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Sample records for chelated uranyl ions

  1. New chelation strategies for the uranyl ion

    International Nuclear Information System (INIS)

    Traditional approaches to the design of metal-ion-specific complexing agents have relied to a great extent on the creation of a ligand cavity of the appropriate size and coordination number to accommodate the targeted metal ion. Oxo-metal ions, such as uranyl, cannot be dealt with as spherically symmetric charged atoms and thus present both a special challenge and offer a unique advantage for specific chelation in solution. To maximize recognition of the anisotropic UO22+ ion, new tripodal hexadentate ligands have been prepared providing three carboxyl moieties each to act as a bidentate donor group. The novel ligand design concept, ligand syntheses, and thermodynamic results related to the uranyl complex characterization are presented

  2. Chlorimetric studies on the chelation of uranyl ion with 2:4-dihydroxy acetophenone oxime

    International Nuclear Information System (INIS)

    In a non-aqueous medium, uranyl ion forms an orange yellow complex with 2:4-dihydroxy acetophenone oxime (DHAO). The composition of the complex has been found to be UO2(DHAO)2. The stability constant of the complex was found to be 3.78x108 and the free energy formation ΔF=11.90K. cal at 300C. the phenolic hydrogen has been replaced by uranyl ion and coordinated through the oxime's nitrogen. (author)

  3. Adsorption of uranyl ion by chelate-type adsorbent with amidoxime and amidoxime/carboxyl group

    International Nuclear Information System (INIS)

    Complete text of publication follows. Uranium recovery from seawater is important for security of future energy supply. The main difficulty in the recovery process arises from the low concentration (∼3 ppb) of the uranyl ion in seawater, whereas other metal ions are abundantly present. Thus, development of selective adsorbents with a high adsorption rate and a large adsorption capacity is essential for the economic recovery uranyl ion. The polymeric adsorbents containing the amidoxime group are mostly promising, but information on their adsorption characterization in the presence of other abundantly metal ions such as sodium, calcium, etc. is still insufficient. In order to obtain uranium from seawater, the resins with amidoxime and amidoxime/carboxylic acid group were prepared by radiation-induced polymerization of aclylonitrile (AN) and AN/acrylic acid and by the subsequent amidoximation of cyano group of poly(AN), respectively. The resins with amidoxime and amidoxime/carboxylic acid groups were characterized by FT-IR, FT-Raman, solid state 13C-NMR, SEM, thermal (TGA/DSC) analysis, and elemental analysis, respectively. The adsorption of uranyl ion was examined. In resin with amidoxime group, the uranyl uptake increased with increasing amidoxime content. The adsorption rate of uranyl ion by resin with amidoxime/carboxylic acid was higher than that of resin with amidoxime group

  4. Sequestering agent for uranyl chelation: new bi-naphtyl ligands

    International Nuclear Information System (INIS)

    The synthesis of phosphonate, sulfocatecholamide (CAMS) and hydroxy-pyridinone (HOPO) bi-naphtyl ligands is presented. Their binding abilities for uranyl cation were determined by UV spectrophotometry in aqueous media versus pH. These titrations showed that the efficiency of these chelating agents depends on the nature of the chelating group. Each ligand shows a more or less pronounced affinity towards uranium. While the bis-phosphonate compound did not show any affinity towards the uranyl ion, the BINHOPO derivative exhibits significant affinity at acidic and neutral pH while the BINCAMS is more efficient at basic pH. (authors)

  5. Potentiometric studies on mixed-ligand chelates of uranyl ion with carboxylic acid phenolic acids

    International Nuclear Information System (INIS)

    Mixed ligand complexes of UO22+ with bidentate carboxylic and phenolic acids have been studied potentiometrically at 30 ± 0.1degC and μ=0.2M (NaClO4). 1:1 and 1:2 complexes of UO22+ with phthalic acid (PTHA), maleic acid (MAE), malonic acid (MAL), quinolinic acid (QA), 5-sulphosalicylic acid (5-SSA), salicylic acid (SA), and only 1:1 complexes in the case of mandelic acid (MAD) have been detected. The formation of 1:1:1 mixed ligand complexes has been inferred from simultaneous equilibria in the present study. The values of ΔlogK, Ksub(DAL), Ksub(2LA) or Ksub(2AL) for the ternary complexes have been calculated. The stabilities of mixed ligand complexes depend on the size of the chelate ring and the stabilities of the binary complexes. (author). 15 refs

  6. 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

  7. 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

  8. 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.

  9. Synthesis of New Bis(3-hydroxy-4-pyridinone) Ligands as Chelating Agents for Uranyl Complexation

    OpenAIRE

    Bo Jin; Rongzong Zheng; Rufang Peng; Shijin Chu

    2016-01-01

    Five new bis(3-hydroxy-4-pyridinone) tetradentate chelators were synthesized in this study. The structures of these tetradentate chelators were characterized by 1H-NMR, 13C-NMR, FT-IR, UV-vis, and mass spectral analyses. The binding abilities of these tetradentate chelators for uranyl ion at pH 7.4 were also determined by UV spectrophotometry in aqueous media. Results showed that the efficiencies of these chelating agents are dependent on the linker length. Ligand 4b is the best chelator and ...

  10. Synthesis of New Bis(3-hydroxy-4-pyridinone) Ligands as Chelating Agents for Uranyl Complexation.

    Science.gov (United States)

    Jin, Bo; Zheng, Rongzong; Peng, Rufang; Chu, Shijin

    2016-01-01

    Five new bis(3-hydroxy-4-pyridinone) tetradentate chelators were synthesized in this study. The structures of these tetradentate chelators were characterized by ¹H-NMR, (13)C-NMR, FT-IR, UV-vis, and mass spectral analyses. The binding abilities of these tetradentate chelators for uranyl ion at pH 7.4 were also determined by UV spectrophotometry in aqueous media. Results showed that the efficiencies of these chelating agents are dependent on the linker length. Ligand 4b is the best chelator and suitable for further studies. PMID:27005598

  11. Uranyl ion uptake by polyaniline

    International Nuclear Information System (INIS)

    Polyaniline (Pani) was synthesized by the chemical oxidation of aniline. The batch mode experiments showed that Pani could be used for the separation of metal ions like uranyl from a mixture. UO22+ was converted into its anionic complex using suitable complexing agent like thiocyanate and the anionic complex is taken up by Pani. Interference studies showed that uranyl ion can be selectively taken up in presence of transition metal ions present in some binary mixtures. (author)

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

    International Nuclear Information System (INIS)

    Functional surfactants were synthesised by grafting a chelating group (amino-acid residue) to the tip of a poly-ethoxylated nonionic surfactant chain (CiEj: CiH2i+1(OCH2CH2)jOH)) or in a branched position. CiEj 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 CiEj and complexing agent solubilized in the micelles. This reveals a synergistic effect of the covalent bond between the chelating group and the nonionic surfactant CiEj. This paper presents a systematic study of the extraction and aggregation properties and the influence of the nature of the ions. (authors)

  13. 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.

  14. Photochemical reduction of uranyl ion with triphenylphosphine

    International Nuclear Information System (INIS)

    Photochemical reduction of uranyl ion with triphenylphosphine has been studied in acetone-water medium in the presence of sulphuric acid at 346nm, 400nm and 434nm wavelengths. The photochemical reduction is of second order and increases with increase in hydrogen ion concentration. Absorption spectra of uranyl ion in acidic medium and uranyl ion with triphenylphosphine do not show any ground state complex formation. The value of quantum yield increases with the wavelength of the radiation increase from 346 to 434nm. Plots of reciprocal of quantum yield for the formation of U(IV) versus reciprocal [triphenylphosphine] are linear. Products characterized by UV and visible, IR and TLC show the formation of U(IV) and triphenylphosphine oxide. On the basis of above observations mechanism of the photochemical reduction has been proposed. (author)

  15. 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.)

  16. Luminescence enhancement of uranyl ion by benzoic acid in acetonitrile

    International Nuclear Information System (INIS)

    Uranyl ion is known for its characteristic green luminescence and therefore luminescence spectroscopy is a suitable technique for characterizing different uranyl species. In aqueous medium, luminescence of uranyl ion is generally weak due to its quenching by water molecules and therefore in order to enhance the luminescence of uranyl ion in aqueous medium, luminescence enhancing reagents such as H3PO4, H2SO4, HCIO4 have been widely used. The other method to enhance the uranyl luminescence is by ligand sensitized luminescence, a method well established for lanthanides. In this work, luminescence of uranyl ion is found to be enhanced by benzoic acid in acetonitrile medium. In aqueous medium benzoic acid does not enhance the uranyl luminescence although it forms 1:1 and 1:2 complexes with uranyl ion. Luminescence spectra of uranyl benzoate revealed that enhancement is due to sensitization of uranyl luminescence by benzoate ions. UV-Vis spectroscopy has been utilized to characterize the specie formed in the in acetonitrile medium. UV-Vis spectroscopy along with luminescence spectra revealed that the specie to be tribenzoate complex of uranyl (UO2 (C6H5COO)3)- having D3h symmetry. (author)

  17. 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

  18. Using lanthanide chelates and uranyl compounds for diagnostic by fluoroimmunoassays

    International Nuclear Information System (INIS)

    The importance of the luminescence of lanthanide ions and UO22+ is related to its peculiar characteristics, e.g. long lifetime and line-like emission bands in the visible, which make these ions unique among the species that are known to luminescence. Recent developments in the field of supramolecular chemistry have allowed the design of ligands capable of encapsulating lanthanide ions, thus forming kinetically inert complexes. By introduction of chromophoric groups in these ligands, an intense luminescence of the ion can be obtained via the 'antenna effect', defined as a light conversion process involving distinct absorbing (ligand) and emitting (metal ion) components. In such a process, the quantities that contribute to the luminescence intensity are the efficiency of the absorption, the efficiency of the ligand-metal energy transfer, and the efficiency of the metal luminescence. Encapsulation of lanthanide ions with suitable ligands may therefore give rise to 'molecular devices' capable to emit strong, long-lived luminescence. Besides the intrinsic interest in their excited state properties, compounds of lanthanide ions, in particular of the Eu3+ and Tb3+ ions, and now UO22+ are important for their potential use as luminescent labels for biological species in fluoroimmunoassays (FIAs). This is most interesting because fluorimetric labeling represents an alternative method to the use of radioactive labels, which has long been the most common way of quantifying immunoreactions. In this article we report information about luminescent materials, which gave a good signal to quantify biological molecules by TR-FIA, DELFIA , DSLFIA, RIA and FRET. (author)

  19. Electroreduction of uranyl ion in aqueous calcium nitrate solutions

    International Nuclear Information System (INIS)

    The electroreduction of uranyl ions in buffered and unbuffered 0.5 M calcium nitrate has been studied using polarography, cyclic voltammetry, chronopotentiometry, and chronoamperometry. The results are compared with those in molten calcium nitrate tetrahydrate. (author)

  20. Complexation of the uranyl ion with aquatic humic acid

    International Nuclear Information System (INIS)

    The complexation of the uranyl(VI) ion with aquatic humic acid from Gorleben groundwater (Gohy-573) is studied in 0.1 M NaClO4 at pH 4 under argon atmosphere. The concentration range investigated is from 1 x 10-7 to 1 x 10-5 mol/l for the uranyl ion and from 1 x 10-6 to 1.12 x 10-5 mol/l for the humic acid. Three different experimental methods are applied to separate the uncomplexed uranyl ion from the uranyl humate complex, using differences of the two species in size by ultrafiltration at the pore size of about 1 nm, in charge by anion exchange separation and in spectroscopic properties by time resolved laser fluorescence spectroscopy (TRLFS). No reduction of U(VI) to U(IV) is observed in the course of the humate complexation process. The experimental results confirm that the prevailing complexation reaction is charge neutralization of the UO2+2 ion with two proton exchanging sites of humic acid. At pH 4 in 0.1 M NaClO4, where the hydrolysis of the uranyl ion appears negligible, the fraction of proton exchanging sites of the humic acid that can be occupied by the uranyl ion (called the loading capacity (LC) of the uranyl ion) is determined to be 0.185±0.003. The complexation constant evaluated by taking the loading capacity into account is found to be logβ = 6.16±0.13, which is a grand average of all values determined by the three experimental procedures under consideration. This value is valid for the humate complexation of the non-hydrolyzed uranyl ion, being independent of pH and ionic strength. (orig.)

  1. 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)

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

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Caroline Hastenreiter; Santos, Bruno Zolotareff dos; Yamamura, Amanda Pongeluppe Gualberto; Yamaura, Mitiko, E-mail: hc.caroline@gmail.co, E-mail: bzsantos@gmail.co, E-mail: amandaifusp@yahoo.com.b, E-mail: myamaura@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2009-07-01

    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{sup -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)

  3. 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

  4. Method of producing weakly acidic cation exchange resin particles charged with uranyl ions

    Energy Technology Data Exchange (ETDEWEB)

    Abdelmonem, N.; Ringel, H.; Zimmer, E.

    1981-07-21

    Weakly acidic cationic ion exchange resin particles are charged with uranyl ions by contacting the particles step wise with aqueous uranyl nitrate solution at higher uranium concentrations from stage to stage. An alkaline medium is added to the uranyl nitrate solution in each stage to increase the successive pH values of the uranyl nitrate solution contacting the particles in dependence upon the uranium concentration effective for maximum charging of the particles with uranyl ions.

  5. Complexation effects on uranyl ion spectra

    International Nuclear Information System (INIS)

    The uranyl complexes of (i) mono furfural 4-(2-pyridyl thio semicarbazonato), (ii) bis-3-methyl-4-(p-methyl phenylazo)-5-pyrazolonato, (iii) bis-2-AC-benzofuranato and (iv) bis-3-acetyl-4-hydroxy coumarinate, are prepared, isolated and characterized by chemical analysis for the first time. The spectra of these complexes along with uranyl nitrate have been recorded at 293 K by using nujol mull technique. The force constants are evaluated by Wilson's FG matrix method and the effects of complexation on U-O force constants and bond distances in uranyl nitrate are discussed. (author)

  6. 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)

  7. Mechanistic studies on uranyl ion initiated photopolymerization of acrylamide

    International Nuclear Information System (INIS)

    The mechanism of the uranyl ion photoinitiated polymerization of acrylamide has been studied in aqueous solutions and in acetone. Steady-state and dynamic luminescence quenching studies show that initiation proceeds through a thermally activated bimolecular interaction between *UO22+ and monomer involving electron or charge transfer. Results from various studies show that the mechanism previously suggested for this process, involving energy transfer, is incorrect. ESR studies suggest that initiation involves formation of a uranium(V)-radical pair. Polymerization then proceeds through a radical mechanism in both solvents. With the exception of the chloride, the yields do not depend upon the counter-ion. Polymer is frequently produced with adsorbed uranyl ions, which can be separated by dialysis. In agreement with previous studies, photopolymerization proceeds without significant overall reduction in the uranyl concentration. It is shown that this is probably due to any intermediate uranium(V) being reoxidized by monomer, with concurrent thermal initiation of polymerization. (orig.)

  8. 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)

  9. Synergistic extraction of uranyl ion with acylpyrazolones and dicyclohexano-18-crown-6

    International Nuclear Information System (INIS)

    Synergistic extraction of uranyl ion with acylpyrazolones such as 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5 (HPMTFP, pKa=2.7), 1-phenyl-3-methyl-4-acetylpyrazolone (HPMAP, pKa=3.8) or 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (HPMBP, pKa=4.2) in combination with dicyclohexano-18-crown-6 (DC-18-C6) was studied at various fixed temperatures. The results indicate that the equilibrium constants of the organic phase addition reaction, log Ks, at 30 deg C are almost constant for the above three systems. Thermodynamic data for chelate extraction with HPMTFP evaluated by the temperature coefficient method indicates that a hydrated chelate is extracted into the organic phase. (author) 19 refs.; 6 figs

  10. 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

  11. New chemistry of the uranyl ion in non aqueous media

    International Nuclear Information System (INIS)

    This work deals with new aspects of the chemistry of the uranyl(VI) ion {UO2}2+ in anhydrous polar organic solvents such as the activation of the reputedly inert U-Oyl bond and the controlled reduction of this species which represent a particularly active field of research that attracts much attention for both its fundamental aspects and applications. Treatment of uranyl(VI) compounds UO2X'2 (X' = I, OTf, Cl) with Me3SiX (X = Cl, Br, I) reagents, in various anhydrous polar organic solvents, has been first considered. In most cases, reduction into tetravalent species with complete de-oxygenation of the uranyl {UO2}2+ ion is observed. The reaction is particularly efficient in acetonitrile where the tetravalent [UX4(MeCN)4] complexes, which are useful precursors in uranium chemistry, are isolated. In the course of these reactions, the influence of the solvent, the nature of X' and X in the UO2X'2 precursor and the Me3SiX reagent are pointed out. Reaction of the uranyl(VI) UO2X2 (X = I, Cl, OTf, NO3) precursors with the anionic MC5R5 (M = K, R = H, Me; M= Li, R = Me; M= Tl, R = H) reagents did not lead to the organometallic [(η5-C5R5)nUO2X2-n] species (n = 1, 2) but to pentavalent uranyl(V) complexes. This method is a facile and rapid route towards the formation of stable pentavalent uranyl which offers promising sources for further U(V) chemical developments and for fundamental and applied interests. Their structure is strongly dependent on the nature of the solvent, the additional ligands X and of the M+ cation. In pyridine, the {UO2(py)5}+ ion appears to be an ubiquitous and a quite stable entity. The coordinating properties of the basic oxo groups, which coordinate easily to M+ ions (M= Li, K, Tl), favour structural diversity with formation of hetero-polymetallic complexes such as [{UO2(py)5}{MX(py)2}] (M= Li, X I), [{UO2(py)5}{MX2(py)2}]∞ (M= K, Tl, X= OTf; M= K, X= I), [{UO2(py)5}(M2X3)]∞ (M= Li, X= OTf) or [{UO2(py)5}2(M3X5)]∞ (M= K; X= OTf). With

  12. A method for separating uranium from an aqueous solution containing uranyl ions and contaminating ions

    International Nuclear Information System (INIS)

    Description is given of a method for separating uranium from contaminating ions in an aqueous solution containing uranyl ions. In a first step, the contaminating ions are extracted by a first solvent containing a reagent capable of forming a soluble complex with the uranyl ions. The solvent is separated by means of a separator liquid, which is subsequently extracted by a solvent containing an amine, then, said amine is separated by means of a sufficient amount of ammonium carbonate solution for precipitating an uranium complex which is subsequently recovered. This can be applied to the extraction of uranium from phosphoric or sulphuric solutions or from sodium carbonate

  13. 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)

  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. 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)

  16. 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)

  17. 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%.

  18. 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

  19. Density functional theory and molecular dynamics study of the uranyl ion (UO₂)²⁺.

    Science.gov (United States)

    Rodríguez-Jeangros, Nicolás; Seminario, Jorge M

    2014-03-01

    The detection of uranium is very important, especially in water and, more importantly, in the form of uranyl ion (UO₂)²⁺, which is one of its most abundant moieties. Here, we report analyses and simulations of uranyl in water using ab initio modified force fields for water with improved parameters and charges of uranyl. We use a TIP4P model, which allows us to obtain accurate water properties such as the boiling point and the second and third shells of water molecules in the radial distribution function thanks to a fictitious charge that corrects the 3-point models by reproducing the exact dipole moment of the water molecule. We also introduced non-bonded interaction parameters for the water-uranyl intermolecular force field. Special care was taken in testing the effect of a range of uranyl charges on the structure of uranyl-water complexes. Atomic charges of the solvated ion in water were obtained using density functional theory (DFT) calculations taking into account the presence of nitrate ions in the solution, forming a neutral ensemble. DFT-based force fields were calculated in such a way that water properties, such as the boiling point or the pair distribution function stand. Finally, molecular dynamics simulations of a water box containing uranyl cations and nitrate anions are performed at room temperature. The three peaks in the oxygen-oxygen radial distribution function for water were found to be kept in the presence of uranyl thanks to the improvement of interaction parameters and charges. Also, we found three shells of water molecules surrounding the uranyl ion instead of two as was previously thought. PMID:24573498

  20. Construction of Uranyl Selective Electrode Based on Complex of Uranyl Ion with New Ligand Carboxybenzotriazole in PVC Matrix Membrane

    Science.gov (United States)

    Abu-Dalo, M. A.; Al-Rawashdeh, N. A. F.; Al-Mheidat, I. R.; Nassory, N. S.

    2015-10-01

    In the present study uranyl selective electrodes in polyvinyl chloride (PVC) matrix membrane were prepared based on a complex of uranyl ion (UO2) with carboxybenzotriazole (CBT) as ligand. The effect of the nature of plasticizer in PVC matrix were evaluated using three different plasticizers, these are dibutyl phthalate (DBP), dioctyl phthalate (DOP) and bis(2-ethylhexyl) sebacate (BHS). The results of this study indicated that the best plasticizer could be used is the DBP, which may be attributed to its lowest viscosity value compared to DOP and BHS. The electrodes with DBP as plasticizer exhibits a Nernstian response with a slope of 28.0 mV/ decade, over a wide range of concentration from 3.0×10-5-6.0×10-2 M and a detection limit of 4.0×10-6 M. It can be used in the pH range of 4.0-10.0 with a response time of less than 10 s for DBP and 25 s for both DOP and BHS. The effects of ions interferences on the electrode response were evaluated. The di- and tri-valent cations were found to interfere less than univalent cations, which was attributed to the high diffusion and the exchange rate between the univalent ions and the uranyl ion solution. The electrodes were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron microscopy (SEM). The results of the standard addition method were satisfactory with errors less than 7%. The developed electrode was found to be fast, sensitive and reliable indicated its potential use in measuring the uranly ion concentration in the field.

  1. Flotation of uranyl ions by alkylcarboxylic acid salts of potassium

    International Nuclear Information System (INIS)

    Physical and chemical features of uranyl cation flotation by potassium salts of fatty acids from diluted solutions are presented. Maximum degree of uranyl flotation is shown to occur in the range of pH=5-6 which corresponds to flotoactive forms of UO22+(OH)+ and to the form of collector as RCOO-. Efficiency of collector first increases with the length of hydrocarbon radical (due to decreasing sublate solubility) and then declines (due to increasing electrokinetic potential). Increase of the temperature of solutions leads to an increase in sublate solubility and to a decrease in the extent of uranyl flotation. 8 refs.; 4 figs.; 2 tabs

  2. Synthesis of uranyl ion imprinted polymer and its application in analysis

    International Nuclear Information System (INIS)

    Uranyl ion imprinted polymer beads were prepared by the copolymerization of styrene monomer and divinyl benzene as crosslinking agent in methanol solution,with the UO22+-o-dihydroxybenzene-4-vinyl pyridine ternary complex as template, the 2, 2'-azo-bis-isobutyronitrile as initiator and UO22+ as the imprinting ion. The uranyl ions were removed from the polymer beads by treating with 6 mol/L HCl, leaving behind cavities that match uranyl ion in size. The treated polymer beads can preconcentrate uranyl ions from dilute aqueous solutions. The adsorption efficiency can reach 99% or above with good selectivity when pH is in the range of 5-7 and the adsorption time is more than 20 min. The elution rate can reach above 99% under the conditions of concentration of HCl being above 1.0 mol/L, elution time more than 20 min and the elution Janume more than 5 times the Janume of ion imprinted polymer. The uranyl ion imprinted polymer beads have been successfully applied to determine micro-uranium in brine samples. The results are satisfactory compared with NBS method.(authors)

  3. Magnetic nanoparticles with an imprinted polymer coating for the selective extraction of uranyl ions

    International Nuclear Information System (INIS)

    We have synthesized ferromagnetic nanoparticles with an imprinted polymer coating that is capable of adsorbing and extracting uranyl ions. The adsorbent was characterized using infrared spectroscopy, elemental analysis, X-ray powder diffraction analysis, and scanning electron microscopy. The effects of sample pH, sample volume, weight of the adsorbent, contact time and of other ions have been investigated in the batch extraction mode. The performance of the material was compared to that of particles coated with a non-imprinted polymer. The adsorbent containing the imprinted coating displays higher sorption capacity and better selectivity to uranyl ions. The method was successfully applied to the determination of uranyl ions in water samples. (author)

  4. Kinetic studies of uranyl ion adsorption on acrylonitrile (AN) / polyethylene glycol (PEG) interpenetrating networks (IPN)

    International Nuclear Information System (INIS)

    The kinetics of the adsorption of uranyl ions on amidoximated acrylonitrile (AN)/ polyethylene glycol (PEG) interpenetrating network (IPNs) from aqueous solutions was studied as a function of time and temperature. Adsorption analyses were performed for definite uranyl ion concentrations of 1x10-2M and at four different temperatures as 290K, 298K, 308K and 318K. Adsorption time was increased from zero to 48 hours. Adsorption capacities of uranyl ions by PEG/AN IPNS were determined by gamma spectrometer. The results indicate that adsorption capacity increases linearly with increasing temperature. The max adsorption capacity was found as 602 mgu/g IPN at 308K. Adsorption rate was evaluated from the curve plotted of adsorption capacity versus time, for each temperature. Rate constants for uranyl ions adsorption on amidoximated ipns were calculated for 290K, 298K, 308K and 318K at the solution concentration of 1x10-2M . The results showed that as the temperature increases the rate constant increases exponentially too. The mean activation energy of uranyl ions adsorption was found as 34.6 kJ/mole by using arrhenius equation. (author)

  5. 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.

  6. 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)

  7. 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.

  8. 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.

