonal antibody(MoAb) B43(of IgG1 subtype) to a bifunctional chelator 6-[p-(bromoacetamido) benzyl]-l,4,8,11-tetraazacyclotetradecane-N,N',N",N'"-tetraacetic acid (BAT) via the thiol groups in the hinge distal to the antigenbinding site of the Fab'. Methods: B43 was cleaved using a simple 2-step method.First, stable F(ab')2 was produced by pepsin treatment. Fab' with free thiol in the hinge region was then obtained by cysteine reduction of F(ab')2. Second, a sitespecific conjugation of Fab' to thiol-specific BAT was performed in a one-step reaction. Results: The Fab' fragment had approximately 1.8 free thiol groups per molecule after cysteine reduction. The conjugation efficiency and the chemical yield were approximately 1.28 moles chelator/Fab' and 74% of the initial concentration of Fab', respectively. The F(ab')2, Fab' and Fab'-BAT all maintained reasonable antigen-binding properties. 67Cu labeling of the conjugate under standard conditions did not impair the immunoreactivity of Fab'-BAT. Conclusion: This is a simple and efficient method for producing immunoreactive conjugates of Fab'-BAT, which can be used to make radiometal-labeled conjugates for further diagnostic and therapeutic applications.

  13. Molecular Simulations of the Diffusion of Uranyl Carbonate Species in Nanosized Mineral Fractures

    Science.gov (United States)

    Kerisit, S.; Liu, C.

    2010-12-01

    Uranium is a major groundwater contaminant at uranium processing and mining sites as a result of intentional and accidental discharges of uranium-containing waste products into subsurface environments. Recent characterization has shown that uranium preferentially associates with intragrain and intra-aggregate domains in some of the uranium-contaminated sediments collected from the US Department of Energy Hanford Site [1, 2]. In these sediments, uranium existed as precipitated and/or adsorbed phases in grain micropores with nano- to microscale sizes. Desorption and diffusion characterization studies and continuum-scale modeling indicated that ion diffusion in the microfractures is a major mechanism that led to preferential uranium concentration in the microfracture regions and will control the future mobility of uranium in the subsurface sediments [1, 3-4]. However, the diffusion properties of uranyl species in the intragrain regions, especially at the solid-liquid interface, are still poorly understood. Therefore, a general aim of this work is to provide atomic-level insights into the contribution of microscopic surface effects to the slow diffusion process of uranyl species in porous media with nano- to microsized fractures. In this presentation, we will first present molecular dynamics (MD) simulations of feldspar-water interfaces to investigate their interfacial structure and dynamics and establish a theoretical framework for subsequent simulations of water and ion diffusion at these interfaces [5]. We will then report on MD simulations carried out to probe the effects of confinement and of the presence of the mineral surface on the diffusion of water and electrolyte ions in nanosized feldspar fractures [6]. Several properties of the mineral-water interface were varied, such as the fracture width, the ionic strength of the contacting solution, and the surface charge. Our calculations reveal a 2.0-2.5 nm interfacial region within which the diffusion properties of

  14. Isotherm And Kinetic Studies On The Electrosorption Of Uranyl Tricarbonate Complex [UO{sub 2}(CO{sub 3}){sub 3}]{sup 4-} From Aqueous Solutions By Activated Carbon Electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Ismail, Aznan Fazli; Yim, Man Sung [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of)

    2015-05-15

    Many types of adsorbent materials have been developed over the past 50 years, and the most recognizable is amidoxime based materials which is known to have high affinity in in chelating uranyl ions from seawater. However, the fabrication cost of amidoxime based materials was high which lead to high uranium extraction cost. In recent studies, use of porous carbon materials combined with the electrosorption technique was shown to have high selectivity for uranium separation from seawater. It is clear that the electrosorption capacity increase with the increasing of electrolyte concentration. The investigated activated carbon electrode still not reach the maximum adsorption capacity in the test condition. The morphology analysis confirmed that the fabricated activated carbon electrode has a porous structure, where BET analysis has revealed that the size of the pores can be categorized in mesopores region which is the optimum condition for electrosorption purposes. Other than that, the FT-IR analysis has enough evident that the molecular interaction of the activated carbon electrode involves the intermolecular interaction (physical crosslink/bonding) and stable for electrosorption application.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  17. Μethods of iron chelation therapy: a bibliographic review

    Directory of Open Access Journals (Sweden)

    Maria Agapiou

    2012-01-01

    Full Text Available "Iron Chelation Therapy" is a term used to describe the procedure of removing excess iron from the body, which is applied after a total of approximately 20 blood transfusions or when serum ferritin levels rise above 1000 ng/ml. Aim: The purpose of the present paper is a retrospective search in bibliography, concerning the methods of iron chelation treatment for patients with hemochromatosis owing to their undergoing multiple blood transfusions. Method: The methology followed, included the search for review and research studies, in electronic databases as well as scientific haematology journals, mostly regarding recent entries in greek and international bibliography. Results: According to the bibliography, chelation therapy compounds have significantly changed the patients' clinical features and have substantially improved their quality of life, along with their outcome over time. However, the level of patient compliance to treatment still remains the basic problem of iron chelation therapy. Conclusions: Even though the discovery of orally administered chelating agents can qualify as an auspicious accomplishment, research fields should cover a much wider spectrum, in order to improve the effectiveness of iron chelation treatment.

  18. Cage-like bifunctional chelators, copper-64 radiopharmaceuticals and PET imaging using the same

    Energy Technology Data Exchange (ETDEWEB)

    Conti, Peter S.; Cai, Hancheng; Li, Zibo; Liu, Shuanglong

    2016-08-02

    Disclosed is a class of versatile Sarcophagine based bifunctional chelators (BFCs) containing a hexa-aza cage for labeling with metals having either imaging, therapeutic or contrast applications radiolabeling and one or more linkers (A) and (B). The compounds have the general formula ##STR00001## where A is a functional group selected from group consisting of an amine, a carboxylic acid, an ester, a carbonyl, a thiol, an azide and an alkene, and B is a functional group selected from the group consisting of hydrogen, an amine, a carboxylic acid, and ester, a carbonyl, a thiol, an azide and an alkene. Also disclosed are conjugate of the BFC and a targeting moiety, which may be a peptide or antibody. Also disclosed are metal complexes of the BFC/targeting moiety conjugates that are useful as radiopharmaceuticals, imaging agents or contrast agents.

  19. Sodium dodecyl sulfate coated alumina modified with a new Schiff's base as a uranyl ion selective adsorbent

    International Nuclear Information System (INIS)

    A simple and selective method was used for the preconcentration and determination of uranium(VI) by solid-phase extraction (SPE). In this method, a column of alumina modified with sodium dodecyl sulfate (SDS) and a new Schiff's base ligand was prepared for the preconcentration of trace uranyl(VI) from water samples. The uranium(VI) was completely eluted with HCl 2 M and determined by a spectrophotometeric method with Arsenazo(III). The preconcentration steps were studied with regard to experimental parameters such as amount of extractant, type, volume and concentration of eluent, pH, flow rate of sample source and tolerance limit of diverse ions on the recovery of uranyl ion. A preconcentration factor more than 200 was achieved and the average recovery of uranyl(VI) was 99.5%. The relative standard deviation was 1.1% for 10 replicate determinations of uranyl(VI) ion in a solution with a concentration of 5 μg mL-1. This method was successfully used for the determination of spiked uranium in natural water samples.

  20. Treatment of uranyl nitrate and flouride solutions; Tratamiento de soluciones que contienen nitrato de uranilo y fluoruros

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigo Otero, A.; Rodrigo Vilaseca, F.; Morales Calvo, G.

    1977-07-01

    A theoretical study on the fluoride complexes contained in uranyl and aluminium solutions has been carried out. Likewise concentration limits and Duhring diagrams for those solutions have been experimentally established. As a result, the optimum operation conditions for concentration by evaporation in the treatment plant, have been deduced. (Author) 12 refs.

  1. Voltammetry of uranyl chloride in the LiCl - KCl eutectic; Voltammetrie du chlorure d'uranyle dans l'eutectique LiCl - KC1

    Energy Technology Data Exchange (ETDEWEB)

    Fondanaiche, J.C. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1965-07-01

    Spent UO{sub 2} - PuO{sub 2} fuels can be reprocessed in a molten salt media. Uranium dioxide can easily be dissolved as UO{sub 2}Cl{sub 2} in a molten salt bath using chlorine gas. A study of quantitative analysis of an uranyl chloride solution in the LiCl-KCl eutectic at 400 C has been performed here using voltammetry (a large area-graphite indicator electrode has been employed). The precision which is obtained is around 6 per cent for concentrations below 10{sup -2} M. Precision decreases slightly for more concentrated solutions. The study of polarization curves allowed to give a reduction mechanism for the UO{sub 2}{sup ++} ion. For dilute solutions, this reduction proceeds through the UO{sub 2}{sup +} ion. But interpretation of current-potential curves is made difficult by the dismutation reaction of the UO{sub 2} ion and by the fact that the surface of the indicator electrode is not renewed. (author) [French] Le traitement des combustibles a base d'oxydes (UO{sub 2} - PUO{sub 2}) peut etre effectue au moyen des sels fondus. Le bioxyde d'uranium passe aisement en solution sous forme de UO{sub 2}Cl{sub 2} dans un bain de sels fondus par action du chlore. Nous avons etudie ici l'analyse quantitative d'une solution de chlorure d'uranyle dans l'eutectique LiCl - KCl a 400 C par voltammetrie (electrode indicatrice de graphite d'assez grande surface). La precision est d'environ 6 pour cent pour les concentrations inferieures a 10{sup -2} M; elle est legerement moins bonne pour les solutions plus concentrees. L'examen des courbes de polarisation a permis de donner un mecanisme de reduction de l'ion UO{sub 2}: pour les solutions diluees, cette reduction se fait par l'intermediaire de l'ion UO{sub 2}{sup +}. Mais l'interpretation des courbes intensite-potentiel est rendue delicate par la reaction de dismutation de l'ion UO{sub 2}{sup +} et par le fait que la surface de l'electrode indicatrice n

  2. THE STUDIES ON CHELATING FIBER V.ADSORPTION BEHAVIOR OF Au3+ ONTO CHELATING FIBER CONTAINING AMIDOXIME GROUPS

    Institute of Scientific and Technical Information of China (English)

    LINWeiping; LUYun; 等

    1992-01-01

    The adsorption behavior of ionic gold onto chelating fiber containing amidoxime groups was investigated. The chelating fiber presents high adsorption capacity for ionic gold Au3+(up to 626mg/g,when the content of amidoxime group reaches 7.59mmol/g),and possesses the ability to reduce the Au3+ into metallic gold,In the redox process,the amidoxime group is oxidized into carboxyl group.

  3. Monoclonal antibodies

    International Nuclear Information System (INIS)

    Monoclonal antibodies (MAbs) are antibodies having single specificity for a given antigen site (epitope). The development of hybridoma technology and the relative ease by which MAbs can be prepared has revolutionized many aspects of serological applications in diagnosis and differentiation of disease producing agents. The property of monospecificity offers advantages in diagnostic applications over polyclonal sera in that tests can be defined exactly with regard to the antigen detected and the affinity of reaction between the given antigenic site and the monoclonal reagent. In addition, MAbs offer better possibilities for test standardization, because the same reagent can be used in different laboratories. Such an MAb can be supplied by a central laboratory or 'grown' from hybridoma cells, ensuring that the resultant product is identical from laboratory to laboratory and that the part of the test involving the MAb reaction is the same. The methodologies for inoculation regimes, mice, cloning methods, selection of fusion partners, etc., have been validated extensively in developed country laboratories. The decision to establish a MAb production facility must be examined on a strict cost-benefit basis, since it is still expensive to produce a product. There are many MAbs available that should be sought to allow exploitation in developing tests. If a production facility is envisaged, it should produce reagents for national needs, i.e. there should be a clear problem oriented approach whereby exact needs are defined. In the field of veterinary applications, MAbs are the central reagent in many immunoassays based on the enzyme linked immunosorbent assay (ELISA). The development of specific tests for diagnosing diseases is dominated by MAbs and has been fuelled by a strong research base, mainly in developed countries allied to developing countries through the study of related diseases. Thus, there are very many assays dependent on MAbs, some of which form the basis of

  4. Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF α mediators

    Energy Technology Data Exchange (ETDEWEB)

    Orona, N.S. [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); Tasat, D.R., E-mail: deborah.tasat@unsam.edu.ar [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); School of Dentistry, University of Buenos Aires, M. T. de Alvear 2142 (1122), Buenos Aires (Argentina)

    2012-06-15

    Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO{sub 3} 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO{sub 3}. We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O{sub 2}{sup −}). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O{sub 2}{sup −} may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O{sub 2}{sup −} may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through

  5. Characterization of the effect of serum and chelating agents on Staphylococcus aureus biofilm formation; chelating agents augment biofilm formation through clumping factor B

    Science.gov (United States)

    Abraham, Nabil Mathew

    investigated the molecular basis of this phenomenon. Deletion and complementation analysis and thereafter antibody based inhibition assays confirmed a functional role for the surface adhesin clumping factor B as the causative determinant associated with the increased biofilm phenotype. Finally, we investigated the regulation of clumping factor B-mediated biofilm formation and the basis for the strain dependence. Regulation was determined to occur via two novel post-translational networks- one affecting ClfB activity, mediated by Ca2+ binding to the EF-Hand domain, and the other affecting protein stability, mediated by the enzymatic activity of the metalloprotease-aureolysin. Polymorphisms within the aureolysin gene sequence, between strains, was identified as the basis for some strains forming robust biofilms within chelated media versus other than do not exhibit this phenotype.

  6. Monoclonal antibodies.

    Science.gov (United States)

    2009-01-01

    The ability to produce and exploit monoclonal antibodies (mAbs) has revolutionized many areas of biological sciences. The unique property of an mAb is that it is a single species of immunoglobulin (IG) molecule. This means that the specificity of the interaction of the paratopes on the IG, with the epitopes on an antigenic target, is the same on every molecule. This property can be used to great benefit in immunoassays to provide tests of defined specificity and sensitivity, which improve the possibilities of standardization. The performance of assays can often be determined relating the actual weight of antibody (hence the number of molecules) to the activity. Often the production of an mAb against a specific epitope is the only way that biological entities can be differentiated. This chapter outlines the areas involving the development of assays based on mAbs. The problems involved address include the physical aspects of mAbs and how they may affect assay design and also the implications of results based on monospecific reagents. Often these are not fully understood, leading to assays that are less than satisfactory, which does not justify the relatively high cost of preparing and screening of mAbs. There are many textbooks and reviews dealing with the preparation of mAbs, the principles involved, and various purification and manipulative methods for the preparation of fragments and conjugation. There has been little general information attempting to summarize the best approaches to assay design using mAbs. Much time can be wasted through bad planning, and this is particularly relevant to mAbs. A proper understanding of some basic principles is essential. It is beyond the scope of this chapter to discuss all aspects, but major areas are highlighted. PMID:19219589

  7. Uranyl ion sorption mechanisms on titanium oxide: a multi-scale approach

    Energy Technology Data Exchange (ETDEWEB)

    Vandenborre, J.; Drot, R.; Simoni, E.; Dong, W.; Du, J. [Universite Paris XI, Institut de Physique Nucleaire, Batiment 100, 91406 Orsay cedex (France); Dossot, M.; Humbert, B.; Ehrhardt, J.J. [Laboratoire de Chimie Physique et Microbiologie pour l' Environnement, CNRS - Universite Nancy I, 54600 Villers-les-Nancy (France)

    2005-07-01

    Full text of publication follows: Radionuclides retention mechanisms onto mineral phases is of primary importance for nuclear waste management. The aim of the presented study is to demonstrate that it is possible to predict the retention properties of a methodological powdery substrate from the study of its natural crystallographic orientations. Among the radionuclides of interest, U(VI) can be seen as a model of the radionuclides oxo-cations. The substrate under study is the titanium oxide (TiO{sub 2}). In fact, rutile can be found as powder and also as manufactured single crystal which allows to study the retention processes on perfectly known crystallographic planes. Since the repartition of the different crystallographic orientations are known for the powder, the results obtained for the single crystals can directly be used to account for the powder retention properties. By using combined spectroscopic techniques such as TRLFS, XPS, DRIFT and SHG, it is possible to determine the nature of the reactive surface sites and also the surface species. XPS and TRLFS measurements allowed to determine that two same uranyl surface species were formed on titania (110) and (001). Only, the relative intensities of these species vary with the surface coverage. Atomic Force Microscopy was carried out to verify that no surface precipitation occurs for the higher surface coverages. Moreover, these analysis have also evidenced that the U(VI) sorption is homogeneous. These observations were corroborated by SHG experiments (mainly for (001)) which have also shown that the sorption occurs, in a first step, onto preferential surface symmetry axis. For rutile powder, the preferential crystallographic orientations are (110), (100) and (101) in the ratio 60/20/20. TRLFS and XPS experiments have shown that two uranyl surface species are formed whatever the pH value ranged from 1 to 5. The spectroscopic characteristics of these species are the same as the ones observed on (110) and (001

  8. Ab initio coordination chemistry for nickel chelation motifs.

    Science.gov (United States)

    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.

  9. Ab initio coordination chemistry for nickel chelation motifs.

    Directory of Open Access Journals (Sweden)

    R Jesu Jaya Sudan

    Full Text Available 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.

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

    Science.gov (United States)

    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

  11. Temperature effect on uranyl retention by phosphated substrates and strontium titanate

    Energy Technology Data Exchange (ETDEWEB)

    Almazan-Torres, G.; Finck, N.; Garcia, G.; Drot, R.; Simoni, E. [University Paris XI, Nuclear Physics Institute, Radiochemistry Group, 91406 Orsay (France); Charbonnel, M.C. [CEA Valrho, DRCP/SCPS/LCAM, 30207 Bagnols/ceze (France); Catalette, H. [Electricite de France, Development and Research, Les Renardieres, 77818 Moret-sur-Loing cedex (France)

    2005-07-01

    Full text of publication follows: The assessment of an underground disposal of nuclear wastes requires an accurate knowledge of all the processes involved in the solid/liquid interactions. Sorption/desorption phenomena are part of them and could enhance retardation of radio-toxic elements migration. Radionuclides sorption onto various mineral substrates was extensively studied at room temperature but the literature is very poor for higher temperatures more relevant for storage conditions (e.g. 360 K). The knowledge of thermodynamic values such as {delta}H is required to extrapolate room temperature data to higher temperatures but such a prediction implies to assume that the mechanisms remain the same. The goal of this study is to investigate the uranyl sorption mechanisms onto various minerals (Zr{sub 2}O(PO{sub 4}){sub 2}, ZrP{sub 2}O{sub 7} and SrTiO{sub 3}) for temperature ranged from 298 K to 363 K in order to check if the processes remain unchanged for the overall conditions. The powdery solids were synthesized to avoid impurities and characterized using XRD and IR spectroscopy. The specific surface area of all substrates is a few square-meters per gram. Classical batch experiments were performed for an initial uranyl concentration of 10{sup -4} M, in NaClO{sub 4} medium and for a solid-over-solution ratio equals 10 g.L{sup -1}. The systems were studied at room temperature and the retention mechanisms were perfectly defined. Potentiometric titrations of the three substrates were carried out to determine the acid-base behavior of the solid surfaces (pH{sub pzc}, acidity constants) together with a structural investigation of the uranyl surface species. This last point was achieved by performing X-ray photoelectron (XPS) and time-resolved laser-induced fluorescence (TRLIF) spectroscopies. Then, the reacting uranyl species as well as the active surface sites were identified for room temperature conditions which allows one to model the sorption edges on the basis

  12. Extraction of lanthanide(III) and uranyl(VI) from nitric acid solution by malonamides

    International Nuclear Information System (INIS)

    The extractive properties of two malonamide extractants, DMDBO3NPDA and DMDBMA were investigated for the extraction of lanthanide(III) and uranyl(VI) ions in benzene-nitric acid systems. It was found that DMDBO3NPDA has a higher extractive capacity than DMDBMA. The difference in their extracting capacities is discussed, based on the enthalpy changes for the extraction reactions and IR data for complexes of metal nitrates with malonamides. In addition, the applicability of a mixed solvent of n-dodecane and some aliphatic alcohols as a diluent for DMDBO3NPDA was examined. the longer the carbon chain and the higher the concentration of the aliphatic alcohol, the more the phase compatibility improves. The distribution ratios of neodymium(III) ion increase with an increase in the carbon chain length of linear aliphatic alcohol and with a decrease in its concentration

  13. Differential pulse voltametric determination of low level uranium in uranyl nitrate raffinate samples

    International Nuclear Information System (INIS)

    A differential pulse voltammetric method for the determination of uranium in uranyl nitrate raffinate samples of uranium oxide plant has been described. The sample aliquot is treated with concentrated sulphuric acid and diluted. Voltammogram of this sample is run between 0 to -450 mV in a linear sweep using a HMDE as working electrode, Pt auxiliary electrode and Ag/AgCl reference electrode. The peak current ip of the peak obtained at - 200±20 mV is proportional to the concentration of uranium present in raffinate. Amount of uranium in the sample is determined by standard addition. The values compared well with those obtained by potentiometry, spectrophotometry and wavelength dispersive x-ray fluorimetry. A precision of ±0.01gl-1 is obtained. (author)

  14. Development of the process for production of UO2 powder by atomization of uranyl nitrate

    International Nuclear Information System (INIS)

    A method of direct conversion of uranyl nitrate hexahydrate (UNH) solution to ceramic grade uranium dioxide powders by thermal denitration in a furnace that combines atomization nozzle and a gas stirred bed is described. The main purpose of this work is to show that this alternative process is technically viable, specially if the recovery of the scrap generated in the nuclear fuel pellet production is required, without further generation of new liquid wastes. The steps for the development of the denitration unit as well as the characteristics of the final powders are described. Powder production experiments have been carried out for different atomization gas pressures and furnace upper section temperatures. Determination of impurity content, specific surface area, particle size and pore size distribution, density, U content, and O/U rate of uranium dioxide powders have been done; phase identification and morphology studies have also been performed. Sintered pellets have been studied by hydrostatic density determination and microstructure analyses. (author)

  15. The extraction and effect in the system uranyl nitrate-dietyl ether-water

    International Nuclear Information System (INIS)

    The solute transfer of uranyl nitrate from diethyl ether to water has been studied in a spray column using water as dispersed phase and a direction of extraction from ether to water. The column is 102 cm long and has a diameter of 4,7 cm. The entrances of the phases are 77 cm apart. The rates of flow of both phases have been used as variables and the concentration of the continuous phase has been determined at different heights. The curves of logarithm of concentration of the continuous phase vs. distance to interphase show the present of a drop of concentration in the entrance of the continuous phase. This depends on the rates of flow of the phases. No effect in the entrance of the dispersed phase has been found. (Author) 20 refs

  16. The final effect of extraction system in the uranyl nitrate-water-diethyl ether

    International Nuclear Information System (INIS)

    The solute transfer of uranyl nitrate from diallylether to water has been studied in a spray column using water as dispersed phase and a direction of extraction from ether to water. The column is 102 cm. long has a diameter of 4. 7 cm. The entrances of the phases are 7 7 cm. apart. The rates of flow of both phases have been used as variables and the concentration of the continuous phase has been determined; at different heights. The curves of logarithm of concentration of the continuous phase vs , distance to interphase show the presence of a drop of concentration in the entrance of the continuous phase. This depends on the rates of flow of the phases. No effect in the entrance of the dispersed phase has been found. (Author)

  17. Fabrication of uranium dioxide of different granulation from uranyl nitrate by ammonia diuranate

    International Nuclear Information System (INIS)

    Uranium dioxide is most frequently produced by reduction of higher oxides (UO3, U3O8) or reduction of uranium salts (uranium diuranate, uranium peroxide, uranyl oxalate). Reduction is most frequently done in hydrogen or carbon monoxide atmosphere under temperatures from 500 - 1700 deg C. One of the most frequently methods for producing uranium oxide is certainly reduction of ammonia diuranate by hydrogen (ADU method). Properties of uranium dioxide obtained by ADU method depend on properties of the initial substance. Investigations shown in this report are concerned with determining the properties of UO2 powders for determining the connection between their properties and conditions of fabrication and reduction of ADU and U3O8

  18. The Influence of the Linker Geometry in Bis(3-hydroxy-N-methyl-pyridin-2-one) Ligands on Solution-Phase Uranyl Affinity

    Energy Technology Data Exchange (ETDEWEB)

    Szigethy, Geza; Raymond, Kenneth

    2010-08-12

    Seven water-soluble, tetradentate bis(3-hydroxy-N-methyl-pyridin-2-one) (bis-Me-3,2-HOPO) ligands were synthesized that vary only in linker geometry and rigidity. Solution phase thermodynamic measurements were conducted between pH 1.6 and pH 9.0 to determine the effects of these variations on proton and uranyl cation affinity. Proton affinity decreases by introduction of the solubilizing triethylene glycol group as compared to un-substituted reference ligands. Uranyl affinity was found to follow no discernable trends with incremental geometric modification. The butyl-linked 4Li-Me-3,2-HOPO ligand exhibited the highest uranyl affinity, consistent with prior in vivo decorporation results. Of the rigidly-linked ligands, the o-phenylene linker imparted the best uranyl affinity to the bis-Me-3,2-HOPO ligand platform.

  19. Analysis of uranyl in solution through the formation of luminescent complexes; Analisis de uranilo en solucion mediante la formacion de complejos luminiscentes

    Energy Technology Data Exchange (ETDEWEB)

    Garcia G, N.; Ordonez R, E.; Barrera D, C.E. [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)

    2008-07-01

    The luminescence is one of the techniques used to determine the speciation of those complex that forms the uranyl in the solid-liquid interphase of distinct zirconium phosphates, also has the advantage that it allows to carry out its quantification at mid of high ion forces, because it has been demonstrated that this detection technique and quantification is reliable and sufficiently quick in the obtaining of results. For it that in this work, the quantification of the uranyl is presented by means of a luminescent complex with the aim of phosphates that avoid the fluorescence signal extinction, then the uranyl ion is very sensitive to the medium that contains it (pH, ion force, concentration, etc.) for what was necessary to establish the analysis conditions of the uranyl ion without signal lost, in inferior concentrations to 1X10{sup -3} M at mid of sodium perchlorate 0.5 M. (Author)

  20. Method and apparatus for producing uranyl peroxide (UO/sub 4/ . 2H/sub 2/O) from uranium and uranium alloy pieces

    International Nuclear Information System (INIS)

    This patent describes a method of producing uranyl peroxide (UF/sub 4/ . 2H/sub 2/O) from uranium-bearing metal pieces comprising: dissolving the uranium-bearing metal pieces in a first aqueous solution containing nitric acid and at least 0.5% but no more than 2.0% fluoboric acid to provide a second aqueous solution which includes uranyl ions (UO/sub 2//sup +2/) and nitric and fluoboric acids; adding hydrogen peroxide to the second aqueous solution to precipitate uranyl peroxide out of the second solution and provide a third aqueous solution containing nitric and fluoboric acid; and separating the uranyl peroxide from the third aqueous solution

  1. Comprehensive analysis of the renal transcriptional response to acute uranyl nitrate exposure

    Directory of Open Access Journals (Sweden)

    Argiles Angel

    2006-01-01

    Full Text Available Abstract Background Chemical and radiological toxicities related to uranium acute exposure have been widely studied in nuclear fuel workers and military personnel. It is well known that uranyl nitrate induces acute renal failure (ARF. However, the mechanisms of this metal-induced injury are not well defined at the molecular level. Results Renal function and histology were assessed in mice receiving uranyl nitrate (UN(+ and controls (UN(-. To identify the genomic response to uranium exposure, serial analysis gene expression (SAGE of the kidney was performed in both groups. Over 43,000 mRNA SAGE tags were sequenced. A selection of the differentially expressed transcripts was confirmed by real-time quantitative PCR and Western blotting. UN(+ animals developed renal failure and displayed the characteristic histological lesions of UN nephropathy. Of the >14,500 unique tags identified in both libraries, 224 had a modified expression level; they are known to participate in inflammation, ion transport, signal transduction, oxidative stress, apoptosis, metabolism, and catabolism. Several genes that were identified had not previously been evaluated within the context of toxic ARF such as translationally controlled tumor protein, insulin like growth factor binding protein 7 and ribosomal protein S29, all apoptosis related genes. Conclusion We report a comprehensive description of the UN induced modifications in gene expression levels, including the identification of genes previously unrelated to ARF. The study of these genes and the metabolisms they control should improve our understanding of toxic ARF and enlighten on the molecular targets for potential therapeutic interventions.

  2. The Key Role of U28 in the Aqueous Self-Assembly of Uranyl Peroxide Nanocages.

    Science.gov (United States)

    Falaise, Clément; Nyman, May

    2016-10-01

    For 11 years now, the structural diversity and aesthetic beauty of uranyl-peroxide capsules have fascinated researchers from the diverse fields of mineralogy, polyoxometalate chemistry, and nuclear fuel technologies. There is still much to be learned about the mechanisms of the self-assembly process, and the role of solution parameters including pH, alkali template, temperature, time, and others. Here we have exploited the high solubility of the UO2 (2+) /H2 O2 /LiOH aqueous system to address the effect of the hydroxide concentration. Important techniques of this study are single-crystal X-ray diffraction, small-angle X-ray scattering, and Raman spectroscopy. Three key phases dominate the solution speciation as a function of time and the LiOH/UO2 (2+) ratio: the uranyl-triperoxide monomer [UO2 (O2 )3 ](4-) and the two capsules [(UO2 )(O2 )(OH)]24 (24-) (U24 ) and [(UO2 )(O2 )1.5 ]28 (28-) (U28 ). When the LiOH/U ratio is around three, U28 forms rapidly and this cluster can be isolated in high yield and purity. This result was most surprising and challenges the hypothesis that alkali templating is the most important determinant in the cluster geometry. Moreover, analogous experiments with KOH, NH4 OH, and TEAOH (TEA=tetraethylammonium) also rapidly yield U28 , which suggests that U28 is the kinetically favored species. Complete mapping of the pH-time phase space reveals only a narrow window of the U28 dominance, which is why it was previously overlooked as an important kinetic species in this chemical system, as well as others with different counterions. PMID:27539640

  3. Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium

    International Nuclear Information System (INIS)

    The extraction properties of octa-phosphinoylated para-tert butyl calix[8]arene (prepared in the laboratory) in chloroform towards uranyl ions from an aqueous-acidic-salty medium (HNO3-3.5 NaNO3) containing uranyl nitrate salt, was investigated. Two spectroscopic techniques UV/Vis and Luminescence were used for this study. The latter permitted analyze the fluorescence from the uranyl ions influenced by the surrounding medium. Both permitted to learn about the power of this calixarene as extractant towards the mentioned ions. Its extraction ability or capability using this calixarene at 5.91 x 10-4 M towards the uranyl ions was 400% as determined by UV/Vis while fluorescence revealed 100% of uranyl ion extraction. A closed analysis of the results obtained by using these techniques revealed that the stoichiometry of the main extracted species was 1calixarene:2 uranyl ions. The loading capacity of the calixarene ligand towards the uranyl ions was also investigated using both techniques. UV/Vis resulted to be inadequate for quantifying exactly the loading capacity of the calixarene whereas luminescence was excellent indeed, using a 5.91 x 10-4 M calixarene concentration, its loading capacity was 0.157 M of free uranyl ions from 0.161 M of uranyl ions present in the aqueous-acidic-salty medium. The extracts from the ability and capacity studies were concentrated to dryness, purified and the dried extracts were analyzed by infrared and neutron activation analysis. By these techniques it was demonstrated that during the extraction of the uranyl ions by the calixarene ligand they form thermodynamically and kinetically stable complexes, since in the solid state, the 1:2, calixarene; uranyl ions stoichiometry was kept with the minimum formula: (UO2)2B8bL8(NO3)4(H2O)4CHCl3(CH3OH)3 the methanol molecules come from its purification. It is proposed that B8bL8 calixarene in chloroform medium is a good extractant for the treatment of nuclear wastes or radioactive wastes containing

  4. Theoretical first step towards an understanding of the uranyl ion sorption on the rutile TiO{sub 2}(110) face. A DFT periodic and cluster study

    Energy Technology Data Exchange (ETDEWEB)

    Perron, H. [Univ. Paris XI, Inst. de Physique Nucleaire, Orsay (France); EDF-R and D, Dept. Materiaux et Mecanique des Composants, Les Renardieres, Ecuelles (France); Domain, C.; Catalette, H. [EDF-R and D, Dept. Materiaux et Mecanique des Composants, Les Renardieres, Ecuelles (France); Roques, J.; Drot, R.; Simoni, E. [Univ. Paris XI, Inst. de Physique Nucleaire, Orsay (France)

    2006-07-01

    First results of a periodic and cluster density functional theory (DFT) study of the uranyl ion (UO{sub 2}{sup 2+}) sorption onto the rutile TiO{sub 2}(110) face, based on plane wave and localised basis sets, are presented. A five layers slab with its most internal layer frozen to bulk positions was found to be a good surface model. In a first step and as reference data for the sorption process, the [UO{sub 2}(H{sub 2}O){sub n}]{sup 2+} systems, with n = 4 to 6 were studied. Relative solvation energies confirmed that the uranyl ion adopt a pentacoordinated structure in aqueous solution. From localised approach, an overall 0.91 electron transfer from the first hydration shell to the uranyl ion was calculated. Then, a periodic study of the uranyl sorption on a simplified hydroxylated TiO{sub 2}(110) surface model was investigated. The resulting optimised structural parameters, for the three possible adsorption sites, show that the sorbed uranyl ion first coordination shell (saturated by three water molecules) plays an important role to model the adsorption process. Both methodologies (plane waves and localised atomic orbitals) were also used with a cluster model and gave similar results in agreement with experimental data. This first step in the understanding of the uranyl ion sorption onto the simplified hydroxylated TiO{sub 2}(110) surface shows that hydrogen bonds should be included in the model in order to perform a more accurate description of the uranyl ion sorption process. A study with this surface model is currently performed in order to calculate the relative stabilities between the different uranyl adsorption sites and to compare with the experimental data. (orig.)

  5. Electron-Transfer Oxidation of Chlorophenols by Uranyl Ion Excited State in Aqueous Solution. Steady-State and Nanosecond Flash Photolysis Studies

    OpenAIRE

    Sarakha, Mohamed; Bolte, Michèle; Burrows, Hugh D.

    2000-01-01

    The oxidation of chlorophenols by photoexcited uranyl ion was studied in aqueous solution at concentrations where the ground-state interactions were negligible. Nanosecond flash photolysis showed that a clean electron-transfer process from the chlorophenols to the excited uranyl ion is involved. This is suggested to lead to the formation of a U(V)/chlorophenoxyl radical pair complex. The efficiency of this charge-transfer process is unity for the three chlorophenols. However, low product yiel...

  6. Synthesis and Characteristics of A Novel Heavy Metal Ions Chelator

    Institute of Scientific and Technical Information of China (English)

    LIU Zhuannian; SONG Yejing; HAN Xiaogang

    2012-01-01

    Polyacrylamide-urea-sulfanilamide(PUS) was prepared as a novel heavy metal ions chelator and successfully used to simultaneously remove heavy metals from wastewater effluents.The effects of reaction parameters (sodium hydroxide,material ratio,temprature and contact time) were monitored to specify the best synthesis conditions.PUS was chemically characterized by means of infrared spectroscopy (FTIR) and ultraviolet-visible (UV-Vis).The simultaneous chelation performance of PUS towards selected heavy metals ions,Ni2+,Cu2+,Pb2+,Zn2+,Cd2+ was discussed,showing that Ni2+,Cu2+,Pb2+,Zn2+ could be better chelated.It is indicated that the synthesized PUS is a potential remediation material when used for the treatment of wastewater containing metal ions.

  7. Antioxidant, Free Radical Scavenging and Metal Chelating Characteristics of Propolis

    Directory of Open Access Journals (Sweden)

    Hikmet Geckil

    2005-01-01

    Full Text Available This study was undertaken to determine the reducing characteristics, metal chelating capability, anti-lipid peroxidative and antiradical properties of propolis compared to two widely used artificial antioxidants, Butylated Hydroxyanisole (BHA and Butylated Hydroxytoluene (BHT. The water and ethanol extracts of propolis showed significantly a different degree of metal chelating, radical scavenging activity and reducing power. In general, ethanol extracts of propolis showed higher activity regarding these parameters. Synthetic antioxidants showed better activities than both propolis extracts for antioxidant properties, utilizing a -carotene bleaching method. At higher concentrations, the reducing power of ethanol extract of propolis was similar to that of artificial antioxidants. The metal chelating activity of both water and ethanol extracts of propolis was comparable to that of EDTA and significantly higher than both BHA and BHT.

  8. Inositol hexa-phosphate: a potential chelating agent for uranium

    Energy Technology Data Exchange (ETDEWEB)

    Cebrian, D.; Tapia, A.; Real, A.; Morcillo, M.A. [Radiobiology Laboratory, Radiation Dosimetry Unit, Department of Environment, CIEMAT, Avda Complutense 22, 28040 Madrid (Spain)

    2007-07-01

    Chelation therapy is an optimal method to reduce the radionuclide-related risks. In the case of uranium incorporation, the treatment of choice is so far i.v infusion of a 1.4% sodium bicarbonate solution, but the efficacy has been proved to be not very high. In this study, we examine the efficacy of some substances: bicarbonate, citrate, diethylenetriamine pentaacetic acid (DTPA), ethidronate (EHBP) and inositol hexa-phosphate (phytic acid) to chelate uranium using a test developed by Braun et al. Different concentrations of phytic acid, an abundant component of plant seeds that is widely distributed in animal cells and tissues in substantial levels, were tested and compared to the same concentrations of sodium citrate, bicarbonate, EHBP and DTPA. The results showed a strong affinity of inositol hexa-phosphate for uranium, suggesting that it could be an effective chelating agent for uranium in vivo. (authors)

  9. Inositol hexa-phosphate: a potential chelating agent for uranium

    International Nuclear Information System (INIS)

    Chelation therapy is an optimal method to reduce the radionuclide-related risks. In the case of uranium incorporation, the treatment of choice is so far i.v infusion of a 1.4% sodium bicarbonate solution, but the efficacy has been proved to be not very high. In this study, we examine the efficacy of some substances: bicarbonate, citrate, diethylenetriamine pentaacetic acid (DTPA), ethidronate (EHBP) and inositol hexa-phosphate (phytic acid) to chelate uranium using a test developed by Braun et al. Different concentrations of phytic acid, an abundant component of plant seeds that is widely distributed in animal cells and tissues in substantial levels, were tested and compared to the same concentrations of sodium citrate, bicarbonate, EHBP and DTPA. The results showed a strong affinity of inositol hexa-phosphate for uranium, suggesting that it could be an effective chelating agent for uranium in vivo. (authors)

  10. Timing of early chelating therapy for acute uranium intoxication

    International Nuclear Information System (INIS)

    Rats were treated with DTPA and H-73-10 intraperitoneal injections 15 minutes to 4 days after acute uranium intoxication. The mortality and changes in body weight, kidney weight, renal histology and histochemistry were investigated. The results show that the renal damage could be diminished significantly by chelating therapy started 15 minutes and 6 hours after urnium poisoning. Single large dose injection (1 g/kg weight) of H-73-10 yielded the best result, and daily 0.5 g/kg of H-73-10 injection for 5 days is the next, both are better than single injection of DTPA (1 g/kg body weight). One day after intoxication there was still some protective effect. On the contrary, if the chelating therapy started 2-4 days after urnium poisoning it would increase the renal damage and the mortality. This is of great value to the correct selection of timing of chelating therapy for uranium intoxication

  11. [Antinuclear antibodies].

    Science.gov (United States)

    Cabiedes, Javier; Núñez-Álvarez, Carlos A

    2010-01-01

    Anti-nuclear antibodies (ANA) are immunoglobulin directed against autologous cell nuclear and cytoplasmic components. Besides the autoimmune ANA there are other ANA that can be detected in circulation, like natural and infectious ANA. Because of its high sensibility, detection of the ANA must be done by indirect immunofluorescence (IIF) as screening test and all of those positive samples are convenient to confirm its specificity by ELISA, western blot or other techniques. Positive ANA detected by IIF must be evaluated taking in to account the pattern and titer. The following recommended step is the specificity characterization (reactivity against extractable nuclear antigens [ENA], dsDNA, etc.) which is useful for the diagnosis and follow up of patients with autoimmune diseases, and by such reasoning, its detection must be performed in an orderly and reasonable way using guides or strategies focused to the good use and interpretation of the autoantibodies. The objective of this review is to present a compilation of the literature and our experience in the detection and study of the ANA.

  12. Clinical monitoring and management of complications related to chelation therapy in patients with β-thalassemia.

    Science.gov (United States)

    Saliba, Antoine N; El Rassi, Fuad; Taher, Ali T

    2016-01-01

    Iron chelating agents - deferoxamine (DFO), deferiprone (DFP), and deferasirox (DFX) - are used to treat chronic iron overload in patients with β-thalassemia in an attempt to reduce morbidity and mortality related to siderosis. Each of the approved iron chelating agents has its own advantages over the others and also has its own risks, whether related to over-chelation or not. In this review, we briefly discuss the methods to monitor the efficacy of iron chelation therapy (ICT) and the evidence behind the use of each iron chelating agent. We also portray the risks and complications associated with each iron chelating agent and recommend strategies to manage adverse events. PMID:26613264

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

    Science.gov (United States)

    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...

  14. Efficacy of chelation therapy to remove aluminium intoxication.

    Science.gov (United States)

    Fulgenzi, Alessandro; De Giuseppe, Rachele; Bamonti, Fabrizia; Vietti, Daniele; Ferrero, Maria Elena

    2015-11-01

    There is a distinct correlation between aluminium (Al) intoxication and neurodegenerative diseases (ND). We demonstrated how patients affected by ND showing Al intoxication benefit from short-term treatment with calcium disodium ethylene diamine tetraacetic acid (EDTA) (chelation therapy). Such therapy further improved through daily treatment with the antioxidant Cellfood. In the present study we examined the efficacy of long-term treatment, using both EDTA and Cellfood. Slow intravenous treatment with the chelating agent EDTA (2 g/10 mL diluted in 500 mL physiological saline administered in 2 h) (chelation test) removed Al, which was detected (using inductively coupled plasma mass spectrometry) in urine samples collected from patients over 12 h. Patients that revealed Al intoxication (expressed in μg per g creatinine) underwent EDTA chelation therapy once a week for ten weeks, then once every two weeks for a further six or twelve months. At the end of treatment (a total of 22 or 34 chelation therapies, respectively), associated with daily assumption of Cellfood, Al levels in the urine samples were analysed. In addition, the following blood parameters were determined: homocysteine, vitamin B12, and folate, as well as the oxidative status e.g. reactive oxygen species (ROS), total antioxidant capacity (TAC), oxidized LDL (oxLDL), and glutathione. Our results showed that Al intoxication reduced significantly following EDTA and Cellfood treatment, and clinical symptoms improved. After treatment, ROS, oxLDL, and homocysteine decreased significantly, whereas vitamin B12, folate and TAC improved significantly. In conclusion, our data show the efficacy of chelation therapy associated with Cellfood in subjects affected by Al intoxication who have developed ND.

  15. Chelation of heavy metals by potassium butyl dithiophosphate

    Institute of Scientific and Technical Information of China (English)

    Ying Xu; Zhigang Xie; Lu Xue

    2011-01-01

    Potassium butyl dithiophosphate (PBD) was developed and introduced as a new chelating agent for heavy metal removal.The synthesized PBD were characterized by IR and NMR.The effects of pH, chelating agent dosage, and other heavy metal ions on the performance of PBD in Cd2+ removal from water are investigated.Experimental results showed that the chelating agent could be used to treat acidic heavy metal wastewater.The Cd2+ removal was not affected by solution pH value within the range of 2 to 6.The Cd2+ removal rate could reach over 99%.Therefore, the deficiency of the precipitation process using hydroxide under alkaline condition can be overcome.Without the need for pH adjustment, the method could save on costs.If Cd2+ co-exists with Pb2+ and Cu2+, the affinity of the chelating agent with these three heavy metal ions was in the order of: Cu2+ > Pb2+ > Cd2+.Through PBD chelating precipitation,all the contents of Pb2+, Cd2+, and Cu2+ in wastewater met the standard levels through a one-step treatment.The one-step treatment process was superior to the process (sectional treatment is required) of precipitation with hydroxide.When the pH was between 3 and 11, the amount of leached chelated Cd2+ was much lower than that obtained by precipitation with hydroxide.Therefore, the risk of environmental pollution could be further reduced.

  16. Sorption of uranyl(VI) cations on suspended silicate: effects of N-donor ligands, carboxylic acids, organic cosolvents, and metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Pathak, P.N.; Choppin, G.R. [Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry

    2007-07-01

    Sorption of uranyl ion, UO{sub 2}{sup 2+}, on silicate particles (3.00g/L) was studied in sodium perchlorate solution as a function of pcH and ionic strength at 298 K. The effects of different ligands (e.g., N-donors, carboxylic acids) on the uranyl sorption were investigated. At I = 0.20 M (NaClO{sub 4}), uranyl sorption on silicate increased from ca. 6% (pcH 3.0) to ca. 99% (at pcH 6.5), above which a small decrease was observed. A synergistic enhancement in uranyl sorption was observed in the presence of N-donor ligands such as 1,10-phenanthroline and ethylenediamine in the pcH range 3 to 4.5 as compared to that in the absence of ligands. Carboxylic acids inhibited the sorption in the order: citric acid > malonic acid > nitrilotriacetic acid > iminodiacetic acid > sulfosalicylic acid > succinic acid > glycolic acid. The presence of organic cosolvents such as dimethylsulfoxide, glycerol and tetrahydrofuran had no significant influence on the uranyl sorption profile. Uranyl sorption decreased marginally in the presence of 1.00 x 10{sup -3} M Eu(III). (orig.)

  17. Surface modified magnetic Fe{sub 3}O{sub 4} nanoparticles as a selective sorbent for solid phase extraction of uranyl ions from water samples

    Energy Technology Data Exchange (ETDEWEB)

    Sadeghi, Susan, E-mail: ssadeghi@birjand.ac.ir [Department of Chemistry, Faculty of Science, University of Birjand, P.O. Box. 97175/615, Birjand (Iran, Islamic Republic of); Azhdari, Hoda [Department of Chemistry, Faculty of Science, University of Birjand, P.O. Box. 97175/615, Birjand (Iran, Islamic Republic of); Arabi, Hadi [Magnetism and Superconducting Research Lab, Department of Physics, Faculty of Science, University of Birjand, P.O. Box. 97175/615, Birjand (Iran, Islamic Republic of); Moghaddam, Ali Zeraatkar [Department of Chemistry, Faculty of Science, University of Birjand, P.O. Box. 97175/615, Birjand (Iran, Islamic Republic of)

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer A new sorbent based on functionalized magnetite nanoparticles with quercetin is reported. Black-Right-Pointing-Pointer The quercetin based magnetic nanoparticles could be used as a sorbent to remove toxic uranyl ions from water samples. Black-Right-Pointing-Pointer The sorbent provides a rapidly and easy separation of uranyl ions only by using a permanent magnet. Black-Right-Pointing-Pointer This technique is considered more efficient separation compared to conventional filtering or centrifuging methods for the removing of the sorbent. - Abstract: In this study, silica-coated magnetic nanoparticles modified with quercetin were synthesized by a sol-gel method. These magnetic nanoparticles were assessed as a new solid phase sorbent for extraction of uranyl ions from aqueous solutions. The crystal and chemical structures and magnetic property of the new sorbent were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectrophotometer (FT-IR), and vibration sample magnetometer (VSM). The experimental parameters affecting the extraction efficiency of uranyl ions from aqueous solutions using the synthesized sorbent were optimized by means of the response surface methodology. The adsorption equilibrium of uranyl ions onto the sorbent was explained by Langmuir isotherm and maximum monolayer adsorption capacity was found 12.33 mg/g. The synthesized sorbent was applied to extraction of uranyl ions from different water samples.

  18. Effect of the temperature and oxalic acid in the uranyl sorption in zircon; Efecto de la temperatura y acido oxalico en la sorcion de uranilo en circon

    Energy Technology Data Exchange (ETDEWEB)

    Ordonez R, E.; Almazan T, M. G.; Garcia G, N. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Hernandez O, R., E-mail: eduardo.ordonez@inin.gob.mx [Instituto Tecnologico de Veracruz, Ingenieria Quimica, Miguel Angel de Quevedo No. 2779, 91860 Veracruz (Mexico)

    2012-10-15

    In this work the results of the temperature effect study are presented on uranyl solutions adsorbed on zirconium silicate (ZrSiO{sub 4}) and also on the compounds formed in surface with oxalic acid. The adsorption isotherms of uranyl on hydrated zircon with NaClO{sub 4} 0.5 M, show an increase of the uranyl sorption efficiency when increasing the temperature from 20 to 4 C with a sudden descent in this efficiency when changing the temperature at 60 C. The uranyl sorption efficiency increases to hydrate the zircon with a solution of oxalic acid 0.1 M, maintaining the same tendency regarding to the temperatures of the sorption in medium NaClO{sub 4} 0.5 M. The complex formation in the zircon surface with organic acids of low molecular weight increases the fixation of the uranyl in solution due to the formation of ternary systems, in the order Zircon/A. Organic/Uranyl, without altering their response to the temperature. (Author)

  19. Structure-configurational entropy and its effect on the thermodynamic stability of uranyl phases: With special application for geological disposal of nuclear waste

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Spent UO2 fuel will rapidly be altered to U6+ phases in nuclear waste repositories. Because most uranyl phases are based on sheet or chain structures and usually contain several molecular water groups, site-mixing, vacancies, as well as disorder in the orientation of hydrogen bonds may occur. A systematic survey of the published crystallographic data for uranates, uranyl oxide hydrates, phosphates, silicates, carbonates, and sulfates demonstrates that site-mixing apparently occurs in the structures of at least 31 uranyl phases. Calculations of the ideal site-mixing entropy indicate that the residual contribution that arises from substitution and vacancies to the third-law entropies of some uranyl phases is large. A brief examination of the crystal chemistry of water molecules in uranyl phases suggests that considerable residual entropy may be caused by the disorder of hydrogen bonds associated with interstitial H2O groups. In the geochemical environment that expected to occur in the near-field of nuclear waste repositories, the existence of structure-configurational entropy may reduce the uranium concentration of several log units in solutions equilibrated with some uranyl phases. Therefore, compositional analysis and structural determinations must be made on the samples used in calorimetric measurements, and the calorimetric data must be combined with solubility data to evaluate the thermodynamic stability of the interested phases.

  20. Occurrence of an Octa-nuclear Motif of Uranyl Isophthalate with Cation-Cation Interactions through Edge-Sharing Connection Mode

    International Nuclear Information System (INIS)

    An uranyl isophthalate has been hydrothermally synthesized at 200 degrees C for 24 h, from a mixture of uranyl nitrate, isophthalic acid, and hydrazine in water. It was characterized by single-crystal analysis [triclinic, P1-bar a = 7.3934(3) Angstrom, b = 13.3296(5) Angstrom, = 15.4432(5) Angstrom, α = 111.865(2)degrees, β = 90.637(2)degrees, γ 104.867(2)degrees, V = 1355.49(9) Angstrom3] and different spectroscopic techniques (Raman, IR-ATR, UV visible), The 3D structure of the phase (UO2)8O2(OH)4(H2O)4(1,3-bdc)4.4H2O (1,3-bdc = 1,3-benzenedicarboxylate) reveals octa-nuclear units based on the association of 7-fold coordinated uranyl cations (pentagonal bipyramid) involving a rare case of cation cation interaction together with edge-sharing polyhedral connection mode. UV visible absorption spectroscopy confirmed that uranium was only involved in the structure as uranyl forms (excluding the assigning four uranyl presence of tetravalent or pentavalent uranium). Additionally, μ-Raman and IR-ATR experiments allowed contributions to the four types of uranyl entities in the structure, in agreement with the XRD analysis. (authors)

  1. Regularities in aluminium and indium chemisorption on chelating polymeric sorbents

    International Nuclear Information System (INIS)

    Complexation properties of synthesized polymer chelate sorbents: substituted of polystyrene-azo-pyrocatechol are investigated and correlations between pK'OH of functional groups of sorbents as well as pH50 values of chelation and constants of stability (lgKstab) are established for studying regularities of effect of structure and acid-base properties of functional groups of sorbents on the parameters of Al3+ and In3+ chemical sorption. Established correlations make it possible to predict the physicochemical parameters of sorbents and sorption of metal ions with the aim of separation and concentration of aluminium and indium micro account from the objects of different origin

  2. Development of radioactivity labelling method of new antibody by using the antibody engineering

    International Nuclear Information System (INIS)

    With an aim to develop a method to produce labelled antibodies with low immunogenicity, two recombinant fusion proteins; scFv-His and scFv-MTβ were produced using gene engineering techniques. The former was constructed with scFv-antibody and histidine hexamer, a metal-chelated protein (or peptide). The latter was done with scFv-antibody and β-domain of metallothionein. Then, antigen-binding activity and metal-binding activity of these fusion proteins were determined using gel-filtration chromatography and ELISA. The main antigen-binding activity of scFv-His preparation was detected in a domain of about 25-30 kDa, which agreed with the peak of 29 kDa corresponding to the presumed molecular weight for the protein. Whereas the antigen-binding activity of scFv-MTβ was found in a domain of 30-35 kDa, which agreed with 32 kDa, the presumed molecular weight of scFv-MTβ. Gel-filtration chromatography of scFv-His preparation after the addition of Cu2+ ion revealed an optical absorption at 280 nm and a Cu-peak near at 14 kDa. These results suggested that the metal affinity of the histidine-hexamer was too weak to chelate Cu2+ in a solution. The chromatography of scFv-MTβ preparation added with Cd2+ showed a peak of Cd appeared around a position of about 20 kDa but the peak was not coincident with that of the antigen-binding activity (ca. 30 kDa), suggesting that the present preparation of scFv-MTβ had no Cd-binding activity due to metal-exchange reaction. Based on these results, problems on the production of recombinant scFv-antibody fused with metal-binding domain of cystein-binding type or histidine-binding one were discussed. (M.N.)

  3. Mechanistic study of the interaction of uranyl ions with zirconium oxide and zirconium silicate; Etude mecanistique de l'interaction des ions uranyle avec l'oxyde et le silicate de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Lomenech, C

    2002-04-01

    This work deals with structural and thermodynamic studies of the sorption of uranyl species on zircon and zirconia. After determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, thermodynamic data were obtained using alpha spectrometry, for different uranyl concentrations, different background electrolytes (NaClO{sub 4} or KNO{sub 3}) and different ionic strengths. The structural identification of the surface complexes and sorption sites was carried out using several spectroscopies: XPS spectroscopy allowed a determination of the nature of the sorption sites ({identical_to}Zr-O- on zirconia and {identical_to}Si-O- on zircon). Whereas fluorescence decay measurements gave the number of surface species, the combined use of XPS spectroscopy and laser spectro-fluorimetry enabled us to correlate differences in bonding energies and emission wavelengths with differences in the nature of the background electrolyte or in the pH of sorption; DRIFT spectroscopy was a powerful tool for the determination of the presence of sorbed uranyl nitrate species. EXAFS results clearly showed a splitting of the equatorial oxygen atoms in two shells, corresponding to a polydentate, inner-sphere complex. EXAFS results also indicated strong similarities between dry samples and in situ experiments, which confirms the validity of all the spectroscopic measurements. Macroscopic thermodynamic data were then modeled using a surface complexation model (2 pK and constant capacitance models), the results of the structural study being used as constraints for the simulation code FITEQL. (author)

  4. A rapid, single vessel method for preparation of clinical grade ligand conjugated monoclonal antibodies

    International Nuclear Information System (INIS)

    A rapid, single vessel method for the preparation of clinical grade chelate conjugated monoclonal antibodies has been developed. By use of an Amicon concentrator with reservoir, each of the steps necessary for the preparation of the conjugated drug may be performed in a single vessel. Advantages include reduced risk of metal, pyrogen and bacterial contamination; buffer exchanges are achieved rapidly and efficiently using a continuous dilution method. The radiolabeling efficiency, the radiochemical purity, the total immunoreactivity and the affinity of the final product have been evaluated in the production of CHXA-DTPA-chelate conjugated HuM195. The characteristics compare favorably to those achieved using our conventional synthetic methods

  5. Preparation of U3O8 by calcination from ammonium uranyl carbonate in microwave fields: Process optimization

    International Nuclear Information System (INIS)

    Highlights: • The U3O8 was prepared first from ammonium uranyl carbonate using microwave. • A quadratic model was developed to optimize the process conditions. - Abstract: The effects of process conditions on preparation of U3O8 by calcination from ammonium uranyl carbonate in microwave fields were assessed and optimized for maximizing the total uranium as well as calcination temperature, adopting as Central Composite Design (CCD) methodology. The process variables assessed were calcination temperature, calcination duration and mass of sample. A quadratic model relating the process variables and the total amount of uranium and U3O8 was proposed eliminating the insignificant parameters. The optimal calcination conditions were estimated to be a calcination temperature of 942.75 K, calcination duration of 8.78 min, with the corresponding total uranium and U3O8 to be 82.07% and 31.33%, respectively

  6. Questions and Answers: The NIH Trial of EDTA Chelation Therapy for Coronary Heart Disease

    Science.gov (United States)

    ... NIH Trial of EDTA Chelation Therapy for Coronary Heart Disease Preliminary results from the Trial to Assess Chelation ... and complete it. Study Background What is coronary heart disease? Coronary heart disease (CHD) is the most common ...