  9. Decorporation of metal ions by chelating agents

    International Nuclear Information System (INIS)

    Simple model designs to simulate the effect of therapeutical chelating agents on the behaviour of metals in mammal organisms with and without excretion have been derived and analytical solutions given for the corresponding differential equations. The possibilities of these models in the short-term description of plasma kinetics of various metals, the competition of the therapeutical ligands with proteins for the metal and of the metabolism of chelating agents were tested and the properties applying extreme conceivable parameters were analyzed. The simple models were successsively expanded in logical sequence, so that it was possible to qualitatively well describe over a long period of time, the metallic kinetics in plasma, organs and urine, the retention of the ligands and their effect on the metal excretion. Two suggestions were given to describe the so-called after-effect, an increased excretion of the metal at times when the ligand is almost completely excreted and their different behaviour after injecting the metal chelate is given. Calculations on the therapy with several ligand data as well as on dose fractionation are described resting on the ratios in the plutonium-239 chosen model parameters and the determining mechanisms analyzed. (orig./MG)

  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. f-Element Ion Chelation in Highly Basic Media

    International Nuclear Information System (INIS)

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

  12. Extraction rate of metal ion by chelating agent

    International Nuclear Information System (INIS)

    In order to clarify the extraction mechanism of metal ion by a chelating agent, it is problematic to infer the mechanism on the basis of the dependence of the extraction rate upon the concentration of the agent. For this purpose, the information as follows is essential: (1) computation of physical chemistry constants of the chelating agent, (2) the reaction rate for chelate formation with the metal ion in the water phase and the mechanism, and (3) the measurement of the extraction rate by use of the apparatus for which the oil/water interface area and the interface-material transfer coefficient are known. It is then necessary to establish the design guidance of reaction field and separation field via the accumulation of the experimental results. (Mori, K.)

  13. 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)

  14. Sorption of uranyl and thorium(IV) ions by dodecavanadium acid from diluted nitric acid solutions

    International Nuclear Information System (INIS)

    Sorption of uranyl by dodecavanadium acid (DDVA) proceeds according to ion exchange mechanism in the region of relatively low values of its concentration - (0.8-2.0) x 10-3 mol/l. Th(IV) sorption practically not depends on solution pH value in interval of pH 1.5-2.5 and changes significantly in dependence on its initial concentration. Maximal values of DDVA capacity differ for Th(IV) and UO22+ (9 and 6.3 mg-equi/g) respectively. X-ray phase analysis establishes the composition of uranyl compounds obtained during DDVA contact with concentrated solutions of uranyl nitrate that is UO2(VO3)2·nH2O

  15. 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)

  16. 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

  17. 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

  18. 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

  19. Stability and kinetics of uranyl ion complexation by macrocycles in propylene carbonate

    International Nuclear Information System (INIS)

    A thermodynamic study of uranyl ion complexes formation with different macrocyclic ligands was realized in propylene carbonate as solvent using spectrophotometric and potentiometric techniques. Formation kinetics of two UO2 complexes: a crown ether (18C6) and a coronand (22) was studied by spectrophotometry in propylene carbonate with addition of tetraethylammonium chlorate 0.1M at 250C. Possible structures of complexes in solution are discussed

  20. 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.

  1. Doping of graphene nanomeshes by ion-chelation

    Science.gov (United States)

    Maarouf, Ahmed; Nistor, Razvan; Afzali, Ali; Kuroda, Marcelo; Newns, Dennis; Martyna, Glenn

    2013-03-01

    Graphene nanomeshes (GNM's) are formed by the creation of a superlattice of pores in graphene. Depending upon the pore shape, size, superlattice constant and symmetry, GNM's can be semimetallic, or semiconducting with a fractional eV band gap, allowing them to be fruitfully employed in applications that pristine graphene cannot. In this work, first principles calculations are used to study the doping of semiconducting GNM's using a chemically motivated approach. It is shown that ion-chelation leads to a stable doping of the GNM's, and that it occurs within a rigid band doping picture. Such chelated or ``crown'' GNM structures are thus stable, high mobility semiconducting materials which can serve as building blocks for novel graphene-based nanoelectronics applications.

  2. Study of hydrolysis and complexing of uranyl ions in sulfate solutions at elevated temperatures

    International Nuclear Information System (INIS)

    A study was made of uranyl ion hydrolysis at elevated temperatures in the absence of complex formation in dilute nitrate solutions by measuring the pH. It was found that hydrolysis in the temperature range from 50 to 1500C and a total U(VI) concentration of 10-2 to 10-5 M occurs basically by the three reactions. The data was processed by computer to calculate the equilibrium constants of these reactions and to obtain equations for these constants as functions of temperature. Taking into account hydrolysis, the pH measurements for the uranyl sulfate solutions were used to calculate the equilibrium constants of the dissociation reaction of the sulfate complex. The dissociation constants as functions of temperature were also found. 22 refs., 3 tabs

  3. 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)

  4. Coordination of the uranyl ion in solution and ionic liquids : a combined UV-Vis absorption and EXAFS study

    OpenAIRE

    Servaes, Kelly

    2007-01-01

    The uranyl ion (UO22+) has been extensively studied for decades and nowadays it is still a hot topic in a number of contemporary issues like nuclear waste treatment and the Balkan syndrome. Therefore, besides our fundamental interest in this complex system, the aim of this study was to provide a convenient and straightforward approach to identify the structure of various uranyl complexes formed in solution. To achieve this goal, spectroscopic techniques like UV-Vis absorption spectroscopy, ...

  5. Determination of the stability of the uranyl ion sipped in τ-hydrogen phosphate of zirconium in sodic form

    International Nuclear Information System (INIS)

    The stability of the uranyl sipped in the zirconium τ-hydrogen phosphate in sodic form (τ-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 10-4 and 10-5 of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO4. 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 τ-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

  6. 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.

  7. Adsorption of uranyl ions in nanoparticles of magnetite

    International Nuclear Information System (INIS)

    This work studied the uranium (VI) adsorption, in the form of UO22+ ions, of the nitride solution by the syntetic magnetite. This solution was prepared by precipitation adding a solution of NaOH to the solution containing the ions Fe2+. The time of contact and the isothermal of equilibrium of ions UO22+ adsorption was verified. The isothermal of equilibrium presented more concordance with the Freundlich model, which characterized a heterogeneous adsorption surface of the magnetite. The great advantage of this technology is the combination of two separation techniques, by adsorption and magnetic, resulting in a highly efficient and reusable system

  8. Determination of trace uranyl ions in aquatic medium by a useful and simple method

    International Nuclear Information System (INIS)

    Determination of trace uranyl ions was performed by using mixed micellar system and spectrophotometric determination. The method is based on cloud point extraction of uranyl ions after formation of an ion-association complex in the presence of Celestine Blue and sodium dodecyl sulfate. Then, the formed complex was extracted to non-ionic surfactant phase of Triton X-114 at pH 8.0. The optimal extraction and reaction conditions (e.g. concentrations and types of surfactants, concentration of complex forming agent, incubation conditions) were studied and analytical characteristics of the method (e.g. limit of detection, linear range, pre-concentration factor) were obtained by experimental studies. Linearity was obeyed in the range of 50-1,500 ng mL-1 for uranium(VI) ion and the detection limit of is 14.20 ng mL-1. The interference effects of common ions were also tested and validation studies were performed by using recovery test. The method was applied to the determination of uranium(VI) in several real samples. (author)

  9. 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

  10. Investigation of the role of chelating ligand in the synthesis of ion-imprinted polymeric resins on the selective enrichment of uranium(VI)

    International Nuclear Information System (INIS)

    Uranyl ion-imprinted polymeric (IIP) resins were prepared by dissolving stoichiometric amounts of uranyl nitrate and selected chelating ligands, viz. salicylaldoxime, catechol, succinicacid, 5,7-dichloroquinoline-8-ol and 4-vinyl pyridine in 2-methoxy ethanol (porogen) and copolymerizing thermally in the presence of 2-hydroxyethylmethacrylate (HEMA) and ethyleneglycol-dimethacrylate (EGDMA), using 2,2'-azobisisobutyronitrile (initiator). Again, IIP resins were also prepared on similar lines by utilizing ternary [uranium-non-vinylated ligand-vinylated ligand (4-vinyl pyridine)] complexes. Non-imprinted polymeric resins were identically prepared in both cases without the use of uranyl imprint ion. The percent enrichment and retention capacity studies showed significant imprinting effect in all cases. However, ion-imprinted polymeric resins formed with succinic acid (SA) or 5,7-dichloroquinoline-8-ol (DCQ) and 4-vinylpyridine (VP) alone gave quantitative enrichment and various parameters that influence the enrichment and elution were then optimized. The percent enrichment of uranium from synthetic seawater solutions was found to be 25.0 ± 0.5 and 83.0 ± 0.8 for SA-VP and DCQ-VP systems, respectively. The DCQ-VP-based IIP resins were successfully tested for the recovery of uranium from real seawater samples

  11. 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.

  12. Interaction of 4-amino 6-hydroxy 2-thiopyrimidine with uranyl ion in presence of other ligands

    International Nuclear Information System (INIS)

    Interaction of uranyl ion with 4-amino 6-hydroxy 2-thiopyrimidine(AHTP) in presence of other ligands such as oxalic acid (Ox), malonic acid (Mal), O-aminophenol (OAP), o-phenylenediamine (OPDA), 2, 2'-bipyridyl (Bipy), 1, 10-phenanthrolene (Phen) and ethylenediamine (En) has been investigated by potentiometric method. The ternary complexes are formed in stepwise manner in which AHTP behaves as secondary ligand. The formation constants of ternary complexes have been reported at 35 degC and μ = 0.10 M (KNO3) in aqueous medium. (author)

  13. 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

  14. Uranyl ion behaviour in perchloric media and its extraction by TBP CCl/sub 4/

    Energy Technology Data Exchange (ETDEWEB)

    Yahia, A. (Centre de Developpement des Materiaux, Commissariat aux Energies Nouvelles, Alger (Algeria)); Benali-Baitich, O. (Universite des Sciences et de la Technologie Houari Boumediene (USTHB), Institut de Chimie, Alger (Algeria))

    The behaviour of uranyl ion in aqueous solution of perchloric acid (O < Cub(HC104) < 13 mol.1/sup -1/) shows that for an acidity higher than 9 mol.1/sup -1/, there is formation of a monoperchlorato complex. The extraction of uranly perchlorate from aqueous perchloric solutions by TBP diluted CC1/sub 4/ as a function of uranium and perchloric acid concentrations enabled us on one hand, to concluded that UO/sub 2//sup + +/ is solvated by 2 TBP molecules, and on the other hand, to determine the composition of the coextracted HC1O/sub 4/ solvated species.

  15. Quenching of excited uranyl ion during its photochemical reduction by triphenylphosphine: Part III

    International Nuclear Information System (INIS)

    Relative rates of bimolecular quenching of excited uranyl ion by some mono and di-substituted benzene derivatives have been measured during its photochemical reduction with triphenylphosphine. For the related compounds in a series it has been found that substituent groups enriching the aromatic π-electron cloud due to resonance stabilization, show an enhanced photophysical quenching action. The substituents decreasing the π-electron cloud and delocalization of positive charger over the benzene ring decrease the quenching action. (author). 16 refs., 2 figs., 1 tab

  16. A relativistic study of the photochemistry of the uranyl(VI) ion in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Real, F.; Wahlgren, U. [Alballova University Center, Stockholm University, Fysikum, 104-91 Stockholm, (Sweden); Vallet, V. [Laboratoire PhLAM, Universite des Sciences et Technologies de Lille 1 CNRS UMR8523, 59655 Villeneuve d Ascq Cedex, (France); Marian, C. [Institut fur Theoretische Chemie und Computerchemie Heinrich-Heine-Universitat Universitatsstr. 40225 Dusseldorf (Georgia); Grenthe, I. [KTH Royal Institute of Technology, Inorganic Chemistry Se-10044 Stockholm, (Sweden)

    2007-07-01

    Complete text of publication follows: The U-O bond in the uranyl(VI) ion is in general considered to be kinetically inert in thermal reactions, such as isotope exchange reactions. However, a fast isotope exchange can take place in photochemical reactions under UV irradiation as exemplified by the reaction: U{sup 17}O{sub 2}(H{sub 2}O){sub 5}{sup 2+} + H{sub 2}*0 {yields} U{sup 17}O{sub 2}(H{sub 2}O){sub 5}{sup 2+} + H{sub 2}O (1) Under daylight, no exchange takes place, or the rate of exchange is very slow. This suggests that the reaction involves the excited-states of the uranyl(VI). 1) A comparison between wave-function theory and density-functional theory: The first part of this talk will discuss benchmark calculations of the excited states of the bare uranyl(VI) ion so that we can choose the computational cost effective ab initio method for the study of the photochemistry of actinide compounds. Before exploring the mechanism of exchange it is necessary to have information on the chemistry of the excited states and their electronic structure. It seems reasonable to assume that 'yl'-isotope exchange is related to the U-O{sub yl} stretching modes and following the work of Pierloot and van Besien [1] we have therefore studied the a{sub g}- and a{sub u}-modes of the U-O{sub yl} bond using different methods such as CASPT2, TD-DFT and DFT-MRCI and different basis set and description of the heavy-element. The scalar-relativistic effects were included using either the Douglas-Kroll Hamiltonian in the case of all-electron calculations or an RECP small core from the Stuttgart Library. The {sup 3}{gamma}{sub g} state seems to be a good candidate for the photochemically 'active' state where the increase of the U-O{sub yl} localizes the wave function and gives distant 'yl' oxygen attains radical character. 2) Photochemistry of the uranyl(VI) in aqueous solution: In the case of the photochemistry of the uranyl(VI), we suggest that the first step

  17. EDTA and DTPA modified ligands as sequestering agents for uranyl decorporation

    International Nuclear Information System (INIS)

    Synthesis of modified EDTA and DTPA ligands and determination of their binding affinities for the uranyl cation are described. Thanks to a screening method, based on a chromophoric complex displacement procedure, chelating properties were studied in aqueous media under various pH conditions for evaluation of their in vivo uranyl-removal efficacy. Each ligand showed a more or less pronounced affinity for uranium. Specific ligands based on EDTA or DTPA analogues containing sulfo-catechol-amide (CAMS) were found to exhibit a significant affinity towards uranyl ion in acidic, neutral or basic conditions. (authors)

  18. Synthesis of amidoxime chelating fiber and its adsorption properties for Cu(II) ion

    International Nuclear Information System (INIS)

    In order to obtain the chelating fiber for adsorbing metal ions in apple juice, the effect of different conditions on adsorption properties of chelating fiber for Cu(II) ion were discussed, such as pH and the time of ad- sorption. The isotherm of adsorption has bee confirmed. The desorption and its regeneration were simply discussed, too. The results showed that the chelating fiber had good kinetic property and the adsorbed equilibrium completed almost within 20-30 min. The adsorption properties was affected by the temperature and pH. The adsorption process fits the isothermal equation of Freundlich. The chelating fiber could be used repeatedly. (authors)

  19. 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

  20. Establishment of a luminescence technique for the quantification of uranyl ion in a KNO3 media

    International Nuclear Information System (INIS)

    The study of the storage of high level radioactive residuals that contain uranium, it makes necessary that in the sorption studies is counted with a reliable technique and not pollutant for the quantification of this element. Presently work intends a technique for the quantification of the uranyl ion using the luminescence technique, which allows not to generate radioactive or industrial residuals. It was used a solution of uranyl nitrate in KNO3 0.5 M media. The solutions were adjusted to a pH of 1.48+0.03. A statistical study for the analysis of the data of fluorescence, about the maximum value of the peak, total area under the curve and area under the it curves is shown, being the best correlation for the concentration curve versus maximum of the peak, adjusted with a polynomial of second grade. The study of stability of the solutions with regard to the time is reported and that the technique proposal works for the interval of concentrations among 1 x 10-2 M and 6 x 10-5 M. (Author)

  1. 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.

  2. Study of the equilibrium of the reaction of uranyl ions with Arsenazo III

    International Nuclear Information System (INIS)

    A solvent containing 0.2M HCL, dioxane and ethanol in a volume ratio 1:2:2 was found to be well suited for the spectrophotometric determination of uranyl with Arsenazo III. The absorbance at the analytical wavelength of 652 nm is lowered in the presence of nitrate and, in particular, sulphate ions. Three models of the system composition were computer processed: the presence of M:L=1:1 complexes, of M:1=1:2 complexes, and of both of them simultaneously, and the latter was found to be most likely. The calculated stability constants were log β1=5.42 and log β2=9.75, the calculated absorption maxima lay at 604 and 650 nm for the 1:1 complex and at 606 and 652 nm for the 1:2 complex. (author). 5 figs., 1 tab., 4 refs

  3. Relationship of the vibrational frequency of the uranyl ion with the uranium electronegativity

    International Nuclear Information System (INIS)

    It has been demonstrated that the vibrational asymmetric frequency of the uranyl ion, it experiences a consistent spectrochemical displacement with the variations of electronegativity of the uranium in their complexes. The values of the electronegativity of the uranium they were dear by means of calculations that it involves measures of those lengths of the connection uranium-oxygen, obtained by vibrational spectroscopy, effective nuclear charges and the Allred and Rochow equation. The results show the evidence of a natural order that relates to the vibrational frequency with the electronegativity of the uranium atom; settling down that if the electronegativity is graph against it bond length to the oxygen or to it frequency value, a simple relationship is obtained as a form to obtain clear responses in absence of complementary information. (Author)

  4. Characterization of Standard Reference Material 2941, uranyl-ion-doped glass, spectral correction standard for fluorescence

    International Nuclear Information System (INIS)

    Standard Reference Material (SRM) 2941 is a cuvette-shaped, uranyl-ion-doped glass, recommended for use for relative spectral correction of emission and day-to-day performance validation of fluorescence spectrometers. Properties of this standard that influence its effective use or contribute to the uncertainty in its certified emission spectrum have been explored here. These properties include its photostability, absorbance, dissolution rate in water, anisotropy, temperature coefficient of fluorescence intensity, and fluorescence lifetimes. The expanded uncertainties in the certified spectrum are about 4% around the peak maximum at 526 nm, using an excitation wavelength of 427 nm. The SRM also exhibits a strong resistance to photodegradation, with no measurable decrease in fluorescence intensity even after 8 h of laser irradiation

  5. Determination of uranium in environmental matrices by chelation ion chromatography using a high performance substrate dynamically modified with 2,6-pyridinedicarboxylic acid

    International Nuclear Information System (INIS)

    Chelation ion chromatography, involving a high efficiency neutral polystyrene-divinylbenzene resin dynamically coated with 2,6-pyridinedicarboxylic acid, has been developed as a novel technique for the quantitative determination of uranium in complex matrices. An isocratic separation method, using an eluent consisting of 1M KNO3, 0.5 M HNO3 and 0.1 mM 2,6-pyridinedicarboxylic acid, allowed the uranyl ion to elute away from matrix interferences in under ten minutes. Detection was achieved using an Arsenazo III post column reaction system. Good recoveries were obtained from spiked mineral water and sea water and the standard addition curves produced good linearity (r2 > 0.997) with a detection limit, calculated as twice baseline noise, of 20 μg L-1. The procedure was applied to the determination of trace uranium in standard reference water and sediment samples. The results obtained compared well with the certified values for uranium. (orig.)

  6. 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

  7. 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

  8. 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...

  9. 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.

  10. Complexation or uranyl ion. II. Complexation of uranyl ion in the VP-IAp anion exchanger phase during sorption from carbonate media

    International Nuclear Information System (INIS)

    The complicated process of increased uranium sorption from carbonate medium by the strongly basic anion exchanger VP-1Ap after additional treatment with alkaline solution was studied by IR spectroscopy. The process is related to the formation of certain complex forms of uranyl, differing in degree of polymerization, in which polynuclear forms predominate

  11. Simultaneous Determination of Chelating Agents by Ion-Suppression and Ion-Pair Chromatography in Wastewater

    International Nuclear Information System (INIS)

    This article describes two methods for analysing chelating agents found in nuclear waste. First, ion-suppression chromatography using an anion exchange stationary phase and mobile phase consisting of a nitric acid solution and pure water gradient. UV detection was performed at 330 nm after the reaction with a post-column reagent composed of iron nitrate in perchloric acid. Secondly, ion-pair chromatography with a mobile phase consisting of a mixture of nitric acid, tetra-butyl-ammonium hydrogeno-sulphate, tetra-butyl-ammonium hydroxide and iron chloride. A reversed-phase material was used as a stationary phase and detection was performed by direct measurement of the UV absorption at 260 nm. The quantification limits were lower for ion-pair chromatography than for ion-suppression chromatography. Both methods were easy to implement and allow a multi-element separation in less than 30 min with low detection limits. (authors)

  12. Simultaneous Determination of Chelating Agents by Ion-Suppression and Ion-Pair Chromatography in Wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Dodi, Alain; Bouscarel, Maelle [Commissariat a l' energie atomique - C.E.A, Centre d' Etude de Cadarache, Laboratoire d' Analyses Radiochimiques et Chimiques, St Paul lez Durance (France)

    2008-07-01

    This article describes two methods for analysing chelating agents found in nuclear waste. First, ion-suppression chromatography using an anion exchange stationary phase and mobile phase consisting of a nitric acid solution and pure water gradient. UV detection was performed at 330 nm after the reaction with a post-column reagent composed of iron nitrate in perchloric acid. Secondly, ion-pair chromatography with a mobile phase consisting of a mixture of nitric acid, tetra-butyl-ammonium hydrogeno-sulphate, tetra-butyl-ammonium hydroxide and iron chloride. A reversed-phase material was used as a stationary phase and detection was performed by direct measurement of the UV absorption at 260 nm. The quantification limits were lower for ion-pair chromatography than for ion-suppression chromatography. Both methods were easy to implement and allow a multi-element separation in less than 30 min with low detection limits. (authors)

  13. 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.)

  14. Polyvinyl alcohol fibers with functional phosphonic acid group. Synthesis and adsorption of uranyl (VI) ions in aqueous solutions

    International Nuclear Information System (INIS)

    PVA functionalized with vinylphosphonic acid was prepared as a new adsorbent for uranyl (VI) adsorption from aqueous solutions. The vinylphosphonic acid was cografted onto PVA fibers by preirradiation grafting technique. The adsorbent were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The adsorbent was observed to possess a fibrous structure and was bonded with phosphonic acid groups successfully. The adsorbent was used for the adsorption of low levels uranyl (VI) ions from aqueous solutions. The influence of analytical parameters including pH, adsorption time, amount of adsorbent, metal ion concentration, and temperature were investigated on the recovery of uranyl (VI) ion in aqueous solution. The maximum adsorption capacity (32.1 mg g-1) and fast equilibrium time (30 min) were achieved at pH of 4.5 at room temperature. Thermodynamic parameters (ΔH° = 2.695 kJ mol-1; ΔS° = 31.15 J mol-1 K-1; ΔG° = -6.748 kJ mol-1) show the adsorption of an exothermic process and spontaneous nature, respectively. The possible coordination mechanism was illustrated. Adsorption and desorption coexist in aqueous solutions and then the system becomes equilibrium. (author)

  15. 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

  16. Separation and direct UV detection of complexed lanthanides, thorium and uranyl ions with 2-thenoyltrifluoroacetone by using capillary zone electrophoresis

    International Nuclear Information System (INIS)

    Separation and detection of lanthanides, thorium and uranyl ions by capillary zone electrophoresis in the presence of 2-thenoyltrifluoroacetone (HTTA) as UV-absorbing complexing agent were investigated. The separation of positively charged complexes is partially improved by using a competing ligand in buffer with HTTA for metal ions. When 2-hydroxyisobutyric acid (HIBA) is used as competing ligand, complete separation of thorium, uranyl and lanthanides ions were observed. Some separation parameters such as pH value, the concentration of carrier electrolyte, applied voltage, the concentration of ligand in buffer and the temperature were also optimized. Under the selected conditions, the complete separation of thorium and uranyl from each other and from lanthanides was accomplished in only 12 min using 1 mmol/L HTTA, 50 mmol/L HIBA, 5 mmol/L NaNO3, 5 % methanol with a pH 5.2 at a capillary temperature of 25 deg C. Direct photometric detection at 210 nm using a voltage of 25 kV and an electrokinetic injection (100 mm for 6 s) were used. (author)

  17. Ionothermal synthesis of uranyl compounds that incorporate imidazole derivatives

    Science.gov (United States)

    Wylie, Ernest M.; Dustin, Megan K.; Smith, Jeremy S.; Burns, Peter C.

    2013-01-01

    Ionothermal reactions of uranyl nitrate with various salts in methylimidazolium-based ionic liquids have produced single crystals of three uranyl compounds that incorporate imidazole derivatives as charge-balancing cations. (C4H7N2)[(UO2)(PO3F)(F)] (1) crystallizes in space group C2, a=17.952(1) Å, b=6.9646(6) Å, c=8.5062(7) Å, β=112.301(1)°, (C6H11N2)2[(UO2)(SO4)2] (2) crystallizes in space group C2/c, a=31.90(1) Å, b=9.383(5) Å, c=13.770(7) Å, β=93.999(7)° and (C6H11N2)[(UO2)2(PO4)(HPO4) (3) crystallizes in space group P21/n, a=9.307(2), b=18.067(4), c=9.765(2), β=93.171(2). The U6+ cations are present as (UO2)2+ uranyl ions coordinated by three O atoms and two F atoms in 1 and five O atoms in 2 and 3 to give pentagonal bipyramids. The structural unit in 1 is composed of F-sharing dimers of uranyl pentagonal bipyramids linked into sheets through corner-sharing fluorophosphate tetrahedra. The structural unit in 2 is composed of uranyl pentagonal bipyramids with one chelating sulfate tetrahedron linked into chains by three other corner-sharing sulfate tetrahedra. In 3, the structural unit is composed of chains of uranyl pentagonal bipyramids linked into sheets through edge- and corner-sharing phosphate and hydrogen phosphate tetrahedra. N-methylimidazolium cations occupy the interstitial space between the uranyl fluorophosphate sheets in 1, whereas 1-ethyl-3-methylimidazolium cations link the uranyl sulfate and phosphate units in 2 and 3 into extended structures.

  18. Investigation of Uranyl Nitrate Ion Pairs Complexed with Amide Ligands using Electrospray Ionization Ion Trap Mass Spectrometry and Density Functional Theory

    International Nuclear Information System (INIS)

    Ion populations formed from electrospray of uranyl nitrate solutions containing different amides vary depending on ligand nucleophilicity and steric crowding at the metal center. The most abundant species were ion pair complexes having the general formula (UO2(NO3)(amide)n=2,3)+, and complexes containing the amide conjugate base, reduced uranyl UO2+, and a 2+ charge were also formed. The formamide experiment produced the greatest diversity of species that stems from weaker amide binding leading to dissociation and subsequent solvent coordination or metal reduction. Experiments using methyl formamide, dimethyl formamide, acetamide, and methyl acetamide produced ion pair and doubly charged complexes that were more abundant, and less abundant complexes containing solvent or reduced uranyl. This pattern is reversed in the dimethylacetamide experiment, which displayed reduced doubly charged complexes and augmented reduced uranyl complexes. DFT investigations of the tris-amide ion pair complexes showed that inter-ligand repulsion distorts the amide ligands out of the uranyl equatorial plane, and that complex stabilities do not increase with increasing amide nucleophilicity. Elimination of an amide ligand largely relieves the interligand repulsion, and the remaining amide ligands become closely aligned with the equatorial plane in the structures of the bis-amide ligands. The studies show that the phenomenological distribution of coordination complexes in a metal-ligand electrospray experiment is a function of both ligand nucleophilicity and interligand repulsion, and that the latter factor begins exerting influence even in the case of relatively small ligands like the substituted methyl-formamide and methyl-acetamide ligands.

  19. Investigation of Uranyl Nitrate Ion Pairs Complexed with Amide Ligands using Electrospray Ionization Ion Trap Mass Spectrometry and Density Functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Gary S. Groenewold; Adriana Dinescu; Michael T. Benson; Garold L. Gresham; Michael J. van Stipdonk

    2011-04-01

    Ion populations formed from electrospray of uranyl nitrate solutions containing different amides vary depending on ligand nucleophilicity and steric crowding at the metal center. The most abundant species were ion pair complexes having the general formula [UO2(NO3)(amide)n=2,3]+, and complexes containing the amide conjugate base, reduced uranyl UO2+, and a 2+ charge were also formed. The formamide experiment produced the greatest diversity of species that stems from weaker amide binding leading to dissociation and subsequent solvent coordination or metal reduction. Experiments using methyl formamide, dimethyl formamide, acetamide, and methyl acetamide produced ion pair and doubly charged complexes that were more abundant, and less abundant complexes containing solvent or reduced uranyl. This pattern is reversed in the dimethylacetamide experiment, which displayed reduced doubly charged complexes and augmented reduced uranyl complexes. DFT investigations of the tris-amide ion pair complexes showed that inter-ligand repulsion distorts the amide ligands out of the uranyl equatorial plane, and that complex stabilities do not increase with increasing amide nucleophilicity. Elimination of an amide ligand largely relieves the interligand repulsion, and the remaining amide ligands become closely aligned with the equatorial plane in the structures of the bis-amide ligands. The studies show that the phenomenological distribution of coordination complexes in a metal-ligand electrospray experiment is a function of both ligand nucleophilicity and interligand repulsion, and that the latter factor begins exerting influence even in the case of relatively small ligands like the substituted methyl-formamide and –acetamide ligands.

  20. 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

  1. Preparation of maleic anhydride using a catalyst containing a uranyl ion

    International Nuclear Information System (INIS)

    A process is described for converting benzene, an ethylenically unsaturated aliphatic hydrocarbon having from 4 to 5 carbon atoms per molecule and from 1 to 2 olefinic double bonds, and in which the 4 carbon atom hydrocarbon is unbranched, or a monoethylenically unsaturated straight-chain aldehyde having from 4 to 5 carbon atoms per molecule and wherein the olefinic double bond is in the beta position with respect to the carbonyl group, to maleic anhydride by catalytic oxidation in the presence of a catalyst comprising a uranyl ion, especially uranium phosphate. One preferred form of the catalyst consists of an intimate chemical admixture of vanadium, uranium, phosphorus, and oxygen in which the uranium to phosphorus mole ratio is from 0.2:1 to 2:1, the phosphorus to oxygen mole ratio is from 0.1:1 to 0.35:1; and the vanadium to uranium atomic ratio is from 0.1:1 to 2:1. A method of preparation of the catalyst composition is also disclosed

  2. 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)

  3. 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

  4. Extraction of uranyl ion using solvent containing TTA in room temperature ionic liquids

    International Nuclear Information System (INIS)

    Due to the growing energy demand and limited resources of fossil fuels, nuclear energy is emerging as one of the most dependable energy sources in the twenty first century. However, due to limited uranium resources, used as the fuel element in the nuclear reactors, it is required to develop efficient separation methods for the recovery of uranium from various sources. These recovery methods use ion-exchange or solvent extraction based separation methods. Though solvent extraction based separation methods have been preferred for the recovery of U due to easy scale up possibility and rapidity, their major disadvantages include use of volatile organic compounds (VOC) which pose threat to the Environment. Of late, room temperature ionic liquids are considered as possible alternative to the conventional diluents with excellent efficiencies. There are reports on uranium extraction using ionic liquids with extractants like TBP, CMPO, TODGA, etc. however, there is no report available on extraction of U using TTA (thionyltrifluoroacetone). The present paper deals with studies on the extraction of uranyl ion from pH solutions using solutions of TTA in several room temperature ionic liquids viz. (C4mim)(PF6), (C6mim)(PF6), (C8mim)(PF6), (C4mim)(NTf2), (C6mim)(NTf2), (C8mim)(NTf2). The work presents the extraction data for U using 0.05 M TTA from buffered solutions at various pH containing 233U tracer. As shown, DU values increases at higher pH values and the D values were quite high as compared to that of molecular diluents

  5. Thiophene-based ligands as potential new metal ion chelation units in nuclear medicine

    International Nuclear Information System (INIS)

    An effort to explore new metal chelation units for radiopharmaceutical metal ion chelation applications has led us to the 2,5-dialkylamide-3,4-dihydroxythiophene type chelators. The ligand synthesis allows for facile asymmetric substitution that produces the amide-ester. Also, the monobenzyl derivative was obtained and structurally characterized in the P-1 space group with unit cell dimensions a = 10.111(3) A, b 11.761(3) A, c = 12.014(3) A , α = 72.987(5) .deg., β = 88.576(5) .deg., γ = 71.441(5) .deg., V = 1291.3(6) A3, Z = 2. The asymmetric hydrogen bonding pattern suggests the alternative salicylate-type metal chelation is accessible

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

    International Nuclear Information System (INIS)

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Paine, R.T.

    2000-12-12

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

  8. Synthesis and characterization of new ion-imprinted polymer for separation and preconcentration of uranyl (UO{sub 2}{sup 2+}) ions

    Energy Technology Data Exchange (ETDEWEB)

    Ahmadi, Seyed Javad, E-mail: sjahmadi@aeoi.org.ir [Nuclear Fuel Cycle School, Nuclear Science and Technology Research Institute, P.O. Box: 11365-8486, Tehran (Iran, Islamic Republic of); Noori-Kalkhoran, Omid [Faculty of Nuclear Engineering, University of Shahid Beheshti, Tehran (Iran, Islamic Republic of); Shirvani-Arani, Simindokht [Nuclear Fuel Cycle School, Nuclear Science and Technology Research Institute, P.O. Box: 11365-8486, Tehran (Iran, Islamic Republic of)

    2010-03-15

    UO{sub 2}{sup 2+} 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.

  9. Metal Ions Extraction with Glucose Derivatives as Chelating Reagents in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    Guo Chen YANG; Hai Jian YANG

    2006-01-01

    A series of glucose derivatives have been used as chelating reagents to extract metal ions in supercritical carbon dioxide. With perfluoro-1-octanesulfonic acid tetraethylammonium salt as additive, glucose derivatives were selective for Sr2+ and Pb2+ extraction in supercritical carbon dioxide.

  10. Adsorption behavior of uranyl ions onto amino-type adsorbents prepared by radiation-induced graft copolymerization

    International Nuclear Information System (INIS)

    Amino-type adsorbents (ATAs) were prepared by radiation-induced graft copolymerization of 4-hydroxybutyl acrylate glycidyl ether (HB) onto a polyethylene-coated polypropylene (PE/PP) duplex fiber of a non-woven fabric, and modified with different amines of ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and diethylamine (DEA). The adsorption behavior of uranyl ions onto the ATAs was studied in batch experiments. The effects of the contact time, initial concentration of the ions, temperature, and pH value. The salinity were investigated along with the adsorption kinetics and the adsorption isotherms. The kinetic experimental data followed the pseudo second-order kinetic model, and the adsorption isotherms correlated well with the Langmuir model. The ATAs showed good efficiency in adsorbing uranyl ions, with the best saturation adsorption capacity being 64.26 mg g-1 for ATA-DETA within 120 min. The temperature dependence of ATA- DETA was quite abnormal and the quickest behavior was obtained at 25℃, ATAs showed good adsorption capacity over a wide pH range of 4.0-8.5, and HCl could be used in the elution process. Salinity of the solution had great effect on the adsorption capacity, 3.5% salinity resulted in a 55% loss of capacity from ATA-DETA. The selectivity of ATA-DETA showed an order of: UO22+≈ Fe3+ > Zn2+ > VO3- > Co2+ > Ni2+. (authors)

  11. Quantification of thorium in uranium matrix by chelation ion chromatography (CIC)

    International Nuclear Information System (INIS)

    The present work describes an optimized procedure for the determination of thorium in uranium oxide by chelation ion chromatography technique. The method involves a two stage separation of matrix element by employing solvent extraction and ion exchange. Chromatographically thorium has been separated from the traces of other metallic impurities and the matrix element which is expected to be present in trace quantity even after employing prior separations. (author)

  12. Multi-scale study of the interaction mechanisms of aquo-uranyl ions with titanium oxide surfaces (powders and monocrystals)

    International Nuclear Information System (INIS)

    The aim of this work is the study, at a molecular scale, of the sorption mechanisms corresponding to UO22+ /TiO2 system. The first step of the study is the hydrated solid characterization and the second step is the sorption mechanisms study. The work is performed using a multi-scale approach, which is composed by three parts. At first, we have obtained macroscopic data corresponding to the uranyl retention on the solid. Moreover, we have used CD-MUSIC model in order to calculate the surface acidity constants of the hydrated solid. In a second part, we have performed a multi-spectroscopic study (TRLFS, XPS, DRIFT, SHG) in order to characterize the system at a molecular scale. Finally, all these results were obtained on the solid TiO2 under different forms (rutile or anatase phases and (110), (001), (111) rutile single crystals). From the structural results, we have determined that there are two sorption sites towards the free uranyl ion onto the titania surface, whatever the studied solid (powder and single crystal). Moreover, these two reactive sorption sites don't present the same reactivity towards free uranyl ion: the more reactive sorption site is assigned to a bridging-bridging oxygen atoms and the less reactive sorption site is assigned to a bridging-top oxygen atoms. Thus, using this methodology, we can conclude that it is possible to understand the powder surface properties using the single crystals surface results. Finally, with the multi-scale approach, we have used the spectroscopic results obtained on UO22+/TiO2 system as constraints during macroscopic data simulation using a surface complexation model (CCM). (author)

  13. Ionothermal synthesis of uranyl compounds that incorporate imidazole derivatives

    International Nuclear Information System (INIS)

    Ionothermal reactions of uranyl nitrate with various salts in methylimidazolium-based ionic liquids have produced single crystals of three uranyl compounds that incorporate imidazole derivatives as charge-balancing cations. (C4H7N2)[(UO2)(PO3F)(F)] (1) crystallizes in space group C2, a=17.952(1) Å, b=6.9646(6) Å, c=8.5062(7) Å, β=112.301(1)°, (C6H11N2)2[(UO2)(SO4)2] (2) crystallizes in space group C2/c, a=31.90(1) Å, b=9.383(5) Å, c=13.770(7) Å, β=93.999(7)° and (C6H11N2)[(UO2)2(PO4)(HPO4) (3) crystallizes in space group P21/n, a=9.307(2), b=18.067(4), c=9.765(2), β=93.171(2). The U6+ cations are present as (UO2)2+ uranyl ions coordinated by three O atoms and two F atoms in 1 and five O atoms in 2 and 3 to give pentagonal bipyramids. The structural unit in 1 is composed of F-sharing dimers of uranyl pentagonal bipyramids linked into sheets through corner-sharing fluorophosphate tetrahedra. The structural unit in 2 is composed of uranyl pentagonal bipyramids with one chelating sulfate tetrahedron linked into chains by three other corner-sharing sulfate tetrahedra. In 3, the structural unit is composed of chains of uranyl pentagonal bipyramids linked into sheets through edge- and corner-sharing phosphate and hydrogen phosphate tetrahedra. N-methylimidazolium cations occupy the interstitial space between the uranyl fluorophosphate sheets in 1, whereas 1-ethyl-3-methylimidazolium cations link the uranyl sulfate and phosphate units in 2 and 3 into extended structures. - Graphical abstract: The synthesis of uranyl compounds by ionothermal treatment is explored, and provides three novel compounds and insights concerning the role of water in controlling the structural units. Highlights: ► Ionothermal syntheses have produced three new uranyl compounds. ► Imidazole derivatives are incorporated as charge-balancing agents. ► X-ray and spectroscopic analyses reveal variability between imidazole derivatives. ► This method offers synthetic insight in the

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

    OpenAIRE

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

    2007-01-01

    The final step in heme biosynthesis, insertion of ferrous iron into protoporphyrin IX, is catalyzed by protoporphyrin IX ferrochelatase (E.C. 4.99.1.1). It is demonstrated that the pre-steady state human ferrochelatase (R115L) shows a stoichiometric burst of product formation and substrate consumption, consistent with a rate determining step following metal-ion chelation. Detailed analysis shows that chelation requires at least two steps, rapid binding followed by a slower (k ca. 1 s−1) irrev...

  15. Chelation of Schiff bases with rare earth metal ions - thermodynamic study

    International Nuclear Information System (INIS)

    Chelating tendencies of 5-chloro-orthohydroxy acetophenone-p-chloro phenyl anil and 5-chloro-orthohydroxy acetophenone-p-bromo phenyl anil towards the f-block metal ions have been investigated potentiometrically at various temperatures in 60:40 ethanol-water medium and 0.1M (NaClO4) ionic strength. Formation of 1:1 and 1:2 chelates was detected. Thermodynamic parameters for metal-ligand stability constants have been obtained by the temperature coefficie nt method. (author). 7 refs

  16. Isolation and Utilization of Corn Cobs Hemisellulose as Chelating Agent for Lead Ions

    International Nuclear Information System (INIS)

    Corn cobs is an agricultural byproduct containing polysaccharide composed of cellulose, hemicelluloses and lignin. Hemicelluloses has a hydroxyl and carbonyl functional groups which can be used as chelating agent for metal ions. The purpose of this study was to isolate and evaluate corncobs hemicelluloses as a chelating agent toward lead ion. Graphite furnace spectrophotometry at 283.3 nm was used to determine the residual lead ion in solution. The research's result showed that the highest yield of hemicelluloses (12.04 %) was obtained from delignication with 0,03 M NaOH in 60 % ethanol and 3 % H2O2, hemicelluloses isolation with 500 ml of 0.2 M NaOH, and precipitation with 1:4 ratio of 10 % acetic acid in 95 % ethanol. The 300 mg corn cobs hemicelluloses has chelating effect for 40 mg lead solution at (39.52±0.1350) mg or 98.80 %, that the corn cobs hemicelluloses can be used as a chelating agent for lead. (author)

  17. Fluorescence enhancement by chelation of Eu3+ and Tb3+ ions in sol-gels

    International Nuclear Information System (INIS)

    Chelation of rare-earth (RE) ions is investigated as a means of enhancing the optical properties of RE-doped silica sol-gels. Two chelating agents--2,6-pyridine-dicarboxylic acid (PDC) and 3-pyridinepropionic acid (PPA) and two different synthesis techniques are studied. Eu(PDC) gels exhibit intense 5D0→7F2 fluorescence in the red under UV excitation and long fluorescence lifetimes compared to Eu(PPA) gels and to gels without a chelating agent. This behavior indicates that the PDC molecule remains associated with the Eu after incorporation into the gel. Similar behavior is seen for 5D4→7F5 green fluorescence in Tb(PDC)

  18. 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)

  19. The effect of external stimuli on the uranyl ions uptake capacity of poly(N-vinyl 2-pyrrolidone/itaconic acid) hydrogels prepared by gamma rays

    International Nuclear Information System (INIS)

    The effect of external stimuli such as pH of the solution, ionic strength and temperature on the uranyl ions uptake capacity of poly(N-vinyl 2-pyrrolidone/itaconic acid) (P(VP/IA)) hydrogels was investigated. Polyelectrolyte P(VP/IA) hydrogels with varying compositions were prepared in the form of rods from ternary mixtures of N-vinyl 2-pyrrolidone/itaconic acid/water. Uranyl adsorption capacity of hydrogels were found to increase from 26.7 to 70 (mg UO22+ /g dry gel) with decreasing pH of the swelling solution. Adsorption studies have shown that other stimuli, such as temperature and ionic strength of the swelling solution have also influence on the uranyl ions uptake capacity of P(VP/IA) hydrogels

  20. 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).

  1. Strong basic anion exchangers with adsorption properties for chlorocomplex uranyl ion

    International Nuclear Information System (INIS)

    Full text: Styrene-divinylbenzene copolymers (S-DVB) are still the most commonly used as starting copolymers in the synthesis of ion exchangers with special destinations, such as the enrichment process of 235U due to their high chemical resistance. For this purpose, a special concern has been lately focused on the preparation of macroporous strong basic anion exchangers containing one or two hydroxyalkyl substituents. An average pore radius around 1000 A, which is correlated with a high permanent porosity, a good stability of the resin in HCl with concentrations up to 8 N, a thermal resistance up to 150 deg C at least and a high mechanical strength are the main characteristics requested for this purpose. In a previous work we have reported the preparation of some macroporous S-DVB copolymers with sizes in the range 90-200 μm by employing 2-ethyl-1-hexanol as a porogen, at a high dilution of monomers (D ≥ 0.55) and their subsequent transformation in macroporous strong basic anion exchangers with an average pore radius higher than 50 nm. In the present study, the characteristics of the starting S-DVB macroporous copolymers synthesized in the presence of N-butyl alcohol (nBA) as porogen and those of the strong basic anion exchangers derived therefrom have been studied. Activation by chloromethylation reaction of the macroporous S-DVB copolymers was performed with paraformaldehyde (CH2O)n/trimethylchlorosilane (TMCS) in the presence of FeCl3 as catalyst, in chloroform as a reaction medium. Strong basic anion exchangers with diethyl 2-hydroxyethyl benzylammonium groups were obtained by the amination of the chloromethylated S-DVB copolymers with diethyl 2-hydroxyethylamine (DEHEA). The corresponding strong basic anion exchangers showed an ionic exchange capacity in the range 1.8-2.2 meq/g, depending on the crosslinking degree and the dilution of the starting copolymer, and an average pore radius, rp, around 80 nm. Such characteristics make these resins promising

  2. Chelation Properties of Modified Humic Acids Toward Some Trivalent Lanthanide Ions

    International Nuclear Information System (INIS)

    Three kinds of humic acids, Fluka (I), Fluka (II), and Ega-chemie (III) were modified through condensation with formaldehyde to afford polymers I, II, and III, respectively. The chelation behavior of these modified humic acids polymers towards the trivalent lanthanide metal-ions, La3+, Ce3+, Nd3+, Sm3+, and Gd3+ was studied by a batch equilibration technique at 25 deg. C as a function of contact time, pH, counter ion and counter ion concentration. The highest metal-ion uptake of the three polymers was achieved at pH 7.0 and by using perchlorate as a counter ion. Results of the study have revealed that polymer II has the highest metal-ion uptake capacity, and that the metal-ion uptake falls in the order: Gd3+ > Sm3+ > Nd3+ > La3+ ≅ Ce3+

  3. 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

  4. Synergistic extraction of uranyl and plutonyl ions with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) and some some aliphatic sulphoxides

    International Nuclear Information System (INIS)

    Extraction of uranyl and plutonyl ions with 1-phenyl-3-methyl-4-benzoyl pyrazolone-5 (HPMBP) and some long chain aliphatic sulphoxides has been studied and the equilibrium constants for the organic phase addition reaction have been determined for both the systems. (author). 8 refs

  5. Uranyl ion extraction with conventional PUREX/TRUEX ligands assessed by electroanalytical chemistry at micro liquid/liquid interfaces.

    Science.gov (United States)

    Stockmann, Tom J; Ding, Zhifeng

    2011-10-01

    The facilitated ion transfer (FIT) of uranyl or dioxouranium (UO(2)(2+)) was studied electrochemically using a micro interface between two immiscible electrolytic solutions (micro-ITIES) in order to evaluate the complexation stoichiometry and complexation constants (β) of two widely used ligands in spent fuel reprocessing: tributylphosphate (TBP) and octyl(phenyl)-N,N-diisobutylcarbamoylmethyl-phosphine oxide (CMPO). For the first time, discrete interfacial complexation reaction steps of varying uranyl to the two ligands ratios were resolved using the micro-ITIES hosted at the tip of a 25 μm diameter glass capillary. Two stoichiometries for UO(2)NO(3)TBP(n)(+) were determined including n = 3 and 4 with β values of 3.2 × 10(11) and 3.9 × 10(13), respectively. Subsequently, three distinct complexation reactions of CMPO with UO(2)(2+) were discovered corresponding to UO(2)NO(3)CMPO(2)(+), UO(2)NO(3)CMPO(3)(+), and UO(2)CMPO(5)(2+) whose respective complexation constants were determined to be 8.0 × 10(11), 8.8 × 10(14), and 6.5 × 10(32). The participation of nitrate anions in these complexation reactions is also discussed. PMID:21848323

  6. 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)

  7. Synthesis and characterisation of 8-hydroxyquinoline-bovine serum albumin conjugates as metal ion chelating proteins

    International Nuclear Information System (INIS)

    A derivative of 8-hydroxyquinoline (8-quinolinol, oxine) with a linking bridge containing a carboxylic group was covalently coupled to bovine serum albumin by the N-hydroxysuccinimide method to obtain stable monomeric conjugates with oxine to protein mole ratios up to 37. These conjugates were characterised spectrophotometrically and their complexation properties were confirmed by spectral analysis with and without the addition of Al(III), Cd(II), Co(II), Cu(II), Hg(II), Mn(II), Ni(II), Pb(II), V(IV), U(VI) and Zn(II) ions added. The maximum number of ions bound by these chelating proteins was determined spectrophotometrically by titration with metal ions at pH 6.0. The conjugates with a substitution ratio (moles of 8-hydroxyquinoline bound/mole of albumin) less than about 8 showed 1:1 binding with metal ions, while conjugates with higher substitution ratios were able to complex with 2:1 ratio of 8-hydroxyquinoline to metal ion. Association and dissociation kinetics of complexation with copper(II) ions showed a complex mechanism. The spectral and binding properties of these metal ion-binding proteins confirm that the coupling of the 8-hydroxyquinoline derivative to bovine serum albumin gives stable, water soluble, macromolecular chelating agents that retain the complexing ability of the original ligand. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  8. 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

  9. Effect of temperature on the mechanisms of interaction between uranyl ion and zirconium oxo-phosphate

    International Nuclear Information System (INIS)

    Uranium sorption onto Zr2O(PO4)2 has been studied between 298 K and 363 K, in 0.1 M NaClO4 medium. Potentiometric titrations were realized to determine temperature dependency of the acid-base properties (pHpcn, acidity constants). Classical batch experiments were performed at different temperatures. The sorption experiments revealed that the uranium sorption onto Zr2O(PO4)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: (≡ZrOH)2UO22+ and (≡PO)2UO2. Besides the stability constants for the surface complexes, the thermodynamic parameters ΔH0 and ΔS0 were determined using the van't Hoff equation. The enthalpy values associated to the U(VI) retention onto Zr2O(PO4)2, determined by the temperature dependence of the stability constants, testify that the formation of the complex (≡PO)2UO2 (55 kJ/mol) is endothermic, while no influence of the temperature was observed for the formation of the complex (≡ZrOH)2UO22+. The adsorption reaction of the last complex is then driven by entropy. In addition, calorimetric measurements of uranium sorption onto Zr2O(PO4)2 were carried out to directly quantify the enthalpy associated to the retention processes. (author)

  10. DESORPTION OF METAL IONS FROM KRAFT PULPS. PART 1. CHELATION OF HARDWOOD AND SOFTWOOD KRAFT PULP WITH EDTA

    OpenAIRE

    Kim Granholm; Leo Harju; Ari Ivaska

    2010-01-01

    Chelation of unbleached and oxygen bleached hardwood and softwood kraft pulps with EDTA was studied. The main focus was on the desorption of magnesium, manganese, and iron due to their impact in TCF-bleaching. Desorption of other metal ions present were also studied in order to get an over-all estimation of the metal ion concentrations and their desorption during chelation. By using the concept of side reaction coefficients, an estimation of the chelating strength of EDTA at different pH can ...

  11. High-performance chelation chromatography of metal ions on sorbents with grafted iminodiacetic acid

    International Nuclear Information System (INIS)

    Chromatographic behavior of some alkaline earth, transition, heavy (including uranium) and rare earth metal ions on a group of complexing sorbents, containing surface functional groups of imidodiacetic acid, was studied. Conditions, under which metal retention is determined by complexing on the sorbent surface, were defined and main principles of a new variant of liquid chromatography, i.e. high-performance chelating chromatography of metal ions (HPCCI) were formulated. It is shown that under optimal conditions metal retention correlates linearly in bilogarithmic coordinates with stability constants of the relevant metal complexes. Potentialities of HPCCI analytic application to analysis of objects featuring complex composition were considered

  12. 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

  13. Heavy metal ion uptake properties of polystyrene-supported chelating polymer resins

    Indian Academy of Sciences (India)

    A Ravikumar Reddy; K Hussain Reddy

    2003-06-01

    Metal ion uptake properties of polystyrene-supported chelating polymer resins functionalized with (i) glycine, (ii) hydroxy benzoic acid, (iii) Schiff base and (iv) diethanol amine have been investigated. The effects of pH, time and initial concentration on the uptake of metal ions have been studied. The uptake of metal ion depends on pH. The resins are more selective at pH 10 for Pb(II) and Hg(II), whereas at pH 6 they are found to be Cd(II) and Cr(VI) selective. Metal ion uptake properties of resins follow Freundlich’s equation. The resins are recyclable and are therefore employed for the removal of heavy metal pollutants from industrial waste water.