  7. Iron chelating active packaging: Influence of competing ions and pH value on effectiveness of soluble and immobilized hydroxamate chelators.

    Science.gov (United States)

    Ogiwara, Yoshiko; Roman, Maxine J; Decker, Eric A; Goddard, Julie M

    2016-04-01

    Many packaged foods utilize synthetic chelators (e.g. ethylenediaminetetraacetic acid, EDTA) to inhibit iron-promoted oxidation or microbial growth which would result in quality loss. To address consumer demands for all natural products, we have previously developed a non-migratory iron chelating active packaging material by covalent immobilization of polyhydroxamate and demonstrated its efficacy in delaying lipid oxidation. Herein, we demonstrate the ability of this hydroxamate-functionalized iron chelating active packaging to retain iron chelating capacity; even in the presence of competing ions common in food. Both immobilized and soluble hydroxamate chelators retained iron chelating capacity in the presence of calcium, magnesium, and sodium competing ions, although at pH 5.0 the presence of calcium reduced immobilized hydroxamate iron chelation. A strong correlation was found between colorimetric and mass spectral analysis of iron chelation by the chelating packaging material. Such chelating active packaging may support reducing additive use in product formulations, while retaining quality and shelf life. PMID:26593563

  8. Iron chelating active packaging: Influence of competing ions and pH value on effectiveness of soluble and immobilized hydroxamate chelators.

    Science.gov (United States)

    Ogiwara, Yoshiko; Roman, Maxine J; Decker, Eric A; Goddard, Julie M

    2016-04-01

    Many packaged foods utilize synthetic chelators (e.g. ethylenediaminetetraacetic acid, EDTA) to inhibit iron-promoted oxidation or microbial growth which would result in quality loss. To address consumer demands for all natural products, we have previously developed a non-migratory iron chelating active packaging material by covalent immobilization of polyhydroxamate and demonstrated its efficacy in delaying lipid oxidation. Herein, we demonstrate the ability of this hydroxamate-functionalized iron chelating active packaging to retain iron chelating capacity; even in the presence of competing ions common in food. Both immobilized and soluble hydroxamate chelators retained iron chelating capacity in the presence of calcium, magnesium, and sodium competing ions, although at pH 5.0 the presence of calcium reduced immobilized hydroxamate iron chelation. A strong correlation was found between colorimetric and mass spectral analysis of iron chelation by the chelating packaging material. Such chelating active packaging may support reducing additive use in product formulations, while retaining quality and shelf life.

  9. Sequestration of zinc oxide by fimbrial designer chelators

    DEFF Research Database (Denmark)

    Kjærgaard, Kristian; Sørensen, Jack K; Schembri, Mark;

    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 x 10(7) independent clones was screened for binding to Zn...

  10. Laccase Immobilization by Chelated Metal Ion Coordination Chemistry

    Directory of Open Access Journals (Sweden)

    Qingqing Wang

    2014-09-01

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

  11. Iron chelator daphnetin against Pneumocystis carinii in vitro

    Institute of Scientific and Technical Information of China (English)

    叶彬; 郑玉强; 武卫华; 张静

    2004-01-01

    Background Although there are several drugs and drug combinations for the treatment of Pneumocystis carinii (P. carinii) pneumonia, all drugs have the toxicity as well as low efficacy. Iron chelators have been proposed as a source of new drugs for combating these infections. We hypothesized that iron chelators would suppress the growth of P. carinii by deprivation of the nutritional iron required for growth. In this study, a short-term axenic culture system of P. carinii was established. Daphnetin (7,8-dihydroxycoumarin), a known iron chelator, was demonstrated to exhibit in vitro activity against P. carinii in this system. Methods P. carinii organisms were obtained from the lungs of immunosuppressed rats. The culture system consisted of Iscove Dulbecco Eagle's Minimum Essential Medium (IMDM), supplemented with S-adenosyl-L-methionine, N-acetylglucosamine, putrescine, L-cysteine, L-glutamine, 2-mercaptoethanol, and fetal bovine serum, and was maintained at 37℃, in 5% CO2, 95% O2, at the optimal pH of 8.0. The culture system was used to assess the effect of daphnetin on the proliferation of P. carinii organisms. The ultrastructures of the treated organisms were observed by transmission electron microscopy.Conclusions Daphnetin can suppress the growth of P. carinii in vitro. The efficacy of daphnetin in suppressing the the growth of P. carinii in vitro is related to its ability to chelate iron.

  12. Reversal of haemochromatotic cardiomyopathy in beta thalassaemia by chelation therapy.

    OpenAIRE

    Politi, A; M. Sticca; Galli, M

    1995-01-01

    Haemochromatotic cardiomyopathy is the main cause of morbidity and mortality in patients with beta thalassaemia major. Once congestive heart failure develops most patients die in a few months. Congestive heart failure was reversed and echocardiographic findings were restored to normal in a 24 year old woman with beta thalassaemia who resumed treatment with chelation therapy (desferrioxamine).

  13. Synthesis and characterization of new ion-imprinted polymer for separation and preconcentration of uranyl (UO22+) ions

    International Nuclear Information System (INIS)

    UO22+ ion-imprinted polymer materials used for solid-phase extraction were prepared by copolymerization of a ternary complex of uranyl ions with styrene and divinyl benzene in the presence of 2,2'-azobisisobutyronitrile. The imprinted particles were leached by HCl 6 M. Various parameters in polymerization steps such as DVB/STY ratio, time of polymerization and temperature of polymerization were varied to achieve the most efficient uranyl-imprinted polymer. X-ray diffraction (XRD), infra-red spectroscopy (IR), thermo gravimetric analysis (TGA), UV-vis and nitrogen sorption were used to characterize the polymer particles. The XRD results showed that uranyl ions were completely removed from the polymer after leaching process. IR Analysis indicated that the N,N'-ethylenebis(pyridoxylideneiminato) remained intact in the polymer even after leaching. Some parameters such as pH, weight of the polymer, elution time, eluent volume and aqueous phase volume which affects the efficiency of the polymer were studied.

  14. Interaction of lanthanide cations and uranyl ion with the calcium/proton antiport system in Mycobacterium phlei.

    Science.gov (United States)

    Agarwal, N; Kalra, V K

    1983-01-19

    Uranyl ions (UO2+(2)) and lanthanide cations (La3+, Nd3+, Sm3+, Eu3+, Tb3+ and Dy3+) at 100-200 microM concentration inhibited active transport of Ca2+, mediated by respiratory linked substrates as well as by ATP hydrolysis, without affecting respiration and membrane-bound ATPase activity, in inside-out membrane vesicles of Mycobacterium phlei. The extent of inhibition in the uptake of Ca2+, mediated by ATP hydrolysis, increased with increase in ionic radii of these cations. Lanthanide cations did not dissipate the formation of a proton gradient, as measured by determining the effect either on the uptake of [14C]methylamine or energy-linked quenching of the fluorescence of 9-aminoacridine. However, uranyl ion (UO2+(2+)) caused reversal of the energy-linked quenching of 9-aminoacridine. UO2+(2)) concentration yielding 50% of Vmax (S0.5) was approx. 15 microM. Kinetic studies revealed that inhibition in the uptake of Ca2+ was competitive with UO2+(2) while non-competitive with rare-earth metals. It is proposed that inhibition in the uptake of Ca2+ by uranyl ion occurs as a result of UO2+(2) transport into the interior of vesicles in exchange for protons, while lanthanide cations are not being transported but affect the binding of Ca2+ to the membrane, presumably to the Ca2+/H+ antiporter. PMID:6838872

  15. Commentary on the Abuse of Metal Chelation Therapy in Patients with Autism Spectrum Disorders

    OpenAIRE

    Brent, Jeffrey

    2013-01-01

    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 ...

  16. Chelator induced phytoextraction and in situ soil washing of Cu

    International Nuclear Information System (INIS)

    In a soil column experiment, we investigated the effect of 5 mmol kg-1 soil addition of citric acid, ethylenediamine tetraacetate (EDTA), diethylenetriamine-pentaacetate (DTPA) and [S,S]-stereoisomer of ethylenediamine-disuccinate (EDDS) on phytoextraction of Cu from a vineyard soil with 162.6 mg kg-1 Cu, into the test plant Brassica rapa var. pekinensis. We also examined the use of a horizontal permeable barrier, composed of layers of nutrient enriched sawdust and apatite, for reduction of chelator induced Cu leaching. The addition of all chelators, except citric acid, enhanced Cu mobility and caused leaching of 19.5-23% of initial total Cu from the soil column. However, Cu plant uptake did not increase accordingly; the most effective was the EDDS treatment, in which plant Cu concentration reached 37.8±1.3 mg kg-1 Cu and increased by 3.3-times over the control treatment. The addition of none of the chelators in the concentration range from 5 to 15 mmol kg-1 exerted any toxic effect on respiratory soil microorganisms. When EDDS was applied into the columns with horizontal permeable barriers, only 0.53±0.32% of the initial total Cu was leached. Cu (36.7%) was washed from the 18 cm soil layer above the barrier and accumulated in the barrier. Our results indicate that rather than for a reduction of Cu leaching during rather ineffective chelate induced Cu phytoextraction, horizontal permeable barriers could be more effective in a new remediation technique of controlled in situ soil washing of Cu with biodegradable chelates

  17. Chelator induced phytoextraction and in situ soil washing of Cu

    Energy Technology Data Exchange (ETDEWEB)

    Kos, Bostjan; Lestan, Domen

    2004-11-01

    In a soil column experiment, we investigated the effect of 5 mmol kg{sup -1} soil addition of citric acid, ethylenediamine tetraacetate (EDTA), diethylenetriamine-pentaacetate (DTPA) and [S,S]-stereoisomer of ethylenediamine-disuccinate (EDDS) on phytoextraction of Cu from a vineyard soil with 162.6 mg kg{sup -1} Cu, into the test plant Brassica rapa var. pekinensis. We also examined the use of a horizontal permeable barrier, composed of layers of nutrient enriched sawdust and apatite, for reduction of chelator induced Cu leaching. The addition of all chelators, except citric acid, enhanced Cu mobility and caused leaching of 19.5-23% of initial total Cu from the soil column. However, Cu plant uptake did not increase accordingly; the most effective was the EDDS treatment, in which plant Cu concentration reached 37.8{+-}1.3 mg kg{sup -1} Cu and increased by 3.3-times over the control treatment. The addition of none of the chelators in the concentration range from 5 to 15 mmol kg{sup -1} exerted any toxic effect on respiratory soil microorganisms. When EDDS was applied into the columns with horizontal permeable barriers, only 0.53{+-}0.32% of the initial total Cu was leached. Cu (36.7%) was washed from the 18 cm soil layer above the barrier and accumulated in the barrier. Our results indicate that rather than for a reduction of Cu leaching during rather ineffective chelate induced Cu phytoextraction, horizontal permeable barriers could be more effective in a new remediation technique of controlled in situ soil washing of Cu with biodegradable chelates.

  18. Influence of pH on the sorption behaviour of uranyl ions in mesoporous MCM-41 and MCM-48 molecular sieves

    International Nuclear Information System (INIS)

    The sorption of uranyl ions in mesoporous MCM-41 and MCM-48 was accomplished with the help of a direct-template-exchange route, and the progress was monitored as a function of pH of the precursor uranyl nitrate solution. Under identical conditions of synthesis, around one and a half times larger amount of uranium was found to be sorbed in MCM-48 (∼12.5wt.%) as compared to MCM-41 (∼9.5wt.%). Further, the powder X-ray diffraction (XRD) data revealed that the expansion of unit cell parameters and broadening of reflections of the uranium containing samples depended on the pH of the precursor uranyl solution. Likewise, the Fourier transform infrared spectroscopy (FT-IR) studies showed a progressive decrease in the frequency of the axial OUO asymmetric stretching vibrational band, νa(UO) of the anchored uranyl groups with the increase of pH of the exchanging uranyl solution. The presence of two bands at ∼920 and 879cm-1 for uranyl exchanged samples prepared at pH > 5 indicated the presence of trinuclear (UO2)3(OH)5+ species. The occlusion of uranium thus depends upon the pore structure of the host material and the nature and dimension of the hydrolysis species formed at a particular pH of uranyl solution. Furthermore, the template-exchange of hexavalent uranium in MCM-41 and MCM-48 not only results in the formation of bulky hydrolysis species in the mesovoids, but also substitutes (isomorphously) in the silicate matrix resulting in the formation of UMCM-41 and UMCM-48

  19. Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions

    Energy Technology Data Exchange (ETDEWEB)

    Stewart, B.D.; Amos, R.T.; Nico, P.S.; Fendorf, S.

    2010-03-15

    Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl

  20. Hydrothermal Synthesis of Disulfide-Containing Uranyl Compounds. In Situ Ligand Synthesis versus Direct Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Rowland, Clare E. [George Washington Univ., Washington, DC (United States); Belai, Nebebech [George Washington Univ., Washington, DC (United States); Knope, Karah E. [George Washington Univ., Washington, DC (United States); Cahill, Christopher L. [George Washington Univ., Washington, DC (United States)

    2010-01-29

    Three disulfide-containing uranyl compounds, [UO2(C7H4O2S)3]·H2O (1), [UO2(C7H4O2S)2(C7H5O2S)] (2), and [UO2(C7H4O2S)4] (3) have been hydrothermally synthesized. Both in situ disulfide bond formation from 3- and 4-mercaptobenzoic acid (C7H5O2S, MBA) to yield 3,3'- and 4,4'-dithiobisbenzoic acid (C14H8O4S2, DTBA) and direct assembly with the presynthesized dimeric ligands have been explored. While the starting materials 4-MBA and 4,4'-DTBA both yield 2 via in situ ligand synthesis and direct assembly, respectively, we observe the formation of 1 from the starting material 3-MBA via in situ ligand synthesis and of 3 from the direct assembly of the uranyl cation with 3,3'-DTBA. Concurrently with the synthesis of 1 and 2, we have observed the in situ formation of the crystalline dimeric organic species, 3,3'-DTBA, [(C7H5O2S)2] (4) and 4,4'-DTBA, [(C7H5O2S)2] (5). Herein we report the synthesis and crystallographic characterization of 1-5, as well as observations regarding the utility of product formation via direct assembly and in situ ligand synthesis.

  1. Passage of TBP-uranyl complexes from aqueous-organic interface to the organic phase: insights from molecular dynamics simulation.

    Science.gov (United States)

    Sahu, Pooja; Ali, Sk Musharaf; Shenoy, Kalasanka Trivikram

    2016-08-24

    The present study reports molecular dynamics simulations for biphasic systems comprising tributyl phosphate (TBP) in dodecane and uranyl nitrate in the aqueous phase, which are key chemical species in the well-known Pu-U extraction (PUREX) process. An attempt has been made to understand the nature of interface and mechanism of 'TBP associated uranyl' crossing under neutral and acidic conditions. Results show that the solvent density undergoes large fluctuation near the interface depending on the nature of the aqueous-organic phase. The study provides compelling evidence of experimentally observed reorganization of interfacial complexes at the interface and their structural reformation during extraction. It has been observed that the surface active nature of TBP and their interfacial coverage is modulated by the nature of incorporated solute species and their location with respect to the interface. Also, the TBP structuring near the interface is destroyed when an acidic interface is considered rather than a neutral one which favors the uranyl extraction. With an acidic interface, the water humidity of organic phase was observed to be increased in the experiments. Furthermore, the acid/water solubility in the organic phase was observed to be influenced by selection of acid models and their concentration. Simulations with high acid concentration show water pocket formation in the organic phase. However, in the case of dissociated ions or a mixture of both, no such water pool is observed and the extracted water remains dispersed in the organic phase, having the tendency to be replaced by HNO3 because of preferred TBP·HNO3 complexation over TBP·H2O. Most remarkably, the present study makes evident the TBP-induced charge redistribution of uranyl complexes during migration from the interface to the bulk organic phase, which contributes to drive uranyl complexes such as UO2·NO3·4TBP, UO2·5TBP and UO2·NO3·3TBP·HNO3 in the organic phase, and this was reestablished by

  2. Examining the fixation kinetics of chelated and non-chelated copper and the applications to micronutrient management in semiarid alkaline soils

    Science.gov (United States)

    Udeigwe, T. K.; Eichmann, M. B.; Menkiti, M. C.; Kusi, N. Y. O.

    2016-02-01

    This study examined and compared the fixation and fixation kinetics of copper (Cu) in chelated (ethylene diamine tetraacetic acid, EDTA) and non-chelated mixed systems of micronutrients in the semiarid soils of the Southern High Plains, USA, using findings from Cu extraction studies and kinetic models. Approximately, 22 % more Cu was fixed in the non-chelated system compared to the chelated within the first 14 days with only 7 % difference between the two systems by day 90. Findings suggest a decrease in the effectiveness of chelated micronutrients over time, highlighting the significance of timing even when chelated micronutrients are used. The strengths of the relationship of change in available Cu with respect to other micronutrients (iron (Fe), manganese (Mn), and zinc (Zn)) were higher in the non-chelated system (R2: 0.68-0.94), compared to the chelated (R2: 0.42-0.81), with slopes of 0.40 (Cu-Fe), 0.31 (Cu-Mn), and 1.04 (Cu-Zn) in the non-chelated system and 0.26 (Cu-Fe), 0.22 (Cu-Mn), and 0.90 (Cu-Zn) in the chelated system. Reduction in the amount of available Cu was best described by the power function model (R2 = 0.91, SE = 0.081) in the non-chelated system and second-order model (R2 = 0.95, SE = 0.010) in the chelated system. The applications generated from this study could be used as tools for improved micronutrient management and also provide baseline data for future work in other semiarid/arid alkaline soils of the world. Findings are also more applicable to field settings, an improvement over related previous studies.

  3. Analysis of 99Mo Production Capacity in Uranyl Nitrate Aqueous Homogeneous Reactor using ORIGEN and MCNP

    International Nuclear Information System (INIS)

    99mTc is a very useful radioisotope in medical diagnostic procedure. 99mTc is produced from 99Mo decay. Currently, most of 99Mo is produced by irradiating 235U in the nuclear reactor. 99Mo mostly results from the fission reaction of 235U targets with a fission yield about 6.1%. A small additional amount is created from 98Mo neutron activation. Actually 99Mo is also created in the reactor fuel, but usually we do not extract it. The fuel will become spent fuel which is a highly radioactive waste. 99Mo production system in the aqueous homogeneous reactor offers a better method, because all of the 99Mo can be extracted from the fuel solution. Fresh reactor fuel solution consists of uranyl nitrate dissolved in water. There is no separation of target and fuel in an aqueous homogeneous reactor where target and fuel become one liquid solution, and there is no spent fuel generated from this reactor. Simulation of the extraction process is performed while reactor in operation (without reactor shutdown). With an extraction flow rate of 3.6 L/h, after 43 hours of reactor operation the production of 99Mo is relatively constant at about 98.6 curie/hour. (author)

  4. Solution chemistry for models of enterobactin and tannin with uranyl ion

    International Nuclear Information System (INIS)

    In order to develop optimum design of sequestering agents the solution chemistry for models of enterobactin such as Tiron [4,5-dihydroxy-5-benzendisulfonate], nCat[4-nitrocatechol],3,4,3-LICAMS [N1,N5,N10,N14-tetra(2,3-dihydroxy-5-sulfobenzoyl)-tetraazatetradecane] with UO22+ has been investigated. Tannin, which is a polyphenol and inexpensive substance, may probably be used in separation science of nuclear industry. Therefore, the solution chemistry of Tannin with uranyl ion has also been studied. The behaviour of solution chemistry, including eight systems--Tiron and Tiron-U(VI) nCat and nCat-U(VI),3,4,3-LICAMS and 3,4,3-LICAMS-U(VI) as well as Tannin and Tannin-U(VI), has been examined by pH-spectrophotometrc titration method. These experiments have established that U(VI) complexes with these ligands via phenolic groups. This work has offered important data for the design of actinide-specific sequestering agents

  5. Critical Parameters of Complex Geometries of Intersecting Cylinders Containing Uranyl Nitrate Solution

    Energy Technology Data Exchange (ETDEWEB)

    J. B. Briggs (INEEL POC); R. E. Rothe

    1999-06-14

    About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a ''tree'') having long, thin arms (or ''branches'') extending up to four directions off the column. Arms are equally spaced from one another in vertical planes, and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves with each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year.

  6. Analysis of 99Mo Production Capacity in Uranyl Nitrate Aqueous Homogeneous Reactor using ORIGEN and MCNP

    Directory of Open Access Journals (Sweden)

    A. Isnaeni

    2014-04-01

    Full Text Available 99mTc is a very useful radioisotope in medical diagnostic procedure. 99mTc is produced from 99Mo decay. Currently, most of 99Mo is produced by irradiating 235U in the nuclear reactor. 99Mo mostly results from the fission reaction of 235U targets with a fission yield about 6.1%. A small additional amount is created from 98Mo neutron activation. Actually 99Mo is also created in the reactor fuel, but usually we do not extract it. The fuel will become spent fuel which is a highly radioactive waste. 99Mo production system in the aqueous homogeneous reactor offers a better method, because all of the 99Mo can be extracted from the fuel solution. Fresh reactor fuel solution consists of uranyl nitrate dissolved in water. There is no separation of target and fuel in an aqueous homogeneous reactor where target and fuel become one liquid solution, and there is no spent fuel generated from this reactor. Simulation of the extraction process is performed while reactor in operation (without reactor shutdown. With an extraction flow rate of 3.6 L/h, after 43 hours of reactor operation the production of 99Mo is relatively constant at about 98.6 curie/hour

  7. Improvement of the cloud point extraction of uranyl ions by the addition of ionic liquids.

    Science.gov (United States)

    Gao, Song; Sun, Taoxiang; Chen, Qingde; Shen, Xinghai

    2013-12-15

    The cloud point extraction (CPE) of uranyl ions by different kinds of extractants in Triton X-114 (TX-114) micellar solution was investigated upon the addition of ionic liquids (ILs) with various anions, i.e., bromide (Br(-)), tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)) and bis[(trifluoromethyl)sulfonyl]imide (NTf2(-)). A significant increase of the extraction efficiency was found on the addition of NTf2(-) based ILs when using neutral extractant tri-octylphosphine oxide (TOPO), and the extraction efficiency kept high at both nearly neutral and high acidity. However, the CPE with acidic extractants, e.g., bis(2-ethylhexyl) phosphoric acid (HDEHP) and 8-hydroxyquinoline (8-HQ) which are only effective at nearly neutral condition, was not improved by ILs. The results of zeta potential and (19)F NMR measurements indicated that the anion NTf2(-) penetrated into the TX-114 micelles and was enriched in the surfactant-rich phase during the CPE process. Meanwhile, NTf2(-) may act as a counterion in the CPE of UO2(2+) by TOPO. Furthermore, the addition of IL increased the separation factor of UO2(2+) and La(3+), which implied that in the micelle TOPO, NTf2(-) and NO3(-) established a soft template for UO2(2+). Therefore, the combination of CPE and IL provided a supramolecular recognition to concentrate UO2(2+) efficiently and selectively.

  8. Synthesis, structural investigation and kinetic studies of uranyl(VI) unsymmetrical Schiff base complexes

    Indian Academy of Sciences (India)

    Zahra Asadi; Mozaffar Asadi; Azade Zeinali; Mohammad Ranjkeshshorkaei; Karla Fejfarova; Vaclav Eigner; Michal Dusek; Aliakbar Dehnokhalaji

    2014-11-01

    Uranyl(VI) complexes with unsymmetrical N2O2 Schiff base ligands were synthesized and characterized. Their characterization was performed using UV-Vis, 1H NMR, cyclic voltammetry, single-crystal X-ray crystallography, IR, TG and C.H.N. techniques. X-ray crystallography of the complexes show that beside coordination of the tetradentate Schiff base, one DMF molecule is also coordinated. In order to investigate the effect of the substitutional groups of the Schiff base on the oxidation and reduction potentials, we used the cyclic voltammetry method. Electrochemistry of these complexes showed that the presence of electron releasing groups accelerates oxidation of the complexes. The kinetics of thermal decomposition was studied using thermal gravimetric method (TG) and Coats-Redfern equation. According to Coats-Redfern plots, the kinetics of thermal decomposition of the studied complexes is first-order in all stages. Also the kinetics and mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was carried out in solution, using spectrophotometric method. As a result, the second order rate constants at four temperatures and the activation parameters were calculated showing an associative mechanism for all corresponding complexes. It was concluded that the steric and the electronic properties of the complexes influence the reaction rate significantly.

  9. Hydrothermal Synthesis, Crystal Structure and Luminescent Properties of an Organically Templated 2-D Uranyl Sulfate

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    An organically templated 2-D uranyl sulfate, {(C2H8N)[(UO2)Cl(SO4)(H2O)]}n 1, has been hydrothermally synthesized . The crystal and molecular structures have been determined by X-ray crystallography method and spectral techniques. 1 belongs to mono- clinic, space group P21/c with a = 8.3545(17), b = 10.550(2), c = 12.370(3)(A), β = 102.64(3)°, V = 1063.9(4)(A)3, Mr = 464.64, Dc = 2.901 g/cm3, F(000) = 836, μ = 15.710 mm-1, Z = 4, the final R = 0.0286 and wR = 0.0685 for 10164 observed reflections with I > 2σ(I). 1 presents a two-dimensional layer-like structure constructed from infinite anionic [(UO2)Cl(H2O)(SO4)]- layers with [C2H8N]+ cations balancing the charge and a number of intermolecular hydrogen bonds (C-H…O and O-H…Cl) existing in the solid state. The fluorescence properties of 1 have also been discussed.

  10. Chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

    International Nuclear Information System (INIS)

    The standard covers analytical procedures to determine compliance of nuclear-grade uranyl nitrate solution to specifications. The following methods are described in detail: uranium by ferrous sulfate reduction-potassium dichromate titrimetry and by ignition gravimetry; specific gravity by pycnometry; free acid by oxalate complexation; thorium by the Arsenazo(III) (photometric) method; chromium by the diphenylcarbazide (photometric) method; molybdenum by the thiocyanate (photometric) method; halogens separation by steam distillation; fluorine by specific ion electrode; halogen distillate analysis: chloride, bromide and iodide by amperometric microtitrimetry; bromine by the fluorescein (photometric) method; sulfate sulfur by (photometric) turbidimetry; phosphorus by the molybdenum blue (photometric) method; silicon by the molybdenum blue (photometric) method; carbon by persulfate oxidation-acid titrimetry; nonvolatile impurities by spectrography; volatile impurities by rotating-disk spark spectrography; boron by emission spectrography; impurity elements by spark source mass spectrography; isotopic composition by multiple filament surface-ionization mass spectrometry; uranium-232 by alpha spectrometry; total alpha activity by direct alpha counting; fission product activity by beta and gamma counting; entrained organic matter by infrared spectrophotometry

  11. Sorption of strontium on uranyl peroxide: implications for a high-level nuclear waste repository.

    Science.gov (United States)

    Sureda, Rosa; Martínez-Lladó, Xavier; Rovira, Miquel; de Pablo, Joan; Casas, Ignasi; Giménez, Javier

    2010-09-15

    Strontium-90 is considered the most important radioactive isotope in the environment and one of the most frequently occurring radionuclides in groundwaters at nuclear facilities. The uranyl peroxide studtite (UO2O2 . 4H2O) has been observed to be formed in spent nuclear fuel leaching experiments and seems to have a relatively high sorption capacity for some radionuclides. In this work, the sorption of strontium onto studtite is studied as a function of time, strontium concentration in solution and pH. The main results obtained are (a) sorption is relatively fast although slower than for cesium; (b) strontium seems to be sorbed via a monolayer coverage of the studtite surface, (c) sorption has a strong dependence on ionic strength, is negligible at acidic pH, and increases at neutral to alkaline pH (almost 100% of the strontium in solution is sorbed above pH 10). These results point to uranium secondary solid phase formation on the spent nuclear fuel as an important mechanism for strontium retention in a high-level nuclear waste repository (HLNW).