  14. 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. PMID:26331776

  15. 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

  16. 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)

  17. The fabrication and study of metal chelating stationary phases for the high performance separation of metal ions

    International Nuclear Information System (INIS)

    The preparation and characterisation of chelating sorbents suitable for the high efficiency separation of trace metals in complex samples, using a single column and isocratic elution, is described. Hydrophobic, neutral polystyrene divinylbenzene resins were either impregnated with chelating dyes or dynamically modified with heterocyclic organic acids, using physical adsorption and chemisorption processes respectively. A hydrophilic silica substrate was covalently bonded with a chelating aminomethylphosphonic acid group, to assess the chelating potential of this molecule. These substrates were characterised in terms of metal retention capability (selectivity coefficients and capacity factors), separation performance, column efficiency and suitability for analytical applications. Chelating molecules with different ligand groups were found to have unique selectivity patterns dependant upon the conditional stability constants of the chelate. Other factors, including mobile phase constituents - complexing agents, ionic strength and pH, column length and column capacity were additionally investigated to examine their effect upon the separation profiles achieved. The promising metal separation abilities illustrated by a number of these chelating columns were exploited for the determination of trace toxic metals in complex sample matrices using High Performance Chelation Ion Chromatography (HPCIC). This included the determination of beryllium in a certified stream sediment, uranium in seawater and a certified stream sediment, and cadmium, lead and copper in a certified rice flour. The results for each analysis fell within the certified limits, and reproducibility was good. The optimisation of post column detection systems using chromogenic ligands additionally gave good detection limits for the metals in each separation system. (author)

  18. Disaggregation ability of different chelating molecules on copper ion-triggered amyloid fibers.

    Science.gov (United States)

    Zhu, Linyi; Han, Yuchun; He, Chengqian; Huang, Xu; Wang, Yilin

    2014-08-01

    Dysfunctional interaction of amyloid-β (Aβ) with excess metal ions is proved to be related to the etiology of Alzheimer's disease (AD). Using metal-binding compounds to reverse metal-triggered Aβ aggregation has become one of the potential therapies for AD. In this study, the ability of a carboxylic acid gemini surfactant (SDUC), a widely used metal chelator (EDTA), and an antifungal drug clioquinol (CQ) in reversing the Cu(2+)-triggered Aβ(1-40) fibers have been systematically studied by using turbidity essay, BCA essay, atomic force microscopy, transmission electron microscopy, and isothermal titration microcalorimetry. The results show that the binding affinity of Cu(2+) with CQ, SDUC, and EDTA is in the order of CQ > EDTA > SDUC, while the disaggregation ability to Cu(2+)-triggered Aβ(1-40) fibers is in the order of CQ > SDUC > EDTA. Therefore, the disaggregation ability of chelators to the Aβ(1-40) fibers does not only depend on the binding affinity of the chelators with Cu(2+). Strong self-assembly ability of SDUC and π-π interaction of the conjugate group of CQ also contributes toward the disaggregation of the Cu(2+)-triggered Aβ(1-40) fibers and result in the formation of mixed small aggregates. PMID:25051063

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

    International Nuclear Information System (INIS)

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

  20. Metal-ion chelation chromatography on silica-immobilized 8-hydroxyquinoline

    International Nuclear Information System (INIS)

    A chromatographically useful packing is prepared by immobilizing 8-hydoxyquinoline on Porasil. This material, whose capacity is about 50 μequiv/g, behaves with an efficiency of about 0.2 to 0.5 mm/theoretical plate but is capable of separating such similar metal ions as Co-Ni, Cd-Pb-Zn, and La-Gd-Yb at trace levels employing both isocratic and continuous gradient elution. On a fundamental level, the relationship between solution chelate stability and chromatographic behavior is described. 9 figures, 2 tables

  1. 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

  2. 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.

  3. 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.

  4. Temperature effects on the interaction mechanisms between the europium (III) and uranyl ions and zirconium diphosphate; Effets de la temperature sur les mecanismes d'interaction entre les ions europium (3) et uranyle et le diphosphate de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Finck, N

    2006-10-15

    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)

  5. F-Element ion chelation in highly basic media. 1998 annual progress report

    International Nuclear Information System (INIS)

    'A large percentage of high-level radioactive waste (HLW) produced in the DOE complex over the last thirty years temporarily resides in storage tanks maintained at highly basic pH. The final permanent waste remediation plan will probably require that liquid and solid fractions be chemically treated in order to partition and concentrate the dominate hazardous emitters from the bulk of the waste. This is no small task. Indeed, there does not exist a well developed molecular chemistry knowledge base to guide the development of suitable separations for actinide and fission products present in the strongly basic media. The goal of this project is to undertake fundamental studies of the coordination chemistry of f-element ions and their species formed in basic aqueous solutions containing common waste treatment ions (e.g., NO3-, CO32-, organic carboxylates, and EDTA), as well as new waste scrubbing chelators produced in this study.'

  6. Fast removal of heavy metal ions and phytic acids from water using new modified chelating fiber

    Institute of Scientific and Technical Information of China (English)

    Li Xu; Jin Nan Wang; Ying Meng; Ai Min Li

    2012-01-01

    The graft copolymerization of acrylic acid (AA) onto polyethylene glycol terephthalate (PET) fiber initiated by benzoy peroxide (BPO) was carried out in heterogeneous media.Moreover,modification of the grafted PET fiber (PET-AA) was done by changing the carboxyl group into acylamino group through the reaction with dimethylamine.The modified chelating fiber (NDWJN 1) was characterized using elementary analysis,SEM and FT-IR spectroscopy.Adsorption kinetic curves indicated that NDWJN1 could fast remove heavy metal ions and phytic acids from water effectively.Furthermore,batch kinetic studies indicated that heavy metal ions adsorbed to NDWJN1 could be fitted well by both pseudo-first-order and pseudo-second-order adsorption equations,but the intra-particle diffusion plaved a dominant role in the adsorption of phvtic acids.

  7. The influence of the chelated metal ion on the fragmentation pathways of metal complexes of 5-nitro-octaethylporphyrin

    International Nuclear Information System (INIS)

    Tandem mass spectrometric analyses of suite of 10 divalent complexes of 5-nitro-octaethylporphyrin reveals that the fragmentation pathway is influenced by the chelated metal ion. The porphyrins undergo a novel cleavage of the macrocyclic ring. Surprisingly, the expected β-cleavage of the alkyl substituents is not very significant for many of the complexes. In this paper the mass spectra of the metalloporphyrins are compared and the role of the chelated metal ion will be discussed. The effect of the rate of heating on the mass spectra of the molecules will also be discussed

  8. 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

  9. 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.

  10. 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

  11. Synthesis and evaluation of water-soluble chelating polymers for the selective removal of actinide metal ions

    International Nuclear Information System (INIS)

    A major goal of our research program is to develop polymer supported ion specific ligand systems for the removal of actinides and other hazardous metals from wastewaters. The advantage of water-soluble polymers in metal ion separation processes is that the homogeneity of the system allows for more rapid exchange kinetics than ion exchange or chelating resins. A number of water-soluble chelating polymers have been synthesized by the functionalization or commercially available polyamine precursors with various ligand moieties such as hydroxamates. The ability of these polymers to complex with metal ion to give soluble complexes which can be separated and concentrated by ultrafiltration under different pH conditions have been examined

  12. Chelation in Metal Intoxication

    OpenAIRE

    Flora, Swaran J.S.; Vidhu Pachauri

    2010-01-01

    Chelation therapy is the preferred medical treatment for reducing the toxic effects of metals. Chelating agents are capable of binding to toxic metal ions to form complex structures which are easily excreted from the body removing them from intracellular or extracellular spaces. 2,3-Dimercaprol has long been the mainstay of chelation therapy for lead or arsenic poisoning, however its serious side effects have led researchers to develop less toxic analogues. Hydrophilic chelators like meso-2,3...

  13. Ferrous Ion Chelating, Superoxide Anion Radical Scavenging and Tyrosinase Inhibitory Properties of Pure and Commercial Essential Oils of Anetrhum Graveolens

    Directory of Open Access Journals (Sweden)

    Sh Darvish Alipour Astaneh

    2013-04-01

    Full Text Available Introduction: Despite slight toxicities of essential oils, they are not under strict control in many countries. Anethum graveolens is widely consumed and its essential oils are at public reach. This study was designed to study essential oils of Anethum graveolens. Methods: The biological properties of pure and commercial essential oils of Anethum graveolens were investigated. In fact, Ferrous ion chelating activity, superoxide anion radical scavenging property, tyrosinase inhibition and total flavonoids of the oils were determined. Results: Chelating activity of 7.8 µg of EDTA was equivalent to 2 µg of the pure oil. The oils had superoxide anion radical scavenging activities which may be related to their total phenol and flavonoid contents. IC50 of ferrous ion chelating, antityrosiase and superoxide anion radical scavenging activities of pure and commercial oils were 1.3, 1.4, 1 and (171.6, 589, 132 µg respectively. Antityrosiase activity of 6.4 µg pure oil was equal to 1000 µg of the commercial oil. Conclusion: Anethum possesses antioxidative and free radical scavenging properties. This oil chelates ferrous ions and superoxide radicals. It is effective in formation of reactive toxic products. Anethum has good potentials regarding its applications in food and drug industries.

  14. Electrokinetic migration studies on removal of chromium and uranyl ions from 904-A trench soil

    International Nuclear Information System (INIS)

    This report describes a laboratory-scale study, in which electrokinetic migration technology was used to remove chromium and uranium, as well as other ions, from soil taken from a bore hole adjacent to the 904-A trench at the Savannah River Technology Center. Imposition of an electric current on humid (not saturated) soil successfully caused cations to migrate through the pore water of the soil to the cathode, where they were captured in an ISOLOCKTm polymer matrix and in a cation exchange resin incorporated in the polymer. Chemicals circulated through the anode/polymer and cathode/polymer were able to control pH excursions in the electrokinetic-cells by reacting with the H+ and OH- generated at the anode and cathode, respectively. The study indicates that ions adsorbed on the surface of the soil as well as those in the pores of soil particles can be caused to migrate through the soil to an appropriate electrode. After 10 days of operation at 20--25 V and 2 mA, approximately 65% of the chromium was removed from two 3.5 kg soil samples. A 57% removal of uranium was achieved. The study shows that electrokinetic migration, using the ISOLOCK trademark polymer will be effective as an in situ treatment method for the removal of metal ion contaminants in soil adjacent to the 904-A trench

  15. Electrokinetic migration studies on removal of chromium and uranyl ions from 904-A trench soil

    Energy Technology Data Exchange (ETDEWEB)

    Bibler, J.P.; Meaker, T.F.; O`Steen, A.B.

    1992-09-30

    This report describes a laboratory-scale study, in which electrokinetic migration technology was used to remove chromium and uranium, as well as other ions, from soil taken from a bore hole adjacent to the 904-A trench at the Savannah River Technology Center. Imposition of an electric current on humid (not saturated) soil successfully caused cations to migrate through the pore water of the soil to the cathode, where they were captured in an ISOLOCKTm polymer matrix and in a cation exchange resin incorporated in the polymer. Chemicals circulated through the anode/polymer and cathode/polymer were able to control pH excursions in the electrokinetic-cells by reacting with the H{sup +} and OH{sup {minus}} generated at the anode and cathode, respectively. The study indicates that ions adsorbed on the surface of the soil as well as those in the pores of soil particles can be caused to migrate through the soil to an appropriate electrode. After 10 days of operation at 20--25 V and 2 mA, approximately 65% of the chromium was removed from two 3.5 kg soil samples. A 57% removal of uranium was achieved. The study shows that electrokinetic migration, using the ISOLOCK{trademark} polymer will be effective as an in situ treatment method for the removal of metal ion contaminants in soil adjacent to the 904-A trench.

  16. 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)

  17. pH-metric studies of mixed ligand complexes of uranyl ion with 4-amino 2,6-dihydroxy pyrimidine and some selected ligands

    International Nuclear Information System (INIS)

    Interaction of uranyl ion with 4-amino 2, 6-dihydroxy pyrimidine (ADHP) in presence of other ligands such as oxalic acid (Ox), malonic acid (Mal), O-aminophenol (OAP). O-phenylenediamine (OPDA), 2,2' bipyridyl (Bipy), 1, 10-phenanthroline (Phen) and ethylenediamine (En) has been investigated by potentiometric studies. The ternary complexes are formed in stepwise manner in which ADHP behaves as secondary ligand. The stability constants of ternary complexes have been reported at 35 degC and at μ = 0.01M (KNO3) in aqueous medium. (author). 11 refs., 1 fig., 1 tab

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

    Directory of Open Access Journals (Sweden)

    Dongwei Zhong

    2015-04-01

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

  19. Scale-up preparation of uranium amalgam from uranyl ion using two-compartment electrolyzer

    International Nuclear Information System (INIS)

    A solid uranium amalgam containing as high as 1.7 gU/ml Hg was prepared electrolytically using a two-compartment electrolyzer separated with a cation exchange membrane at a kilogram scale. The design and operation characteristics of the electrolyzer is described. The results indicate that ca. 170 g of uranium ion in an aqueous solution could be reduced to metallic state by forming amalgam within 4 h with a current efficiency of 30% and uranium recovery of more than 80%. (author)

  20. Synthesis of some salicylic acid derivatives and studies of their interaction with uranyl ion

    International Nuclear Information System (INIS)

    Some unsubstituted and substituted bis-derivatives of salicylic acid were synthesized and their acidity constants determined spectrophotometrically in 61.10% aqueous ethanol. The stability constants of complexes which these compounds form with the UO22+ ion were determined spectrophotometrically using the method of continuous variation under the following conditions: pH 3.58 and 3.98, 61.10% aqueous ethanol, μ=0.5 (LiCl), 25±1 degC. (author). 3 figs., 2 tabs., 8 refs

  1. Materials based on uranyl ion and their potential for solar energy conversion cells

    Energy Technology Data Exchange (ETDEWEB)

    Felinto, Maria Claudia F.C.; Maceta, Luiz Felipe M.; Luiz, Jose Eduardo M. Sa; Parra, Duclerc F. [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil)]. E-mail: mfelinto@ipen.br; Brito, Hermi F.; Teotonio, Ercules E.S. [Sao Paulo Univ., SP (Brazil). Inst. de Quimica]. E-mail: hefbrito@iq.usp.br

    2005-07-01

    In this work it is described synthesis, characterization and spectroscopic study of the supermolecules of UO{sub 2}{sup 2+} and octaacetatecalix[8]arene. The compounds obtained were characterized by complexation analysis for determine U{sup 6+} concentration, infrared spectra and luminescence spectra. The results agree with the following composition UO{sub 2}(MS){sub 2} is contained in octaacetatecalix[8]arene and UO{sub 2}(TCA){sub 2} is contained in octaacetatecalix[8]arene (where MS is methanesulfonate and TCA is trichloroacetate). The IR analyses show coordination of counter ion and the inclusion on the calixarene cavity. The life time behavior as a first order exponential decay for UO{sub 2}(TCA){sub 2}.(H{sub 2}O)octaacetatecalix[8]arene and UO{sub 2}(MS){sub 2}.(H{sub 2}O)octaacetatecalix[8]arene. (author)

  2. Electrokinetic migration studies on removal of chromium and uranyl ions from 904-A trench soil

    Energy Technology Data Exchange (ETDEWEB)

    Bibler, J.P.; Meaker, T.F.; O' Steen, A.B.

    1992-09-30

    This report describes a laboratory-scale study, in which electrokinetic migration technology was used to remove chromium and uranium, as well as other ions, from soil taken from a bore hole adjacent to the 904-A trench at the Savannah River Technology Center. Imposition of an electric current on humid (not saturated) soil successfully caused cations to migrate through the pore water of the soil to the cathode, where they were captured in an ISOLOCKTm polymer matrix and in a cation exchange resin incorporated in the polymer. Chemicals circulated through the anode/polymer and cathode/polymer were able to control pH excursions in the electrokinetic-cells by reacting with the H[sup +] and OH[sup [minus

  3. Separation and determination of trace metal ions using organic chelating reagents

    International Nuclear Information System (INIS)

    The four reagents tested were N,N-dihexylacetamide (DHA), 2,6-diacetylpyridine bis(furoylhydrazone) (H2dapf), 1,3-dimethyl-4-acetyl-2-pyrazolin-5-one (DMAP) and N-methylfurohydroxamic acid (NMFHA). DHA and H2dapf were investigated for their complex formation with uranium, and DMAP and NMFHA were used as chelating agents in high performance liquid chromatography (HPLC). Uranium(VI) is preferentially extracted from nitric acid solutions using DHA in toluene. The extraction characteristics of the U-DHA complex are studied. A 119,000 μgL-1 U solution is analyzed for twenty-six elements. The U is extracted with DHA, and the trace metal ions are then determined by inductively coupled plasma-mass spectrometry. Uranium must be removed from the sample before analysis to prevent ionization suppression. H2dapf is synthesized and characterized. Studies of the complexation of metal ions with H2dapf is described. U(VI) forms a stable complex with H2dapf, and a procedure for selectively determining trace U by spectrophotometry is presented. DMAP complexes of Cu(II), Fe(III), Ga(III), Th(IV), U(VI), V(V), and Zr(IV) are separated using reversed phase HPLC. NMFHA complex of Al(III), Fe(III), Hf(IV), Nb(V), Sb(III), and Zr(IV) are separated using reversed phase HPLC. NMFHA is also used to separate uranium(VI) from trace lanthanide ions. 266 refs., 46 figs., 24 tabs

  4. Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium; Determinacion de la capacidad extractiva del p-ter-butilocalix[8]areno octa-fosfinoilado hacia iones uranilo de un medio acuo-acido salino

    Energy Technology Data Exchange (ETDEWEB)

    Serrano V, E. C.

    2011-07-01

    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 (HNO{sub 3}-3.5 NaNO{sub 3}) 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{sup -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{sup -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: (UO{sub 2}){sub 2}B{sub 8}bL{sup 8}(NO{sub 3}){sub 4}(H{sub 2}O){sub 4}CHCl{sub 3}(CH{sub 3}OH){sub 3} the methanol molecules come from its purification. It is proposed that B{sub 8}bL{sup 8} calixarene in

  5. Removal of aqueous uranyl ions by magnetic functionalized carboxymethylcellulose and adsorption property investigation

    International Nuclear Information System (INIS)

    Highlights: • The solvent in this synthetic is only water, it is very friendly to the environment. • Adsorbent with active surface rich in functional groups. • A magnetism is linked to this material and make it easy to separation. • Synthesis is in a facile pathway, the temperature are lower than 100 °C. • The maximum adsorption capacity toward uranium(VI) is 122.48 mg/g at 45 °C. - Abstract: Magnetic carboxymethylcellulose (CMC/Fe3O4) was used as a framework adsorption material to remove uranium ions from aqueous solutions. Carboxyl functional groups were grafted onto the CMC/Fe3O4. The maximum adsorption capacity of the magnetic composite toward U(VI) was 122.48 mg/g. Kinetic and thermodynamic parameters of the adsorption process were estimated. The pseudo-second-order model was more suitable and it proved to be an endothermic and spontaneous process. The Langmuir and Freundlich models were applied to evaluate the adsorption isotherm. The data matched well with Langmuir model after equilibrium was reached and with Freundlich model before equilibrium was reached

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

    Science.gov (United States)

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

    2016-01-01

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

  7. A new chelating ion-exchanger containing p-bromophenylhydroxamic acid as functional group

    International Nuclear Information System (INIS)

    A new chelating resin based on macroreticular acrylonitrile-divinylbenzene copolymer and containing hydroxamic acid functional groups has been synthesized. It is highly-stable in acidic and alkaline solutions. The sorption characteristics of Cu(II), Cd(II), Pb(II), Zn(II), U(VI), Cr(VI), V(V), Co(II), Ni(II), Ca(II) and Mg(II) have been investigated over the pH range 1.0-6.0. The effect of various electrolytes at different ionic strengths on the Ksub(d) values for Cu(II), Cd(II), Pb(II) and Zn(II) has been studied systematically. Chromatographic separations of copper(II) and nickel(II) from cobalt(II), and of uranium(VI) from chromium(VI) by selective sorption at controlled pH, have been developed. The ion-exchanger can be used for purification of inorganic salts, and analysis of brass and bauxite. (author)

  8. F-Element ion chelation in highly basic media. Annual progress report, October 1, 1996 - July 1, 1997

    International Nuclear Information System (INIS)

    'The specific fundamental chemical objectives of this project are to: (1) study the chemical speciation of Sr and Ln ions in basic media formed in aqueous solutions with and without classical chelation agents (e.g., EDTA, polyphosphates, and organic carboxylates); (2) prepare pyridine N-oxide phosphonate and phosphonoacetate chelators of the types 1--3 and characterize their ionization properties by titrimetric techniques; (3) study the interactions of 5--7 with soluble oxide-hydroxide metallate species and higher molecular weight sols, gels and precipitates containing Sr and Ln ions, as time permits, interactions with oxide-hydroxide metallates of U, Th, Ba, Al and Fe will also be studied; (4) study the interactions of newly designed phosphonate ligands with oxide-hydroxide metallate species; (5) transfer the fundamental coordination chemistry revealed here to research groups at LANL and PNNL that will utilize the results to improve tank waste treatment protocols.'

  9. 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)

  10. Optimization of fuel cell membrane electrode assemblies for transition metal ion-chelating ordered mesoporous carbon cathode catalysts

    OpenAIRE

    Johanna K. Dombrovskis; Cathrin Prestel; Anders E. C. Palmqvist

    2014-01-01

    Transition metal ion-chelating ordered mesoporous carbon (TM-OMC) materials were recently shown to be efficient polymer electrolyte membrane fuel cell (PEMFC) catalysts. The structure and properties of these catalysts are largely different from conventional catalyst materials, thus rendering membrane electrode assembly (MEA) preparation parameters developed for conventional catalysts not useful for applications of TM-OMC catalysts. This necessitates development of a methodology to incorporate...

  11. Chelating resin from functionalization of chitosan with complexing agent 8-hydroxyquinoline: application for metal ions on line preconcentration system

    International Nuclear Information System (INIS)

    This study describes the functionalization of biopolymer chitosan, using the complexing agent 8-hydroxyquinoline (oxine) by reaction of diazotization. The chelating resin was characterized by degree of deacetylation, infrared, Raman spectroscopy. The efficiency of the chelating resin and accuracy of the proposed method was evaluated by the metal ion recovery technique in the analysis of potable water, lake water, seawater and a certified sample of oyster tissue. The metal ions Cd(II) and Cu(II) in the samples were previously enriched in a minicolumn and flow injection flame atomic absorption spectrometry (FI-FAAS) determined the concentrations of the analytes. The chelating resin exhibited high selectivity for Cd(II) at pH 7 and for Cu(II) at pH 10. The eluent concentration was tested by the use of HNO3 in concentrations of 0.1-3 mol l-1 maximum response was obtained at 0.5 mol l-1 for Cd(II) and Cu(II), with R.S.D. values of 0.4%. The analytes gave relative standard deviations (R.S.D.) of 1.5 and 0.7% for solutions of Cd(II) and Cu(II), respectively (n = 7) containing 20 μg l-1 of the metal ions, defining a high reproducibility. The limits of detection (LOD) were 0.1 μg l-1 for Cd(II) and 0.4 μg l-1 for Cu(II). The analytical properties of merit were obtained using the parameters previously optimized with preconcentration time of 90 s. The chelating resin showed chemical stability within a wide range of pH and the efficiency was not altered for the preconcentration of the metal ions during all the experiments

  12. 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)

  13. Elaboration of y-fanjasite catalysts containing radioactive elements such as uranyl ion in order to obtain aromatic solvents and heavy amines

    International Nuclear Information System (INIS)

    The present work has shown the possibility of ammonia alkylation by n-octanol-l in gaseous phase, in presence of zeolitic catalysts. These catalysts are Y faujasitic types being used in waste water demineralization containing radioactive elements such as uranyl ion. This ion gives to the Y faujasite similar activity and selectivity as those of catalysts containing rare earths or transition metals. Toluene disproportionation has permitted to test beforehand catalysts destined to ammonia alkylation and to compare their mechanism. We have also proved the possibility to produce heavy amines such as tertiary amines which are used as uranium extractant agent. Some zeolites such as ZSM-5, beta, X, A, analcime, HS and Y faujasite type are prepared by hydrothermal synthesis method and characterized by some analysis techniques

  14. Thermodynamic study of chelation of rare earth(III) ions with 2,3-dihydroxynaphthalene (DON)

    International Nuclear Information System (INIS)

    The chelation of 2,3-dihydroxynaphthalene with trivalent La, Pr, Nd, Sm, Gd, Tb, Dy, Ho and Y has been studied pH-metrically at 30deg +- 0.5deg in aqueous ethanol (10% v/v) at different ionic concentrations (0.05, 01, 0.15 and 0.2M KNO3). Formation of 1:1 chelates are indicated. The order of stability is found to be Ho > Dy > Tb > Y> Gd > Sm > Nd > Pr > La. The thermodynamic stability constants and free energies of chelation have been reported. (author)

  15. Effects of metal ion chelators on DNA strand breaks and inactivation produced by hydrogen peroxide in Escherichia coli: detection of iron-independent lesions.

    OpenAIRE

    Asad, N R; A.C. Leitão

    1991-01-01

    In order to study the role of metallic ions in the H2O2 inactivation of Escherichia coli cells, H2O2-sensitive mutants were treated with metal ion chelators and then submitted to H2O2 treatment. o-Phenanthroline, dipyridyl, desferrioxamine, and neocuproine were used as metal chelators. Cell sensitivity to H2O2 treatment was not modified by neocuproine, suggesting that copper has a minor role in OH production in E. coli. On the other hand, prior treatment with iron chelators protected the cell...

  16. Effect of Metal Ions, Chelating Agent and SH-Reagents on Radish (Raphanus sativus L.) Root β-Amylase

    OpenAIRE

    Sarowar Jahan M.G.; M. Shaela Pervin; M. Shariar Shovon; DEV SHARMA S.C.; Narayan Roy; M. Habibur Rahman

    2012-01-01

    Metal ions play vital roles in enzymes. They may also show sensitivity to various sulfhydryl reagents and chelating reagents. Effect of some metal ions, EDTA and sulfhydryl reagents on the activity of partially purified β-amylase of radish root were studied. Amylolytic activity of purified enzyme was increased substantially in the presence of Ca2+, Mg2+, and Zn2+. Some other divalent cations Cu2+, Pb2+, Sn2+, and Hg2+ almost completely ceased the enzyme activity. Cobalt (II), Manganese (II), ...

  17. Density functional modelling of the interaction between the uranyl ion and TiO2 and NiFe2O4 surfaces

    International Nuclear Information System (INIS)

    This study, performed within the framework of a collaboration between the IPN in Orsay and EDF, takes place within the problematic of radioactivity control in geological depository or in nuclear power plants. The interaction mechanisms of ions at solid / liquid interfaces are often very complex and thus very hard to characterize. The use of atomic modelling, and more particularly of ab initio type calculations such as the density functional theory, allow to access to surface complexes structural and energetic properties. First, this theoretical approach has been validated on the experimentally uranyl / rutile TiO2 well-known system. The systematic comparisons between experimental data and theoretical results have allowed to demonstrate the ability of this approach to properly describe this complex system. Then, a similar study has been performed as a predictive tool on the uranyl / NiFe2O4 system which is not characterized experimentally. The goal of these studies was to determine if theoretical calculations are able to bring usable and reliable data when the experimental studies are too hard to set up. (author)

  18. Adsorption equilibrium of uranium from seawater on chelating resin containing amide oxime group

    International Nuclear Information System (INIS)

    Chelating resins containing amide oxime group were synthesized by radiation-induced graft polymerization. The amount of the amide oxime groups was controlled below about 0.1 mol per kg of base polymer. The adsorption equilibrium of uranium from seawater on this resin was investigated. It was suggested that two neighboring amide oxime groups on the grafted chain captured one uranyl ion, and that single amide oxime ligand had little capacity for the adsorption of uranium. The adsorption equilibrium was correlated by a Langmuir-type equation. The content of neighboring amide oxime groups was 0.406 x 10-3 mol per kg of base polymer, which corresponded to 0.39 % of the total amount of amide oxime groups. The apparent stoichiometric stability constant for the complex of uranyl ion with the neighboring amide oxime groups in seawater was calculated to be 10-21.7. (author)

  19. Research on the chelation between luteolin and Cr(III) ion through infrared spectroscopy, UV-vis spectrum and theoretical calculations

    Science.gov (United States)

    Gao, Li-Guo; Wang, Hua; Song, Xiao-Li; Cao, Wei

    2013-02-01

    The chelation between luteolin and Cr(III) ion is studied using the theoretical methods. Many different potential complexes, formed with natural and deprotonated luteolin chelating bare and hydrated Cr(III) ion, respectively, are studied by using Density Functional Theory method. Both total and binding energies are calculated. The results from the studies indicate that Cr(III) ion is affine in forming a complex with luteolin at the 5-hydroxy-4-keto site and that deprotonated luteolin has stronger chelating power than natural luteolin. The reactivity differences between luteolin and luteolin-Cr(III) complexes are observed through comparison of their Conceptual DFT reactivity indices. Apart from the theoretical studies, the experiments are performed to modify the theoretical conclusions. Meanwhile, luteolin-Cr(III) complex has been synthesized, and the chelation site is analyzed using IR spectroscopy and UV/vis spectrum. The experimental results are found to have the same conclusions as those by theoretical studies.

  20. Synthetic and structural studies of uranyl complexes

    International Nuclear Information System (INIS)

    The complex chemistry of uranyl nitrate with mono and bi-functional neutral extractants shows, that it forms 1:2 and 1:1 complexes respectively. The structures of the isolated complexes show, that the water molecules from the primary coordination sphere of (UO2(NO3)2.2H2O) are replaced by the extractants completely and adopt a hexagonal bi-pyramidal geometry. However, the structural chemistry of uranyl nitrate with the tri-functional extractants show, that one of the nitrates acts as a monodentate ligand to maintain the hexagonal bi-pyramidal geometry. The complex chemistry of uranyl bis(β-diketonates) with the neutral monodentate extractants shows that the water molecule from the primary sphere of (UO2(β-diketonate)2.H2O) is replaced by the ligands, to form a pentagonal bi-pyramidal geometry around uranyl group. However, the structural chemistry of bi-functional neutral extractants with uranyl bis(β-diketonates) shows either mono or bi-nuclear uranyl complexes depending upon the stoichiometry of the uranyl ion used. (author)

  1. Liquid-liquid extraction of uranyl by TBP: the TBP and ions models and related interfacial features revisited by MD and PMF simulations.

    Science.gov (United States)

    Benay, G; Wipff, G

    2014-03-20

    We report a molecular dynamics (MD) study of biphasic systems involved in the liquid-liquid extraction of uranyl nitrate by tri-n-butylphosphate (TBP) to hexane, from "pH neutral" or acidic (3 M nitric acid) aqueous solutions, to assess the model dependence of the surface activity and partitioning of TBP alone, of its UO2(NO3)2(TBP)2 complex, and of UO2(NO3)2 or UO2(2+) uncomplexed. For this purpose, we first compare several electrostatic representations of TBP with regards to its polarity and conformational properties, its interactions with H2O, HNO3, and UO2(NO3)2 species, its relative free energies of solvation in water or oil environments, the properties of the pure TBP liquid and of the pure-TBP/water interface. The free energies of transfer of TBP, UO2(NO3)2, UO2(2+), and the UO2(NO3)2(TBP)2 complex across the water/oil interface are then investigated by potential of mean force (PMF) calculations, comparing different TBP models and two charge models of uranyl nitrate. Describing uranyl and nitrate ions with integer charges (+2 and -1, respectively) is shown to exaggerate the hydrophilicity and surface activity of the UO2(NO3)2(TBP)2 complex. With more appropriate ESP charges, mimicking charge transfer and polarization effects in the UO2(NO3)2 moiety or in the whole complex, the latter is no more surface active. This feature is confirmed by MD, PMF, and mixing-demixing simulations with or without polarization. Furthermore, with ESP charges, pulling the UO2(NO3)2 species to the TBP phase affords the formation of UO2(NO3)2(TBP)2 at the interface, followed by its energetically favorable extraction. The neutral complexes should therefore not accumulate at the interface during the extraction process, but diffuse to the oil phase. A similar feature is found for an UO2(NO3)2(Amide)2 neutral complex with fatty amide extracting ligands, calling for further simulations and experimental studies (e.g., time evolution of the nonlinear spectroscopic signature and of surface

  2. Studies of inclusion complexes between cyclodextrins and polyazamacrocyclic chelates of lanthanide (III) ions

    OpenAIRE

    Henriques, Elsa S.; Bastos, Margarida; Geraldes, Carlos F. G. C.; Ramos, Maria João

    2003-01-01

    The complexes between [gamma]-cyclodextrin and lanthanide (III) chelates of the polyazamacrocycles DOTA (DOTA [reverse not equivalent] 1,4,7,10-tertraazacyclododecane-1,4,7,10-tetraacetate) and DOTP (DOTP [reverse not equivalent] 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetramethylenephosphonate) have been thought out to enhance the potential of such chelates as contrast agents for MRI. Given the actual demand for the design of new contrast agents, we thought it worthwhile to confirm previous ...

  3. 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

  4. Mixed chelates of some trivalent lanthanide ions containing (trans-1,2-cyclohexylenedinitrilo)tetraacetate and norleucinate

    International Nuclear Information System (INIS)

    Formation constants of mixed chelates with (trans-1,2-cyclohexylenedinitrilo)tetra-acetate (DCTA) as primary ligand and norleucinate (nle) as secondary ligand with metal ions La(III), Ce(III), Pr(III), Sm(III), Gd(III), Tb(III), Dy(III), Er(III), and Yb(III) have been determined by the modified potentiometric pH titration method of Irving-Rossotti in aqueous medium at (295 ± 1) K and fixed ionic strenght of μ=0.1 M (NaClO4). Formation constants of binary complexes of the metal ions with the secondary ligand have also been determined under identical conditions. The mixed chelates were found to be more stable than the binary ones. The order of stabilities in terms of metal ions is La(III)< Ce(III)< Pr(III)< Sm(III)< Gd(III)< Tb(III)< Dy(III)< Er(III)< Yb(III) for binary and ternary complexes with a prominent 'Gadolinium break'. (authors)

  5. Adsorption of Cu(II), Hg(II), and Ni(II) ions by modified natural wool chelating fibers

    International Nuclear Information System (INIS)

    The graft copolymerization of ethyl acrylate (EA) onto natural wool fibers initiated by potassium persulphate and Mohr's salt redox initiator system in limited aqueous medium was carried out in heterogeneous media. Ester groups of the grafted copolymers were partially converted into hydrazide function groups followed by hydrazone formation through reaction with isatin. Also the application of the modified fibers for metal ion uptake was studied using Cu(II), Hg(II) and Ni(II). The modified chelating fibers were characterized using FTIR spectroscopy, SEM and X-ray diffraction.

  6. Adsorption of Cu(II), Hg(II), and Ni(II) ions by modified natural wool chelating fibers

    Energy Technology Data Exchange (ETDEWEB)

    Monier, M., E-mail: monierchem@yahoo.com [Chemistry Department, Drexel University, Philadelphia, PA (United States); Chemistry Department, Faculty of Science, Mansoura University, Mansoura (Egypt); Ayad, D.M.; Sarhan, A.A. [Chemistry Department, Faculty of Science, Mansoura University, Mansoura (Egypt)

    2010-04-15

    The graft copolymerization of ethyl acrylate (EA) onto natural wool fibers initiated by potassium persulphate and Mohr's salt redox initiator system in limited aqueous medium was carried out in heterogeneous media. Ester groups of the grafted copolymers were partially converted into hydrazide function groups followed by hydrazone formation through reaction with isatin. Also the application of the modified fibers for metal ion uptake was studied using Cu(II), Hg(II) and Ni(II). The modified chelating fibers were characterized using FTIR spectroscopy, SEM and X-ray diffraction.

  7. Adsorption of Cu(II), Hg(II), and Ni(II) ions by modified natural wool chelating fibers.

    Science.gov (United States)

    Monier, M; Ayad, D M; Sarhan, A A

    2010-04-15

    The graft copolymerization of ethyl acrylate (EA) onto natural wool fibers initiated by potassium persulphate and Mohr's salt redox initiator system in limited aqueous medium was carried out in heterogeneous media. Ester groups of the grafted copolymers were partially converted into hydrazide function groups followed by hydrazone formation through reaction with isatin. Also the application of the modified fibers for metal ion uptake was studied using Cu(II), Hg(II) and Ni(II). The modified chelating fibers were characterized using FTIR spectroscopy, SEM and X-ray diffraction. PMID:19962235

  8. 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

  9. Protective effects of ion-imprinted chitooligosaccharides as uranium-specific chelating agents against the cytotoxicity of depleted uranium in human kidney cells

    International Nuclear Information System (INIS)

    Occupational internal contamination with depleted uranium (DU) compounds can induce radiological and chemical toxicity, and an effective and specific uranium-chelating agent for clinical use is urgently needed. The purpose of this study was to investigate whether a series of synthesized water-soluble metal-ion-imprinted chitooligosaccharides can be used as uranium-specific chelating agents, because the chitooligosaccharides have excellent heavy metal ion chelation property and the ion-imprinting technology can improve the selective recognition of template ions. DU-poisoned human renal proximal tubule epithelium cells (human kidney 2 cells, HK-2) were used to assess the detoxification of these chitooligosaccharides. The DU-chelating capacity and selectivity of the chitooligosaccharides were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Cell viability, cellular accumulation of DU, membrane damage, DNA damage, and morphological changes in the cellular ultrastructure were examined to assess the detoxification of these chitooligosaccharides. The results showed that the Cu2+-imprinted chitooligosaccharides, especially the Cu2+-imprinted glutaraldehyde-crosslinked carboxymethyl chitooligosaccharide (Cu-Glu-CMC), chelated DU effectively and specifically, and significantly reduced the loss of cell viability induced by DU and reduced cellular accumulation of DU in a dose-dependent manner, owing to their chelation of DU outside cells and their prevention of DU internalization. The ultrastructure observation clearly showed that Cu-Glu-CMC-chelated-DU precipitates, mostly outside cells, were grouped in significantly larger clusters, and they barely entered the cells by endocytosis or in any other way. Treatment with Cu-Glu-CMC also increased the activity of antioxidant enzymes, and reduced membrane damage and DNA damage induced by DU oxidant injury. Cu-Glu-CMC was more effective than the positive control drug, diethylenetriaminepentaacetic acid (DTPA), in

  10. Structure-Activity Relationships and Identification of Optmized CC-Chemokine Receptor CCR1, 5, and 8 Metal-Ion Chelators

    DEFF Research Database (Denmark)

    Chalikiopoulos, Alexander; Thiele, Stefanie; Malmgaard-Clausen, Mikkel;

    2013-01-01

    Chemokine receptors are involved in trafficking of leukocytes and represent targets for autoimmune conditions, inflammatory diseases, viral infections, and cancer. We recently published CCR1, CCR8, and CCR5 agonists and positive modulators based on a three metal-ion chelator series: 2,2'-bipyridine...... bipyridine (23). The structure-activity relationships contribute to small-molecule drug development, and the novel chelators constitute valuable tools for studies of structural mechanisms for chemokine receptor activation....

  11. Chemical enrichment and separation of uranyl ions in aqueous media using novel polyurethane foam chemically grafted with different basic dyestuff sorbents.

    Science.gov (United States)

    El-Shahat, M F; Moawed, E A; Farag, A B

    2007-01-15

    The new type of the grafted polyurethane foam sorbents were prepared by coupling polyether polyol, toluene diisocyanate and basic dyestuff (Methylene blue, Rhodamine B and Brilliant green). The Me.B-PUF, Rh.B-PUF and Br.G-PUF were characterized using UV/vis, IR and TGA. The adsorption properties and chromatographic behaviour of these new adsorbents for preconcentration and separation of uranium(VI) ions at low concentrations from aqueous thiocyanate media were investigated by a batch process. The maximum sorption of U(VI) was in the pH ranges 1-4. The kinetics of sorption of the U(VI) by the Grafted-PUF were found to be fast with half life of sorption (t(1/2)) in 2.43min. The average sorption capacity of different sorbents 0.124meqg(-1) for uranyl ions, enrichment factors approximately 40 and the recovery 98-100% were achieved (R.S.D. approximately 0.73%). The basic dyestuff Grafted-PUF could be used many times without decreasing their capacities significantly. The value of the Gibbs free energy (DeltaG) for the sorbents is -7.3kJmol(-1), which reflects the spontaneous nature of sorption process. The sorption mechanism of the metal ion onto Grafted-PUF was also discussed. PMID:19071294

  12. Chitosan-functionalized gold nanoparticles for colorimetric detection of mercury ions based on chelation-induced aggregation

    International Nuclear Information System (INIS)

    We are presenting a colorimetric assay for mercury (II) ions. It is based on citosan-functionalized gold nanoparticles (AuNPs) that act as a signaling probe. Hg (II) induces the aggregation of the chitosan-AuNPs through a chelation reaction that occurs between chitosan and Hg (II). This results in a strong decrease of the absorbance of the modified AuNPs and a color change from red to blue. This sensing system displays excellent selectivity over other metal ions and a detection limit as low as 1.35 μM which is lower than the allowed level of Hg (II) in drinking water (30 μM) as defined by World Health Organization. The method is inexpensive, facile, sensitive, and does not require the addition of other reagents in order to improving sensitivity. (author)

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

    Science.gov (United States)

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

    2009-08-21

    The study of chelating compounds is very important to solve problems related to human metal overload. 3-Hydroxy-3-pyridinones (HP), namely deferiprone, have been clinically used for chelating therapy of Fe and Al over the last decade. A multi-disciplinary search for alternative molecules led us to develop poly-(3-hydroxy-4-pyridinones) to increase metal chelation efficacy. We present herein a complexation study of a new bis-(3-hydroxy-4-pyridinone)-EDTA derivative with a set of M(3+) hard metal ions (M = Fe, Al, Ga), as well as Zn(2+), a biologically relevant metal ion. Thus a systematic aqueous solution equilibrium study was performed using potentiometric and spectroscopic techniques (UV-Vis, NMR methods). These set of results enables the establishment of specific models as well as the determination of thermodynamic stability constants and coordination modes of the metal complexes. The results indicate that this ligand has a higher affinity for chelating to these hard metal ions than deferiprone, and that the coordination occurs mostly through the HP moieties. Furthermore, it was also found that this ligand has a higher selectivity for chelating to M(3+) hard metal ions (M = Fe, Al, Ga) than Zn(2+). PMID:20449110

  14. Effect of pH on the release of radionuclides and chelating agents from cement-solidified decontamination ion-exchange resins collected from operating nuclear power stations

    International Nuclear Information System (INIS)

    Data are presented on the physical stability and leachability of radionuclides and chelating agents from cement-solidified decontamination ion-exchange resin wastes collected from two operating commercial light water reactors. Small-scale waste--form specimens collected during solidifications performed at the Brunswick Steam Electric Plant Unit 1 and at the James A. FitzPatrick Nuclear Power Station were leach-tested and subjected to compressive strength testing in accordance with the Nuclear Regulatory Commission's ''Technical Position on Waste Form'' (Revision 1). Samples of untreated resin waste collected from each solidification vessel before the solidification process were analyzed for concentrations of radionuclides, selected transition metals, and chelating agents to determine the quantities of these chemicals in the waste-form specimens. The chelating agents included oxalic, citric, and picolinic acids. In order to determine the effect of leachant chemical composition and pH on the stability and leachability of the waste forms, waste-form specimens were leached in various leachants. Results of this study indicate that differences in pH do not affect releases from cement-solidified decontamination ion-exchange resin waste forms, but that differences in leachant chemistry and the presence of chelating agents may affect the releases of radionuclides and chelating agents. Also, this study indicates that the cumulative releases of radionuclides and chelating agents are similar for waste- form specimens that decomposed and those that retained their general physical form. 36 refs., 60 figs., 28 tabs

  15. Determination of molybdenum, chromium and vanadium by ion-pair high-pressure liquid chromatography based on precolumn chelation with 4-(2-pyridylazo)resorcinol

    International Nuclear Information System (INIS)

    A reversed-phase ion-pair liquid chromatography-spectrophotometric detection system for the separation and simultaneous determination of molybdenum, chromium and vanadium is described. The chelates of the metal ions with 4-(2-pyridylazo)resorcinol are separated on a Zorbax CN column with 1 x 10-3M tetrabutylammonium iodide and 0.01M KH2P04-Na2HP04 buffer (pH 7.50) in 30:70 v/v methanol-water mixture as the mobile phase, at a flow rate of 1.0 ml/min. The chelates are detected spectrophotometrically at 540 nm. (author)

  16. Studies of inclusion complexes between cyclodextrins and polyazamacrocyclic chelates of lanthanide (III) ions

    International Nuclear Information System (INIS)

    The complexes between γ-cyclodextrin and lanthanide (III) chelates of the polyazamacrocycles DOTA (DOTA ≡ 1,4,7,10-tertraazacyclododecane-1,4,7,10-tetraacetate) and DOTP (DOTP ≡ 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetramethylenephosphonate) have been thought out to enhance the potential of such chelates as contrast agents for MRI. Given the actual demand for the design of new contrast agents, we thought it worthwhile to confirm previous results for the equilibrium constant K obtained by one of us by NMR on the DOTP complex, as well as to determine K for a new one with DOTA. Further, we wanted to study and quantify the interactions present in these complexes, with a view to improve them in newly designed complexes. The interactions between γ-cyclodextrin and the lanthanide (III)-polyazamacrocyclic chelates, [Tm(DOTP)]5-, and [Gd(DOTA)]- were then studied by isothermal calorimetry (ITC) and molecular dynamics. The calorimetric experiments can be interpreted by considering that in both cases there is a weak association, characterized by low values for the equilibrium constant as well as for the molar enthalpy change for complex formation, at T=298.15 K. The K value for the complex with DOTP obtained now by ITC is of the same order of magnitude of the one determined previously by NMR. Further, the complex formation seems rather insensitive to the macrocycle, as the values now obtained by ITC for the DOTA complex are very similar to the ones obtained for the DOTP complex. We have also carried out molecular dynamics simulations on these very same inclusion complexes, which provided quantitative data on the interactions present, as well as a plausible explanation for the data obtained, leading to the proposal of possible solutions to improve the modelling of new contrast agents on a host-guest basis

  17. Adsorption of hazardous ions from radioactive waste on chelating cloth filter

    Energy Technology Data Exchange (ETDEWEB)

    Othman, Sameh H. [Second Research Reactor, Nuclear Research Center, Atomic Energy Authority, Cairo P.O. 13759 (Egypt)]. E-mail: othman_sameh@yahoo.com; Sohsah, Mustfa A. [Second Research Reactor, Nuclear Research Center, Atomic Energy Authority, Cairo P.O. 13759 (Egypt); Ghoneim, Mohammad M. [Second Research Reactor, Nuclear Research Center, Atomic Energy Authority, Cairo P.O. 13759 (Egypt); Sokkar, Hesham H. [National Center for Radiation Research and Technology, Atomic Energy Authority (Egypt); Badawy, Sayed M. [Chemistry Department, Faculty of Science, Cairo University (Egypt); El-Anadouli, Bahgat E. [Chemistry Department, Faculty of Science, Cairo University (Egypt)

    2006-02-15

    A cloth filter was synthesized by grafting of acrylonitrile/methacylic acid (AN/MAA {approx}80%/20% molar ratio) onto cotton cloth using a radiation-induced technique followed by amidoximation reaction. The fate of adsorption of radionuclide (e.g. U(VI)) on chelating cloth filter (CCF) from radioactive waste was investigated. The adsorption ability of the CCF increases as pH increases from 6 to 10. The predominant composition of the resulting complex was determined. A chemical adsorption mechanism was confirmed by examining the relationships between the adsorbed amount of radionuclide and the contact time.

  18. Adsorption of hazardous ions from radioactive waste on chelating cloth filter

    International Nuclear Information System (INIS)

    A cloth filter was synthesized by grafting of acrylonitrile/methacylic acid (AN/MAA ∼80%/20% molar ratio) onto cotton cloth using a radiation-induced technique followed by amidoximation reaction. The fate of adsorption of radionuclide (e.g. U(VI)) on chelating cloth filter (CCF) from radioactive waste was investigated. The adsorption ability of the CCF increases as pH increases from 6 to 10. The predominant composition of the resulting complex was determined. A chemical adsorption mechanism was confirmed by examining the relationships between the adsorbed amount of radionuclide and the contact time

  19. Controlled hydrothermal growth of ZnO nanostructures by sequestering the Zn metal ions with the chelating agent EDTA

    Science.gov (United States)

    Ram, S. D. Gopal; Ravi, G.; Manikandan, MR.; Mahalingam, T.; Anbu Kulandainathan, M.

    2011-10-01

    In the present work, a controlled growth of ZnO nanostructures by manipulating Zn metal ion concentration by the chelating action of ethylene diaminetetra acetic acid in hydrothermal method is studied. EDTA produces metal-chelate complex by the formation of bidentate ligand with Zn 2+ in the solution and diminishes the reactivity of Zn metal cations. Concentration of EDTA in the mother solution was varied in different ranges like 3, 5 and 10 mM while retaining the zinc metal salt and the NaOH concentration the same. Three different morphologies of wurtzite structured ZnO nanostructures such as nanorods-bunch, separate/discrete uniformly sized hexagonal nanorods and tapered flower petals like shapes are achieved by 3, 5 and 10 mM strengths of EDTA, respectively. The medium concentration 5 mM of EDTA is found to have moderate control over producing ZnO nanostructures of uniform diameter and a high aspect (length to diameter) ratio. An array of vertically aligned free standing ZnO nanorods with uniform spacing is successfully achieved by the addition of 5 mM of EDTA in the mother solution and the same is studied for its fluorescence property at an excitation of 325 nm and it has exhibited a characteristic UV emission of ZnO around 383 nm.

  20. Quantification of uranyl in presence of citric acid

    International Nuclear Information System (INIS)

    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)

  1. Development of a novel terbium chelate-based luminescent chemosensor for time-resolved luminescence detection of intracellular Zn2+ ions.