  12. Rapid determination of uranium in uranyl nitrate solutions by gamma spectrometry

    International Nuclear Information System (INIS)

    Uranium-235 emits gamma rays of 185.7 kev with 54% yield. Gamma spectrometry with this gamma ray presents an excellent method for the estimation of sup(235)U and hence the total uranium concentration by knowing the isotopic ratios. This paper deals with a system which uses 3 inches x 2 inches NaI detector and a microprocessor based 4 K multichannel analyser for assaying liquid samples. A software gain correction method was used in the system to eliminate errors due to amplifier gain shift. Three different ranges of concentrations of uranium in natural uranyl nitrate solution have been studied. Using known, standard samples, calibration graphs of cps Vs concentration have been obtained. Linearity has been observed upto the uranium concentration of about 80 gms/litre while non-linearity due to self-absorption was found in the higher range. An exponential relationship ; y=aesup(-bx) was used for fitting the data in the non-linear range. This method can be used to determine the uranium concentration in all the three ranges of concentration which have been studied, in a rapid and non-destructive way. The standard deviation in the concentration range of 50-80 gms of U per litre was found to be ±1% for a 300 secs. counting time. (author). 1 refs., 4 figs

  13. Temperature effects on the interaction mechanisms between the europium (III) and uranyl ions and zirconium diphosphate

    International Nuclear Information System (INIS)

    Temperature should remain higher than 25 C in the near field environment of a nuclear waste repository for thousands years. In this context, the aim of this work is to study the temperature influence on the interaction mechanisms between europium (III) and uranyl ions and zirconium diphosphate, as well as the influence of a complexing medium (nitrate) on the sorption of the lanthanide. The experimental definition of the equilibria was achieved by combining a structural investigation with the macroscopic sorption data. Surface complexes were characterized at all temperatures (25 C to 90 C) by TRLFS experiments carried out on dry and in situ samples using an oven. This characterization was completed by XPS experiments carried out at 25 C on samples prepared at 25 C and 90 C. The reaction constants (surface hydration and cations sorption) were obtained by simulating the experimental data with the constant capacitance surface complexation model. The reaction constants temperature dependency allowed one to characterize thermodynamically the different reactions by application of the van't Hoff relation. The validity of this law was tested by performing microcalorimetric measurements of the sorption heat for both cations. (author)

  14. High temperature interaction studies on equimolar nitrate mixture of uranyl nitrate hexahydrate and gadolinium nitrate hexahydrate

    International Nuclear Information System (INIS)

    Rare earths including gadolinium form a sizeable fraction of the fission products in the nuclear fission of fissile material in the reactor. These fission products can interact with uranium dioxide fuel and can form various compounds which can alter the thermal behavior of the fuel. The mixed oxide formed due to the high temperature interactions of mixture of uranyl nitrate hexahydrate (UNH) and gadolinium nitrate hexahydrate (GdNH) has been studied using thermal and X- ray diffraction techniques. The equimolar mixture of UNH and GdNH was prepared by mixing the weighed amount of individual nitrates and grinding gently with mortar and pestle. Thermogravimetry (TG) measurements were carried out by separately heating 100 mg of mixture and individual nitrates at heating rate of 10°C min-1 using Netzsch thermal analyzer (Model No.: STA 409 PC Luxx) in high purity nitrogen atmosphere with a flow rate of 120 mL min-1. The XRD measurement was carried out on a Philips X-ray diffractometer (Model PW1710) using nickel-filtered Cu-Kα radiation

  15. Removal of cadmium from fish sauce using chelate resin.

    Science.gov (United States)

    Sasaki, Tetsuya; Araki, Ryohei; Michihata, Toshihide; Kozawa, Miyuki; Tokuda, Koji; Koyanagi, Takashi; Enomoto, Toshiki

    2015-04-15

    Fish sauce that is prepared from squid organs contains cadmium (Cd), which may be present at hazardous concentrations. Cd molecules are predominantly protein bound in freshly manufactured fish sauce, but are present in a liberated form in air-exposed fish sauce. In the present study, we developed a new method for removing both Cd forms from fish sauce using chelate resin and a previously reported tannin treatment. Sixteen-fold decreases in Cd concentrations were observed (0.78-0.05 mg/100 mL) following the removal of liberated Cd using chelate resin treatment, and the removal of protein-bound Cd using tannin treatment. Major nutritional components of fish sauce were maintained, including free amino acids and peptides, and angiotensin I-converting enzyme inhibitory and antioxidant activities.

  16. Lanthanides caged by the organic chelates; structural properties.

    Science.gov (United States)

    Smentek, Lidia

    2011-04-13

    The structure, in particular symmetry, geometry and morphology of organic chelates coordinated with the lanthanide ions are analyzed in the present review. This is the first part of a complete presentation of a theoretical description of the properties of systems, which are widely used in technology, but most of all, in molecular biology and medicine. The discussion is focused on the symmetry and geometry of the cages, since these features play a dominant role in the spectroscopic activity of the lanthanides caged by organic chelates. At the same time, the spectroscopic properties require more formal presentation in the language of Racah algebra, and deserve a separate analysis. In addition to the parent systems of DOTA, DOTP, EDTMP and CDTMP presented here, their modifications by various antennas are analyzed. The conclusions that have a strong impact upon the theory of the energy transfer and the sensitized luminescence of these systems are based on the results of numerical density functional theory calculations.

  17. Lanthanides caged by the organic chelates; structural properties

    Science.gov (United States)

    Smentek, Lidia

    2011-04-01

    The structure, in particular symmetry, geometry and morphology of organic chelates coordinated with the lanthanide ions are analyzed in the present review. This is the first part of a complete presentation of a theoretical description of the properties of systems, which are widely used in technology, but most of all, in molecular biology and medicine. The discussion is focused on the symmetry and geometry of the cages, since these features play a dominant role in the spectroscopic activity of the lanthanides caged by organic chelates. At the same time, the spectroscopic properties require more formal presentation in the language of Racah algebra, and deserve a separate analysis. In addition to the parent systems of DOTA, DOTP, EDTMP and CDTMP presented here, their modifications by various antennas are analyzed. The conclusions that have a strong impact upon the theory of the energy transfer and the sensitized luminescence of these systems are based on the results of numerical density functional theory calculations.

  18. Improved paramagnetic chelate for molecular imaging with MRI

    Science.gov (United States)

    Winter, Patrick; Athey, Phillip; Kiefer, Garry; Gulyas, Gyongyi; Frank, Keith; Fuhrhop, Ralph; Robertson, David; Wickline, Samuel; Lanza, Gregory

    2005-05-01

    The relaxivity and transmetallation of two lipophilic paramagnetic chelates incorporated onto perfluorocarbon nanoparticles, i.e., gadolinium-methoxy-tetraazacyclododecane-tetraacetic acid phosphatidylethanolamine (Gd-MeO-DOTA-PE) and gadolinium-methoxy-tetraazacyclododecane-tetraacetic acid triglycine phosphatidylethanolamine (Gd-MeO-DOTA-triglycine-PE (Gd-MeO-DOTA-triglycine-PE)), were compared to a prototypic gadolinium-diethylene-triamine-pentaacetic acid bis-oleate (Gd-DTPA-BOA) paramagnetic formulation. Nanoparticles with MeO-DOTA-based chelates demonstrated higher relaxivity (40% higher for Gd-MeO-DOTA-PE and 55% higher for Gd-MeO-DOTA-triglycine-PE) and less transmetallation than the original Gd-DTPA-BOA-based agent.

  19. MULTIDENTATE TEREPHTHALAMIDATE AND HYDROXYPYRIDONATE LIGANDS: TOWARDS NEW ORALLY ACTIVE CHELATORS

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. A novel antimycobacterial compound acts as an intracellular iron chelator.

    Science.gov (United States)

    Dragset, Marte S; Poce, Giovanna; Alfonso, Salvatore; Padilla-Benavides, Teresita; Ioerger, Thomas R; Kaneko, Takushi; Sacchettini, James C; Biava, Mariangela; Parish, Tanya; Argüello, José M; Steigedal, Magnus; Rubin, Eric J

    2015-04-01

    Efficient iron acquisition is crucial for the pathogenesis of Mycobacterium tuberculosis. Mycobacterial iron uptake and metabolism are therefore attractive targets for antitubercular drug development. Resistance mutations against a novel pyrazolopyrimidinone compound (PZP) that is active against M. tuberculosis have been identified within the gene cluster encoding the ESX-3 type VII secretion system. ESX-3 is required for mycobacterial iron acquisition through the mycobactin siderophore pathway, which could indicate that PZP restricts mycobacterial growth by targeting ESX-3 and thus iron uptake. Surprisingly, we show that ESX-3 is not the cellular target of the compound. We demonstrate that PZP indeed targets iron metabolism; however, we found that instead of inhibiting uptake of iron, PZP acts as an iron chelator, and we present evidence that the compound restricts mycobacterial growth by chelating intrabacterial iron. Thus, we have unraveled the unexpected mechanism of a novel antimycobacterial compound.

  1. Tetracycline in uranyl nitrate intoxication: Its action on renal damage and U retention in bone

    International Nuclear Information System (INIS)

    In acute intoxication, uranium (U) not only inhibits bone formation but its excretion in urine also causes renal damage. The former effect is ameliorated by tetracycline (TC), probably due to its chelation property, which might also prevent U deposition in bone. Chemical determination of U incorporated in bone and a histological study of the kidneys were performed on animals injected with U and then treated with TC. The results showed that TC was unable to prevent the binding of U to bone while it exacerbated U-induced renal damage

  2. Meta-analysis of the safety of iron chelating agents

    OpenAIRE

    Li, Niya; 李妮婭

    2014-01-01

    Background: Thalassaemia is a genetic disorder disease, one of the most clinically relevant haemoglobinopathies in paediatric population. It interferes with the synthesis of haemoglobin chain. For the sake of maintaining the serum haemoglobin at a normal level, regular blood cell transfusion is required to the patients with thalassaemia. In general, patients with thalassaemia are often diagnosed at an early age and need to take a life-long iron chelating therapy to prevent the multi-organ...

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

    Science.gov (United States)

    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.

  4. Decontamination of process equipment using recyclable chelating solvent

    Energy Technology Data Exchange (ETDEWEB)

    Jevec, J.; Lenore, C.; Ulbricht, S. [Babcock & Wilcox, Co., R& DD, Alliance, OH (United States)

    1995-10-01

    The Department of Energy (DOE) is now faced with the task of meeting decontamination and decommissioning obligations at numerous facilities by the year 2019. Due to the tremendous volume of material involved, innovative decontamination technologies are being sought that can reduce the volumes of contaminated waste materials and secondary wastes requiring disposal. This report describes the results of the performance testing of chelates and solvents for the dissolution of uranium.

  5. Elucidating Interactions between DMSO and Chelate-Based Ionic Liquids.

    Science.gov (United States)

    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.

  6. Hydroxyurea could be a good clinically relevant iron chelator.

    Directory of Open Access Journals (Sweden)

    Khushnooma Italia

    Full Text Available Our previous study showed a reduction in serum ferritin of β-thalassemia patients on hydroxyurea therapy. Here we aimed to evaluate the efficacy of hydroxyurea alone and in combination with most widely used iron chelators like deferiprone and deferasirox for reducing iron from experimentally iron overloaded mice. 70 BALB/c mice received intraperitonial injections of iron-sucrose. The mice were then divided into 8 groups and were orally given hydroxyurea, deferiprone or deferasirox alone and their combinations for 4 months. CBC, serum-ferritin, TBARS, sTfr and hepcidin were evaluated before and after iron overload and subsequently after 4 months of drug therapy. All animals were then killed. Iron staining of the heart and liver tissue was done using Perl's Prussian Blue stain. Dry weight of iron in the heart and liver was determined by atomic absorption spectrometry. Increased serum-ferritin, TBARS, hepcidin and dry weight of iron in the liver and heart showed a significant reduction in groups treated with iron chelators with maximum reduction in the group treated with a combination of deferiprone, deferasirox and hydroxyurea. Thus hydroxyurea proves its role in reducing iron from iron overloaded mice. The iron chelating effect of these drugs can also be increased if given in combination.

  7. The removal of strontium from the mouse by chelating agents

    Energy Technology Data Exchange (ETDEWEB)

    Ortega, A.; Gomez, M.; Domingo, J.L.; Corbella, J.

    1989-07-01

    The effects of the chelating agents monosodium glutamate, Tiron, tartaric acid, ascorbic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6), 2,3-dimercaptosuccinic acid (DMSA), succinic acid, malic acid, ethylendiaminetetraacetic acid (EDTA), ethylenglycol-bis-(beta-amino-ethylether)-N,N'tetraacetic acid (EGTA), cyclohexane-diaminetetraacetic acid (CDTA) and diethylentria-minepentaacetic acid (DTPA) on the distribution and excretion of intraperitoneally injected strontium were investigated in male Swiss mice. Strontium nitrate was given at a dose equal to 3.78 mmol/kg and ten minutes after, chelators were administered intraperitoneally at doses approximately equal to one-fourth of their respective LD50 values. DTPA, followed by CDTA, EDTA and tartaric acid, was consistently the most effective in increasing the urinary excretion of strontium. Only ascorbic acid increased significantly the fecal excretion of strontium. CDTA, DTPA and ascorbic acid were also the most effective chelators in reducing the concentration of strontium found in various tissues. CDTA, DTPA and tartaric acid are the most effective agents of those tested in the removal of strontium after a single administration.

  8. Mercury removal in utility wet scrubber using a chelating agent

    Science.gov (United States)

    Amrhein, Gerald T.

    2001-01-01

    A method for capturing and reducing the mercury content of an industrial flue gas such as that produced in the combustion of a fossil fuel or solid waste adds a chelating agent, such as ethylenediaminetetraacetic acid (EDTA) or other similar compounds like HEDTA, DTPA and/or NTA, to the flue gas being scrubbed in a wet scrubber used in the industrial process. The chelating agent prevents the reduction of oxidized mercury to elemental mercury, thereby increasing the mercury removal efficiency of the wet scrubber. Exemplary tests on inlet and outlet mercury concentration in an industrial flue gas were performed without and with EDTA addition. Without EDTA, mercury removal totaled 42%. With EDTA, mercury removal increased to 71%. The invention may be readily adapted to known wet scrubber systems and it specifically provides for the removal of unwanted mercury both by supplying S.sup.2- ions to convert Hg.sup.2+ ions into mercuric sulfide (HgS) and by supplying a chelating agent to sequester other ions, including but not limited to Fe.sup.2+ ions, which could otherwise induce the unwanted reduction of Hg.sup.2+ to the form, Hg.sup.0.

  9. Antibacterial and antibiofilm effects of iron chelators against Prevotella intermedia.

    Science.gov (United States)

    Moon, Ji-Hoi; Kim, Cheul; Lee, Hee-Su; Kim, Sung-Woon; Lee, Jin-Yong

    2013-09-01

    Prevotella intermedia, a major periodontopathogen, has been shown to be resistant to many antibiotics. In the present study, we examined the effect of the FDA-approved iron chelators deferoxamine (DFO) and deferasirox (DFRA) against planktonic and biofilm cells of P. intermedia in order to evaluate the possibility of using these iron chelators as alternative control agents against P. intermedia. DFRA showed strong antimicrobial activity (MIC and MBC values of 0.16 mg ml(-1)) against planktonic P. intermedia. At subMICs, DFRA partially inhibited the bacterial growth and considerably prolonged the bacterial doubling time. DFO was unable to completely inhibit the bacterial growth in the concentration range tested and was not bactericidal. Crystal violet binding assay for the assessment of biofilm formation by P. intermedia showed that DFRA significantly decreased the biofilm-forming activity as well as the biofilm formation, while DFO was less effective. DFRA was chosen for further study. In the ATP-bioluminescent assay, which reflects viable cell counts, subMICs of DFRA significantly decreased the bioactivity of biofilms in a concentration-dependent manner. Under the scanning electron microscope, P. intermedia cells in DFRA-treated biofilm were significantly elongated compared to those in untreated biofilm. Further experiments are necessary to show that iron chelators may be used as a therapeutic agent for periodontal disease. PMID:23329319

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

    Science.gov (United States)

    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.

  11. Monoclonal antibodies and cancer

    International Nuclear Information System (INIS)

    The usefulness of radiolabeled monoclonal antibodies for imaging and treatment of human (ovarian) cancer was investigated. A review of tumor imaging with monoclonal antibodies is presented. Special attention is given to factors that influence the localization of the antibodies in tumors, isotope choice and methods of radiolabeling of the monoclonal antibodies. Two monoclonal antibodies, OC125 and OV-TL3, with high specificity for human epithelial ovarian cancer are characterized. A simple radio-iodination technique was developed for clinical application of the monoclonal antibodies. The behavior of monoclonal antibodies in human tumor xenograft systems and in man are described. Imaging of tumors is complicated because of high background levels of radioactivity in other sites than the tumor, especially in the bloodpool. A technique was developed to improve imaging of human tumor xenographs in nude mice, using subtraction of a specific and a non-specific antibody, radiolabeled with 111In, 67Ga and 131I. To investigate the capability of the two monoclonal antibodies, to specifically localize in human ovarian carcinomas, distribution studies in mice bearing human ovarian carcinoma xenografts were performed. One of the antibodies, OC125, was used for distribution studies in ovarian cancer patients. OC125 was used because of availability and approval to use this antibody in patients. The same antibody was used to investigate the usefulness of radioimmunoimaging in ovarian cancer patients. The interaction of injected radiolabeled antibody OC125 with circulating antigen and an assay to measure the antibody response in ovarian cancer patients after injection of the antibody is described. 265 refs.; 30 figs.; 19 tabs

  12. Comparison of DOTA and NODAGA as chelators for 64Cu-labeled immunoconjugates

    International Nuclear Information System (INIS)

    Introduction: Bifunctional chelators have been shown to impact the biodistribution of monoclonal antibody (mAb)-based imaging agents. Recently, radiolabeled 1,4,7-triazacyclononane,1-glutaric acid-4,7-acetic acid (NODAGA)-peptide complexes have demonstrated improved in vivo stability and performance compared to their 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) counterparts. Here, we investigated if similar utility could be achieved with mAbs and compared 64Cu-labeled DOTA and NODAGA-immunoconjugates for the detection of epithelial cell adhesion molecule (EpCAM) in a prostate cancer model. Methods: DOTA and NODAGA-immunoconjugates of an EpCAM targeting mAb (mAb7) were synthesized and radiolabeled with 64Cu (DOTA: 40 °C for 1 hr; NODAGA: 25 °C for 1 hr). The average number of chelators per mAb was quantified by isotopic dilution, and the biological activity of the immunoconjugates was evaluated by flow cytometry and ELISA. Radioligand assays were performed to compare cellular uptake and determine the dissociation constant (Kd) and maximum number of binding sites (Bmax) for the immunoconjugates using DsRed-transfected PC3-cells. A PC3-DsRed xenograft tumor model was established in nude mice and used to perform biodistribution studies to compare organ uptake and pharmacokinetics. Results: 64Cu-DOTA-mAb7 and 64Cu-NODAGA-mAb7 were prepared with chelator/protein ratios of 2–3 and obtained in comparable radiochemical yields ranging from 59 to 71%. Similar immunoreactivity was observed with both agents, and mock labeling studies indicated that incubation at room temperature or 40 °C did not affect potency. 64Cu-NODAGA-mAb7 demonstrated higher in vitro cellular uptake while 64Cu-DOTA-mAb7 had higher Kd and Bmax values. From the biodistribution data, we found similar tumor uptake (13.44 ± 1.21%ID/g and 13.24 ± 4.86%ID/g for 64Cu-DOTA-mAb7 and 64Cu-NODAGA-mAb7, respectively) for both agents at 24 hr, although normal prostate tissue was significantly

  13. Alkali-metal ion coordination in uranyl(VI) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li(+)-, Na(+)- and K(+)-uranyl(VI)-peroxide-carbonate systems.

    Science.gov (United States)

    Zanonato, Pier Luigi; Szabó, Zoltán; Vallet, Valerie; Di Bernardo, Plinio; Grenthe, Ingmar

    2015-10-01

    The constitution and equilibrium constants of ternary uranyl(vi) peroxide carbonate complexes [(UO2)p(O2)q(CO3)r](2(p-q-r)) have been determined at 0 °C in 0.50 M MNO3, M = Li, K, and TMA (tetramethyl ammonium), ionic media using potentiometric and spectrophotometric data; (17)O NMR data were used to determine the number of complexes present. The formation of cyclic oligomers, "[(UO2)(O2)(CO3)]n", n = 4, 5, 6, with different stoichiometries depending on the ionic medium used, suggests that Li(+), Na(+), K(+) and TMA ions act as templates for the formation of uranyl peroxide rings where the uranyl-units are linked by μ-η(2)-η(2) bridged peroxide-ions. The templating effect is due to the coordination of the M(+)-ions to the uranyl oxygen atoms, where the coordination of Li(+) results in the formation of Li[(UO2)(O2)(CO3)]4(7-), Na(+) and K(+) in the formation of Na/K[(UO2)(O2)(CO3)]5(9-) complexes, while the large tetramethyl ammonium ion promotes the formation of two oligomers, TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-). The NMR spectra demonstrate that the coordination of Na(+) in the five- and six-membered oligomers is significantly stronger than that of TMA(+); these observations suggest that the templating effect is similar to the one observed in the synthesis of crown-ethers. The NMR experiments also demonstrate that the exchange between TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-) is slow on the (17)O chemical shift time-scale, while the exchange between TMA[(UO2)(O2)(CO3)]6(11-) and Na[(UO2)(O2)(CO3)]6(11-) is fast. There was no indication of the presence of large clusters of the type identified by Burns and Nyman (M. Nyman and P. C. Burns, Chem. Soc. Rev., 2012, 41, 7314-7367) and possible reasons for this and the implications for the synthesis of large clusters are briefly discussed.

  14. A Lanthanide Ion-Decorated Uranyl-Organic Two-Dimensional Assembly with all-cis 1, 2, 3, 4, 5, 6-Cyclohexanehexacarboxylic Acid

    International Nuclear Information System (INIS)

    The reaction of an equimolar mixture of uranyl and lanthanide nitrates with all-cis 1, 2, 3, 4, 5, 6-cyclohexanehexacarboxylic acid (H6L) under hydrothermal conditions gives the isomorphous complexes [UO2Ln(HL)(H2O)7].H2O (Ln = Pr, Eu, Tb, Er), which are rare examples of uranyl lanthanide hetero-metallic species. The three carboxylate groups in equatorial positions on the cyclohexane ring are bound to uranyl ions, thus generating a (63) hexagonal two-dimensional network. One of the carboxylate groups in an axial position dictates the [Ln(H2O)7]3+ group, resulting in the sheets being decorated by lanthanide ions on both sides. (author)

  15. Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite–selenates

    Energy Technology Data Exchange (ETDEWEB)

    Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru [Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg (Russian Federation); Kovrugin, Vadim M.; Tyumentseva, Olga S.; Mikhaylenko, Pavel A.; Krivovichev, Sergey V. [Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg (Russian Federation); Tananaev, Ivan G., E-mail: vladgeo17@mail.ru [National Research Nuclear University MEPhI, pr. Pobedy 48, 456783 Ozersk (Russian Federation)

    2015-09-15

    Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (I), [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O)] (II), [C{sub 4}H{sub 15}N{sub 3}][H{sub 3}O]{sub 0.5}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 2.93}(SeO{sub 3}){sub 0.07}(H{sub 2}O)](NO{sub 3}){sub 0.5} (III), [C{sub 2}H{sub 8}N]{sub 3}[H{sub 5}O{sub 2}][(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub 2}(H{sub 2}O){sub 5} (IV), [C{sub 2}H{sub 8}N]{sub 2}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 4}(HSeO{sub 3})(H{sub 2}O)](H{sub 2}SeO{sub 3}){sub 0.2} (V), [C{sub 4}H{sub 12}N]{sub 3}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 5}(H{sub 2}O)] (VI), and [C{sub 2}H{sub 8}N]{sub 3}(C{sub 2}H{sub 7}N)[(UO{sub 2}){sub 3}(SeO{sub 4}){sub 4}(HSeO{sub 3})(H{sub 2}O)] (VII) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite–selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U–O{sub br}–Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers. - Graphical abstract: Crystal structures of the seven novel Se-contaning uranyl oxysalts that contain protonated organic molecules as interlayer species have been investigated from the viewpoints of topology of interpolyhedral linkages, isomeric variations and flexibility of structural units. - Highlights: • Single crystals of seven novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used

  16. [VGKC-complex antibodies].

    Science.gov (United States)

    Watanabe, Osamu

    2013-04-01

    Various antibodies are associated with voltage-gated potassium channels (VGKCs). Representative antibodies to VGKCs were first identified by radioimmunoassays using radioisotope-labeled alpha-dendrotoxin-VGKCs solubilized from rabbit brain. These antibodies were detected only in a proportion of patients with acquired neuromyotonia (Isaacs' syndrome). VGKC antibodies were also detected in patients with Morvan's syndrome and in those with a form of autoimmune limbic encephalitis. Recent studies indicated that the "VGKC" antibodies are mainly directed toward associated proteins (for example LGI-1 and CASPR-2) that complex with the VGKCs themselves. The "VGKC" antibodies are now commonly known as VGKC-complex antibodies. In general, LGI-1 antibodies are most commonly detected in patients with limbic encephalitis with syndrome of inappropriate secretion of antidiuretic hormone. CASPR-2 antibodies are present in the majority of patients with Morvan's syndrome. These patients develop combinations of CNS symptoms, autonomic dysfunction, and peripheral nerve hyperexcitability. Furthermore, VGKC-complex antibodies are tightly associated with chronic idiopathic pain. Hyperexcitability of nociceptive pathways has also been implicated. These antibodies may be detected in sera of some patients with neurodegenerative diseases (for example, amyotrophic lateral sclerosis and Creutzfeldt-Jakob disease).

  17. Succinylated polylysine as a possible link between an antibody molecule and deferoxamine

    Energy Technology Data Exchange (ETDEWEB)

    Slinkin, M.A.; Klibanov, A.L.; Khaw, B.A.; Torchilin, V.P. (USSR Cardiology Research Center, Academy of Medical Sciences, Moscow (USSR))

    1990-07-01

    Modification of antibodies with chelating polymers may be helpful for radioimmunoimaging, radioimmunotherapy, and NMR tomography. Succinylated polylysine was activated with carbodiimide/N-hydroxysulfosuccinimide in dimethyl sulfoxide and isolated as a dry solid. Sulfosuccinimide-esterified polymer was used for the two-stage coupling of an amino-containing chelating agent (deferoxamine) to monoclonal R11D10 (IgG) or its Fab fragment. Conjugates were separated from free components by using gel-chromatography and anion-exchange chromatography. Antibody-coupling efficiency and the loss of its immunoreactivity upon modification have been studied for polymers with different deferoxamine content. Specific binding of 67Ga to the corresponding antigen via the conjugate has been demonstrated.

  18. Chelation therapy in Wilson's disease: from D-penicillamine to the design of selective bioinspired intracellular Cu(I) chelators.

    Science.gov (United States)

    Delangle, Pascale; Mintz, Elisabeth

    2012-06-01

    Wilson's disease is an orphan disease due to copper homeostasis dysfunction. Mutations of the ATP7B gene induces an impaired functioning of a Cu-ATPase, impaired Cu detoxification in the liver and copper overload in the body. Indeed, even though copper is an essential element, which is used as cofactor by many enzymes playing vital roles, it becomes toxic when in excess as it promotes cytotoxic reactions leading to oxidative stress. In this perspective, human copper homeostasis is first described in order to explain the mechanisms promoting copper overload in Wilson's disease. We will see that the liver is the main organ for copper distribution and detoxification in the body. Nowadays this disease is treated life-long by systemic chelation therapy, which is not satisfactory in many cases. Therefore the design of more selective and efficient drugs is of great interest. A strategy to design more specific chelators to treat localized copper accumulation in the liver will then be presented. In particular we will show how bioinorganic chemistry may help in the design of such novel chelators by taking inspiration from the biological copper cell transporters.

  19. Synthesis and optical properties of macrocyclic lanthanide(III) chelates as new reagents for luminescent biolabeling.