    Science.gov (United States)

    Ye, Zhiqiang; Wang, Guilan; Chen, Jinxue; Fu, Xiaoyan; Zhang, Wenzhu; Yuan, Jingli

    2010-11-15

    Time-resolved luminescence detection technique using lanthanide chelates as luminescent probes or sensors is a highly sensitive and widely used tool for the luminescence detections of various biological and bioactive molecules. The essential of this technique is the developments of various functional luminescent probes or sensors that can selectively recognize the biological targets. In this work, a dual-chelating ligand N,N,N(1),N(1)-{2,6-bis(3'-aminomethyl-1'-pyrazolyl)-4-[N,N-bis(2-picolyl)amino-methylenepyridine]} tetrakis(acetic acid) (BBATA) has been designed and synthesized. The luminescence of its Tb(3+) chelate is very weak, but can be selectively and strongly enhanced upon reaction with Zn(2+) ions. Thus a Tb(3+) chelate-based luminescent chemosensor, BBATA-Tb(3+), for highly selective and sensitive time-resolved luminescence detection of Zn(2+) ions was developed. To confirm the utility of new chemosensor for the detection of intracellular Zn(2+) ions, the performance of BBATA-Tb(3+) as a chemosensor for time-resolved luminescent imaging detection of Zn(2+) ions in living cells was investigated. The results demonstrated the efficacy and advantage of the new luminescent chemosensor for time-resolved luminescence detection of intracellular Zn(2+) ions. PMID:20846845

  2. Chelatization of Metals Ion (Cu2+, Cd2+ and Cr3+) with ProcessYield of Humic Acid from Peat Soil

    International Nuclear Information System (INIS)

    The chelation of metals ion (Cu2+, Cd2+ and Cr3+) with processyields of humic acid from peat soil has been done. The chelatizationcalculation was carried out using a mathematical model of the metals ionneutralization to the humic acid functional group. The model has superioritydue to the introduction of the humic acid concentration conditional and theloading capacity. Chelation is expected to obtain the constant experimentthat agrees with environmental conditional were the chelatization to takeplaces. By the tree neck flask of bath reactor, 250 ml volume at thetemperature of 25 oC chelation have been done and the AAS was used toanalyzes the yield. By mathematical calculate was obviously proved that thechelation constants was not influenced by pH, ionic strength and origin peatsoils. As log β, chelation constants of Cu2+, Cd2+ and Cr3+ were4.67 (± 0.02); 5.98 (± 0.02) and 6.09 (± 0.01) for humic acid fromSumatra I (Silaut III) and 4.68 (± 0.01); 5.97 (± 0.02) and 6.09 (±0.02) for Sumatra II (Silaut IV). While chelation constant Cu2+, Cd2+ andCr3+ from Kalimantan were 4.66 (± 0.03); 5.99 (± 0.01); 6.08 (±0.02). (author)

  3. Establishment of a luminescence technique for the quantification of uranyl ion in a KNO{sub 3} media; Establecimiento de una tecnica de luminiscencia para la cuantificacion del ion uranilo en medio de KNO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Contreras R, A. [UAEM, A.P. 2-139, 50000 Toluca, Estado de Mexico (Mexico); Fernandez V, S.M.; Ordonez R, E. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)

    2005-07-01

    The study of the storage of high level radioactive residuals that contain uranium, it makes necessary that in the sorption studies is counted with a reliable technique and not pollutant for the quantification of this element. Presently work intends a technique for the quantification of the uranyl ion using the luminescence technique, which allows not to generate radioactive or industrial residuals. It was used a solution of uranyl nitrate in KNO{sub 3} 0.5 M media. The solutions were adjusted to a pH of 1.48+0.03. A statistical study for the analysis of the data of fluorescence, about the maximum value of the peak, total area under the curve and area under the it curves is shown, being the best correlation for the concentration curve versus maximum of the peak, adjusted with a polynomial of second grade. The study of stability of the solutions with regard to the time is reported and that the technique proposal works for the interval of concentrations among 1 x 10{sup -2} M and 6 x 10{sup -5} M. (Author)

  4. Optimization of fuel cell membrane electrode assemblies for transition metal ion-chelating ordered mesoporous carbon cathode catalysts

    Directory of Open Access Journals (Sweden)

    Johanna K. Dombrovskis

    2014-12-01

    Full Text Available Transition metal ion-chelating ordered mesoporous carbon (TM-OMC materials were recently shown to be efficient polymer electrolyte membrane fuel cell (PEMFC catalysts. The structure and properties of these catalysts are largely different from conventional catalyst materials, thus rendering membrane electrode assembly (MEA preparation parameters developed for conventional catalysts not useful for applications of TM-OMC catalysts. This necessitates development of a methodology to incorporate TM-OMC catalysts in the MEA. Here, an efficient method for MEA preparation using TM-OMC catalyst materials for PEMFC is developed including effects of catalyst/ionomer loading and catalyst/ionomer-mixing and application procedures. An optimized protocol for MEA preparation using TM-OMC catalysts is described.

  5. Optimization of fuel cell membrane electrode assemblies for transition metal ion-chelating ordered mesoporous carbon cathode catalysts a

    Science.gov (United States)

    Dombrovskis, Johanna K.; Prestel, Cathrin; Palmqvist, Anders E. C.

    2014-12-01

    Transition metal ion-chelating ordered mesoporous carbon (TM-OMC) materials were recently shown to be efficient polymer electrolyte membrane fuel cell (PEMFC) catalysts. The structure and properties of these catalysts are largely different from conventional catalyst materials, thus rendering membrane electrode assembly (MEA) preparation parameters developed for conventional catalysts not useful for applications of TM-OMC catalysts. This necessitates development of a methodology to incorporate TM-OMC catalysts in the MEA. Here, an efficient method for MEA preparation using TM-OMC catalyst materials for PEMFC is developed including effects of catalyst/ionomer loading and catalyst/ionomer-mixing and application procedures. An optimized protocol for MEA preparation using TM-OMC catalysts is described.

  6. Fe304磁流体对铀(VI)的吸附研究%The Adsorption Behavior of Uranyl Ion on the Fe304 Ferro Fluids

    Institute of Scientific and Technical Information of China (English)

    贾继云; 袁亚莉; 黄芬; 徐丽华; 刘雅兰; 黄笑寒

    2011-01-01

    为降低铀对环境的影响,研究纳米磁流体对铀(VI)的吸附行为.用沉淀法制备了磁粒径10~20nm的Fe2O2磁流体,考察了该磁磁流体对铀(VI)吸附的各种影响因素,结果表明:在纳米磁流体浓度为2.5∥L、温度35~C、pH=3、吸附时间t=30min的条件下,对3×1014mol/L铀的吸附萃取率可达到84.15%.该吸附过程符合假设的二级动力学模型.%The water based ferrofluids with saturated magnetization 10 -20 nm was pre- pared by chemical coprecipitation, which was characterized by TEM. The adsorption of Ura- nyl ion on the of ferrofluids was studied in this paper. The result indicates that the optimum experiment condition is the ferro fluids ion of 2.5 g/L, temperature35~C , pH value 3 and adsorption time 30 rain, under which circumstances, the extraction rate of the Uranyl ion (3 x 10-4tool/L) reaches 84. 15%. The adsorption process follows kinetics, which indi- cates the adsorption is a monolaper adsorption.

  7. Cobalt(III) complexes of [3(5)]adamanzane, 1,5,9,13-tetraazabicyclo[7.7.3]nonadecane. Report of an inert, chelate hydrogen carbonate ion

    DEFF Research Database (Denmark)

    Broge, Louise; Søtofte, Inger; Olsen, Carl Erik; Springborg, Johan

    2001-01-01

    .H2O (3a). The coordination geometry around the cobalt(III) ion is a distorted octahedron with the inorganic ligands at cis-positions. Complex 2 is the second example of a cobalt(III) complex for which the X-ray structure,sfiows a chelate binding mode of the hydrogen carbonate entity. The pK(a) value...

  8. Preparation of carboxy-group-contained polyvinyl alcohol amidoxime chelate fiber by preirradiation grafting and its adsorbability for Au(III) ions

    International Nuclear Information System (INIS)

    Carboxy-group-contained polyvinyl alcohol amidoxime chelate fiber (PVAAO-AAc) was synthesized by preirradiation graft copolymerization and amidoximation. The radiation dose and ratio of monomers, acrylonitrile and acrylic acid, influence the value of grafting rate, amidoxime group component and adsorption capacity. The properties of adsorbing Au(III) ions was systematic studied in the paper. (author)

  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. 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

  11. FINAL REPORT. F-ELEMENT ION CHELATION IN HIGHLY BASIC MEDIA

    Science.gov (United States)

    A large body of data has been collected over the last fifty years on the chemical behaviorof f-element ions. The ions undergo rapid hydrolysis reactions in neutral or basic aqueoussolutions that produce poorly understood oxide-hydroxide species; therefore, most of thefundament...

  12. Synthesis and uranyl ion adsorption study of cross-linked allyl propionate-maleic anhydride-styrene terpolymer

    OpenAIRE

    AKPEROV, Elchin; MAHARRAMOV, Abel; AKPEROV, Oktay

    2010-01-01

    Allyl propionate-maleic anhydride-styren terpolymer has been modified with glycerin in order to prepare a new cross-linked functional polymer sorbent. The synthesized cross-linked polymer sorbent has a network structure and contains carboxylic acid, carbonyl, hydroxy, and ester groups, all of which are capable ofinteracting with metal ions. The sorption behavior of UO22+ ions under optimum sorption conditions was determined. The sorption properties of the sorbent were determined unde...

  13. Production of large quantities of 90Y by ion-exchange chromatography using an organic resin and a chelating agent

    International Nuclear Information System (INIS)

    The performance of a system composed of an organic cation exchanger (Dowex 50Wx8) and a chelating agent (EDTA) previously described for the successful production of 90Y via a 90Sr/90Y generator is assessed under dynamic conditions. In an attempt to overcome the established limitation of ion-exchange resins for the separation of subcurie quantities of activity, 90Y is repeatedly isolated from an 11.8-GBq (320 mCi) 90Sr cow using a three-column tandem arrangement. The high recovery and radionuclidic purity obtained for 90Y and the parameters of the separation (time, eluant concentration, pH and flow rate range) strongly suggest that Ci quantities of 90Y can be handled satisfactorily by the ion-exchange method. No replacement or treatment of the cow, low waste generation and 90Sr losses less than 0.1% after each run were observed during the present study which, in combination with the low cost of this resin, may result in an attractive alternate method for the production of large quantities of 90Y.

  14. Thermodynamic parameters and stabilities of some rare-earth metal ion chelates of alpha-valine

    International Nuclear Information System (INIS)

    Solution equilibrium for some rare-earth metal ions with valine have been studied potentiometrically in aqueous medium at temperature from 25 to 55 deg. C and ionic strength from 0.1 to 1.0 mol dm/sup -3/NaClO/sub 4/. The thermodynamic parameters delta H, delta S, delta G for the formation process were evaluated in terms of temperature, ionic strength and nature of metal ion present. The stability of the complexes was found to: La(III)< Nd(III)< Gd(III)< Eu(III)Yb(III)< Lu(III). (author)

  15. Conversion of agonist site to metal-ion chelator site in the β2-adrenergic receptor

    OpenAIRE

    Elling, Christian E.; Thirstrup, Kenneth; Holst, Birgitte; Thue W. Schwartz

    1999-01-01

    Previously metal-ion sites have been used as structural and functional probes in seven transmembrane receptors (7TM), but as yet all the engineered sites have been inactivating. Based on presumed agonist interaction points in transmembrane III (TM-III) and -VII of the β2-adrenergic receptor, in this paper we construct an activating metal-ion site between the amine-binding Asp-113 in TM-III—or a His residue introduced at this position—and a Cys residue substituted for Asn-312 in TM-VII. No inc...

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

    DEFF Research Database (Denmark)

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

    1999-01-01

    Previously metal-ion sites have been used as structural and functional probes in seven transmembrane receptors (7TM), but as yet all the engineered sites have been inactivating. Based on presumed agonist interaction points in transmembrane III (TM-III) and -VII of the beta(2)-adrenergic receptor,...

  17. 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

  18. Synthesis, Characterization and Some Properties of Chelating Polymers for Metal Ion Sorption

    International Nuclear Information System (INIS)

    Ion-exchange membranes have been prepared by radiation induced grafting using simultaneous technique based on low cost starting material and established process technologies. Methacrylic acid (MAA) and styrene (Sty) were selected as the grafted monomers to provide two different types of functional groups. Currently; there is much on going research for developing non fluorinated polymers with better performance and lower cost as alternative ion exchange membrane materials. The polymer chosen for this study is low density polyethylene (LDPE) film of two different thicknesses (40 and 70μm). The influence of grafting conditions, i.e. the effect of total irradiation dose and comonomer concentration and compositions have been investigated. These are important parameters in correlation with the grafting yield because they can markedly influence the composition of the resulting copolymer. Once grafted, the materials were readily sulfonated using concentrated sulfuric acid or chlorosulfonic acid in dichloroethane to produce a selection of graft copolymers with performer properties. The grafting and sulfonation of the membranes were confirmed by (FTIR) X-ray diffraction (XRD) and thermal analysis (TGA, DSC). The physicochemical properties of the prepared membranes such as, ion exchange capacity (IEC), equilibrium swelling and electrical conductivity of the grafted membranes and their derivatives were investigated as a function of composition and degree of grafting. The range of ion exchange capacities obtained with different degrees of grafting of MAA/Sty of composition (50/50) that sulfonated with sulfuric acid was in the range of 1.9-3.4 meq/g, whenever, for membranes that sulfonated with chlorosulfonic acid the IEC of 4.2 meq/g was achieved which is better than most of the commercially available membranes in addition to their low cost. The possibility of practicable use of membranes in various fields, such as the removal of some heavy metal ions is investigated.

  19. 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

  20. Affinity of the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) for large metal ions of higher charge. A crystallographic and thermodynamic study of PDA complexes of thorium(IV) and the uranyl(VI) ion.

    Science.gov (United States)

    Dean, Nolan E; Hancock, Robert D; Cahill, Christopher L; Frisch, Mark

    2008-03-17

    The hydrothermal synthesis and structures of [UO2(PDA)] (1) and [Th(PDA)2(H2O)2].H2O (2) (PDA = 1,10-phenanthroline-2,9-dicarboxylic acid) are reported. 1 is orthorhombic, Pnma, a = 11.1318(7) A, b = 6.6926(4) A, c = 17.3114(12) A, V = 1289.71(14), Z = 4, R = 0.0313; 2 is triclinic, P1, a = 7.6190(15) A, b = 10.423(2) A, c = 17.367(4) A, alpha = 94.93(3) degrees , beta = 97.57(3) degrees , gamma = 109.26(3) degrees , V = 1278.3(4) A (3), Z = 2, R = 0.0654. The local geometry around the U in 1 is a pentagonal bipyramid with the two uranyl oxygens occupying the apical positions. The donor atoms in the plane comprise the four donor atoms from the PDA ligand (average U-N = 2.558 and U-O = 2.351 A) with the fifth site occupied by a bridging carboxylate oxygen from a neighboring UO2/PDA individual. The PDA ligand in 1 is exactly planar, with the U lying in the plane of the ligand. The latter planarity, as well as the near-ideal U-O and U-N bond lengths, and O-U-N and N-U-N bond angles within the chelate rings of 1 suggest that PDA binds to the uranyl cation in a low-strain manner. In 2, there are two PDA ligands bound to the Th (average Th-N = 2.694 and Th-O = 2.430 A) as well as two water molecules (Th-O = 2.473 and 2.532 A) to give the Th a coordination number of 10. The PDA ligands in 2 are bowed, with the Th lying out of the plane of the ligand. Molecular mechanics calculations suggest that the distortion of the PDA ligands in 2 arises because of steric crowding. UV spectroscopic studies of solutions containing 1:1 ratios of PDA and Th(4+) in 0.1 M NaClO4 at 25 degrees C indicate that log K1 for the Th(4+)/PDA complex is 25.7(9). The latter result confirms the previous prediction that complexes of PDA with metal ions of higher charge and an ionic radius of about 1.0 A such as Th(IV) would have remarkably high log K1 values with PDA. The origins of this very high stability are discussed in terms of a synergy between the pyridyl and the carboxylate donor groups of PDA

  1. Alarming use of chelation therapy

    OpenAIRE

    Crisponi, Guido; Nurchi, Valeria Marina; Lachowicz, Joanna I.; Crespo-Alonso, Miriam; Zoroddu, Maria Antonietta; Peana, Massimiliano Francesco

    2014-01-01

    Chelation therapy is a consolidated medical procedure used primarily to hinder the effects of toxic metal ions on human tissues. Its application spans a broad spectrum of disorders, ranging from acute metal intoxication to genetic metal-overload. The use of chelating agents is compromised by a number of serious side effects, mainly attributable to perturbed equilibrium of essential metal ion homeostasis and dislocation of complexed metal ions to dangerous body sites. For this reason, chelatio...

  2. 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

  3. Selective removal of Ag+ ions from nitric acid medium by alginate microcapsules, Lewatite TP 214 chelating resin, and 200 CT strongly acidic ion exchanger

    International Nuclear Information System (INIS)

    Alginate microcapsules containing bis (2, 4, 4-trimethylpenthyl) monothiophosphinic acid (Cyanex 302) were prepared for the selective removal of Ag+ ions from the reprocessing effluents of FBR-MOX fuel. The Ag+ ions are added for the adjustment of oxidation state of Plutonium. We compared uptake properties of aforementioned microcapsules with those of 200 CT a strongly acidic resin, and Lewatite TP 214, a very selective chelating resin for the Ag+ ions. Most of the uptake properties of the microcapsules were amid the 200 CT and Lewatite, and rather similar to the later. The order of uptake kinetic and breakthrough capacity were the same as: 200 CT > Microcapsules > Lewatite; and for selectivity: Lewatite > Microcapsules > 200 CT. However, high selectivity of Lewatite is rather disadvantageous because it makes the elution operation complicated. Advantages of microcapsules include simple preparation procedure, relatively high selectivity and ease of elution even with 3M nitric acid. However, their total capacity is low. For enhancing the total capacity only increasing the active component is not enough since it deteriorates the kinetics, and the new preparation techniques are necessary which are under study. (author)

  4. COMPARATIVE STUDY OF CHELATION VALUE OF SEVENTEEN PERCENT SELF DEVELOPED AND COMMERCIALLY AVAILABLE ROOT CANAL LUBRICANTS

    OpenAIRE

    Ingale Satish Dinkarrao; Kankariya Rajendra

    2013-01-01

    The main objective of this study is to compare chelation values of 17% self developed & commercially available root canal Lubricants or dental chelating gels as well as to see whether their performance depends on the chelation value or not. The Chelating agent bounds Ca2+ ions of the smear layer & the extent of chelate formation between chelating agent and metal ion is nothing but Chelation Value. Sodium carbonate indicator method is used for determinations of chelation value. Commercially av...

  5. Selective electrochemical sensor for copper (II) ion based on chelating ionophores

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Ashok Kumar [Department of Chemistry, Indian Institute of Technology at Roorkee, Roorkee 247667 (India)]. E-mail: akscyfcy@iitr.ernet.in; Mehtab, Sameena [Department of Chemistry, Indian Institute of Technology at Roorkee, Roorkee 247667 (India); Jain, Ajay Kumar [Department of Chemistry, Indian Institute of Technology at Roorkee, Roorkee 247667 (India)

    2006-08-04

    Plasticized membranes using 3-(2-pyridinyl)-2H-pyrido[1,2,-a]-1,3,5-triazine-2,4(3H)-dithione (L {sub 1}) and acetoacetanilide (L {sub 2}) have been prepared and explored as Cu{sup 2+}-selective sensors. Effect of various plasticizers, viz. chloronaphthalene (China), benzyl acetate (BA), o-nitrophenyloctyl ether (o-NPOE), and anion excluders, sodium tetraphenylborate (NaTPB) and oleic acid (OA) was studied in detail and improved performance was observed at several instances. Optimum performance was observed with dithione derivative (L {sub 1}) having a membrane composition of L {sub 1} (5):PVC (120):o-NPOE (240):OA (10). The sensor works satisfactorily in the concentration range 5.0 x 10{sup -8} to 1.0 x 10{sup -2} M (detection limit 4.0 x 10{sup -8} M) with a Nernstian slope of 29.5 mV decade{sup -1} of activity. Wide pH range (3.0-9.5), fast response time (12 s), non-aqueous tolerance (up to 20%) and adequate shelf life (4 months) indicate the vital utility of the proposed sensor. The potentiometric selectivity coefficient values as determined by match potential method (MPM) indicate good response for Cu{sup 2+} in presence of interfering ions. The proposed electrode comparatively shows good selectivity with respect to alkali, alkaline earth, transition and some rare earth metals ions. The electrode was used for the determination of copper in different milk powder, water samples and as indicator electrode in potentiometric titration of copper ion with EDTA.

  6. Polymeric nanoparticles assembled by metal ion chelation for radionuclide and drug delivery

    Czech Academy of Sciences Publication Activity Database

    Nováková, Michaela; Hrubý, Martin; Filippov, Sergey K.; Karlsson, G.; Macková, Hana; Větvička, David; Špírková, Milena; Kaňková, Dana; Steinhart, Miloš; Štěpánek, Petr; Ulbrich, Karel

    Kottayam : Institute for Holistic Medical Sciences, 2011. s. 21-22. [World Conference on Nanomedicine and Drug Delivery /2./. 11.03.2011-13.03.2011, Kottayam] R&D Projects: GA ČR GPP207/10/P054; GA ČR GA202/09/2078; GA MŠk 1M0505 Institutional research plan: CEZ:AV0Z40500505; CEZ:AV0Z50200510 Keywords : polymer * drug delivery * metal ion assembly Subject RIV: CD - Macromolecular Chemistry

  7. A new method for the rapid identification of tetracycline residues in foods of animal origin - using the Premi?Test in combination with a metal ion chelation assay

    OpenAIRE

    Stead, Sara Lucy; Caldow, Marianne; Sharma, Anisha; Ashwin, Helen Mary; De-Rijk, Angelique; Stark, Jaques

    2007-01-01

    Abstract A post-screening classification assay for tetracycline compounds has been developed and integrated into the previously reported optimised Premi?Test methodology (Stead et al. 2004 and Stead et al. 2005) The new post-antimicrobial screening assay is based on a metal ion chelation using calcium and sodium chloride and has been shown to be specific towards the tetracycline class. The assay is both cost-effective and complementary to the post-screening procedures that have pre...

  8. 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)

  9. Coordination number of uranium in crystal hydrates and hydratoetherates of uranyl halogen acetates

    International Nuclear Information System (INIS)

    The coordination number (CN) of uranyl in some crystal hydrates and crystal solvates of uranyl halogenacetates is discussed. When there is no steric hindrance from the carboxylate ion, the probability of a maximum CN of 6 increases with decrease of the electron-donating capacity of the anion, which can be associated with giometric factors and redistribution of electron density in the inner coordination sphere of uranyl

  10. Coordination number of uranium in crystallohydrates and hydratoethers of uranyl halogenacetates

    Energy Technology Data Exchange (ETDEWEB)

    Baluev, A.V.; Suglobova, I.G.

    1983-01-01

    The problem of coordination number (c. n.) of uranyl in the series of crystallohydrates and crystallosolvates of uranyl halogenacetates is discussed. The probability of the maximum c. n. 6 in the absence of steric obstacles on the part of carboxylate-ion increases with the decrease of electron-donor ability of anion which can be connected both with geometric factors and with electron density redistribution in the internal coordination sphere of uranyl.

  11. On coordination number of uranium in crystallohydrates and hydratoethers of uranyl halogenacetates

    International Nuclear Information System (INIS)

    The problem of coordination number (c. n.) of uranyl in the series of crystallohydrates and crystallosolvates of uranyl halogenacetates is discussed. The probability of the maximum c. n. 6 in the absence of steric obstacles on the part of carboxylate-ion increases with the decrease of electron-donor ability of anion which can be connected both with geometric factors and with electron density redistribution in the internal coordination sphere of uranyl

  12. Coordination number of uranium in crystal hydrates and hydratoetherates of uranyl halogen acetates

    Energy Technology Data Exchange (ETDEWEB)

    Baluev, A.V.; Suglobova, I.G.

    The coordination number (CN) of uranyl in some crystal hydrates and crystal solvates of uranyl halogenacetates is discussed. When there is no steric hindrance from the carboxylate ion, the probability of a maximum CN of 6 increases with decrease of the electron-donating capacity of the anion, which can be associated with giometric factors and redistribution of electron density in the inner coordination sphere of uranyl.

  13. 13C NMR spectra of the uranyl tricarbonate-bicarbonate system

    International Nuclear Information System (INIS)

    The 13C NMR identification of the uranyl tricarbonate complex (important in solution mining of U from ore and conventional carbonate leaching) is reported. The NMR spectra show the transition from slow to fast carbonate exchange between uranyl ion and bulk water in an accessible temperature range. The taller NMR peak at 162.31 ppM is frm HCO3- and the smaller peak at 168.86 ppM is from the uranyl tricarbonate complex

  14. Preparation and characterization of chelating fibers based on natural wool for removal of Hg(II), Cu(II) and Co(II) metal ions from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Monier, M., E-mail: monierchem@yahoo.com [Chemistry Department, Faculty of Science, Mansoura University, 35516 (Egypt); Nawar, N., E-mail: nnawar@mans.edu.eg [Chemistry Department, Faculty of Science, Mansoura University, 35516 (Egypt); Abdel-Latif, D.A. [Chemistry Department, Faculty of Science, Mansoura University, 35516 (Egypt)

    2010-12-15

    The graft copolymerization of acrylonitrile (AN) onto natural wool fibers initiated by KMnO{sub 4} and oxalic acid combined redox initiator system in limited aqueous medium was carried out in heterogeneous media. Moreover, modification of the grafted wool fibers was done by changing the nitrile group (-CN) into cyano-acetic acid {alpha}-amino-acrylic-hydrazide through the reaction with hydrazine hydrate followed by ethylcyanoacetate which eventually produce wool-grafted-poly(cyano-acetic acid {alpha}-amino-acrylic-hydrazide) (wool-g-PCAH) chelating fibers. The application of the modified fibers for metal ion uptake was studied using Hg{sup 2+}, Cu{sup 2+} and Co{sup 2+}. The modified chelating fibers were characterized using FTIR spectroscopy, SEM and X-ray diffraction.

  15. Preparation and characterization of chelating fibers based on natural wool for removal of Hg(II), Cu(II) and Co(II) metal ions from aqueous solutions.