    Science.gov (United States)

    Deslandes, Sébastien; Galaup, Chantal; Poole, Robert; Mestre-Voegtlé, Béatrice; Soldevila, Stéphanie; Leygue, Nadine; Bazin, Hervé; Lamarque, Laurent; Picard, Claude

    2012-11-14

    The convenient and efficient synthesis of two macrocyclic ligands (15- and 18-membered) based on a dipyrido-6,7,8,9-tetrahydrophenazine (dpqc) or 2,2':6',2''-terpyridine (tpy) heterocycle and a DTTA (diethylenetriaminetriacetic acid) skeleton is described. In these ligands the DTTA skeleton contains an additional extracyclic functionality (NH(2) group) suitable for covalent attachment to bioactive molecules. These octa- and nonadentate ligands form very stable and luminescent neutral lanthanide complexes in aqueous solutions at physiological pH. The corresponding Eu(III) and Tb(III) complexes are characterized by a maximum absorption wavelength compatible with nitrogen laser excitation (337 nm) and attractive lifetimes and quantum yields. Further introduction of a maleimide bioconjugatable handle in the Eu(III) complexes was investigated and a valuable luminescence brightness above 1500 dm(3) mol(-1) cm(-1) at 337 nm was obtained with the corresponding Eu(III) tpy-derivative. Finally, these two luminescent chelates were grafted onto thiol residues of a model antibody (Mab GSS11) without loss of their luminescent properties. PMID:23011114

  20. Quasielastic neutron scattering with in situ humidity control: Water dynamics in uranyl fluoride

    Science.gov (United States)

    Miskowiec, A.; Kirkegaard, M. C.; Herwig, K. W.; Trowbridge, L.; Mamontov, E.; Anderson, B.

    2016-03-01

    The structural phase diagram of uranyl fluoride (UO2F2), while incomplete, contains at least one anhydrous crystal structure and a second, zeolite-like structure with the formula [(UO2F2)(H2O)]7 ṡ (H2O)4 that can be produced by adding water to the anhydrous structure. While traditional diffraction measurements can easily differentiate these crystals, additional aqueous structures (in general of the form UO2F2 + xH2O) have been proposed as well. We present results using a novel sample environment setup to intercalate water during a quasielastic neutron scattering measurement over the course of 86 h. Our sample environment allows low-pressure (<2 atm) humid air flow across the sample coupled with a system to control the relative humidity of this air flow between 10% and 70%. The water dynamics in UO2F2 and [(UO2F2)(H2O)]7 ṡ (H2O)4 are sufficiently different to distinguish them, with water in the latter executing a restricted diffusion (D = 2.7 × 10-6 cm2/s) within the structure's accessible pores (r = 3.17 Å) such that the dynamics can be used as a fingerprinting tool. We confirm that water vapor pressure is the driving thermodynamic force for the conversion of the anhydrous structure to [(UO2F2)(H2O)]7 ṡ (H2O)4, and we demonstrate the feasibility of extending this approach to aqueous forms of UO2F2 + xH2O. This method has general applicability to systems in which water content itself is a driving variable for structural or dynamical phase transitions.

  1. Procedure for the obtainment of ammonium uranyl-tricarbonate suitable for the preparation of sinterable UO2

    International Nuclear Information System (INIS)

    Experiments carried out to obtain Ammonium Uranyl-Tricarbonate (AUC) of nuclear purity and with the appropriate physical characteristics to serve as an intermediate stage for the obtainment of sinterable Uranium Dioxide are described. AUC was obtained by precipitation with gaseous ammonium and carbon dioxide from aqueous solutions re-circulation, controlling, in both cases, the flow of the reactive gases, the pH and the temperature. The analyzed working conditions are described, giving also the results from the distribution of the particle size and morphology of the crystals. (M.E.L.)

  2. Influence if acidity and concentration of aqueous uranyl nitrate solutions on the efficiency of uranium absorption by hydrolytic wood lignin

    International Nuclear Information System (INIS)

    Efficiency of uranium(VI) absorption by hydrolytic wood lignin from uranyl nitrate aqueous solutions under static conditions at room temperature, depending on solution acidity and uranium concentration, was studied using the methods of elementary analysis and IR spectroscopy. It was ascertained that hydrolytic lignin manifests a high ability to strong uranium(VI) absorption from low-acid and alkaline solutions. Interaction of uranium(VI) and hydrolytic lignin occurs both according to ion exchange mechanism and at the expense of donor-acceptor bonds formation

  3. Pulse influence on the transfer kinetics between a drop and a liquid in the uranyl nitrate extraction by an hydrocarbon diluted tributylphosphate

    International Nuclear Information System (INIS)

    Extraction kinetics of uranyl nitrate by TBP diluted at 30% in a hydrocarbon is studied, especially transfer by diffusion in the case of droplets. Application is made to pulse columns. The study of transfer coefficient variations of the dispersed phase in the two cases (aqueous continuous phase then organic) shows that in the conditions of acidity corresponding to extraction the transfer coefficient is at most equal to solvation constant of uranyl nitrate by TBP, the maximum value is obtained for a continuous aqueous phase and for continuous organic phase diffusion resistance is important for small drops (d<2 mm)

  4. Effect of supplemental chromium on antibody responses of newly arrived feeder calves to vaccines and ovalbumin.

    OpenAIRE

    Chang, G X; Mallard, B A; Mowat, D N; Gallo, G F

    1996-01-01

    Two trials were conducted to investigate the effects of supplemental chromium (Cr) from organic sources (Cr chelate and high Cr yeast) on antibody responses of newly arrived feeder calves following vaccination with infectious bovine rhinotracheitis (IBR), para-influenza-3 (PI3), bovine respiratory syncytial virus (BRSV), bovine viral diarrhea (BVD) and Pasteurella haemolytica and ovalbumin (OVA). Using cross bred steer calves purchased at sales in Ontario, vaccines and OVA were given on d 0 a...

  5. Effect of supplemental chromium on antibody responses of newly arrived feeder calves to vaccines and ovalbumin.

    Science.gov (United States)

    Chang, G X; Mallard, B A; Mowat, D N; Gallo, G F

    1996-01-01

    Two trials were conducted to investigate the effects of supplemental chromium (Cr) from organic sources (Cr chelate and high Cr yeast) on antibody responses of newly arrived feeder calves following vaccination with infectious bovine rhinotracheitis (IBR), para-influenza-3 (PI3), bovine respiratory syncytial virus (BRSV), bovine viral diarrhea (BVD) and Pasteurella haemolytica and ovalbumin (OVA). Using cross bred steer calves purchased at sales in Ontario, vaccines and OVA were given on d 0 and 21 after arrival in the feedlot. Immune responses of calves were measured as serum specific antibody titres against all antigens on d 0 and 28 or d 35. The anti-OVA antibody responses (trial 2) were further investigated by measuring antibody concentrations of calves weekly until d 55 after arrival in the feedlot. Supplemental Cr (0.14 ppm) from an amino acid-chelated source had no effect on antibody responses to IBR, P13 and BRSV, but enhanced (P < 0.05) antibody titres of calves in response to the BVD vaccine on d 28 or d 35. Supplemental Cr from Cr yeast had no effect on antibody titres of calves to any vaccines. Chromium from both sources (trial 1 and 2) had no effect on antibody responses of calves following vaccination with P. haemolytica. However, supplemental Cr (0.75 ppm) from Cr yeast enhanced (P < 0.05) serum antibody responses of calves to OVA during the primary response (d 14) and secondary response (d 35) following immunization. These data confirmed our previous finding that supplemental Cr can enhance humoral immune response of market-transit stressed calves, but its enhancement on vaccine efficacy was antigen-dependent and variable. PMID:8785720

  6. Structural study of the uranyl and rare earth complexation functionalized by the CMPO; Etude structurale de la complexation de l'uranyle et des ions lanthanides par des calixarenes fonctionnalises par le CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Cherfa, S

    1998-12-10

    In view of reducing the volume of nuclear waste solutions, a possible way is to extract simultaneously actinide and lanthanide ions prior to their ulterior separation.. Historically, the two extractant families used for nuclear waste reprocessing are the phosphine oxides and the CMPO (Carbamoyl Methyl Phosphine Oxide). For a better understanding of the complexes formed during extraction, we undertook structural studies of the complexes formed between uranyl and lanthanide (III) ions and the two classes of ligands cited above. These studies have been performed by X-ray diffraction on single crystals. Recently, a new type of extractants of lanthanide (III) and actinide (III) ions has been developed. When the Organic macrocycle called calixarene (an oligomeric compound resulting from the poly-condensation of phenolic units) is functionalized by a CMPO ligand, the extracting power, in terms of yield and selectivity towards lightest lanthanides, is greatly enhanced compared to the one measured for the single CMPO. Our X-ray diffraction studies allowed us to characterise, in terms of stoichiometry and monodentate or bidentate coordination mode of the CMPO functions, the complexes of calix[4]arene-CMPO (with four phenolic units) with lanthanide nitrates and uranyl. These different steps of characterisation enabled us to determine the correlation between the structures of the complexes and both selectivity and exacerbation of the extracting power measured in the liquid phase. (author)

  7. Preparation of Polysulfone-supported Phosphoramidic Acid Type Chelate Membrane and Its Sorption Properties for Ag+

    Institute of Scientific and Technical Information of China (English)

    WANG Bing; CUI Yong-fang; DU Qi-yun; PEI Guang-ling

    2002-01-01

    A blending chelate filter membrane with high chelate capacity for Ag+ has been prepared by blending of phosphoramidic acid resin and polysulfone. The major parameters influencing structure of the chelate filter membranes such as the blending ratio, phosphoramidic acid resin grain size and temperature of casting solution have been studied. The relationship among the chelate amount of Ag+, pH value, Ag+ concentration and phosphoramidic acid resin grain diameter were examined. The chelate filter membrane had a capacity of1438μg/cm2 for Ag+ under appropriate conditions.Sorption isotherm of Ag + could be expressed with the Freundlich sorption model. The dynamic chelate experiments proved that the sorption and desorption of membranes could be realized simultaneously for Ag+.

  8. CCCCC pentadentate chelates with planar Möbius aromaticity and unique properties

    Science.gov (United States)

    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

  9. Heavy chain only antibodies

    DEFF Research Database (Denmark)

    Moghimi, Seyed Moein; Rahbarizadeh, Fatemeh; Ahmadvand, Davoud;

    2013-01-01

    Unlike conventional antibodies, heavy chain only antibodies derived from camel contain a single variable domain (VHH) and two constant domains (CH2 and CH3). Cloned and isolated VHHs possess unique properties that enable them to excel conventional therapeutic antibodies and their smaller antigen-...... for combating HER2+ breast cancer. © 2013 by Tabriz University of Medical Sciences.......Unlike conventional antibodies, heavy chain only antibodies derived from camel contain a single variable domain (VHH) and two constant domains (CH2 and CH3). Cloned and isolated VHHs possess unique properties that enable them to excel conventional therapeutic antibodies and their smaller antigen......-binding fragments in cancer targeting and therapy. VHHs express low immunogenicity, are highly robust and easy to manufacture and have the ability to recognize hidden or uncommon epitopes. We highlight the utility of VHH in design of new molecular, multifunctional particulate and immune cell-based systems...

  10. Engineering antibody therapeutics.

    Science.gov (United States)

    Chiu, Mark L; Gilliland, Gary L

    2016-06-01

    The successful introduction of antibody-based protein therapeutics into the arsenal of treatments for patients has within a few decades fostered intense innovation in the production and engineering of antibodies. Reviewed here are the methods currently used to produce antibodies along with how our knowledge of the structural and functional characterization of immunoglobulins has resulted in the engineering of antibodies to produce protein therapeutics with unique properties, both biological and biophysical, that are leading to novel therapeutic approaches. Antibody engineering includes the introduction of the antibody combining site (variable regions) into a host of architectures including bi and multi-specific formats that further impact the therapeutic properties leading to further advantages and successes in patient treatment. PMID:27525816

  11. Zinc chelation reduces hippocampal neurogenesis after pilocarpine-induced seizure.

    Directory of Open Access Journals (Sweden)

    Jin Hee Kim

    Full Text Available Several studies have shown that epileptic seizures increase hippocampal neurogenesis in the adult. However, the mechanism underlying increased neurogenesis after seizures remains largely unknown. Neurogenesis occurs in the subgranular zone (SGZ of the hippocampus in the adult brain, although an understanding of why it actively occurs in this region has remained elusive. A high level of vesicular zinc is localized in the presynaptic terminals of the SGZ. Previously, we demonstrated that a possible correlation may exist between synaptic zinc localization and high rates of neurogenesis in this area after hypoglycemia. Using a lithium-pilocarpine model, we tested our hypothesis that zinc plays a key role in modulating hippocampal neurogenesis after seizure. Then, we injected the zinc chelator, clioquinol (CQ, 30 mg/kg, into the intraperitoneal space to reduce brain zinc availability. Neuronal death was detected with Fluoro Jade-B and NeuN staining to determine whether CQ has neuroprotective effects after seizure. The total number of degenerating and live neurons was similar in vehicle and in CQ treated rats at 1 week after seizure. Neurogenesis was evaluated using BrdU, Ki67 and doublecortin (DCX immunostaining 1 week after seizure. The number of BrdU, Ki67 and DCX positive cell was increased after seizure. However, the number of BrdU, Ki67 and DCX positive cells was significantly decreased by CQ treatment. Intracellular zinc chelator, N,N,N0,N-Tetrakis (2-pyridylmethyl ethylenediamine (TPEN, also reduced seizure-induced neurogenesis in the hippocampus. The present study shows that zinc chelation does not prevent neurodegeneration but does reduce seizure-induced progenitor cell proliferation and neurogenesis. Therefore, this study suggests that zinc has an essential role for modulating hippocampal neurogenesis after seizure.

  12. Synthesis and Adsorption Properties of Polystyrene-supported Chelating Resins Containing Heterocyclic Functional Groups

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    A series of new chelating resins with incorporating heterocyclic functional groups:pyridine, thiadizole, benzothizole into macroporous chloromethylated polystyrene were synthesized via hydrophilic spacer arm of polyethylene glycol co ntaining sulfur. These chelating resins were found to show high adsorption capacities for Ag+, Hg2+, Au3+ and Pd2+, and the presence of spacer arm can enhance adsorption ability due to increase the hydrophilicity of the chelating resins.

  13. Red Blood Cell Transfusion Independence Following the Initiation of Iron Chelation Therapy in Myelodysplastic Syndrome

    OpenAIRE

    Leitch, Heather A.; Vickars, Linda M.; Chase, Jocelyn M.; Badawi, Maha A.

    2010-01-01

    Iron chelation therapy is often used to treat iron overload in patients requiring transfusion of red blood cells (RBC). A 76-year-old man with MDS type refractory cytopenia with multilineage dysplasia, intermediate-1 IPSS risk, was referred when he became transfusion dependent. He declined infusional chelation but subsequently accepted oral therapy. Following the initiation of chelation, RBC transfusion requirement ceased and he remained transfusion independent over 40 months later. Over the ...

  14. Performance of Nonmigratory Iron Chelating Active Packaging Materials in Viscous Model Food Systems.

    Science.gov (United States)

    Roman, Maxine J; Decker, Eric A; Goddard, Julie M

    2015-09-01

    Many packaged food products undergo quality deterioration due to iron promoted oxidative reactions. Recently, we have developed a nonmigratory iron chelating active packaging material that represents a novel approach to inhibit oxidation of foods while addressing consumer demands for "cleanˮ labels. A challenge to the field of nonmigratory active packaging is ensuring that surface-immobilized active agents retain activity in a true food system despite diffusional limitations. Yet, the relationship between food viscosity and nonmigratory active packaging activity retention has never been characterized. The objective of this study was to investigate the influence of food viscosity on iron chelation by a nonmigratory iron chelating active packaging material. Methyl cellulose was added to aqueous buffered iron solutions to yield model systems with viscosities ranging from ∼1 to ∼10(5)  mPa·s, representing viscosities ranging from beverage to mayonnaise. Iron chelation was quantified by material-bound iron content using colorimetry and inductively coupled plasma-optical emission spectrometry (ICP-OES).  Maximum iron chelation was reached in solutions up to viscosity ∼10(2)  mPa·s. In more viscous solutions (up to ∼10(4)  mPa·s), there was a significant decrease in iron chelating capacity (P influence of different food hydrocolloids on the performance of nonmigratory iron chelating active packaging was characterized. Methyl cellulose and carrageenan did not compete with the material for specific iron chelation (P > 0.05). Materials retained 32% to 45% chelating capacity when in contact with competitively chelating hydrocolloids guar gum, locust bean gum, and xanthan gum. This work demonstrates the potential application of nonmigratory iron chelating active packaging in liquid and semi-liquid foods to allow for the removal of synthetic chelators, while maintaining food quality.

  15. Behavior of mercury, lead, cesium, and uranyl ions on four SRS soils

    Energy Technology Data Exchange (ETDEWEB)

    Bibler, J.P.; Marson, D.B.

    1992-03-20

    Samples of four Savannah River Site (SRS) soils were tested for sorption behavior with Hg[sup 2+], Pb[sup 2+], UO[sub 2][sup 2+], and Cs[sup +] ions. The purpose of the study was to determine the selectivity of the different soils for these ions alone and in the presence of the competing cations, H[sup +] and Ca[sup 2+]. Distribution constants, Kd's, for the test ions in various solutions have been determined for the four soils. In general, sorption by all of the soils appeared to be more complex than a simple ion exchange or adsorption process. In particular, the presence of organic matter in soil increased the capacity of the soil due to its chelating ability. Similar soils did not react similarly toward each metal cation.

  16. Behavior of mercury, lead, cesium, and uranyl ions on four SRS soils

    Energy Technology Data Exchange (ETDEWEB)

    Bibler, J.P.; Marson, D.B.

    1992-03-20

    Samples of four Savannah River Site (SRS) soils were tested for sorption behavior with Hg{sup 2+}, Pb{sup 2+}, UO{sub 2}{sup 2+}, and Cs{sup +} ions. The purpose of the study was to determine the selectivity of the different soils for these ions alone and in the presence of the competing cations, H{sup +} and Ca{sup 2+}. Distribution constants, Kd`s, for the test ions in various solutions have been determined for the four soils. In general, sorption by all of the soils appeared to be more complex than a simple ion exchange or adsorption process. In particular, the presence of organic matter in soil increased the capacity of the soil due to its chelating ability. Similar soils did not react similarly toward each metal cation.

  17. Chelate-modified polymers for atmospheric gas chromatography

    Science.gov (United States)

    Christensen, W. W.; Mayer, L. A.; Woeller, F. H. (Inventor)

    1980-01-01

    Chromatographic materials were developed to serve as the stationary phase of columns used in the separation of atmospheric gases. These materials consist of a crosslinked porous polymer matrix, e.g., a divinylbenzene polymer, into which has been embedded an inorganic complexed ion such as N,N'-ethylene-bis-(acetylacetoniminato)-cobalt (2). Organic nitrogenous bases, such as pyridine, may be incorporated into the chelate polymer complexes to increase their chromatographic utility. With such materials, the process of gas chromatography is greatly simplified, especially in terms of time and quantity of material needed for a gas separation.

  18. Chelation behaviour of lanthanons with o-arsonodibenzoylmethanephenlylhydrazone

    International Nuclear Information System (INIS)

    The chelate formation reaction of La(III), Pr(III), Nd(III), Gd(III), Ho(III), and Er(III) with o-arsonodibenzoylmethanephenylhydrazone has been investigated potentiometrically and conductometrically in 40 % (ν/ν) aqueous ethanol, ionic strength 0,1 M. The order of stability constants was found to be La Gd 3+: L). The complexes have been isolated in solid state and have been characterized on the basis of elemental analysis and IR data. Coordination occurs through - NH of the hydrazo and - OH of the arsonic groups. (Authors)

  19. Standard test method for gamma energy emission from fission products in uranium hexafluoride and uranyl nitrate solution

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2005-01-01

    1.1 This test method covers the measurement of gamma energy emitted from fission products in uranium hexafluoride (UF6) and uranyl nitrate solution. It is intended to provide a method for demonstrating compliance with UF6 specifications C 787 and C 996 and uranyl nitrate specification C 788. 1.2 The lower limit of detection is 5000 MeV Bq/kg (MeV/kg per second) of uranium and is the square root of the sum of the squares of the individual reporting limits of the nuclides to be measured. The limit of detection was determined on a pure, aged natural uranium (ANU) solution. The value is dependent upon detector efficiency and background. 1.3 The nuclides to be measured are106Ru/ 106Rh, 103Ru,137Cs, 144Ce, 144Pr, 141Ce, 95Zr, 95Nb, and 125Sb. Other gamma energy-emitting fission nuclides present in the spectrum at detectable levels should be identified and quantified as required by the data quality objectives. 1.4 This standard does not purport to address all of the safety concerns, if any, associated with its us...

  20. Effects of a low-radiotoxicity uranium salt (uranyl acetate) on biochemical and hematological parameters of the catfish, Clarias gariepinus

    Science.gov (United States)

    Al-Ghanim, Khalid A.; Ahmad, Zubair; Al-Kahem Al-Balawi, Hmoud F.; Al-Misned, Fahad; Maboob, Shahid; Suliman, El-Amin M.

    2016-01-01

    Specimens of Clarias gariepinus were treated with lethal (70, 75, 80, 85, 90, and 95 mg/L) and sub-lethal concentrations (8, 12 and 16 mg/L) of uranyl acetate, a low-radiotoxicity uranium salt. The LC 50 value was registered as 81.45 mg/L. The protein and glycogen concentrations in liver and muscles were decreased in the fish exposed to sub-lethal concentrations. The red blood cell (RBC) and white blood cell (WBC) counts, haemoglobin (Hb) concentration and haematocrit (Hct) values were decreased. Different blood indices like mean corpuscular volume (MCV), mean corpuscular haemoglobin (MCH) and mean corpuscular haemoglobin concentration (MCHC) were negatively affected. Level of plasma glucose was elevated whereas protein was decreased. The level of calcium concentration (Ca) was declined in the blood of exposed fish whereas magnesium (Mg) remains unchanged. The activity level of glutamic-oxaloacetic transaminase (GOT) and glutamic-pyruvic transaminase (GPT) was elevated in exposed fish. These effects were more pronounced in the last period of exposure and in higher concentrations. Results of the present study indicate that uranyl acetate has adverse effects on Clarias gariepinus and causes changes in the biochemical and hematological parameters of the fish.

  1. The Extraction of Uranium as Uranyl Nitrate Complex in The Nitrate Acid Solution by Liquid Membrane Emulsion Technique

    International Nuclear Information System (INIS)

    The extraction of uranium as uranyl nitrate complex in the nitrate acid solution has been carried out using a liquid membrane emulsion technique. The liquid membrane phase is in form of emulsion that consists of kerosene as the solvent, sorbitan monooleat (span-80) as the surfactant, di-2 ethyl phosphoric acids (D2EHPA) as the carrier agent, and phosphoric acids as the internal phase. The optimum conditions for the extraction of uranium as uranyl nitrate complex have been obtained as the following: the organic phase (O) and the water or internal liquid phase (W) ratio in the liquid membrane phase (O/W) was 1, the concentration of nitric acid in the external phase was 3M, the D2EHPH concentration was 10% (v/v), the extraction time was 5 minutes and the agitation speed to achieve a membrane emulsion was 7500 rpm. At this condition the extraction efficiency obtained was 94.24%. The experiments also showed that the amount of extracted uranium by the liquid. membrane emulsion was limited

  2. A nano-sized Uranyl Camphorate Cage and its Use as a Building Unit in a Metal-Organic Framework

    International Nuclear Information System (INIS)

    The reaction of uranyl nitrate with (1R, 3S)-(+)-camphoric acid (H2L) in the presence of 1, 4-diazabicyclo[2.2.2]octane (DABCO) gives the chiral octa-nuclear cage [(UO2)8(L12H8)].12H2O (1), which displays an approximately cubic shape with the metal ions as apexes and an internal cavity of ca. 7 Angstrom in length. Complex 1, which is the first example of a homoleptic nano-sized cage including uranyl ions, can further be used as a supramolecular building block to generate coordination polymers, as exemplified by the compound [Ba(H2O)8]2[(UO2)8Ba2(L12)(H2O)4].8H2O (2), obtained in the presence of Ba(CH3)COO)2. In 2, which retains the overall packing mode of cages present in 1, a two-dimensional assembly is formed through bridging by the carboxylate-bound alkaline-earth metal cations. However, whereas 1 displays extended channels, these are obstructed by counterions in 2. (author)

  3. Development and application of an assay for uranyl complexation by fungal metabolites, including siderophores.

    Science.gov (United States)

    Renshaw, Joanna C; Halliday, Verity; Robson, Geoffrey D; Trinci, Anthony P J; Wiebe, Marilyn G; Livens, Francis R; Collison, David; Taylor, Robin J

    2003-06-01

    An assay to detect UO(2)(2+) complexation was developed based on the chrome azurol S (CAS) assay for siderophores (B. Schwyn and J. B. Neilands, Anal. Biochem. 160:47-56, 1987) and was used to investigate the ability of fungal metabolites to complex actinides. In this assay the discoloration of two dyed agars (one containing a CAS-Fe(3+) dye and the other containing a CAS-UO(2)(2+) dye) caused by ligands was quantified. The assay was tested by using the siderophore desferrioxamine B (DFO), and the results showed that there was a regular, reproducible relationship between discoloration and the amount of siderophore added. The ratio of the discoloration on the CAS-UO(2)(2+) agar to the discoloration on the CAS-Fe(3+) agar was independent of the amount of siderophore added. A total of 113 fungi and yeasts were isolated from three soil samples taken from the Peak District National Park. The fungi were screened for the production of UO(2)(2+) chelators by using the CAS-based assay and were also tested specifically for hydroxamate siderophore production by using the hydroxamate siderophore auxotroph Aureobacterium flavescens JG-9. This organism is highly sensitive to the presence of hydroxamate siderophores. However, the CAS-based assay was found to be less sensitive than the A. flavescens JG-9 assay. No significant difference between the results for each site for the two tests was found. Three isolates were selected for further study and were identified as two Pencillium species and a Mucor species. Our results show that the new assay can be effectively used to screen fungi for the production of UO(2)(2+) chelating ligands. We suggest that hydroxamate siderophores can be produced by mucoraceous fungi. PMID:12788768

  4. Reactive Transport of the Uranyl Ion in Soils, Sediments, and Groundwater Systems

    Energy Technology Data Exchange (ETDEWEB)

    Zachara, John M.; Ilton, Eugene S.; Liu, Chongxuan

    2013-05-16

    Uranium is a ubiquitous trace component in rocks ranging from 1.2 to 1.3 µg g-1 in sedimentary rocks, 2.2 to 15 µg g-1 in granites, and 20 to 120 µg g-1 in phosphates (Langmuir, 1997; Plant et al., 1999). Uranium (U) is released to natural waters in dilute concentrations (generally < 10-7 mole L-1) from the weathering of these sources, with water concentrations in uraniferous geologic terrains, such as the southwestern U.S. (USGS, 2011), being higher (~ 10-6.5 mol L-1). Elevated water-borne concentrations are associated with the weathering of natural ore bodies [~10-6 mol L-1; e.g, (Payne and Airey, 2006)], the extraction and mining of U for armaments (Jiang and Aschner, 2009; WHO, 2001) and nuclear fuels [10-6 to 10-3 mol L-1; (Abdelouas et al., 1999)], and the disposal of waste solids and liquids from nuclear fuels reprocessing and arms production [~ 10-6 to 10-2 mol L-1; e.g., (Wan et al., 2009; Zachara et al., 2007)]. The form of U present in natural waters at high concentration is generally the uranyl ion [e.g., UO22+] which is quite soluble. Groundwater in many parts of the world contains dissolved U originating from natural and anthropogenic sources (ATSDR, 2011; EFSA, 2009). Low levels of dissolved U in drinking water are considered a health concern, causing renal and other effects (Kurttio et al., 2002; Kurttio et al., 2005; Limson Zamora et al., 1998; Nriagu et al., 2012; Raymond-Whish et al., 2007; Selden et al., 2009). The U.S. Environmental Protection Agency has established a regulatory drinking water standard of 30 µg L-1 (1.26 x 10-7 mol L-1) or 30 pCi L-1, whichever is exceeded first. The World Health Organization has recommended an even lower drinking water standard of 15 µg L-1 [6.3 x 10-8 mol L-1; (WHO, 2005)]. Human exposure to U through drinking water is expected to rise as world-wide reliance on groundwater sources increase (ESS, 2010).

  5. An ultra-facile and label-free immunoassay strategy for detection of copper (II) utilizing chemiluminescence self-enhancement of Cu (II)-ethylenediaminetetraacetate chelate.

    Science.gov (United States)

    Ouyang, Hui; Shu, Qi; Wang, Wenwen; Wang, Zhenxing; Yang, Shijia; Wang, Lin; Fu, Zhifeng

    2016-11-15

    The establishment of facile, rapid, sensitive and cost-effective protocols for the detection of heavy metals is of great significance for human health and environmental monitoring. Hereby, an ultra-facile and label-free immunoassay strategy was designed for detecting heavy metal ion by using Cu (II) as the model analyte. Cu (II) reacted previously with ethylenediaminetetraacetate (EDTA) was captured by immobilized monoclonal antibody for Cu (II)-EDTA chelate. Then Cu (II) was detected based on the self-enhancing effect of Cu (II)-EDTA chelate to luminol-H2O2 chemiluminescence reaction. The CL intensity is linear relative with Cu (II) concentration in a very wide range of 1.0-1000ng/mL, with a detection limit of 0.33ng/mL (S/N=3). Since the specificity of this proposed strategy relied on both the specificity of monoclonal antibody and the specificity of luminol-H2O2 system, it could avoid interference from most common ions. The proposed method was used successfully to detect Cu (II) in traditional Chinese medicine and environmental water samples with acceptable recovery values of 82-113%. This proof-of-principle work demonstrated the feasibility of the label-free immunoassay for heavy metal ions, and opened a new avenue for rapid screening and field assay for drug safety, environmental monitoring and clinical diagnosis.

  6. Chelating polymeric beads as potential therapeutics for Wilson's disease.

    Science.gov (United States)

    Mattová, Jana; Poučková, Pavla; Kučka, Jan; Skodová, Michaela; Vetrík, Miroslav; Stěpánek, Petr; Urbánek, Petr; Petřík, Miloš; Nový, Zbyněk; Hrubý, Martin

    2014-10-01

    Wilson's disease is a genetic disorder caused by a malfunction of ATPase 7B that leads to high accumulation of copper in the organism and consequent toxic effects. We propose a gentle therapy to eliminate the excessive copper content with oral administration of insoluble non-resorbable polymer sorbents containing selective chelating groups for copper(II). Polymeric beads with the chelating agents triethylenetetramine, N,N-di(2-pyridylmethyl)amine, and 8-hydroxyquinoline (8HQB) were investigated. In a preliminary copper uptake experiment, we found that 8HQB significantly reduced copper uptake (using copper-64 as a radiotracer) after oral administration in Wistar rats. Furthermore, we measured organ radioactivity in rats to demonstrate that 8HQB radiolabelled with iodine-125 is not absorbed from the gastrointestinal tract after oral administration. Non-resorbability and the blockade of copper uptake were also confirmed with small animal imaging (PET/CT) in mice. In a long-term experiment with Wistar rats fed a diet containing the polymers, we have found that there were no signs of polymer toxicity and the addition of polymers to the diet led to a significant reduction in the copper contents in the kidneys, brains, and livers of the rats. We have shown that polymers containing specific ligands could potentially be novel therapeutics for Wilson's disease.

  7. Functional characterization of the chloroplast ferric chelate oxidoreductase enzyme.

    Science.gov (United States)

    Solti, Adám; Müller, Brigitta; Czech, Viktória; Sárvári, Éva; Fodor, Ferenc

    2014-05-01

    Iron (Fe) has an essential role in the biosynthesis of chlorophylls and redox cofactors, and thus chloroplast iron uptake is a process of special importance. The chloroplast ferric chelate oxidoreductase (cFRO) has a crucial role in this process but it is poorly characterized. To study the localization and mechanism of action of cFRO, sugar beet (Beta vulgaris cv Orbis) chloroplast envelope fractions were isolated by gradient ultracentrifugation, and their purity was tested by western blotting against different marker proteins. The ferric chelate reductase (FCR) activity of envelope fractions was studied in the presence of NAD(P)H (reductants) and FAD coenzymes. Reduction of Fe(III)-ethylenediaminetetraacetic acid was monitored spectrophotometrically by the Fe(II)-bathophenanthroline disulfonate complex formation. FCR activity, that is production of free Fe(II) for Fe uptake, showed biphasic saturation kinetics, and was clearly associated only to chloroplast inner envelope (cIE) vesicles. The reaction rate was > 2.5 times higher with NADPH than with NADH, which indicates the natural coenzyme preference of cFRO activity and its dependence on photosynthesis. FCR activity of cIE vesicles isolated from Fe-deficient plants also showed clear biphasic kinetics, where the KM of the low affinity component was elevated, and thus this component was down-regulated.

  8. Using iron chelating agents to enhance dermatological PDT

    Science.gov (United States)

    Curnow, Alison; Dogra, Yuktee; Winyard, Paul; Campbell, Sandra

    2009-06-01

    Topical protoporphyrin IX (PPIX) induced photodynamic therapy (PDT) of basal cell carcinoma (BCC) produces good clinical outcomes with excellent cosmesis as long as the disease remains superficial. Efficacy for nodular BCC however appears inferior to standard treatment unless repeat treatments are performed. Enhancement is therefore required and is possible by employing iron chelating agents to temporarily increase PPIX accumulation above the levels normally obtained using aminolevulinic acid (ALA) or the methyl ester of ALA (MAL) alone. In vitro studies investigated the effect of the novel iron chelator, CP94 on necrotic or apoptotic cell death in cultured human skin fibroblasts and epidermal carcinoma cells incubated with MAL. Furthermore, following a dose escalating safety study conducted with ALA in patients, an additional twelve nodular BCCs were recruited for topical treatment with standard MAL-PDT +/- increasing doses of CP94. Six weeks later following clinical assessment, the whole treatment site was excised for histological analysis. CP94 produced greater cell death in vitro when administered in conjunction with MAL than this porphyrin precursor could produce when administered alone. Clinically, PDT treatment using Metvix + CP94 was a simple and safe modification associated with a trend of reduced tumor thickness with increasing CP94 dose.

  9. Capillary gas chromatography of metal chelates of diethyl dithiocarbamates

    Energy Technology Data Exchange (ETDEWEB)

    Arain, M.A.; Bhanger, M.I. [Center of Excellence in Analytical Chemistry (Pakistan); Khuhawar, M.Y. [M.A. Kazi Inst. of Chemistry, Univ. of Sindh, Jamshoro (Pakistan)

    2002-03-01

    Capillary GC of metal chelates of diethyl dithiocarbamate (DDTC) was examined on a methylsilicone DB-1 column, (25 meter, 0.2 mm. i.d) with a film thickness of 0.25 {mu}m. Elution was carried out at the initial column temperature of 180 C and programmed at 5 C min{sup -1} to 260 C. Detection was by FID or ECD. Symmetrical peaks with bse line separation were obtained with the metal chelates of copper(II), nickel(II), cobalt(III), manganese(II) and chromium(III). The ECD gave better sensitivity than the FID with a linear calibration range of 5 - 50 {mu}g mL{sup -1} and detection limits 2.0 - 6.0 {mu}g mL{sup -1}, corresponding to 111 - 333 pg of metal ion reaching the detector. The method was applied to the determination of metal ions in water and pharmaceutical preparations with a coefficient of variation (CV) within 4.0%. When compared with a standard flame AAS method the results revealed no significant difference. (orig.)

  10. Selective separation of indium by iminodiacetic acid chelating resin

    Energy Technology Data Exchange (ETDEWEB)

    Fortes, M.C.B.; Benedetto, J.S. [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil); Martins, A.H. [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Engenharia Metalurgica e de Materiais]. E-mail: ahmartin@demet.ufmg.br

    2007-04-15

    - Indium can be recovered by treating residues, flue dusts, slags, and metallic intermediates in zinc smelting. This paper investigates the adsorption characteristics of indium and iron on an iminodiacetic acid chelating resin, Amberlite{sup R} IRC748 (Rohm and Haas Co.-USA). High concentrations of iron are always present in the aqueous feed solution of indium recovery. In addition, the chemical behaviour of iron in adsorptive systems is similar to that of indium. The metal concentrations in the aqueous solution were based on typical indium sulfate leach liquor obtained from zinc hydrometallurgical processing in a Brazilian plant. The ionic adsorption experiments were carried out by the continuous column method. Amberlite{sup R} IRC748 resin had a high affinity for indium under acidic conditions. Indium ions adsorbed onto the polymeric resin were eluted with a 0.5 mol/dm{sup 3} sulphuric acid solution passed through the resin bed in the column. 99.5% pure indium sulfate aqueous solution was obtained using the iminodiacetic acid chelating resin Amberlite{sup R} IRC748. (author)

  11. Deferasirox, an oral chelator in the treatment of iron overload

    Directory of Open Access Journals (Sweden)

    I. Portioli

    2013-05-01

    Full Text Available BACKGROUND Deferasirox is a once-daily oral iron chelator developed for treating iron overload complicating long-term transfusion therapy in patients with diseases such as beta-thalassemia and myelodysplastic syndromes. Iron overload can damage the liver, pancreas and the heart. Deferoxamine, the only other drug approved for iron chelation, can prevent these effects but requires parenteral administration. Deferasirox has been approved after a one-year, open-label trial in patients ≥ 2 years old with beta-thalassemia and transfusional emosiderosis randomized to once-daily oral 5, 10, 20, 30 mg/kg/day in comparison of subcutaneous deferoxamine 20-60 mg/mg/kg/day x 5/week. CONCLUSIONS Deferasirox 20-30 mg/kg/day produced reductions in liver iron concentration (LIC similar to those with deferoxamine. Adverse effect of deferasirox (increases of serum creatinine and aminotransferases, including the gastrointestinal ones, are similar but more frequent than those occurring with deferoxamine. Information is lacking on the effects of deferasirox on cardiac iron and cardiac dysfunction which is the most serious complication of transfusional iron overload.

  12. Effect of temperature on the mechanisms of interaction between uranyl ion and zirconium oxo-phosphate; Effet de la temperature sur les mechanismes d'interaction entre l'ion uranyle et l'oxophosphate de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Almazan Torres, Maria Guadalupe [Universite de Paris XI Orsay, Orsay (France)

    2007-07-01

    Uranium sorption onto Zr{sub 2}O(PO{sub 4}){sub 2} has been studied between 298 K and 363 K, in 0.1 M NaClO{sub 4} medium. Potentiometric titrations were realized to determine temperature dependency of the acid-base properties (pH{sub pcn}, acidity constants). Classical batch experiments were performed at different temperatures. The sorption experiments revealed that the uranium sorption onto Zr{sub 2}O(PO{sub 4}){sub 2} is favoured with the temperature. Structural characterization of the surface complexes was performed by both Time-Resolved Laser-Induced Fluorescence (TRLIF) and EXAFS spectroscopy. The TRLIF measurements vs. temperature revealed two uranyl surface complexes. No influence of the temperature onto the nature surface complex was observed. The EXAFS analysis showed a splitting of the equatorial oxygen atoms in two shells, corresponding to uranyl bidentate, inner-sphere complexes. The obtained structural uranyl surface complex information was used to simulate (using a constant capacitance model) the sorption edges. The proposed complexes equilibrium model consists of the following surface complexes: ({identical_to}ZrOH){sub 2}UO{sub 2}{sup 2+} and ({identical_to}PO){sub 2}UO{sub 2}. Besides the stability constants for the surface complexes, the thermodynamic parameters {delta}H{sup 0} and {delta}S{sup 0} were determined using the van't Hoff equation. The enthalpy values associated to the U(VI) retention onto Zr{sub 2}O(PO{sub 4}){sub 2}, determined by the temperature dependence of the stability constants, testify that the formation of the complex ({identical_to}PO){sub 2}UO{sub 2} (55 kJ/mol) is endothermic, while no influence of the temperature was observed for the formation of the complex ({identical_to}ZrOH){sub 2}UO{sub 2}{sup 2+}. The adsorption reaction of the last complex is then driven by entropy. In addition, calorimetric measurements of uranium sorption onto Zr{sub 2}O(PO{sub 4}){sub 2} were carried out to directly quantify the enthalpy

  13. RBC Antibody Screen

    Science.gov (United States)

    ... the baby is Rh-positive and the mother's antibody status is negative for anti-D, the mother is given additional RhIG. This test also may be used to help diagnose autoimmune-related hemolytic anemia ... when a person produces antibodies against his or her own RBC antigens. This ...

  14. Selection of Recombinant Human Antibodies.

    Science.gov (United States)

    Tomszak, Florian; Weber, Susanne; Zantow, Jonas; Schirrmann, Thomas; Hust, Michael; Frenzel, André

    2016-01-01

    Since the development of therapeutic antibodies the demand of recombinant human antibodies is steadily increasing. Traditionally, therapeutic antibodies were generated by immunization of rat or mice, the generation of hybridoma clones, cloning of the antibody genes and subsequent humanization and engineering of the lead candidates. In the last few years, techniques were developed that use transgenic animals with a human antibody gene repertoire. Here, modern recombinant DNA technologies can be combined with well established immunization and hybridoma technologies to generate already affinity maturated human antibodies. An alternative are in vitro technologies which enabled the generation of fully human antibodies from antibody gene libraries that even exceed the human antibody repertoire. Specific antibodies can be isolated from these libraries in a very short time and therefore reduce the development time of an antibody drug at a very early stage.In this review, we describe different technologies that are currently used for the in vitro and in vivo generation of human antibodies. PMID:27236551

  15. Anti-insulin antibody test

    Science.gov (United States)

    Insulin antibodies - serum; Insulin Ab test; Insulin resistance - insulin antibodies; Diabetes - insulin antibodies ... You appear to have an allergic response to insulin Insulin no longer seems to control your diabetes

  16. Time-Resolved Infrared Reflectance Studies of the Dehydration-Induced Transformation of Uranyl Nitrate Hexahydrate to the Trihydrate Form

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.; Mausolf, Edward J.; Kim, Eunja; Weck, Philippe F.; Buck, Edgar C.; McNamara, Bruce K.

    2015-10-01

    Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO2(NO3)2(H2O)6] often called UNH), the trihydrate [UO2(NO3)2(H2O)3 or UNT], and in very dry environments the dihydrate form [UO2(NO3)2(H2O)2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s the different phases were studied by infrared transmission spectroscopy, but were limited both by instrumental resolution and by the ability to prepare the samples for transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparation and allows dynamic analysis while the sample is exposed to a flow of N2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO2(NO3)2(H2O)6 has a distinct uranyl asymmetric stretch band at 949.0 cm-1 that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm-1. The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO22+ sites. The dehydration of UO2(NO3)2(H2O)6 to UO2(NO3)2(H2O)3 is both a structural and morphological change that has the lustrous lime green UO2(NO3)2(H2O)6 crystals changing to the matte greenish yellow of the trihydrate solid. The phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with but one in the hexahydrate.

  17. THE SYNTHESIS OF URUSHIOL TITANIUM CHELATE POLYMERS AND THEIR STRUCTURAL CHARACTERISTICS

    Institute of Scientific and Technical Information of China (English)

    HU Binghuan; CHEN Wending; LIN Jinhuo

    1993-01-01

    The synthetic method and structural characteristics of urushiol-titanium chelates (UT) and urushiol-titanium chelate polymer for anticorrosive coatings have been studied.Two kinds of coating films made from UT polymer show excellent physico-mechanical properties and possess good chemical resistance to strong acids and alkalis, many kinds of salt solutions and organic solvents,stable at high temperature.

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

    DEFF Research Database (Denmark)

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

    1999-01-01

    in the mutant receptors not by normal catecholamine ligands but instead either by free zinc ions or by zinc or copper ions in complex with small hydrophobic metal-ion chelators. Chelation of the metal ions by small hydrophobic chelators such as phenanthroline or bipyridine protected the cells from the toxic...... effect of, for example Cu(2+), and in several cases increased the affinity of the ions for the agonistic site. Wash-out experiments and structure-activity analysis indicated, that the high-affinity chelators and the metal ions bind and activate the mutant receptor as metal ion guided ligand complexes....... Because of the well-understood binding geometry of the small metal ions, an important distance constraint has here been imposed between TM-III and -VII in the active, signaling conformation of 7TM receptors. It is suggested that atoxic metal-ion chelator complexes could possibly in the future be used...

  19. Synthesis and characterization of dihexyldithiocarbamate as a chelating agent in extraction of gold(III)

    Science.gov (United States)

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

    Energy Technology Data Exchange (ETDEWEB)

    Wai, Chien M. (Moscow, ID); Smart, Neil G. (Workington, GB); Phelps, Cindy (Moscow, ID)

    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.

  1. Synthesis and characterization of dihexyldithiocarbamate as a chelating agent in extraction of gold(III)

    Energy Technology Data Exchange (ETDEWEB)

    Fatimah, Soja Siti, E-mail: soja-sf@upi.edu [Departemen Pendidikan Kimia, Universitas Pendidikan Indonesia, Jl. Dr. Setiabudhi No. 229, Bandung 40154 (Indonesia); Department of Chemistry, Faculty of Mathematics and Natural Sciences, Padjadjaran University, Jl. Raya Bandung-Sumedang, Km. 21, Jatinangor (Indonesia); Bahti, Husein H.; Hastiawan, Iwan [Department of Chemistry, Faculty of Mathematics and Natural Sciences, Padjadjaran University, Jl. Raya Bandung-Sumedang, Km. 21, Jatinangor (Indonesia); Permanasari, Anna [Departemen Pendidikan Kimia, Universitas Pendidikan Indonesia, Jl. Dr. Setiabudhi No. 229, Bandung 40154 (Indonesia)

    2016-02-08

    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, ({sup 1}H, and {sup 13}C), FTIR, and MS-ESI. Data on the synthesis, characterization, and the application of the ligand as a chelating agent are presented.

  2. Design and synthesis of zinc-selective chelators for extracellular applications.

    Science.gov (United States)

    Kawabata, Eri; Kikuchi, Kazuya; Urano, Yasuteru; Kojima, Hirotatsu; Odani, Akira; Nagano, Tetsuo

    2005-01-26

    Zinc (Zn2+) is found in every cell in human bodies. A few millimolar of free Zn2+ exists in the vesicles of presynaptic neurons in the mammalian brain and is released by synaptic activity or depolarization, modulating the function of certain ion channels and receptors. Although various chemical tools for measuring Zn2+ in biological samples, such as fluorescent probes for Zn2+, have been developed, Zn2+-selective chelators have room to be improved. Research on Zn2+ signals in the brain has traditionally employed several chelators, which have several shortcomings for biological applications. Here we report the design, synthesis, and properties of new membrane-impermeable chelators selective for Zn2+ and describe biological applications in hippocampal slices. As a result, our newly designed chelator revealed the first biological implication that presynaptic Zn2+ can be released in the CA1 region. This confirms the utility of these new chelatotrs as extracellular Zn2+ chelators for biological applications.

  3. Red Blood Cell Transfusion Independence Following the Initiation of Iron Chelation Therapy in Myelodysplastic Syndrome

    Directory of Open Access Journals (Sweden)

    Maha A. Badawi

    2010-01-01

    Full Text Available Iron chelation therapy is often used to treat iron overload in patients requiring transfusion of red blood cells (RBC. A 76-year-old man with MDS type refractory cytopenia with multilineage dysplasia, intermediate-1 IPSS risk, was referred when he became transfusion dependent. He declined infusional chelation but subsequently accepted oral therapy. Following the initiation of chelation, RBC transfusion requirement ceased and he remained transfusion independent over 40 months later. Over the same time course, ferritin levels decreased but did not normalize. There have been eighteen other MDS patients reported showing improvement in hemoglobin level with iron chelation; nine became transfusion independent, nine had decreased transfusion requirements, and some showed improved trilineage myelopoiesis. The clinical features of these patients are summarized and possible mechanisms for such an effect of iron chelation on cytopenias are discussed.

  4. A NOVEL METAL CHELATE AFFINITY ADSORBENT FOR PROTEIN UPTAKE

    Institute of Scientific and Technical Information of China (English)

    WANGYongjian; BAIShu; 等

    2001-01-01

    In this article,a spherical chitosan gel crosslinked by epichlorohydrin was prepared.It was then loaded with copper ions to produce a metal chelate affinity adsorbent for protein.The uptake of bovine serum albumin(BSA)by the affinity adsorbent was investigated.and the adsorption capacity for BSA as high as 40mg/g-wet beads was observed.The adsorption equilibrium data was well correlated by the Langmuir equation.The adsorption was considerably affected by pH.In additio.The amount of BSA adsorbed onto the beads decreased with the increasing of aqueous phase ionic strength,so adsorbed BAS can be desorbed by adjusting pH orionic strength of the solution.

  5. Economically dissolving barium sulfate scale with a chelating agent

    Energy Technology Data Exchange (ETDEWEB)

    Richardson, E.A.; Scheuerman, R.E.

    1977-06-21

    A composition is described for dissolving a barium sulfate scale from a subterranean or other relatively remote location into which fluid can be flowed. Fluid is flow-flowed into the remote location so that a stream of fluid contacts and flows along the surface of the scale. The composition and flow rate of the fluid are adjusted so that (1) the scale is contacted by a stream of aqueous solution in which each portion contains enough dissolved aminopolyacetic acid salt chelating agent to dissolve barium sulfate, and (2) substantially all upstream portions of the scale are contacted by a succession of portions of the aqueous liquid which are substantially unsaturated with respect to dissolved barium-chelant complex. (5 claims)

  6. Encapsulation and retention of chelated-copper inside hydrophobic nanoparticles

    DEFF Research Database (Denmark)

    Hervella, Pablo; Parra, Elisa; Needham, David

    2016-01-01

    MOTIVATION: In the field of imaging, (18)F-fluorodeoxyglucose (FDG) PET imaging allows evaluation of glucose metabolism and is the most widely used imaging agent clinically for metastatic cancer. While it can certainly detect the metastatic disease, in order to provide a more fully "individualized...... that our endogenous-inspired nanoparticle strategies for imaging and therapeutics are focused on encapsulating and retaining imaging ions such as copper inside novel hydrophobic nanoparticles. In this paper, we describe a new approach to label the core of hydrophobic nanoparticles composed of Glyceryl...... Trioleate (Triolein) with copper using the hydrophobic chelator Octaethyl porphyrin (OEP). RESEARCH PLAN AND METHODS: The research plan for this study was to (1) Formulate nanoparticles and control nanoparticle size using a modification of the solvent injection technique, named fast ethanol injection; (2...

  7. Chelation-Induced Polymer Structural Hierarchy/Complexity in Water.

    Science.gov (United States)

    Han, Jie; Zhou, Kaiyi; Zhu, Xuechao; Yu, Qiuping; Ding, Yi; Lu, Xinhua; Cai, Yuanli

    2016-08-01

    Understanding nanoscale structural hierarchy/complexity of hydrophilic flexible polymers is imperative because it can be viewed as an analogue to protein-alike superstructures. However, current understanding is still in infancy. Herein the first demonstration of nanoscale structural hierarchy/complexity via copper chelation-induced self-assembly (CCISA) is presented. Hierarchically-ordered colloidal networks and disks can be achieved by deliberate control of spacer length and solution pH. Dynamic light scattering, transmission electron microscopy, and atomic force microscopy demonstrate that CCISA underwent supramolecular-to-supracolloidal stepwise-growth mechanism, and underline amazing prospects to the hierarchically-ordered superstructures of hydrophilic flexible polymers in water. PMID:27219860

  8. Immunological Evaluation of -Thalassemia Major Patients Receiving Oral Iron Chelator Deferasirox

    International Nuclear Information System (INIS)

    Objective: To determine the immune abnormalities and occurrence of infections in transfusion-dependent -thalassemia major patients receiving oral iron chelator deferasirox (DFX). Study Design: An observational study. Place and Duration of Study: Hematology Clinics, King Khalid University Hospital, Riyadh, Saudi Arabia, from July to December 2010. Methodology: Seventeen patients with -thalassemia major (12 females, median age 26 years) receiving deferasirox (DFX) for a median duration of 27 months were observed for any infections and had their immune status determined. Immune parameters studied included serum immunoglobulins and IgG subclasses, serum complement (C3 and C4) and anti-nuclear antibody (ANA) level, total B and T-lymphocytes, CD4+ and CD8+ counts, CD4+/CD8+ ratio, and natural killer (NK) cells. Immunological parameters of the patients were compared with age, gender, serum ferritin level and splenectomy status. Lymphocyte subsets were also compared with age and gender matched normal controls. Results: A considerable reduction in serum ferritin was achieved by DFX from a median level of 2528 to 1875 mol/l. Serum IgG levels were increased in 7 patients. Low C4 levels were found in 9 patients. Total B and T-lymphocytes were increased in 14 patients each, while CD4+, CD8+ and NK cells were increased in 13, 12 and 11 patients respectively. Absolute counts for all lymphocyte subsets were significantly higher compared to the normal controls (p=0.05 for all parameters). Raised levels of IgG were associated with older age, female gender, splenectomized status and higher serum ferritin levels but this did not reach statistical significance except for the higher ferritin levels (p=0.044). Increased tendency to infections was not observed. Conclusion: Patients with -thalassemia major receiving DFX exhibited significant immune abnormalities. Changes observed have been described previously, but could be related to DFX. The immune abnormalities were not associated with

  9. A Novel Europium Chelate Coated Nanosphere for Time-Resolved Fluorescence Immunoassay.

    Directory of Open Access Journals (Sweden)

    Yifeng Shen

    Full Text Available A novel europium ligand 2,2',2'',2'''-(4,7-diphenyl-1,10-phenanthroline-2,9-diyl bis (methylene bis (azanetriyl tetra acetic acid (BC-EDTA was synthesized and characterized. It shows an emission spectrum peak at 610 nm when it is excited at 360 nm, with a large Stock shift (250 nm. It is covalently coated on the surface of a bare silica nanosphere containi free amino groups, using 1-ethyl-3-(3-dimethylaminopropyl carbodiimide hydrochloride and N-Hydroxysuccinimide. We also observed an interesting phenomenon that when BC-EDTA is labeled with a silica nanosphere, the chelate shows different excitation spectrum peaks of about 295 nm. We speculate that the carboxyl has a significant influence on its excitation spectrum. The BC-EDTA/Eu3+coated nanosphere could be used as a fluorescent probe for time-resolved fluorescence immunoassay. We labeled the antibody with the fluorescent nanosphere to develop a nanosphere based hepatitis B surface antigen as a time-resolved fluorescence immunoassay reagent, which is very easy to operate and eliminates potential contamination of Eu3+ contained in the environment. The analytical and functional sensitivities are 0.0037 μg/L and 0.08 μg/L (S/N≥2.0 respectively. The detection range is 0.08-166.67 μg/L, which is much wider than that of ELISA (0.2-5 μg/L. It is comparable to the commercial dissociation-enhanced lanthanide fluoro-immunoassay system (DELFIA reagents (0.2-145 μg/L. We propose that it can fulfill clinical applications.

  10. An experimental and ab initio study on the abiotic reduction of uranyl by ferrous iron

    Science.gov (United States)

    Taylor, S. D.; Marcano, M. C.; Rosso, K. M.; Becker, U.

    2015-05-01

    It is important to understand the mechanisms controlling the removal of uranyl from solution from an environmental standpoint, particularly whether soluble Fe(II) is capable of reducing soluble U(VI) to insoluble U(IV). Experiments were performed to shed light into discrepancies of recent studies about precipitation of U-containing solids without changing oxidation states versus precipitation/reduction reactions, especially with respect to the kinetics of these reactions. To understand the atomistic mechanisms, thermodynamics, and kinetics of these redox processes, ab initio electron transfer (ET) calculations, using Marcus theory, were applied to study the reduction of U(VI)aq to U(V)aq by Fe(II)aq (the first rate-limiting ET-step). Outer-sphere (OS) and inner-sphere (IS) Fe-U complexes were modeled to represent simple species within a homogeneous environment through which ET could occur. Experiments on the chemical reduction were performed by reacting 1 mM Fe(II)aq at pH 7.2 with high (i.e., 0.16 mM) and lower (i.e., 0.02 mM) concentrations of U(VI)aq. At higher U concentration, a rapid decrease in U(VI)aq was observed within the first hour of reaction. XRD and XPS analyses of the precipitates confirmed the presence of (meta)schoepite phases, where up to ∼25% of the original U was reduced to U4+ and/or U5+-containing phases. In contrast, at 0.02 mM U, the U(VI)aq concentration remained fairly constant for the first 3 h of reaction and only then began to decrease due to slower precipitation kinetics. XPS spectra confirm the partial chemical reduction U associated with the precipitate (up to ∼30%). Thermodynamic calculations support that the reduction of U(VI)aq to U(IV)aq by Fe(II)aq is energetically unfavorable. The batch experiments in this study show U(VI) is removed from solution by precipitation and that transitioning to a heterogeneous system in turn enables the solid U phase to be partially reduced. Ab initio ET calculations revealed that OS ET is

  11. Conversion of UF6 to UO2: A quasi-optimization of the ammonium uranyl carbonate process

    International Nuclear Information System (INIS)

    The ammonium uranyl carbonate (AUC) wet conversion process, one of the most important routes for preparation of uranium dioxide from UF6, was intensively investigated for process improvement and product identification. Both process variables and unit equipment were concerned. The target of this task was to prepare high quality UO2 ceramic powder and pellets. From the test results of UO2 pelletizing and sintering, the operation conditions were selected for process optimization. The criteria used in optimization condition determination were the reproducibility of the AUC product and the compressibility, the reactivity, as well as the sinterability of UO2 powder. Experimental results showed that UO2 pellets with sintered density higher than 98% TD were achieved. A set of quasi-optimum conditions for this process was also proposed. (orig.)