    Science.gov (United States)

    Monier, M; Nawar, N; Abdel-Latif, D A

    2010-12-15

    The graft copolymerization of acrylonitrile (AN) onto natural wool fibers initiated by KMnO(4) and oxalic acid combined redox initiator system in limited aqueous medium was carried out in heterogeneous media. Moreover, modification of the grafted wool fibers was done by changing the nitrile group (-CN) into cyano-acetic acid α-amino-acrylic-hydrazide through the reaction with hydrazine hydrate followed by ethylcyanoacetate which eventually produce wool-grafted-poly(cyano-acetic acid α-amino-acrylic-hydrazide) (wool-g-PCAH) chelating fibers. The application of the modified fibers for metal ion uptake was studied using Hg(2+), Cu(2+) and Co(2+). The modified chelating fibers were characterized using FTIR spectroscopy, SEM and X-ray diffraction. PMID:20810212

  16. Preparation and characterization of chelating fibers based on natural wool for removal of Hg(II), Cu(II) and Co(II) metal ions from aqueous solutions

    International Nuclear Information System (INIS)

    The graft copolymerization of acrylonitrile (AN) onto natural wool fibers initiated by KMnO4 and oxalic acid combined redox initiator system in limited aqueous medium was carried out in heterogeneous media. Moreover, modification of the grafted wool fibers was done by changing the nitrile group (-CN) into cyano-acetic acid α-amino-acrylic-hydrazide through the reaction with hydrazine hydrate followed by ethylcyanoacetate which eventually produce wool-grafted-poly(cyano-acetic acid α-amino-acrylic-hydrazide) (wool-g-PCAH) chelating fibers. The application of the modified fibers for metal ion uptake was studied using Hg2+, Cu2+ and Co2+. The modified chelating fibers were characterized using FTIR spectroscopy, SEM and X-ray diffraction.

  17. 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)

  18. Flow-injection in-line complexation for ion-pair reversed phase high performance liquid chromatography of some metal-4-(2-pyridylazo) resorcinol chelates.

    Science.gov (United States)

    Srijaranai, Supalax; Chanpaka, Saiphon; Kukusamude, Chutima; Grudpan, Kate

    2006-02-28

    Flow injection (FI) was coupled to ion-pair reversed phase high performance liquid chromatography (IP-RPHPLC) for the simultaneous analysis of some metal-4-(2-pyridylazo) resorcinol (PAR) chelates. A simple reverse flow injection (rFI) set-up was used for in-line complexation of metal-PAR chelates prior to their separation by IP-RPHPLC. The rFI conditions were: injection volume of PAR 85muL, flow rate of metal stream 4.5mLmin(-1), concentration of PAR 1.8x10(-4)molL(-1) and the mixing coil length of 150cm. IP-RPHPLC was carried out using a C(18)muBondapak column with the mobile phase containing 37% acetonitrile, 3.0mmolL(-1) acetate buffer pH 6.0 and 6.2mmolL(-1) tetrabutylammonium bromide (TBABr) at a flow rate of 1.0mLmin(-1) and visible detection at 530 and 440nm. The analysis cycle including in-line complexation and separation by IP-RPHPLC was 16min, which able to separate Cr(VI) and the PAR chelates of Co(II), Ni(II) and Cu(II). PMID:18970520

  19. Uranyl Oxalate Solubility

    International Nuclear Information System (INIS)

    The solubility of uranyl oxalate was determined at ambient temperature by precipitation in oxalic-nitric solutions, using an initial uranyl concentration of 0.1 mol/L. Oxalic concentration varied from 0.075 to 0.3 mol/L while nitric concentration ranged between 0.75 and 3 mol/L. Dissolution tests, using complementary oxalic-nitric media, were carried out for 550 hours in order to study the kinetic to reach thermodynamic equilibrium. Similar solubility values were reached by dissolution and precipitation. Using the results, it was possible to draw the solubility surface versus oxalic and nitric concentrations and to determine both the apparent solubility constant of UO2C2O4, 3H2O (Ks) and the apparent formation constant of the first uranyl-oxalate complex UO2C2O4 (log β1), for ionic strengths varying between 1 and 3 mol/L. Ks and log β1 values were found to vary from 1.9 10-8 to 9.2 10-9 and from 5.95 to 6.06, respectively, when ionic strength varied from 1 to 3 mol/L. A second model may fit our data obtained at an ionic strength of 3 mol/L suggesting as reported by Moskvin et al. (1959) that no complexes are formed for [H+] at 3 M. The Ks value would then be 1.3 10-8. (authors)

  20. Adsorption performances and mechanisms of the newly synthesized N,N'-di (carboxymethyl) dithiocarbamate chelating resin toward divalent heavy metal ions from aqueous media

    International Nuclear Information System (INIS)

    N,N'-di (carboxymethyl) dithiocarbamate chelating resin (PSDC) was synthesized by anchoring the chelating agent of N,N'-di (carboxymethyl) dithiocarbamate to the chloromethylated PS-DVB (Cl-PS-DVB) matrix, as a new adsorbent for removing divalent heavy metal ions from waste-stream. The physicochemical structures of Cl-PS-DVB and PSDC were elaborately characterized using Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), and were further morphologically characterized using BET and BJH methods. The adsorption performances of PSDC towards heavy metals such as Cu(II), Pb(II) and Ni(II) were systematically investigated, based upon which the adsorption mechanisms were deeply exploited. For the above target, the classic batch adsorption experiments were conducted to explore the kinetics and isotherms of the removal processes with pH-value, initial concentration, temperature, and contact time as the controlling parameters. The kinetic and isotherm data could be well elucidated with Lagergren-second-order equation and Langmuir model respectively. The strong affinity of PSDC toward these target soft acids could be well demonstrated with the electrostatic attraction and chelating interaction caused by IDA moiety and sulphur which were namely soft bases on the concept of hard and soft acids and bases (HASB). Thermodynamic parameters, involving ΔHo, ΔSo and ΔGo were also calculated from graphical interpretation of the experimental data. The standard heats of adsorption (ΔHo) were found to be endothermic and the entropy change values (ΔSo) were calculated to be positive for the adsorption of Cu(II), Pb(II) and Ni(II) ions onto the tested adsorbents. Negative values of ΔGo indicated that adsorption processes for all tested metal ions onto PSDC were spontaneous.

  1. Density functional modelling of the interaction between the uranyl ion and TiO{sub 2} and NiFe{sub 2}O{sub 4} surfaces; Simulation par la theorie de la fonctionnelle de la densite de l'interaction de l'ion uranyle avec les surfaces de TiO{sub 2} et de NiFe{sub 2}O{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Perron, H

    2007-07-15

    This study, performed within the framework of a collaboration between the IPN in Orsay and EDF, takes place within the problematic of radioactivity control in geological depository or in nuclear power plants. The interaction mechanisms of ions at solid / liquid interfaces are often very complex and thus very hard to characterize. The use of atomic modelling, and more particularly of ab initio type calculations such as the density functional theory, allow to access to surface complexes structural and energetic properties. First, this theoretical approach has been validated on the experimentally uranyl / rutile TiO{sub 2} well-known system. The systematic comparisons between experimental data and theoretical results have allowed to demonstrate the ability of this approach to properly describe this complex system. Then, a similar study has been performed as a predictive tool on the uranyl / NiFe{sub 2}O{sub 4} system which is not characterized experimentally. The goal of these studies was to determine if theoretical calculations are able to bring usable and reliable data when the experimental studies are too hard to set up. (author)

  2. Effect of chelating agents and metal ions on nickel bioavailability and chlorophyll fluorescence response in wheat- An approach for attenuation of Ni stress

    Directory of Open Access Journals (Sweden)

    Nilima Patnaik

    2012-08-01

    Full Text Available The objectives of the study are to analyze the physiological changes, biochemical alterations and attenuation of nickel toxicity effects in wheat seedlings under combined applications of Ni ions, metal chelators (EDTA/Citric Acid and metal ions (Zn2+ /Mg2+. Wheat (Triticum aestivum L cv UP262 seedlings were grown hydroponically using different concentrations of Ni up to 7 days along with chelators and metal ions for study. The seedling growth was maximum with NiCl2–Zn2+ (100μM and minimum with NiCl2–EDTA (100μM treatments. Total chlorophyll content was maximum in the seedlings treated with NiCl2-Zn2+ (100μM and minimum in NiCl2-EDTA (100μM treatments. NiCl2–EDTA (100μM showed less Fo and Fm values and therefore, a trend in the decrease in OJIP transient indicates the maximum alteration of photochemical activity of PS-II in presence of NiCl2–EDTA (100μM treatment. Similar observation was found by NiCl2 –EDTA (200μM treatment where Fo and Fm values were noted to decline. High nickel content in roots of the seedlings was noted as compared to shoots.

  3. Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene

    International Nuclear Information System (INIS)

    In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO22+ 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 (NO2) 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 UO2L 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 (ΔlogΒ110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO22+. 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. (author)

  4. Cycloaddition of thiocyanate ion to cyanoguanidine in the presence of uranyl ion: synthesis and crystal structure of (C3N5H6S)2[(UO2)(C2O4)2(H2O)] · C2N4H4

    International Nuclear Information System (INIS)

    Uranyl complex (C3N5H6S)2[(UO2)(C2O4)2(H2O)] ·C2N4H4 has been synthesized, its X-ray diffraction study being conducted. It has been ascertained that the complex is crystallized in triclinic crystal system, space group P1-bar, a=8.5201(11), b=11.4027(14), c=14.329(2)A, α=103.182(5), β=99.607(6), γ=109.698(4)deg, Z=2, ρcalcd=2.258 g/cm3. The structure integrates a complex aquadioxalatouranylate-anion, two crystallographically nonequivalent cations of thioammelinium and a neutral molecule of cyanoguanidine. It is pointed out that uranyl ion serves as a catalyst of thioammelinium formation during synthesis of the complex mentioned

  5. 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)

  6. 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)

  7. Some aspects of chelation chemistry

    International Nuclear Information System (INIS)

    The notions used in chelation chemistry are defined and the possibilities of the experimental recognition of complex formation are described. A review of the quantitative aspects of chelation is given, especially under biological conditions. Some rules concerning the general behaviour of the various metal ions and the organic ligands in chelation phenomena are presented and the specificity problem is discussed. The present status of the decontamination of the main fission products, e.g. rare-earth metals and strontium, with the aid of complexing agents is analysed from a chemical point of view. (author)

  8. 食用菌中多糖与锌离子配合工艺优化%Optimization of chelation of polysaccharide from shiitake mushroom with zinc ion

    Institute of Scientific and Technical Information of China (English)

    陈平; 杜佳; 孙胜敏

    2015-01-01

    采用食用菌为原料,采用微波辅助热水解提取法提取出复合多糖,并用凝胶树脂对提取液中复合多糖进行纯化.对复合多糖与锌离子配合反应及产物进行初步的探讨研究.确定最佳的反应条件为反应温度为60℃、反应时间为60 min、pH值为9.0,在此条件下,锌离子∶多糖配合比为1∶1(物质的量比).采用红外光谱对产物进行了表征.%Compound polysaccharide was extracted using microwave -assisted thermal hy-drolysis extraction method with edible fungus as raw materials and purified by Gel resin.The chelation between compound polysaccharide and zinc ion was preliminarily investigated.The optimal chelation condition was a reaction at 60 ℃, pH=9.0 for 60 min, and a molar ratio between zinc ion and polysaccharide of 1∶1.The product was characterized by infrared spec-troscopy.

  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. Synthesis and some physicochemical characteristics of uranyl benzenesulphonate

    Energy Technology Data Exchange (ETDEWEB)

    Baluev, A.V.; Krylov, S.G.; Suglobova, I.G.; Taranov, A.P.

    1984-11-01

    Crystallohydrate of uranyl benzenesulfonate has been synthesized by the interaction of stoichiometric quantities of UO/sub 3/ with benzene sulphonic acid. The prepared fine crystalline light yellow color powder has the UO/sub 2/(C/sub 6/H/sub 5/S/sub 3/)/sub 2/xH/sub 2/O composition and 73.3 mass% solubility in water at 25 deg C. The salt DT. curve has an intensive endoeffect at 215 deg C which corresponds to the dehydration process and two exo-effects at 350 and 390 deg C corresponding to ion-sulfanate decomposition. The IR-spectra analysis has shown that benzine sulfonate-ion binds two uranyl groupings of the UO/sub 2/-O-S-O-UO/sub 2/ type by two oxygen atoms. The third oxygen atom of the sulfonate group forms stable hydrogen bonds with a water molecule coordinated to uranyl. The uranyl coordination number in the crystallohydrate is 5. The anhydrous uranyl benzene sulfonate is prepared by monohydrate vacuum dehydration at a 1 to 2 Pa pressure, 130 to 150 deg C temperature during 15 h.

  11. Synthesis and some physicochemical characteristics of uranyl benzenesulphonate

    International Nuclear Information System (INIS)

    Crystallohydrate of uranyl benzenesulfonate has been synthesized by the interaction of stoichiometric qulntities of UO3 with benzene sulphonic acid. The prepared f1ne crystalline light yellow color powder has the UO2(C6H5S3)2xH2O composition and 73.3 mass% solubility in water at 25 deg C. The salt DT. curve has an intensive endoeffect at 215 deg C which corresponds to the dehydration process and two exo-effects at 350 and 390 deg C corresponding to ion-sulfanate decomposition. The IR-spectra analysis has shown that benzine sulfonate-ion binds two uranyl groupings of the UO2-O-S-O-UO2 type by two oxygen atoms. The third oxygen atom of the sulfonate group forms stable hydrogen bonds with a water molecule coordinated to uranyl. The uranyl coordination number in the crystallohydrate is 5. The anhydrous uranyl benzene Sulfonate is prepared by monohydrate vacuum dehydration at a 1 to 2 Pa pressure, 130 to 150 deg C temperature during 15 h

  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. 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)

  14. Spectroscopic studies of 2-thenoyltrifluoro acetonate of uranyl salts doped with europium

    International Nuclear Information System (INIS)

    Uranyl compounds present a great potential as luminescence materials. Some examples of applications are: in laser technology, cathode ray tube, X-rays diagnostic. In this work it was studied the synthesis, characterization and spectroscopic properties study of uranyl 2-thenoyl trifluoroacetonate and uranyl 2- thenoyl trifluoroacetonate doped with europium. The compounds were synthesized and characterized by infrared absorption spectroscopy, thermal analysis, scanning electronic microscopy, and electronic spectroscopy of emission and excitation. The Eu3+ ion acted as an effective luminescent probe, however the process of energy transfer from UO22+ to Eu3+ ion has not been efficient. (author)

  15. Investigation on the influence of metal ion impurities on the complexation behavior of generator produced {sup 90}Y with different bifunctional chelators

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Usha; Gamre, Naresh; Chakravarty, Rubel; Pillai, Maroor Raghavan Ambikalmajan; Dash, Ashutosh [Bhabha Atomic Research Centre, Trombay, Mumbai (India). Radiopharmaceuticals Div.

    2014-07-01

    While the {sup 90}Sr/{sup 90}Y generator is the exclusive source of obtaining 'no carrier added' {sup 90}Y for targeted therapy, the presence of trace metals in the radiolabeling solutions poses a serious challenge owing to their ability to diminish the {sup 90}Y complexation yields with bifunctional chelators (BFCs). p-SCN-Bn-PCTA is a novel ligand having faster complexation kinetics with a number of radiometals. In this work, a systematic investigation was performed to evaluate the chelating ability of p-SCN-Bn-PCTA for {sup 90}Y and the influence of trace metal ions on it's complexation with {sup 90}Y in comparison to p-SCN-Bn-DTPA and p-SCN-Bn-DOTA using {sup 90}YCl{sub 3} obtained from an electrochemical generator. Results from our study indicate that while p-SCN-Bn-PCTA gave very good radiolabeling yields with {sup 90}Y when the reaction was carried out by heating for few minutes, it was most sensitive to the presence of trace metals, especially Fe(III). An independent and useful observation is that p-SCN-Bn-PCTA could be considered as the ligand of choice for assessing the chemical purity of generator derived {sup 90}Y.

  16. Effect of chelate ring sizes and their substitution on intensities of hypersensitive transitions of lanthanoids (Ln(III)) ions and j (total quantum number profiles)

    International Nuclear Information System (INIS)

    Full text: Electronic spectral studies of Pr(III), Nd(III), Sm(III) Dy(III), Eu(III) and Tm(III) complexes with some aliphatic and aromatic O-O donor ligands viz., Glycolic (gly), Malonic (main) Succinic (suc), Glutaric (glut), Salicylic (sal), Phthalic acids and Catechol (cat) having varied chelate ring sizes and different substitutions as side chains have been carried out with a view to study the effect of chelate ring sizes on the intensities of hypersensitive and pseudo-hypersensitive transitions in lanthanoids. The intensities of these HST transitions have also been correlated with the total quantum number (J) of the lanthanoid metal ions in order to seek a probable mechanism for the phenomenon hypersensitivity. A comparison of the spectral and nephelauxetic parameters for Pr(III), Nd(III), Sm(III) with Dy(III) Er(III) and Tm(III) exhibit a variation in the bonding pattern from electrostatic to covalo-electrostatic from pre-Gd elements to post-Gd elements. The J-(total) quantum number profiles of the oscillator strength values for the specific HST transitions have also been examined

  17. Raman spectroscopic studies of some uranyl nitrate complexes

    International Nuclear Information System (INIS)

    Laser Raman spectra of uranyl trinitrate complexes (KUO2(NO3)3, RbUO2(NO3)3 CsUO2(NO3)3, NH4UO2(NO3)3) have been measured in the region from 2000 to 10 cm-1. Vibrational assignments have been made on the assumption that all the complexes contain discrete UO2X3- (X = NO3) ions belonging to a point group of D/sub 3h/. A brief discussion is made on the ligation effect of nitrate group on the uranyl bond order from a point of view of molecular orbital theory

  18. 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)

  19. 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...

  20. COMPARATIVE STUDY OF CHELATION VALUE OF SEVENTEEN PERCENT SELF DEVELOPED AND COMMERCIALLY AVAILABLE ROOT CANAL LUBRICANTS

    Directory of Open Access Journals (Sweden)

    Ingale Satish Dinkarrao

    2013-06-01

    Full Text Available The main objective of this study is to compare chelation values of 17% self developed & commercially available root canal Lubricants or dental chelating gels as well as to see whether their performance depends on the chelation value or not. The Chelating agent bounds Ca2+ ions of the smear layer & the extent of chelate formation between chelating agent and metal ion is nothing but Chelation Value. Sodium carbonate indicator method is used for determinations of chelation value. Commercially available gel incorporated in this study was File Rite which has little bit higher chelation value. Self developed chelating gel or root canal lubricants have comparatively lower chelation value. Root canal lubricants having higher chelation value should perform better in shaping & cleaning of root canal better. However because of slight difference in chelation value of self developed & commercially available gel, no significant difference was found out as root canal lubricants, when applied in root canal for 5 minutes.

  1. Temperature and pH driven association in uranyl aqueous solutions

    Directory of Open Access Journals (Sweden)

    M. Druchok

    2012-12-01

    Full Text Available An association behavior of uranyl ions in aqueous solutions is explored. For this purpose a set of all-atom molecular dynamics simulations is performed. During the simulation, the fractions of uranyl ions involved in dimer and trimer formations were monitored. To accompany the fraction statistics one also collected distributions characterizing average times of the dimer and trimer associates. Two factors effecting the uranyl association were considered: temperature and pH. As one can expect, an increase of the temperature decreases an uranyl capability of forming the associates, thus lowering bound fractions/times and vice versa. The effect of pH was modeled by adding H+ or OH- ions to a "neutral" solution. The addition of hydroxide ions OH- favors the formation of the associates, thus increasing bound times and fractions. The extra H+ ions in a solution produce an opposite effect, thus lowering the uranyl association capability. We also made a structural analysis for all the observed associates to reveal the mutual orientation of the uranyl ions.

  2. Influence of ionic and nonionic surfactants on analytical parameters of ion-selective electrodes based on chelating active substances

    Energy Technology Data Exchange (ETDEWEB)

    Wardak, Cecylia [Department of Analytical and Instrumental Analysis, Faculty of Chemistry, M. Curie Sklodowska University, 20031 Lublin (Poland)]. E-mail: cwardak@hermes.umcs.lublin.pl; Marczewska, Barbara [Department of Analytical and Instrumental Analysis, Faculty of Chemistry, M. Curie Sklodowska University, 20031 Lublin (Poland); Lenik, Joanna [Department of Analytical and Instrumental Analysis, Faculty of Chemistry, M. Curie Sklodowska University, 20031 Lublin (Poland)

    2006-02-15

    The effects of the cationic (tetrabutylammonium chloride, TBC), anionic (sodium dodecyl sulfate, SDS) and nonionic (TRITON X-100) surfactants on the potentiometric properties of zinc- and cadmium-selective electrodes (ISEs) were investigated. The studies were carried out with plasticized PVC membranes doped with several new acidic chelating ionophores. The electrode basic analytical parameters, such as measurement range, slope characteristics, detection limit, response time and selectivity coefficients in relation to some inorganic cations in the presence and absence of surfactants, were investigated. As follows from the studies, the presence of surfactants in the sample is responsible first of all for the increase in response time and in detection limit, and a decrease in the characteristic slope as well as reduction of electrode selectivity.

  3. Separation of gold on a selective chelating ion exchanger and in situ determination by gamma-spectroscopy

    International Nuclear Information System (INIS)

    For the separation and determination of low gold concentrations in the sub μg g-1 range in ore and sediment samples an analytical technique has been developed, based on the selective adsorption of gold on the chelating resin, Srafion NMRR, and the in situ determination of the retained gold by instrumental neutron activation analysis (INAA), using the 411.8 keV line of the isotope 198Au. In the case of higher gold concentrations Au could be directly determined in the ore by the technique of loss free counting in spite of the high radioactivity of the investigated samples. By the described procedure it was possible to determine Au amounts in the range of ng g-1 sediments. (author). 24 refs., 1 fig., 2 tabs

  4. 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

  5. Solvent extraction of anionic chelate complexes of lanthanum(III), europium(III), lutetium(III), scandium(III), and indium(III) with 2-thenoyltrifluoroacetone as ion-pairs with tetrabutylammonium ions

    International Nuclear Information System (INIS)

    The solvent extraction of lanthanum(III), europium(III), lutetium(III), scandium(III), and indium(III) in 0.1 mol dm-3 sodium nitrate solutions with 2-thenoyltrifluoroacetone (Htta) in the absence and presence of tetrabutylammonium ions (tba+) into carbon tetrachloride was measured. The extraction of lanthanum(III), europium(III), and lutetium(III) was greatly enhanced by the addition of tba+; this could be explained in terms of the extraction of a ternary complex, M(tta)4-tba+. However, the extractions of scandium(III) and indium(III) were nearly the same when tba+ was added. The data were treated on the basis of the formation equilibrium of the ternary complex from the neutral chelate, M(tta)3, with the extracted ion-pairs of the reagents, tta-tba+, in the organic phase. It was concluded that the degree of association of M(tta)3 with the ion-pair, tta-tba+, is greater in the order La(tta)3 ≅ Eu(tta)3 > Lu(tta)3, or that the stability of the ternary complex in the organic phase is higher in the order La(tta)4-tba+ ≅ Eu(tta)4-tba+ > Lu(tta)4-tba+. This is similar to those of adduct metal chelates of Htta with tributylphosphate (TBP) in synergistic extraction systems. (author)

  6. Detoxication and removal of uranium by phenolic chelating agents

    International Nuclear Information System (INIS)

    The use of phenolic chelating agents for detoxication and removal of uranyl nitrate in mice and rats is reported. Antidotal test: 8102, 7601 and 811 were given 2 mM/kg subcutaneously to mice and 1 mM/kg intramuscularly to rats when the animals were injected i.p. with different doses (100-500 mg/kg) of uranyl nitrate. The results showed that the antidotal effects of 8102 and 7601 were better than 811 in augmenting survival, survival time (day) and renal factor (kidney weight/body weight x100). 8102 was superior to 7601 against higher dose of uranyl nitrate intoxication. Removal test: five phenolic chelating agents (8102, 7601, 811, 7603 and 8307) were studied in rats. The results obtained demonstrated that 8102 and 7601 were better than 811, 7603 and 8307 in increasing U excretion in the urine after acute uranyl nitrate intoxication. The effects of different doses (300-1000 μM/kg) of 8102 was superior to 7601 in increasing U excretion in the urine and decreasing U deposition in the tissues. The toxicity and dose of 8102 in treating uranium intoxication are discussed

  7. Gas phase uranyl activation: formation of a uranium nitrosyl complex from uranyl azide.

    Science.gov (United States)

    Gong, Yu; de Jong, Wibe A; Gibson, John K

    2015-05-13

    Activation of the oxo bond of uranyl, UO2(2+), was achieved by collision induced dissociation (CID) of UO2(N3)Cl2(-) in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2(-) was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2(-) resulted in the loss of N2 to form UO(NO)Cl2(-), in which the "inert" uranyl oxo bond has been activated. Formation of UO2Cl2(-) via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2(-) complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2(-) complex shows that the side-on bonded NO moiety can be considered as NO(3-), suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2(-) to form UO(NO)Cl2(-) and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2(-) and UO2Cl2(-). The observation of UO2Cl2(-) during CID is most likely due to the absence of an energy barrier for neutral ligand loss. PMID:25906363

  8. Gas Phase Uranyl Activation: Formation of a Uranium Nitrosyl Complex from Uranyl Azide

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Yu; De Jong, Wibe A.; Gibson, John K.

    2015-05-13

    Activation of the oxo bond of uranyl, UO22+, was achieved by collision induced dissociation (CID) of UO2(N3)Cl2– in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2– was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2– resulted in the loss of N2 to form UO(NO)Cl2–, in which the “inert” uranyl oxo bond has been activated. Formation of UO2Cl2– via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2– complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2– complex shows that the side-on bonded NO moiety can be considered as NO3–, suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2– to form UO(NO)Cl2– and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2– and UO2Cl2–. The observation of UO2Cl2– during CID is most likely due to the absence of an energy barrier for neutral ligand loss.

  9. 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.