  12. Conversion and Blending Facility highly enriched uranium to low enriched uranium as uranyl nitrate hexahydrate. Revision 1

    International Nuclear Information System (INIS)

    This Conversion and Blending Facility (CBF) will have two missions: (1) convert HEU materials to pure HEU uranyl nitrate (UNH) and (2) blend pure HEU UNH with depleted and natural UNH to produce HEU UNH crystals. The primary emphasis of this blending operation will be to destroy the weapons capability of large, surplus stockpiles of HEU. The blended LEU product can only be made weapons capable again by the uranium enrichment process. To the extent practical, the chemical and isotopic concentrations of blended LEU product will be held within the specifications required for LWR fuel. Such blended LEU product will be offered to the United States Enrichment Corporation (USEC) to be sold as feed material to the commercial nuclear industry. Otherwise, blended LEU Will be produced as a waste suitable for storage or disposal

  13. Conversion and Blending Facility highly enriched uranium to low enriched uranium as uranyl nitrate hexahydrate. Revision 1

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-07-05

    This Conversion and Blending Facility (CBF) will have two missions: (1) convert HEU materials to pure HEU uranyl nitrate (UNH) and (2) blend pure HEU UNH with depleted and natural UNH to produce HEU UNH crystals. The primary emphasis of this blending operation will be to destroy the weapons capability of large, surplus stockpiles of HEU. The blended LEU product can only be made weapons capable again by the uranium enrichment process. To the extent practical, the chemical and isotopic concentrations of blended LEU product will be held within the specifications required for LWR fuel. Such blended LEU product will be offered to the United States Enrichment Corporation (USEC) to be sold as feed material to the commercial nuclear industry. Otherwise, blended LEU Will be produced as a waste suitable for storage or disposal.

  14. Standard test methods for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1999-01-01

    1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solution to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Determination of Uranium 7 Specific Gravity by Pycnometry 15-20 Free Acid by Oxalate Complexation 21-27 Determination of Thorium 28 Determination of Chromium 29 Determination of Molybdenum 30 Halogens Separation by Steam Distillation 31-35 Fluoride by Specific Ion Electrode 36-42 Halogen Distillate Analysis: Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 43 Determination of Chloride and Bromide 44 Determination of Sulfur by X-Ray Fluorescence 45 Sulfate Sulfur by (Photometric) Turbidimetry 46 Phosphorus by the Molybdenum Blue (Photometric) Method 54-61 Silicon by the Molybdenum Blue (Photometric) Method 62-69 Carbon by Persulfate Oxidation-Acid Titrimetry 70 Conversion to U3O8 71-74 Boron by ...

  15. Conceptual design of a uranyl nitrate fueled reactor for the destructive testing of liquid metal fast breeder reactor fuel subassemblies

    International Nuclear Information System (INIS)

    A preliminary design of a uranyl nitrate test reactor is developed, with emphasis placed on the core neutronics and cross section development. ENDF/B-IV cross section data and the AMPX system were used to develop a 25 group neutron cross section library. A series of one-dimensional transport calculations were made in order to arrive at a reference design. Power densities of 16.5 Kw/1 appear to be attainable in the 217 pin FFTF test subassembly, with a peak neutron flux in the test zone of 2.4 x 1014 n/cm2-sec. Other engineering features pertinent to the overall system design are discussed, including: (1) corrosion, (2) treatment of radiolytic gas, (3) heat removal, and (4) reactor control

  16. Effects of Zinc Chelators on Aflatoxin Production in Aspergillus parasiticus

    Science.gov (United States)

    Wee, Josephine; Day, Devin M.; Linz, John E.

    2016-01-01

    Zinc concentrations strongly influence aflatoxin accumulation in laboratory media and in food and feed crops. The presence of zinc stimulates aflatoxin production, and the absence of zinc impedes toxin production. Initial studies that suggested a link between zinc and aflatoxin biosynthesis were presented in the 1970s. In the present study, we utilized two zinc chelators, N,N,N′,N′-tetrakis (2-pyridylmethyl) ethane-1,2-diamine (TPEN) and 2,3-dimercapto-1-propanesulfonic acid (DMPS) to explore the effect of zinc limitation on aflatoxin synthesis in Aspergillus parasiticus. TPEN but not DMPS decreased aflatoxin biosynthesis up to six-fold depending on whether A. parasiticus was grown on rich or minimal medium. Although we observed significant inhibition of aflatoxin production by TPEN, no detectable changes were observed in expression levels of the aflatoxin pathway gene ver-1 and the zinc binuclear cluster transcription factor, AflR. Treatment of growing A. parasiticus solid culture with a fluorescent zinc probe demonstrated an increase in intracellular zinc levels assessed by increases in fluorescent intensity of cultures treated with TPEN compared to controls. These data suggest that TPEN binds to cytoplasmic zinc therefore limiting fungal access to zinc. To investigate the efficacy of TPEN on food and feed crops, we found that TPEN effectively decreases aflatoxin accumulation on peanut medium but not in a sunflower seeds-derived medium. From an application perspective, these data provide the basis for biological differences that exist in the efficacy of different zinc chelators in various food and feed crops frequently contaminated by aflatoxin. PMID:27271668

  17. Mechanistic basis for overcoming platinum resistance using copper chelating agents.

    Science.gov (United States)

    Liang, Zheng D; Long, Yan; Tsai, Wen-Bin; Fu, Siqing; Kurzrock, Razelle; Gagea-Iurascu, Mihai; Zhang, Fan; Chen, Helen H W; Hennessy, Bryan T; Mills, Gordon B; Savaraj, Niramol; Kuo, Macus Tien

    2012-11-01

    Platinum-based antitumor agents are widely used in cancer chemotherapy. Drug resistance is a major obstacle to the successful use of these agents because once drug resistance develops, other effective treatment options are limited. Recently, we conducted a clinical trial using a copper-lowering agent to overcome platinum drug resistance in ovarian cancer patients and the preliminary results are encouraging. In supporting this clinical study, using three pairs of cisplatin (cDDP)-resistant cell lines and two ovarian cancer cell lines derived from patients who had failed in platinum-based chemotherapy, we showed that cDDP resistance associated with reduced expression of the high-affinity copper transporter (hCtr1), which is also a cDDP transporter, can be preferentially resensitized by copper-lowering agents because of enhanced hCtr1 expression, as compared with their drug-sensitive counterparts. Such a preferential induction of hCtr1 expression in cDDP-resistant variants by copper chelation can be explained by the mammalian copper homeostasis regulatory mechanism. Enhanced cell-killing efficacy by a copper-lowering agent was also observed in animal xenografts bearing cDDP-resistant cells. Finally, by analyzing a public gene expression dataset, we found that ovarian cancer patients with elevated levels of hCtr1 in their tumors, but not ATP7A and ATP7B, had more favorable outcomes after platinum drug treatment than those expressing low hCtr1 levels. This study reveals the mechanistic basis for using copper chelation to overcome cDDP resistance in clinical investigations.

  18. Design and Construction of Experiment for Direct Electron Irradiation of Uranyl Sulfate Solution: Bubble Formation and Thermal Hydraulics Studies

    Energy Technology Data Exchange (ETDEWEB)

    Chemerisov, Sergey [Argonne National Lab. (ANL), Argonne, IL (United States); Gromov, Roman [Argonne National Lab. (ANL), Argonne, IL (United States); Makarashvili, Vakho [Argonne National Lab. (ANL), Argonne, IL (United States); Heltemes, Thad [Argonne National Lab. (ANL), Argonne, IL (United States); Sun, Zaijing [Argonne National Lab. (ANL), Argonne, IL (United States); Wardle, Kent E. [Argonne National Lab. (ANL), Argonne, IL (United States); Bailey, James [Argonne National Lab. (ANL), Argonne, IL (United States); Quigley, Kevin [Argonne National Lab. (ANL), Argonne, IL (United States); Stepinski, Dominique [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George [Argonne National Lab. (ANL), Argonne, IL (United States)

    2014-10-01

    Argonne is assisting SHINE Medical Technologies in developing SHINE, a system for producing fission-product 99Mo using a D/T-accelerator to produce fission in a non-critical target solution of aqueous uranyl sulfate. We have developed an experimental setup for studying thermal-hydraulics and bubble formation in the uranyl sulfate solution to simulate conditions expected in the SHINE target solution during irradiation. A direct electron beam from the linac accelerator will be used to irradiate a 20 L solution (sector of the solution vessel). Because the solution will undergo radiolytic decomposition, we will be able to study bubble formation and dynamics and effects of convection and temperature on bubble behavior. These experiments will serve as a verification/ validation tool for the thermal-hydraulic model. Utilization of the direct electron beam for irradiation allows homogeneous heating of a large solution volume and simplifies observation of the bubble dynamics simultaneously with thermal-hydraulic data collection, which will complement data collected during operation of the miniSHINE experiment. Irradiation will be conducted using a 30-40 MeV electron beam from the high-power linac accelerator. The total electron-beam power will be 20 kW, which will yield a power density on the order of 1 kW/L. The solution volume will be cooled on the front and back surfaces and central tube to mimic the geometry of the proposed SHINE solution vessel. Also, multiple thermocouples will be inserted into the solution vessel to map thermal profiles. The experimental design is now complete, and installation and testing are in progress.

  19. HIV Antibody Test

    Science.gov (United States)

    ... be limited. Home Visit Global Sites Search Help? HIV Antibody and HIV Antigen (p24) Share this page: Was this page helpful? Also known as: HIV Screening Tests; AIDS Test; AIDS Screen; HIV Serology; ...

  20. Antinuclear antibody panel

    Science.gov (United States)

    ... blood may be due to: Chronic liver disease Collagen vascular disease Drug-induced lupus erythematosus Myositis (inflammatory muscle disease) ... Saunders; 2011:chap 51. Read More Antibody Arthritis Collagen vascular disease Drug-induced lupus erythematosus Liver disease Scleroderma Systemic ...

  1. Anti-cartilage antibody.

    Science.gov (United States)

    Greenbury, C L; Skingle, J

    1979-08-01

    Antibody to cartilage has been demonstrated by indirect immunofluorescence on rat trachea in the serum of about 3% of 1126 patients with rheumatoid arthritis. Titres ranged from 1:20 to 1:640. The antibody was not found in 284 patients with primary or secondary osteoarthritis or in 1825 blood donors, nor, with the exception of two weak reactors, in 1314 paraplegic patients. In most cases the antibody appears to be specific for native type II collagen. Using this as an antigen in a haemagglutination test 94% of anti-cartilage sera were positive, whereas among 100 rheumatoid control sera there were only three weak positives. More than 80% of patients with antibody had some erosion of articular cartilage, but there was no correlation with age, sex, duration of disease, nor any recognisable clinical event or change.

  2. Magnetic bead-based enzyme-chromogenic substrate system for ultrasensitive colorimetric immunoassay accompanying cascade reaction for enzymatic formation of squaric acid-iron(III) chelate.

    Science.gov (United States)

    Lai, Wenqiang; Tang, Dianping; Zhuang, Junyang; Chen, Guonan; Yang, Huanghao

    2014-05-20

    This work reports on a simple and feasible colorimetric immunoassay with signal amplification for sensitive determination of prostate-specific antigen (PSA, used as a model) at an ultralow concentration by using a new enzyme-chromogenic substrate system. We discovered that glucose oxidase (GOx), the enzyme broadly used in enzyme-linked immunosorbent assay (ELISA), has the ability to stimulate in situ formation of squaric acid (SQA)-iron(III) chelate. GOx-catalyzed oxidization of glucose leads to the formation of gluconic acid and hydrogen peroxide (H2O2). The latter can catalytically oxidize iron(II) to iron(III), which can rapidly (immunoassay protocol with GOx-labeled anti-PSA detection antibody can be designed for the detection of target PSA on capture antibody-functionalized magnetic immunosensing probe, monitored by recording the color or absorbance (λ = 468 nm) of the generated SQA-iron(III) chelate. The absorbance intensity shows to be dependent on the concentration of target PSA. A linear dependence between the absorbance and target PSA concentration is obtained under optimal conditions in the range from 1.0 pg mL(-1) to 30 ng mL(-1) with a detection limit (LOD) of 0.5 pg mL(-1) (0.5 ppt) estimated at the 3Sblank level. The sensitivity displays to be 3-5 orders of magnitude better than those of most commercialized human PSA ELISA kits. In addition, the developed colorimetric immunoassay was validated by assaying 12 human serum samples, receiving in good accordance with those obtained by the commercialized PSA ELISA kit. Importantly, the SQA-based immunosensing system can be further extended for the detection of other low-abundance proteins or biomarkers by controlling the target antibody.

  3. Antibody tumor penetration

    Science.gov (United States)

    Thurber, Greg M.; Schmidt, Michael M.; Wittrup, K. Dane

    2009-01-01

    Antibodies have proven to be effective agents in cancer imaging and therapy. One of the major challenges still facing the field is the heterogeneous distribution of these agents in tumors when administered systemically. Large regions of untargeted cells can therefore escape therapy and potentially select for more resistant cells. We present here a summary of theoretical and experimental approaches to analyze and improve antibody penetration in tumor tissue. PMID:18541331

  4. Expression of Recombinant Antibodies

    OpenAIRE

    Frenzel, André; Hust, Michael; Schirrmann, Thomas

    2013-01-01

    Recombinant antibodies are highly specific detection probes in research, diagnostics, and have emerged over the last two decades as the fastest growing class of therapeutic proteins. Antibody generation has been dramatically accelerated by in vitro selection systems, particularly phage display. An increasing variety of recombinant production systems have been developed, ranging from Gram-negative and positive bacteria, yeasts and filamentous fungi, insect cell lines, mammalian cells to transg...

  5. Uranyl tris-(carbohydrazide) nitrate [UO{sub 2}((N{sub 2}H{sub 3}){sub 2}CO){sub 3}](NO{sub 3}){sub 2}. Synthesis, structure and properties

    Energy Technology Data Exchange (ETDEWEB)

    Leshok, Darya Y.; Samoilo, Alexander A.; Kirik, Sergei D. [Siberian Federal Univ., Krasnoyarsk (Russian Federation); Alekseenko, Vladimir N. [Federal Centre for Nuclear and Radiation Safety, Moscow (Russian Federation); Gavrilov, Peter M.; Alekseenko, Sergei N.; Dyachenko, Anton S. [Mining and Chemical Combine, Zheleznogorsk, Krasnoyarskii region (Russian Federation); Kondrasenko, Alexander A. [NMR Facility at Krasnoyarsk Multiaccesed Centre SB RAN, Krasnoyarsk (Russian Federation)

    2015-07-01

    Uranyl tris-(carbohydrazide) nitrate [UO{sub 2}((N{sub 2}H{sub 3}){sub 2}CO){sub 3}](NO{sub 3}){sub 2} was prepared by the reaction of water solution of dioxouranium(VI) nitrate UO{sub 2}(NO{sub 3}){sub 2}(H{sub 2}O){sub 6} with ethanol solution of carbohydrazide (N{sub 2}H{sub 3}){sub 2}CO in a molar ratio of 1 to 3 in an neutral medium. The substance was characterized by elemental, thermal analysis and IR and {sup 15}N MAS CP NMR spectroscopy. Ab initio crystal structure determination was carried out using X-ray powder diffraction techniques. The compound crystallizes in monoclinic lattice with unit cell parameters: a = 15.193(1) Aa, b = 12.005(1) Aa, c = 10.842(1) Aa, β = 109.15(1) , V = 1868.11 Aa{sup 3}, Z = 4, SG = Cc. The type of carbohydrazide coordination was additionally confirmed by {sup 15}N MAS CP NMR and IR spectroscopy. In the complex ion [UO{sub 2}((N{sub 2}H{sub 3}){sub 2}CO){sub 3}]{sup 2+} three carbohydrazide ligands coordinate to UO{sub 2}{sup 2+} through oxygen and nitrogen forming three five-membered chelate rings. The carbohydrazide rings are tuned to the equatorial plane of complex. The crystal structure consists of zig-zag chains of [UO{sub 2}((N{sub 2}H{sub 3}){sub 2}CO){sub 3}]{sup 2+} cations stretched along c-axis. The cations in the chain are linked by the hydrogen bonds between the cations themselves. The anions are located in the pores between chains and participate in hydrogen bonding between adjacent chains and additionally link the chain sections. The length of the chain section is 5.768 Aa and the angle between sections is 140 . The substance [UO{sub 2}((N{sub 2}H{sub 3}){sub 2}CO){sub 3}](NO{sub 3}){sub 2} is thermally stable up to 215 C and then decomposes with an explosion.

  6. MR imaging of lung ventilation with aerosolized Gadolinium-chelates; MR-Bildgebung der Lungenventilation mittels aerosolierter Gadolinium-Chelate

    Energy Technology Data Exchange (ETDEWEB)

    Haage, P.; Karaagac, S.; Spuentrup, E.; Guenther, R.W. [RWTH Aachen (Germany). Klinik fuer Radiologische Diagnostik; Adam, G. [Universitaetsklinikum Hamburg-Eppendorf (Germany). Abt. fuer Diagnostische und Interventionelle Radiologie

    2003-02-01

    Purpose: To evaluate the feasibility of magnetic resonance assessment of human lung ventilation with aerosolized Gd-chelates in healthy volunteers. Materials and Methods: Five healthy adults (mean age 37 years) were studied with a 1.5 T unit. The volunteers were instructed to inhale the aerosol through an airtight facial mask for 10 minutes. The aerosol was generated with a jet-type small particle nebulizer with attached heater. Ventilation imaging was performed using a respiration-gated dynamic T{sub 1}-weighted turbo spin echo sequence (T{sub R}=199 ms, T{sub E}=8.5 ms, 12 signal averages, slice thickness 10 mm). Pulmonary signal intensity changes were calculated before and after nebulization. Results: The investigation was successfully carried out in all volunteers. An acute or delayed allergic reaction to the aerosolized contrast medium was not observed. In 4 of 5 experiments (80%), a homogeneous signal intensity increase was readily visualized with an average signal increase of 35% after 10 minutes; in one experiment, the aerosol distribution was slightly heterogeneous. (orig.) [German] Ziel: Bestimmung der Durchfuehrbarkeit einer kernspintomographischen Darstellung der Lungenventilation mittels aerosolierter Gd-Chelate bei gesunden Probanden. Methoden: 5 Probanden (Durchschnittsalter 37 Jahre) wurden in einem 1,5T System untersucht. Die Probanden atmeten spontan aerosoliertes Gd-DTPA ueber eine Atemmaske fuer eine Dauer von 10 Minuten. Das Kontrastmittel-Aerosol wurde ueber einen leistungsfaehigen druckluftbetriebenen Vernebler generiert. Die Illustration der Ventilation erfolgte mit einer atemgegateten dynamischen T{sub 1}-gewichteten Turbo-Spin-Echosequenz. Zur Quantitifizerung der Lungenventilation wurden die Signalintensitaeten im Lungengewebe vor und nach Verneblung berechnet. Ergebnisse: Alle Untersuchungen wurden komplikationslos durchgefuehrt und beendet. Eine akute oder verzoegerte Kontrastmittelreaktion wurde nicht beobachtet. In 4 von 5

  7. Determination of the stability of the uranyl ion sipped in {tau}-hydrogen phosphate of zirconium in sodic form; Determinacion de la estabilidad del ion uranilo sorbido en {tau}-hidrogenofosfato de zirconio en forma sodica

    Energy Technology Data Exchange (ETDEWEB)

    Ordonez R, E.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Drot, R.; Simoni, E. [Universite de Paris-Sud-XI, Institut de Physique Nucleaire d' Orsay, Groupe de radiochimie, Bat. 100, 91406 Orsay (France)]. e-mail: edo@nuclear.inin.mx

    2005-07-01

    The stability of the uranyl sipped in the zirconium {tau}-hydrogen phosphate in sodic form ({tau}-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10{sup -4} and 10{sup -5} of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO{sub 4}. The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the {tau}-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

  8. Antibody informatics for drug discovery

    DEFF Research Database (Denmark)

    Shirai, Hiroki; Prades, Catherine; Vita, Randi;

    2014-01-01

    for antibody rational design using computational approaches to affinity and stability improvement, as well as ab-initio and homology-based antibody modeling; (ii) resources for antibody sequences, structures, and immune epitopes and open drug discovery resources for development of antibody drugs; and (iii...

  9. Engineering antibodies for cancer therapy.

    Science.gov (United States)

    Boder, Eric T; Jiang, Wei

    2011-01-01

    The advent of modern antibody engineering has led to numerous successes in the application of these proteins for cancer therapy in the 13 years since the first Food and Drug Administration approval, which has stimulated active interest in developing more and better drugs based on these molecules. A wide range of tools for discovering and engineering antibodies has been brought to bear on this challenge in the past two decades. Here, we summarize mechanisms of monoclonal antibody therapeutic activity, challenges to effective antibody-based treatment, existing technologies for antibody engineering, and current concepts for engineering new antibody formats and antibody alternatives as next generation biopharmaceuticals for cancer treatment.

  10. Generation, Fractionation, and Characterization of Iron-Chelating Protein Hydrolysate from Palm Kernel Cake Proteins.

    Science.gov (United States)

    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. PMID:26720491

  11. Characterization of commercial iron chelates and their behavior in an alkaline and calcareous soil.

    Science.gov (United States)

    Cantera, Rodrigo G; Zamarreño, Angel M; García-Mina, José M

    2002-12-18

    Iron deficiency is a common problem for many plants grown in alkaline and calcareous soils. To correct this problem, iron is supplied to plants as chelates. Several iron chelates are sold under diverse trademarks with different characteristics. This work evaluated 18 commercial products containing the most representative chelated iron sources used in agricultural practice in Spain when the study was done, namely the ferric chelates of EDDHA, EDDHMA, EDDCHA, EDDHSA, EDTA, and DTPA. The chelates were comprehensively characterized and quantitated by several techniques, including several chromatographic methods. Iron and chelate dynamics in soil were also studied in a model alkaline and calcareous soil. Results indicate that, in this model soil, among the different iron compounds studied only FeEDDHA and analogues have the capacity to maintain soluble iron in soil solution over time. These results are in agreement with general experience under field conditions. Furthermore, among the different ortho-ortho isomers of FeEDDHA's, FeEDDHSA and FeEDDCHA showed greater capacity than FeEDDHA and FeEDDHMA to maintain the chelated iron in soil solution over time. PMID:12475278

  12. Function of the iron-binding chelator produced by Coriolus versicolor in lignin biodegradation

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    An ultrafiltered low-molecular-weight preparation of chelating compounds was isolated from a wood-containing culture of the white-rot basidiomycete Coriolus versicolor. This preparation could chelate Fe3+ and reduce Fe3+ to Fe2+, demonstrating that the substance may serve as a ferric chelator, oxygen-reducing agent, and redox-cycling molecule, which would include functioning as the electron transport carrier in Fenton reaction. Lignin was treated with the iron-binding chelator and the changes in structure were investigated by 1H-NMR, 13C-NMR, difference spectrum caused by ionization under alkaline conditions and nitrobenzene oxidation. The results indicated that the iron-binding chelator could destroy the β-O-4 bonds in etherified lignin units and insert phenolic hydroxyl groups. The low-molecular-weight chelator secreted by C. versicolor resulted in new phenolic substructures in the lignin polymer, making it susceptible to attack by laccase or manganese peroxidase. Thus, the synergic action of the iron-binding chelator and the lignocellulolytic enzymes made the substrate more acces- sible to degradation.

  13. Recovery Properties of Polysulfone Hollow Fiber Chelating Membrane Modified with Thiourea for Mercury ( Ⅱ )

    Institute of Scientific and Technical Information of China (English)

    WANG Bing; XIAO Feng; HUANG Lei

    2007-01-01

    The adsorption isotherms of the polysulfone hollow fiber chelating membrane modified with thiourea as chelating groups for Hg2+ were determined. The effects of mobile phase conditions and the operating parameters on removal performance of the chelating membrane for Hg2+ were also investigated. The recovery of Hg2+ decreased at low pH and the optimum range of pH was from 6 to 7. The feed concentration effected on recovery of Hg2+ at the specified loading amount of Hg2+. The Hg2+ could be removed from different concentration feed solution by chelating membrane. The increase of feed flow rate led to slight decrease of recovery of Hg2+ at the specified loading amount of Hg2+. The chelating membrane could be operated at height feed flow rate and a large-scale removal of Hg2+ could be realized. With the increase of load amount, Hg2+ recovery decreased, but the saturation degree of chelating membrane increased. According to required recovery of Hg2+ and the saturation degree of chelating membrane, the optimum loading amount of Hg2+ should be selected in the actual removal of Hg2+.

  14. Function of the iron-binding chelator produced by Coriolus versicolor in lignin biodegradation

    Institute of Scientific and Technical Information of China (English)

    WANG Lu; YAN WenChao; CHEN JiaChuan; HUANG Feng; GAO PeiJi

    2008-01-01

    An ultrafiltered low-molecular-weight preparation of chelating compounds was isolated from a wood-containing culture of the white-rot basidiomycete Coriolus versicolor. This preparation could chelate Fe3+ and reduce Fe3+ to Fe2+, demonstrating that the substance may serve as a ferric chelator,oxygen-reducing agent, and redox-cycling molecule, which would include functioning as the electron transport carrier in Fenton reaction. Lignin was treated with the iron-binding chelator and the changes in structure were investigated by 1H-NMR, 13C-NMR, difference spectrum caused by ionization under alkaline conditions and nitrobenzene oxidation. The results indicated that the iron-binding chelator could destroy the β-O-4 bonds in etherified lignin units and insert phenolic hydroxyl groups. The low-molecular-weight chelator secreted by C. versicolor resulted in new phenolic substructures in the lignin polymer, making it susceptible to attack by laccase or manganese peroxidase. Thus, the synergic action of the iron-binding chelator and the lignocellulolytic enzymes made the substrate more accessible to degradation.

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

    Science.gov (United States)

    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.

  16. Generation, Fractionation, and Characterization of Iron-Chelating Protein Hydrolysate from Palm Kernel Cake Proteins.

    Science.gov (United States)

    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.

  17. Preparation of chitosan-EDTA nanoparticles and the chelating effect of radioactive strontium in vivo

    International Nuclear Information System (INIS)

    Objective: To obtain the CTS-EDTA nanoparticles and investigate their effects of chelating 89Sr2+ in vivo. Method: The CTS-EDTA nanoparticles were prepared by cross-linking CTS-EDTA with polyanion sodium tripolyphosphate ( TPP). And the zwitterionic chelate of the CTS-EDTA nanoparticles was used for promoting the radionuclides excreted in vivo. Results: The CTS-EDTA nanoparticles showed that particle size was uniformity of the spherical nano-particles by TEM, and the average particle size of 10.18 nm by Laser Particle Sizer. we found that CEC-Nano and the CEC had a good chelating effect of radioactive strontium in vivo, after 30 min and 2 h in the medication and the chelating efficiency of radioactive strontium excretion in the femur was significantly higher than the EDTA-Na2. At multiple doses,the chelating efficiency of CEC-Nano and the CEC through the urinary excretion and feces were better than traditional medicines EDTA-Na2. Conclusion: By this experimental method, we can be prepare nanodrugs of chelating radionuclide, it provides a basis for studying the broad-spectrum of radionuclide contamination chelating agents. (authors)

  18. New Insights into the Functional Behavior of Antibodies as Revealed by Binding Studies on an Anti-Uranium Monoclonal Antibody

    Energy Technology Data Exchange (ETDEWEB)

    Blake, Diane A.; Xia Li; Haini Yu; Blake, Robert C.

    2004-03-17

    As part of an ongoing effort to develop immunoassays for chelated uranium(VI) on a hand-held flow fluorimeter, an anti-uranium monoclonal antibody designated as 8A11 was fluorescently labeled using two different strategies. When 8A11 was coupled via reactive lysines to either ALEXATM 488 or Cy5TM, the resulting fluorescent antibody conjugate exhibited positive cooperativity in the presence of its antigen, U(VI) chelated with 2,9-dicarboxy-1,10-phenanthroline (U(VI)-DCP). That is, when one of the two binding sites on the covalently modified 8A11 was occupied with bound antigen, the affinity of the remaining site on the antibody for U(VI)-DCP appeared to increase. Unmodified 8A11 bound U(VI)-DCP with the expected hyperbolic dependence on the concentration of antigen, consistent with independent and equal binding of ligand at both sites. Proteolytic cleavage of the fluorescently conjugated 8A11 to produce the fluorescent monovalent Fab fragment yielded an active preparation that now bound U(VI)-DCP with no evidence of positive cooperativity. Although, in principle, any divalent antibody has the potential to exhibit positive cooperativity in its binding interactions with its antigen, very little literature precedent for this type of behavior exists. Native 8A11 was also noncovalently labeled with highly fluorescent ZENONTM reagents. These reagents are fluorescently-labeled Fab fragments of goat anti-mouse antibodies that bind to the Fc portion of 8A11. These high-affinity, monovalent fluorescent reagents permitted the intact 8A11 mouse antibody to be labeled in situ with no covalent modifications. Incubation of the 8A11 with ZENON 647 produced a fluorescent protein complex that showed an 8-fold higher affinity for U(VI)-DCP than did the free 8A11 alone. Again, very few literature precedents exist for this phenomenon, where agents that bind to the Fc portion of an intact antibody change the affinity of the antibody for the antigen at the structurally distant Fab portion

  19. New Insights into the Functional Behavior of Antibodies as Revealed by Binding Studies on an Anti-Uranium Monoclonal Antibody

    International Nuclear Information System (INIS)

    As part of an ongoing effort to develop immunoassays for chelated uranium(VI) on a hand-held flow fluorimeter, an anti-uranium monoclonal antibody designated as 8A11 was fluorescently labeled using two different strategies. When 8A11 was coupled via reactive lysines to either ALEXATM 488 or Cy5TM, the resulting fluorescent antibody conjugate exhibited positive cooperativity in the presence of its antigen, U(VI) chelated with 2,9-dicarboxy-1,10-phenanthroline (U(VI)-DCP). That is, when one of the two binding sites on the covalently modified 8A11 was occupied with bound antigen, the affinity of the remaining site on the antibody for U(VI)-DCP appeared to increase. Unmodified 8A11 bound U(VI)-DCP with the expected hyperbolic dependence on the concentration of antigen, consistent with independent and equal binding of ligand at both sites. Proteolytic cleavage of the fluorescently conjugated 8A11 to produce the fluorescent monovalent Fab fragment yielded an active preparation that now bound U(VI)-DCP with no evidence of positive cooperativity. Although, in principle, any divalent antibody has the potential to exhibit positive cooperativity in its binding interactions with its antigen, very little literature precedent for this type of behavior exists. Native 8A11 was also noncovalently labeled with highly fluorescent ZENONTM reagents. These reagents are fluorescently-labeled Fab fragments of goat anti-mouse antibodies that bind to the Fc portion of 8A11. These high-affinity, monovalent fluorescent reagents permitted the intact 8A11 mouse antibody to be labeled in situ with no covalent modifications. Incubation of the 8A11 with ZENON 647 produced a fluorescent protein complex that showed an 8-fold higher affinity for U(VI)-DCP than did the free 8A11 alone. Again, very few literature precedents exist for this phenomenon, where agents that bind to the Fc portion of an intact antibody change the affinity of the antibody for the antigen at the structurally distant Fab portion

  20. Physicochemical properties of skim milk powders prepared with the addition of mineral chelators.

    Science.gov (United States)

    Sikand, V; Tong, P S; Vink, Sean; Roy, Soma

    2016-06-01

    The objective of this study was to determine the effect of mineral chelator addition during skim milk powder (SMP) manufacture on the solubility, turbidity, soluble protein, and heat stability (HS). Three chelators (sodium citrate dihydrate, sodium polyphosphate, and disodium EDTA) at 3 different concentrations (5, 15, and 25mM) were added to skim milk concentrate (30% total solids), and the pH was adjusted to 6.65 before spray drying to produce SMP. Spray-dried SMP samples were tested for solubility index (SI). Additionally, samples were reconstituted to contain 9% total solids, adjusted to pH 7.0, and tested for turbidity, protein content from supernatants of ultracentrifuged samples, and HS. Lower SI values were observed for samples treated with 5mM disodium EDTA and sodium polyphosphate than control samples or samples with 5mM sodium citrate dihydrate. Furthermore, lower SI values were observed with an increased level of chelating agents regardless of chelator type. A decreased turbidity value was found with increasing levels of mineral chelating salt treatment. Low turbidity with increasing levels of added chelators may be associated with the dissociation of caseins from micelles. Furthermore, higher protein content was observed in supernatants of ultracentrifuged samples treated with increased level of chelators as compared with the control sample. Higher HS was observed in samples treated with 5mM compared with samples treated with 25mM mineral chelator. The results suggest improved solubility and HS upon addition of mineral chelators to SMP during its manufacture. PMID:27040785

  1. Isomerism in benzyl-DOTA derived bifunctional chelators: implications for molecular imaging.

    Science.gov (United States)

    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.

  2. Different photoluminescent properties of binary and ternary europium chelates doped in PMMA

    International Nuclear Information System (INIS)

    Two kinds of europium-β-diketone chelates, binary Eu(DBM)3 and ternary Eu(DBM)3phen were doped in poly(methyl methacrylate) (PMMA). These chelates show very different photoluminescent (PL) behaviors: the hypersensitive 5D0→7F2 emission bands of Eu(DBM)3phen change slightly with the molar ratios, while those of Eu(DBM)3 change obviously and regularly with the molar ratios. The results of the luminescent lifetimes of 5D0 levels show that the binary chelate exists as two kinds of species in the doped systems, and the lifetimes and contents of each species change with the molar ratios, while the ternary chelate exists as one kind of species in the doped systems. X-ray diffraction (XRD) patterns of the binary chelate doped systems give some diffraction peaks that are different from those of pure chelate and change with the molar ratios, indicating new kinds of crystal structures formed, and consequently, the first coordination sphere of Eu3+ ion changes; while those of the ternary chelate doped systems just show amorphous diffraction halos of the host, indicating that the ternary chelate exist in an amorphous state and disperse well in the host. The FTIR spectra of PMMA also change gradually with increasing the molar ratios of the doped two kinds of chelates, and the XRD patterns show that the amorphous halos of PMMA in the doped systems are different from those of pure PMMA and change with the molar ratios, too, suggesting the interaction between the guest and the host

  3. Chelate effects in sulfate binding by amide/urea-based ligands.

    Science.gov (United States)

    Jia, Chuandong; Wang, Qi-Qiang; Begum, Rowshan Ara; Day, Victor W; Bowman-James, Kristin

    2015-07-01

    The influence of chelate and mini-chelate effects on sulfate binding was explored for six amide-, amide/amine-, urea-, and urea/amine-based ligands. Two of the urea-based hosts were selective for SO4(2-) in water-mixed DMSO-d6 systems. Results indicated that the mini-chelate effect provided by a single urea group with two NH binding sites appears to provide enhanced binding over two amide groups. Furthermore, additional urea binding sites incorporated into the host framework appeared to overcome to some extent competing hydration effects with increasing water content.

  4. The Effect of Chelating Copolymer Additive on the Yttrium Iron Garnet Nanoparticle Formation

    Institute of Scientific and Technical Information of China (English)

    Wang; Cheng-chien

    2007-01-01

    1 Results Yttrium iron garnet (YIG) is a well-known ferromagnetic garnet material and has widely used in electronic devices[1].A new acrylic chelating polymer was developed to act as the additive of the preparation of YIG precursor in our previous study[2].The sintering temperature of YIG nanocrystal obtained by this YIG precursor (ACP) was magnificently descended from 1 000 to 600 ℃.In this study,we were further to study the effect of amount of chelating polymer and the compositions of chelating polyme...

  5. Design, synthesis, and evaluation of polyhydroxamate chelators for selective complexation of actinides

    International Nuclear Information System (INIS)

    Specific chelating polymers targeted for actinides have much relevance to problems involving remediation of nuclear waste. Goal is to develop polymer supported, ion specific extraction systems for removing actinides and other hazardous metal ions from wastewaters. This is part of an effort to develop chelators for removing actinide ions such as Pu from soils and waste streams. Selected ligands are being attached to polymeric backbones to create novel chelating polymers. These polymers and other water soluble and insoluble polymers have been synthesized and are being evaluated for ability to selectively remove target metal ions from process waste streams

  6. Synthesis, characterization and solubility of alkaline earth uranyl carbonates M2[UO2(CO3)3].xH20; M: Mg, Ca, Sr, Ba

    International Nuclear Information System (INIS)

    The release and dispersion of uranium from closed uranium mining sites and the resulting uranium contamination of the natural environment of such sites is a major problem examined in this dissertation. Knowledge of the pollution pathways and processes is indispensable for an assessment of the radiological implications for the human population, to be taken into account in the planning of site rehabilitation work. The formation of secondary uranium minerals may contribute to an immobilization of the uranium, but it is possible as well that such secondary uranium minerals will release uranium. A major task of this dissertation therefore was to examine the conditions of formation of alkaline earth uranyl carbonates in the context of their natural occurrence as observed at some sites, and to answer the question of whether hitherto unknown alkaline earth uranyl carbonates may form in the natural environment, and ought to be taken into account as new source terms. (orig./CB)

  7. Luminescent properties of [UO{sub 2}(TFA){sub 2}(DMSO){sub 3}], a promising material for sensing and monitoring the uranyl ion

    Energy Technology Data Exchange (ETDEWEB)

    Martin-Ramos, Pablo; Silva, Manuela Ramos; Silva, Pedro S. Pereira da [Centro de Fisica da Universidade de Coimbra (CFisUC), Department of Physics, Universidade de Coimbra (Portugal); Costa, Ana L.; Melo, J. Sergio Seixas de [Centro de Quimica de Coimbra, Department of Chemistry, Universidade de Coimbra (Portugal); Pereira, Laura C.J. [Centro de Ciencias e Tecnologias Nucleares, Instituto Superior Tecnico, Universidade de Lisboa, Bobadela LRS (Portugal); Martin-Gil, Jesus, E-mail: pmr@unizar.es [Advanced Materials Laboratory, Escuela Tecnica Superior de Ingenierias Agrarias, University of Valladolid, Palencia (Spain)

    2016-03-15

    An uranyl complex [UO{sub 2}(TFA){sub 2}(DMSO){sub 3}] (TFA=deprotonated trifluoroacetic acid; DMSO=dimethyl sulfoxide) has been successfully synthesized by reacting UO{sub 2}(CH{sub 3}COO){sub 2} ·H{sub 2} O with one equivalent of (CF{sub 3} CO){sub 2} O and DMSO. The complex has been characterized by single-crystal X-ray diffraction, X-ray powder diffraction, elemental analysis, FTIR spectroscopy, thermal analysis and absorption and emission spectroscopies. The spectroscopic properties of the material make it suitable for its application in the sensing and monitoring of uranyl in the PUREX process. (author)

  8. Methods for estimating the enthalpy of formation of inorganic compounds; thermochemical and crystallographic investigations of uranyl salts of group VI elements

    International Nuclear Information System (INIS)

    The first part of this thesis is concerned with parameter methods for estimating the standard enthalpy of formation, ΔH0sub(f), of inorganic compounds. In this type of method the estimate is a function of parameters, assigned to cation and anion, respectively. The usefulness of a new estimation method is illustrated in the case of uranyl sulphide. In the second part of this thesis crystallographic and thermochemical properties of uranyl salts of group VI elements are described. Crystal structures are given for β-UO2SO4, UO2SeO3, and α-UO2SeO4. Thermochemical measurements have been restricted to the determination of ΔH0sub(f)(UO2SO3) and ΔH0sub(f)(UO2TeO3) by means of isoperibol solution calorimetry. (Auth.)

  9. Modular strategy for the construction of radiometalated antibodies for positron emission tomography based on inverse electron demand Diels-Alder click chemistry.

    Science.gov (United States)

    Zeglis, Brian M; Mohindra, Priya; Weissmann, Gabriel I; Divilov, Vadim; Hilderbrand, Scott A; Weissleder, Ralph; Lewis, Jason S

    2011-10-19

    A modular system for the construction of radiometalated antibodies was developed based on the bioorthogonal cycloaddition reaction between 3-(4-benzylamino)-1,2,4,5-tetrazine and the strained dienophile norbornene. The well-characterized, HER2-specific antibody trastuzumab and the positron emitting radioisotopes (64)Cu and (89)Zr were employed as a model system. The antibody was first covalently coupled to norbornene, and this stock of norbornene-modified antibody was then reacted with tetrazines bearing the chelators 1,4,7,10-tetraazacyclo-dodecane-1,4,7,10-tetraacetic acid (DOTA) or desferrioxamine (DFO) and subsequently radiometalated with (64)Cu and (89)Zr, respectively. The modification strategy is simple and robust, and the resultant radiometalated constructs were obtained in high specific activity (2.7-5.3 mCi/mg). For a given initial stoichiometric ratio of norbornene to antibody, the (64)Cu-DOTA- and (89)Zr-DFO-based probes were shown to be nearly identical in terms of stability, the number of chelates per antibody, and immunoreactivity (>93% in all cases). In vivo PET imaging and acute biodistribution experiments revealed significant, specific uptake of the (64)Cu- and (89)Zr-trastuzumab bioconjugates in HER2-positive BT-474 xenografts, with little background uptake in HER2-negative MDA-MB-468 xenografts or other tissues. This modular system-one in which the divergent point is a single covalently modified antibody stock that can be reacted selectively with various chelators-will allow for both greater versatility and more facile cross-comparisons in the development of antibody-based radiopharmaceuticals.

  10. Uranyl complexes formed with a para-t-butylcalix[4]arene bearing phosphinoyl pendant arms on the lower rim. Solid and solution studies

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez, F. de M. [Instituto Nacional de Investigaciones Nucleares, La Marquesa, Ocoyoacac (Mexico). Dept. de Quimica; Varbanov, S. [Bulgarian Academy of Sciences, Sofia (Bulgaria). Inst. of Organic Chemistry with Center of Phytochemistry; Buenzli, J.C.G. [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. of Chemical Sciences and Engineering; Rivas-Silva, J.F.; Ocana-Bribiesca, M.A. [Instituto de Fisica de la BUAP, Puebla (Mexico); Cortes-Jacome, M.A.; Toledo-Antonio, J.A. [Instituto Mexicano del Petroleo/Programa de Ingenieria Molecular (Mexico)

    2012-07-01

    The current interest in functionalized calixarenes with phosphorylated pendant arms resides in their coordination ability towards f elements and capability towards actinide/rare earth separation. Uranyl cation forms 1:1 and 1:2 (M:L) complexes with a tetra-phosphinoylated p-tert-butylcalix[4]arene, B{sub 4}bL{sup 4}: UO{sub 2}(NO{sub 3}){sub 2}(B{sub 4}bL{sup 4}){sub n} . xH{sub 2}O (n = 1, x = 2, 1; n = 2, x = 6, 2). Spectroscopic data point to the inner coordination sphere of 1 containing one monodentate nitrate anion, one water molecule and the four phosphinoylated arms bound to UO{sub 2}{sup 2+} while in 2, uranyl is only coordinated to calixarene ligands. In both cases the U(VI) ion is 8-coordinate. Uranyl complexes display enhanced metal-centred luminescence due to energy transfer from the calixarene ligands; the luminescence decays are bi-exponential with associated lifetimes in the ranges 220 {mu}s < {tau}{sub s} < 250 {mu}s and 630 {mu}s < {tau}{sub L} < 640 {mu}s, pointing to the presence of two species with differently coordinated calixarene, as substantiated by a XPS study of U(4f{sub 5/2,7/2}), O(1s) and P(2p) levels on solid state samples. The extraction study of UO{sub 2}{sup 2+} cation and trivalent rare-earth (Y, La, Eu) ions from acidic nitrate media by B{sub 4}bL{sup 4} in chloroform shows the uranyl cation being much more extracted than rare earths. (orig.)

  11. Preliminary Assessment of Potential for Metal-Ligand Speciation in Aqueous Solution via the Liquid Sampling-Atmospheric Pressure Glow Discharge (LS-APGD) Ionization Source: Uranyl Acetate.

    Science.gov (United States)

    Zhang, Lynn X; Manard, Benjamin T; Powell, Brian A; Marcus, R Kenneth

    2015-07-21

    The determination of metals, including the generation of metal-ligand speciation information, is essential across a myriad of biochemical, environmental, and industrial systems. Metal speciation is generally affected by the combination of some form of chromatographic separation (reflective of the metal-ligand chemistry) with element-specific detection for the quantification of the metal composing the chromatographic eluent. Thus, the identity of the metal-ligand is assigned by inference. Presented here, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) is assessed as an ionization source for metal speciation, with the uranyl ion-acetate system used as a test system. Molecular mass spectra can be obtained from the same source by simple modification of the sustaining electrolyte solution. Specifically, chemical information pertaining to the degree of acetate complexation of uranyl ion (UO2(2+)) is assessed as a function of pH in the spectral abundance of three metallic species: inorganic (nonligated) uranyl, UO2Ac(H2O)n(MeOH)m(+), and UO2Ac2(H2O)n(MeOH)(m)H(+) (n = 1, 2, 3, ...; m = 1, 2, 3, ...). The product mass spectra are different from what are obtained from electrospray ionization sources that have been applied to this system. The resulting relationships between the speciation and pH values have been compared to calculated concentrations of the corresponding uranyl species: UO2(2+), UO2Ac(+), UO2Ac2. The capacity for the LS-APGD to affect both atomic mass spectra and structurally significant spectra for organometallic complexes is a unique and potentially powerful combination.

  12. Geochemical constraints on mobility of uranyl ions in the palaeoproterozoic lithofacies associations of Jhamarkotra formation from Aravalli Supergroup of India

    International Nuclear Information System (INIS)

    ., 2005). On the basis of mineralization and 13C isotope geochemistry Jhamarkotra Formation can be divided into two domains. First domain can be characterized by the stromatolitic rockphosphates mineralization with normal d13C values and second domain with uranium mineralization with enriched d13C values. The positive correlation between uranium occurrences and positive d13C enrichment in the second domain indicates that the mobility of uranyl ions was influenced with the cause of d13C enrichment. Purohit et al., (2005) suggested that microenvironmental factors were responsible for d13C enrichment in the Jhamarkotra Formation. Emphasizing on the uranium bearing, second domain it is suggested that there are two sub-basins. The two sub-basins are divided on the basis of tectono-spatial relationship and depositional environment. One of the sub-basins is the isolated Umra sub-basin which is characterized by hypersaline evaporitic conditions of deposition. Later on the rocks of the sub-basin underwent upper green-schist facies metamorphism and boron metasomatism. Moderately high d13C values observed in the carbonate lithofacies are probably due to precipitation of carbonate under nonequilibrium hypersaline conditions. Umra sub-basin is in close affinity to Ahar River granite Archaean basement, which is the primary source of uranium. Hypersaline fluids generated in the basin represent exceptionally aggressive fluid for uranyl ion mobilization. These brines percolate not only at the base of the basin but also deeply in the basement. Hypersaline conditions led to increased uranyl ion mobility from the proximal basement in the sub-basin leading to accumulation of uranium minerals. The other sub-basin is tectonically designated as the Ghasiar-Karouli shelf-bank belt characterized by hyposaline conditions of deposition. The d13C values of carbonates in the sub-basin are characterized by wide range of values ranging from moderately negative to high positive. Archaeal methanogenesis

  13. Uranyl ion interaction at the water/NiO(100) interface: A predictive investigation by first-principles molecular dynamic simulations

    Science.gov (United States)

    Sebbari, Karim; Roques, Jérôme; Domain, Christophe; Simoni, Eric

    2012-10-01

    The behavior of the UO22+ uranyl ion at the water/NiO(100) interface was investigated for the first time using Born-Oppenheimer molecular dynamic simulations with the spin polarized DFT + U extension. A water/NiO(100) interface model was first optimized on a defect-free five layers slab thickness, proposed as a reliable surface model, with an explicit treatment of the solvent. Water molecules are adsorbed with a well-defined structure in a thickness of about 4 Å above the surface. The first layer, adsorbed on nickel atoms, remains mainly in molecular form but can partly dissociate at 293 K. Considering low acidic conditions, a bidentate uranyl ion complex was characterized on two surface oxygen species (arising from water molecules adsorption on nickel atoms) with d_{U{-O}_{adsorption}}= 2.39 Å. This complex is stable at 293 K due to iono-covalent bonds with an estimated charge transfer of 0.58 electron from the surface to the uranyl ion.

  14. Uranyl ion interaction at the water/NiO(100) interface: A predictive investigation by first-principles molecular dynamic simulations

    Energy Technology Data Exchange (ETDEWEB)

    Sebbari, Karim [EDF-R and D, Departement Materiaux et Mecanique des Composants, Les Renardieres, Ecuelles, 77818 Moret Sur Loing (France); Institut de Physique Nucleaire d' Orsay, Universite Paris-Sud, CNRS UMR 8608, 15 rue Georges Clemenceau, Batiment 100, 91406 Orsay Cedex (France); Roques, Jerome; Simoni, Eric [Institut de Physique Nucleaire d' Orsay, Universite Paris-Sud, CNRS UMR 8608, 15 rue Georges Clemenceau, Batiment 100, 91406 Orsay Cedex (France); Domain, Christophe [EDF-R and D, Departement Materiaux et Mecanique des Composants, Les Renardieres, Ecuelles, 77818 Moret Sur Loing (France)

    2012-10-28

    The behavior of the UO{sub 2}{sup 2+} uranyl ion at the water/NiO(100) interface was investigated for the first time using Born-Oppenheimer molecular dynamic simulations with the spin polarized DFT +U extension. A water/NiO(100) interface model was first optimized on a defect-free five layers slab thickness, proposed as a reliable surface model, with an explicit treatment of the solvent. Water molecules are adsorbed with a well-defined structure in a thickness of about 4 A above the surface. The first layer, adsorbed on nickel atoms, remains mainly in molecular form but can partly dissociate at 293 K. Considering low acidic conditions, a bidentate uranyl ion complex was characterized on two surface oxygen species (arising from water molecules adsorption on nickel atoms) with d{sub U-O{sub a{sub d{sub s{sub o{sub r{sub p{sub t{sub i{sub o{sub n}}}}}}}}}}}=2.39 A. This complex is stable at 293 K due to iono-covalent bonds with an estimated charge transfer of 0.58 electron from the surface to the uranyl ion.

  15. Antibody affinity maturation

    DEFF Research Database (Denmark)

    Skjødt, Mette Louise

    linker for yeast surface display of scFv and scFab fragments, we compared a series of different Gly-Ser-based linkers in display and antigen binding proficiency. We show that these formats of the model antibody can accommodate linkers of different lengths and that introduction of alanine or glutamate......-2. Based on the presented data we suggest that affinity maturation of the model antibody proceeds through multiple incremental steps of subtle improvements. We moreover conclude that the best affinity improved candidates are likely to be obtained through optimization of both the antigen...... fragments by in vivo homologous recombination large combinatorial antibody libraries can easily be generated. We have optimized ordered assembly of three CDR fragments into a gapped vector and observed increased transformation efficiency in a yeast strain carrying a deletion of the SGS1 helicase...

  16. Platinum-conjugated antibodies for application in mass cytometry.

    Science.gov (United States)

    Mei, Henrik E; Leipold, Michael D; Maecker, Holden T

    2016-03-01

    Mass cytometry has overcome limitations of fluorescent single cell cytometry by allowing for the measurement of up to currently ∼40 different parameters on a single cell level. However, the cellular proteome comprises many more potential analytes, and current mass cytometry instrumentation allows for theoretically up to 121 different mass detection channels. The labeling of specific probes with appropriate metal ions is a significant hurdle for exploiting more of mass cytometry's analytical capacity. To this end, we here describe the labeling of antibody with natural abundance or isotopically purified platinum as formulated in cisplatin and circumventing the use of chelator-loaded polymers. We confirm the utility of cisplatin-antibody-conjugates for surface, intracellular, and phosphoepitope-specific immunophenotyping, as well as for application in cell surface CD45-based barcoding. Cisplatin-labeling of antibody increases the analytical capacity of the CyTOF(®) platform by two channels based on available reagents, and has the potential to add a total of six channels for detection of specific probes, thus helping to better extend the analytical mass range of mass cytometers. PMID:26355391

  17. Chelation therapy of thorium deposited in rat lung

    International Nuclear Information System (INIS)

    The effect of calcium diethylenetriaminepentaacetate (CaDTPA) and a siderophore analogue 3,4,3-LI(1,2-HOPO) on decorporation of small and large thorium masses (234Th 46 ng, 234Th 46 ng + 232Th 5 μg per rat) instilled into the lungs was studied. Along with repeated injections, chelating agents were administered continuously by mini-osmotic pumps over 14 d. Treatment with CaDTPA alone was partly successful in the decorporation of both thorium masses. Greater decorporation was achieved with 3,4,3-LI(1,2-HOPO) in pumps and CaDTPA in injections. In the whole body, lungs and skeleton, 23%, 24% and 24% of control radioactivity was found, respectively, for the small mass of thorium. When the large mass of thorium was instilled, only continuous infusion of 3,4,3-LI(1,2-HOPO) at low concentration efficiently prevented transfer of thorium to the skeleton (reduced to 9% of control). Both the whole body and lungs retained 50% of control radioactivity. (author)

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

    Science.gov (United States)

    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.

  19. New method to estimate stability of chelate complexes

    CERN Document Server

    Grigoriev, F V; Romanov, A N; Kondakova, O A; Sulimov, V B

    2009-01-01

    A new method allowing calculation of the stability of chelate complexes with Mg2+ ion in water have been developed. The method is based on two-stage scheme for the complex formation. The first stage is the ligand transfer from an arbitrary point of the solution to the second solvation shell of the Mg2+ ion. At this stage the ligand is considered as a charged or neutral rigid body. The second stage takes into account disruption of coordinate bonds between Mg2+ and water molecules from the first solvation shell and formation of the bonds between the ligand and the Mg2+ ion. This effect is considered using the quantum chemical modeling. It has been revealed that the main contribution to the free energy of the complex formation is caused by the disruption/formation of the coordinate bonds between Mg2+, water molecules and the ligand. Another important contribution to the complex formation energy is change of electrostatic interactions in water solvent upon the ligand binding with Mg2+ ion. For all complexes under...

  20. A membrane-specific tyrosinase chelate: the mitotic regulator?

    Science.gov (United States)

    Kharasch, J A

    1987-06-01

    Cancer's random, reversible, unstable transitions to "normal" structures imply their functional relation. Similar random, continuous, reversible oncogene "mutational transformation" also lacks a consistent hybrid. Positing cancer's "mutationally altered genotype" leads to medically foreign causes, qualities, inducers, suppressors, immune proteins, and viruses. Its random variation, however, opposes the functionally discrete, ordered, stable, irreversible hybrid variation and single-valued transforms of molecular genetics. There, "causal mutational operators" remain unspecified; only consistent single-valued DNA base and amino acid change, as "transform operand", are made explicit. A mitotically "blocked" (normal) and "unblocked" (malignant) stem cell "phenotype", operationally constructed from microscopic data, is therefore viewed within the homeostatic context of open-system enzyme-regulatory equilibrium. This functional, stochastic field distribution between "structurally bound" and "freely dividing" stem cell number discloses their putative regulatory mitotic-blocking factor. A tyrosinase complex, interacting by Cu2+-Fe2+ chelation with a proline hydroxylase divisional enzyme near stem cell ribosomes, maintains steady-state mitotic equilibrium. Based upon familiar medical, biochemical, and energy principles this confronts cancer's pigmentary-depigmentary signs, glycolytic metabolism, elevated serum tyrosinase, defective collagen production, exposed membrane binding sites, and tyrosine's recent growth control role.