  10. Adsorption of Cu(II), Co(II), and Ni(II) ions by modified magnetic chitosan chelating resin

    International Nuclear Information System (INIS)

    Cross-linked magnetic chitosan-isatin Schiff's base resin (CSIS) was prepared for adsorption of metal ions. CSIS obtained was investigated by means of FTIR, 1H NMR, wide-angle X-ray diffraction (WAXRD), magnetic properties and thermogravimetric analysis (TGA). The adsorption properties of cross-linked magnetic CSIS resin toward Cu2+, Co2+ and Ni2+ ions were evaluated. Various factors affecting the uptake behavior such as contact time, temperature, pH and initial concentration of the metal ions were investigated. The kinetic parameters were evaluated utilizing the pseudo-first-order and pseudo-second-order. The equilibrium data were analyzed using the Langmuir, Freundlich, and Tempkin isotherm models. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all systems studied, evidencing chemical sorption as the rate-limiting step of adsorption mechanism and not involving a mass transfer in solution. The best interpretation for the equilibrium data was given by Langmuir isotherm, and the maximum adsorption capacities were 103.16, 53.51, and 40.15 mg/g for Cu2+, Co2+ and Ni2+ ions, respectively. Cross-linked magnetic CSIS displayed higher adsorption capacity for Cu2+ in all pH ranges studied. The adsorption capacity of the metal ions decreased with increasing temperature. The metal ion-loaded cross-linked magnetic CSIS were regenerated with an efficiency of greater than 88% using 0.01-0.1 M ethylendiamine tetraacetic acid (EDTA).

  11. Adsorption of Cu(II), Co(II), and Ni(II) ions by modified magnetic chitosan chelating resin.

    Science.gov (United States)

    Monier, M; Ayad, D M; Wei, Y; Sarhan, A A

    2010-05-15

    Cross-linked magnetic chitosan-isatin Schiff's base resin (CSIS) was prepared for adsorption of metal ions. CSIS obtained was investigated by means of FTIR, (1)H NMR, wide-angle X-ray diffraction (WAXRD), magnetic properties and thermogravimetric analysis (TGA). The adsorption properties of cross-linked magnetic CSIS resin toward Cu(2+), Co(2+) and Ni(2+) ions were evaluated. Various factors affecting the uptake behavior such as contact time, temperature, pH and initial concentration of the metal ions were investigated. The kinetic parameters were evaluated utilizing the pseudo-first-order and pseudo-second-order. The equilibrium data were analyzed using the Langmuir, Freundlich, and Tempkin isotherm models. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all systems studied, evidencing chemical sorption as the rate-limiting step of adsorption mechanism and not involving a mass transfer in solution. The best interpretation for the equilibrium data was given by Langmuir isotherm, and the maximum adsorption capacities were 103.16, 53.51, and 40.15mg/g for Cu(2+), Co(2+) and Ni(2+) ions, respectively. Cross-linked magnetic CSIS displayed higher adsorption capacity for Cu(2+) in all pH ranges studied. The adsorption capacity of the metal ions decreased with increasing temperature. The metal ion-loaded cross-linked magnetic CSIS were regenerated with an efficiency of greater than 88% using 0.01-0.1M ethylendiamine tetraacetic acid (EDTA). PMID:20122793

  12. Adsorption of Cu(II), Co(II), and Ni(II) ions by modified magnetic chitosan chelating resin

    Energy Technology Data Exchange (ETDEWEB)

    Monier, M., E-mail: monierchem@yahoo.com [Department of Chemistry, Drexel University, Philadelphia, PA (United States); Chemistry Department, Faculty of Science, Mansoura University, Mansoura (Egypt); Ayad, D.M. [Chemistry Department, Faculty of Science, Mansoura University, Mansoura (Egypt); Wei, Y., E-mail: weiyen@drexel.edu [Department of Chemistry, Drexel University, Philadelphia, PA (United States); Sarhan, A.A. [Chemistry Department, Faculty of Science, Mansoura University, Mansoura (Egypt)

    2010-05-15

    Cross-linked magnetic chitosan-isatin Schiff's base resin (CSIS) was prepared for adsorption of metal ions. CSIS obtained was investigated by means of FTIR, {sup 1}H NMR, wide-angle X-ray diffraction (WAXRD), magnetic properties and thermogravimetric analysis (TGA). The adsorption properties of cross-linked magnetic CSIS resin toward Cu{sup 2+}, Co{sup 2+} and Ni{sup 2+} ions were evaluated. Various factors affecting the uptake behavior such as contact time, temperature, pH and initial concentration of the metal ions were investigated. The kinetic parameters were evaluated utilizing the pseudo-first-order and pseudo-second-order. The equilibrium data were analyzed using the Langmuir, Freundlich, and Tempkin isotherm models. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all systems studied, evidencing chemical sorption as the rate-limiting step of adsorption mechanism and not involving a mass transfer in solution. The best interpretation for the equilibrium data was given by Langmuir isotherm, and the maximum adsorption capacities were 103.16, 53.51, and 40.15 mg/g for Cu{sup 2+}, Co{sup 2+} and Ni{sup 2+} ions, respectively. Cross-linked magnetic CSIS displayed higher adsorption capacity for Cu{sup 2+} in all pH ranges studied. The adsorption capacity of the metal ions decreased with increasing temperature. The metal ion-loaded cross-linked magnetic CSIS were regenerated with an efficiency of greater than 88% using 0.01-0.1 M ethylendiamine tetraacetic acid (EDTA).

  13. Paramagnetic effects on the NMR spectra of isotropic bicelles with headgroup modified chelator lipids and metal ions.

    Science.gov (United States)

    Tang, Ming; Mao, Kevin; Li, Stacey; Zhuang, Jianqin; Diallo, Koumba

    2016-06-21

    We characterized the paramagnetic effects of nine metal ions on NMR signals of isotropic bicelles with headgroup-modified lipids. We found that Mn(2+), Gd(3+) and Dy(3+) show evidence for influencing NMR signals on the surface more than inside and on the disc edge, providing distance information in the bilayers. PMID:27240538

  14. 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

  15. ESR study of irradiated uranyl salts

    International Nuclear Information System (INIS)

    Results of ESR measurements on gamma-irradiated single crystals of ammonium uranyl nitrate and potassium uranyl nitrate are reported. In ammonium uranyl nitrate, the observed radical is found to have a similar behaviour to irradiated rubidium uranyl nitrate. However, a pair of satellites to the main lines have been observed and they have been interpreted as the simultaneous proton spin-flips. In the case of potassium uranyl nitrate, the observed radicals are also assigned to NO3. The directions of the principal axes of the g-tensor and their values are reported. These results support theoretical predictions based on the electronic structure. (K.B.)

  16. 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

  17. 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)

  18. Determination of actinides in environmental and biological samples using high-performance chelation ion chromatography coupled to sector-field inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Truscott, J B; Jones, P; Fairman, B E; Evans, E H

    2001-08-31

    High-performance chelation ion chromatography, using a neutral polystyrene substrate dynamically loaded with 0.1 mM dipicolinic acid, coupled with sector-field inductively coupled plasma mass spectrometry has been successfully used for the separation of the actinides thorium, uranium, americium, neptunium and plutonium. Using this column it was possible to separate the various actinides from each other and from a complex sample matrix. In particular, it was possible to separate plutonium and uranium to facilitate the detection of the former free of spectral interference. The column also exhibited some selectivity for different oxidation states of Np, Pu and U. Two oxidation states each for plutonium and neptunium were found, tentatively identified as Np(V) and Pu(III) eluting at the solvent front, and Np(IV) and Pu(IV) eluting much later. Detection limits were 12, 8, and 4 fg for 237Np, 239Pu, and 241Am, respectively, for a 0.5 ml injection. The system was successfully used for the determination of 239Pu in NIST 4251 Human Lung and 4353 Rocky Flats Soil, with results of 570+/-29 and 2939+/-226 fg g(-1), respectively, compared with a certified range of 227-951 fg g(-1) for the former and a value of 3307+/-248 fg g(-1) for the latter. PMID:11589474

  19. Evaluation of genotoxicity induced by hydrogen peroxide in the presence of ions chelator Fe2+ (2,2'-dipyridyl) and of Cu2+(neocuproine), in Escherichia coli: involvement of DNA repair mechanisms in the bacteria survival

    International Nuclear Information System (INIS)

    Prior incubation of the E. coli cultures with the iron ions chelator 2,2'-dipyridyl (1 mM) caused an intensification of the lethality and the mutagenesis induced by the hydrogen peroxide, mainly at high concentrations (20 mM). It was also detected an enhancement of DNA strand breaks in this condition. The addition of the copper ions chelator neocuproine blocked partially this phenomenon. The enzymes XthA and Nfo act alternatively in the repair of the lesions induced by H2O2 in the presence of 2,2'-dipyridyl. H2O2 can act synergistically with neocuproine in killing E. coli, causing an enhancement in DNA strand breaks. The recombinational repair, the UvrABC excinuclease and Fpg function appeared to participate in the repair of the synergistic lesions. (author)

  20. Incorporation of rare-earth ions in Mg-Al layered double hydroxides: intercalation with an [Eu(EDTA)] - chelate

    Science.gov (United States)

    Li, Cang; Wang, Ge; Evans, David G.; Duan, Xue

    2004-12-01

    Reaction of an aqueous slurry of an Mg 2Al-NO 3 layered double hydroxide with a four-fold excess of Na[Eu(EDTA)] gives a material which analyses for Mg 0.68Al 0.32(OH) 2[Eu(EDTA)] 0.10(CO 3) 0.11·0.66H 2O. The interlayer spacing of the material is 13.8 Å, corresponding to a gallery height of 9.0 Å, which accords with the maximal dimensions (9-10 Å) of the anion in metal-EDTA complex salts as determined by single crystal X-ray diffraction. Geometrical considerations show that the charge density on the layered double hydroxide layers is too high to be balanced by intercalation of [Eu(EDTA)] - alone, necessitating the co-intercalation of carbonate ions which have a much higher charge density.

  1. Examination on colour reaction of nicotinic acid-ethyl violet-uranyl ternary complex by solvent extraction spectrophotometry

    International Nuclear Information System (INIS)

    The test examination was made on solvent extraction colour reaction of the ternary complex formed by nicotinic acid, ethyl violet and uranyl in cyclohexane+MIBK (methyl isobutyl ketone) or benzene+MIBK. A difference was found between the published results and the authors'. It was shown that there is no chromomagnetic dependence with uranyl ion, but the approximate linear correlation is present with NO3- ion

  2. 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

  3. On the Formation of "Hypercoordinated" Uranyl Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Schoendorff, George E.; De Jong, Wibe A.; van Stipdonk, Michael J.; Gibson, John K.; Rios, Daniel; Gordon, Mark S.; Windus, Theresa L.

    2011-09-05

    Recent gas phase experimental studies suggest the presence of hypercoordinated uranyl complexes. Coordination of acetone (Ace) to uranyl to form hypercoordinated species is examined using density functional theory (DFT) with a range of functionals and second order perturbation theory (MP2). Complexes with up to eight acetones were studied. It is shown that no more than six acetones can bind directly to uranium and that the observed uranyl complexes are not hypercoordinated.

  4. Hybrid uranyl-vanadium nano-wheels.

    Science.gov (United States)

    Senchyk, G A; Wylie, E M; Prizio, S; Szymanowski, J E S; Sigmon, G E; Burns, P C

    2015-06-25

    Hybrid uranyl-vanadium oxide clusters intermediate between transition metal polyoxometalates and uranyl peroxide cage clusters were obtained by dissolving uranyl nitrate in the ionic liquid 3-ethyl-1-methylimidazolium ethyl sulfate mixed with an aqueous solution containing vanadium. Where sulfate was present, wheel-shaped {U20V20} crystallized and contains ten sulfate tetrahedra, and in the absence of added sulfate, {U2V16}, a derivative of {V18}, was obtained. PMID:26008125

  5. High Aluminum Tolerance of Rhodotorula sp.RS1 is Associated with Thickening of the Cell Wall Rather than Chelation of Aluminum Ions*1

    Institute of Scientific and Technical Information of China (English)

    WANG Chao; ZHAO Xue-Qiang; T.AIZAWA; M.SUNAIRI; SHEN Ren-Fang

    2013-01-01

    Aluminum (Al) is very toxic to many living organisms,including plants,animals and microorganisms.However,despite many studies on Al tolerance in plants,little has been reported concerning these mechanisms in microorganisms.In this study,a red yeast,which could tolerate Al3+ concentrations as high as 200 mmol L-1,was isolated from acidic soils,identified as Rhodotorula sp.and designated as RS1.As the medium compositions can greatly affect the responses of microorganisms to Al,two culture mediums,glucose medium (GM) and lysogeny broth medium containing soil extract (S-LBM),were used.During growth of RS1,the pH of medium decreased in GM but increased in S-LBM.These changes in the pH of the media were not induced by Al addition.No or little secretion of organic acids was observed in RS1 growth media.Importantly,the thickness of the cell walls and the ratio of cell wall to biomass of RS1 significantly increased in GM with high Al3+ concentrations.In the presence of 100 mmol Al L-1,78.0% of the total Al of whole cells was present in the thickened cell walls.The Al in cell walls was mostly bound to OH,amide and CO groups of polysaccharides.These results suggest that thickening of the cell wall in response to the high Al3+ concentrations may play an important role in the high tolerance of RS1 to Al and that pH increase of the medium and chelation of Al ions are not involved in Al tolerance of this organism.

  6. 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

  7. Binary copper(II) and uranyl(VI) complexes of glycocyamine, taurine and pyridoxal and ternary complexes involving 2,2'-bipyridine, 1,10-phenanthroline or nitrilotriacetic acid

    International Nuclear Information System (INIS)

    Chelating tendencies of several biologically important compounds viz. glycocyamine (GCN: N-amidino-aminoethanoic acid) taurine (TRN: 2-aminoethanesulphonic acid) and pyridoxal [PDL: 3-hydroxy-5-(hydroxymethyl)-2-methyl-pyridine-4-carbaldehyde] have been examined by pH-metric titration technique in their binary complex formation with copper(II) and uranyl(VI) ions. The work has further been extended to investigating the ternary complex formation involving 2.2'-bipyridine. 1,10-phenanthroline or nitrilotriacetic acid as a primary and TRN and PDL as secondary ligands. All the experiments were carried out at 250C and at an ionic strength of 0.1M (NaCl04) in aqueous or 50% (v/v) aqueous-ethanol medium according to the suitability of the experimental conditions. Stabilities of ternary complexes as compared to those of the corresponding binary complexes of the secondary ligands have also been discussed. (author)

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

    International Nuclear Information System (INIS)

    Two uranyl tungstates, (UO2)(W2O7)(H2O)3 (1) and (UO2)3(W2O8)F2(H2O)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) circle. In 1 the U(VI) cations are present as (UO2)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 (UO2)2+ uranyl oxy-fluoride pentagonal bipyramids present as either [UO2F2O3]-6 or [UO2FO4]-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.

  9. 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.

  10. 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)

  11. Chelation Ion Chromatography on 1-(2-Pyridylazo-2-naphthol Sorbed Stannic Silicate: Selective Separation of Cd2+, Hg2+ and Pb2+ from some Transition Metal Ions

    Directory of Open Access Journals (Sweden)

    Rawat, J.P.

    2011-12-01

    Full Text Available Selective separation of three of the most toxic metal ions Cd2+, Hg2+ and Pb2+ has been achieved on a column packed with 1-(2-pyridylazo-2-naphthol (PAN sorbed stannic silicate using nitric acid solution of pH 1 and 6 as eluents. Adsorption behavior of several metal ions like Al3+, Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+ and Pb2+ on PAN sorbed stannic silicate from aqueous solution at different pH (from 1 to 6 was studied to calculate their distribution coefficients. In addition to the selective separation of Cd2+, Hg2+ and Pb2+ several binary separations of metal ions e. g., Hg2+ - Al3+, Pb2+ - Cr3+, Cd2+ - Cr3+ and Hg2+ - Cr3+ using aqueous solutions of pH 6 and pH 1 aseluents have been successfully achieved on PAN sorbed stannic silicate.

  12. Effectiveness of chelation therapy with time after acute uranium intoxication

    International Nuclear Information System (INIS)

    The effect of increasing the time interval between acute uranium exposure and chelation therapy was studied in male Swiss mice. Gallic acid, 4,5-dihydroxy-1,3- benzenedisulfonic acid (Tiron), diethylenetriaminepentaacetic acid (DTPA), and 5-aminosalicylic acid (5-AS) were administered ip at 0, 0.25, 1, 4, and 24 hr after sc injection of 10 mg/kg of uranyl acetate dihydrate. Chelating agents were given at doses equal to one-fourth of their respective LD50 values. Daily elimination of uranium into urine and feces was determined for 4 days after which time the mice were killed, and the concentration of uranium was measured in kidney, spleen, and bone. The excretion of uranium was especially rapid in the first 24 hr. Treatment with Tiron or gallic acid at 0, 0.25, or 1 hr after uranium exposure significantly increased the total excretion of the metal. In kidney and bone, only administration of Tiron at 0, 0.25, or 1 hr after uranium injection, or gallic acid at 1 hr after uranium exposure significantly reduced tissue uranium concentrations. Treatment at later times (4 to 24 hr) did not increase the total excretion of the metal and did not decrease the tissue uranium concentrations 4 days after uranyl acetate administration. The results show that the length of time before initiating chelation therapy for acute uranium intoxication greatly influences the effectiveness of this therapy

  13. 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)

  14. 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.

  15. Thermal analysis studies of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    The simultaneous thermogravimetry and differential thermal analysis of the ammonium uranyl carbonate powder were performed with heat balance in the following atmosphers: Air, Ar and Ar-8%H2. The thermogravimetry and differential thermal analysis curves of the ammonium uranyl carbonate powder obtained from different source were reported and discussed

  16. Preparation of thin α-particle sources using poly-pyrrole films functionalized by a chelating agent

    International Nuclear Information System (INIS)

    This work takes place in the scope of analysis of the α-particle emitting elements U, Pu and Am present in compound environmental matrix like sols and sediments. The samples diversity and above all the α-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 DU and DAm 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)

  17. Extraction of lanthanide(III) and uranyl(VI) from nitric acid solution by N,N'-dimethyl-N,N'-dibutylmalonamide

    International Nuclear Information System (INIS)

    The extractive properties of N,N'-dimethyl-N,N'-dibutylmalonamide (DMDBMA) and the loading capacity of extraction solvents containing DMDBMA for lanthanide(III) and uranyl(VI) ions in nitric acid solution were investigated. The dependence of the distribution ratio on the concentration of nitric acid shows that DMDBMA has an ability to extract uranyl(VI) ions, while the extracting capacity for lanthanide(III) ions is not enough for the application in practice. 17 refs., 10 figs., 4 tabs

  18. A chelating resin containing trihydroxybenzoic acid as the functional group. Synthesis and adsorption behavior for Th(IV) and U(VI) ions

    International Nuclear Information System (INIS)

    A novel glycidyl methacrylate chelating resin has been synthesized through copolymerization of glycidyl methacrylate (GMA) in the presence of divinylbenzene (DVB), the resulting resin was immobilized with 3,4,5-trihydroxybenzoic acid (THBA) to give GMA/DVB/THBA chelating resin. The adsorption of Th(IV) and U(VI) on GMA/DVB/THBA adsorbent was studied as a function of initial concentration, pH, shaking time and temperature. The novel chelating resin shows a high capacity for Th(IV) and U(VI), maximum adsorption of Th(IV) and U(VI) were 56 and 83.6 mg/g, respectively. Kinetic studies showed that the adsorption follows the pseudo second order model referring to the influence of the textural properties of the resin on the rate of adsorption. Thermodynamic parameters such as ΔH deg and ΔS deg were studied and indicated an endothermic process. (author)

  19. Computer simulation of metal ion equilibria in biofluids. IV. Plutonium speciation in human blood plasma and chelation therapy using polyaminopolycarboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Duffield, J.R.; May, P.M.; Williams, D.R.

    1984-03-01

    An investigation by computer simulation into the nature of Pu(IV) binding to low-molecular ligands in human blood plasma is described. Particular consideration is given to the interactions of various chelating agents which have been or might be used for treating plutonium intoxication. Formation constants of EDTA and DTPA with Cu(II), Mg(II), Mn(II), Zn(II), and Cd(II) have been measured under biologic conditions of temperature and background electrolyte. The relative ability of these and other chelating agents to cause excretion of plutonium and the concomitant loss of certain essential trace metals has thus been assessed.

  20. 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.

  1. 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

  2. Synthesis and characterization of uranyl acetate complexes with some potentially bidentate ligands

    International Nuclear Information System (INIS)

    Complexes of uranyl acetate with three potentially bidentate ligands-nicotinic acid (NA), 2,2'-bipyridyl(2,2'-Bipy) and 4,4'-bipyridyl N,N'-dioxide (4,4'-BipyO2) have been synthesized and characterized on the basis of analytical data, electrical conductance, electronic and IR spectral studies. Uranyl acetate forms 1:1 complexes with 2,2'-Bipy and 4,4'-BipyO2 and a 1:2 complex with NA. It is shown that UO2(NA)2(CH3COO)2 and UO2(2,2'-Bipy)(CH3COO)2 have monomeric structures while UO2(4,4'-BipyO2)(CH3COO)2 has a polymeric chain structure. The acetate groups act as bidentate chelating ligands in these complexes. All the compounds studied are considered to have an overall coordination number eight around uranium(VI). (author). 16 refs

  3. 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

  4. 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.

  5. Metal regeneration of iron chelates in nitric oxide scrubbing

    Science.gov (United States)

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

    1997-08-19

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

  6. 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)

  7. 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...

  8. Extraction of uranyl nitrate from aqueous nitrate solutions by open cell polyurethane foam sponge (OCPUFS)

    International Nuclear Information System (INIS)

    The extraction of uranyl nitrate into open cell polyurethane foam sponge (OCPUFS) from aqueous solution, in the presence of salting agents, was examined. The extraction efficiency was observed to depend on the concentration of uranyl and nitrate ions. The charge of the cation was also found to influence the distribution ratio. The effect of the change in temperature and pH was also studied. The results are interpreted in terms of OCPUFS acting as a viscous organic ether of moderate dielectric constant. (author) 14 refs.; 6 figs

  9. Transmission electron microscopy to visualize the localisation of uranyl phosphate precipitate in E. coli

    International Nuclear Information System (INIS)

    Microbial bioremediation of heavy metal waste can be a superior alternative to physiochemical methods due to its high efficiency and in situ applicability. Among the various processes employed, bioprecipitation of heavy metals with ions like inorganic phosphate is considered to be particularly promising approach for bioremediation of uranium (U). As uranium phosphate precipitate (U(VI)) remains insoluble, it can be a long term and stable sink for U in the environment. Bacterial phosphatases can be efficiently expressed in appropriate host systems and consequently these engineered microbes can be utilized for bioremediation. Our research group has expressed two different phosphatases in E. coli and evaluated the bioremediation potential of these recombinant strains. PhoN, a non-specific acid phosphatase (from Salmonella) exists as a cell-associated protein when expressed in E. coli. On the other hand, when PhoK (alkaline phosphatase from Sphingomonas) is expressed in E. coli, the protein is secreted extracellularly. E. coli-PhoN cells, when incubated with 1 mM uranyl nitrate (pH 6.8) and p-glycerophosphate (GP) as substrate, showed cell-associated uranyl phosphate precipitate. In contrast, E. coli -PhoK cells, exposed to 1 mM uranyl carbonate (pH 9) and β-GP, showed extracellular uranyl phosphate precipitate in solution. Thus, TEM can be effectively used to obtain a vivid pictorial representation of the location of uranyl phosphate precipitate in bacteria. (author)

  10. 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...

  11. Contribution to the study of uranyl salts in butyl phosphate solutions

    International Nuclear Information System (INIS)

    A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from ∼ 1270 cm-1 to ∼ 1180 cm-1. A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author)

  12. 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

  13. 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.

  14. 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)

  15. 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.

  16. 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.

  17. Optimisation and status of chelation therapy

    International Nuclear Information System (INIS)

    The calcium trisodium salt of diethylenetriaminepentaacetic acid (Ca-DTPA) remains the chelating agent of choice for treatment of incorporated actinides. The zinc trisodium salt (Zn-DTPA) represents a less toxic alternative, when Ca-DTPA is contra-indicated as well as for prolonged chelation therapy; in acute incorporation cases it would be less effective than Ca-DTPA. Specific ion binding chelators such as desferrioxamine (DFOA) and linear tetracatechoylamides, e.g., LICAM(C) proved more effective in animals injected with Pu, Th and Np (not with Am!) but only concerning the radioactivity in the bone; that in the kidneys was substantially increased. The combinations of DFOA or LICAM(C) with Ca-DTPA exerted the best overall effects. After incorporation of soluble uranium-compounds, an infusion of sodium bicarbonate seems at present the most reasonable for enhancing the uranium-excretion and prevention of kidney damage. (author)

  18. Lanthanon chelates of monoprotic tridentate schiff base

    International Nuclear Information System (INIS)

    3-(N-thiophene-2-aldimino)propanoic acid (HTP), and its lanthanon chelates were synthesised and studied by physico-chemical techniques. Irving-Rossotti method was followed to determine the dissociation constants of the ligand and formation constants of its lanthanon chelates in aqueous medium (ionic strength μ = 0.01, 0.05 and 0.1 M NaClO4) at 25 0C, 35 0C and 45 0C. Solid lanthanon chelates were characterised by molecular mass, elemental analyses, conductance, magnetic, thermal and spectral analyses and were assigned 1 : 3 (metal-ligand) stoichiometry in which the lanthanon shows nine coordination numbers. Covalent nature of metal-ligand bond was found to increase with increase in atomic number of central lanthanide ion. (author)

  19. On-column tryptic mapping of proteins using metal-ion-chelated magnetic silica microspheres by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    Science.gov (United States)

    Li, Yan; Yan, Bo; Xu, Xiuqing; Deng, Chunhui; Yang, Pengyuan; Shen, Xizhong; Zhang, Xiangmin

    2007-01-01

    Peptide mapping analysis, utilizing an easily replaceable and regenerable on-column enzymatic microreactor with metal-ion-chelated adsorption of enzyme on magnetic silica microspheres, combined with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), was developed. Firstly, magnetic microspheres of small size and strong magnetism were prepared through solvothermal reaction. Thereafter, by introducing tetraethyl orthosilicate (TEOS), magnetic silica (MS) microspheres were formed. Trypsin could then be immobilized onto the MS microspheres based on the Lewis acid-base interaction through the divalent cation chelators such as iminodiacetic acid (IDA), which was chemically bound to the microspheres through the introduction of glycidoxypropyltrimethoxysilane (GLYMO). The trypsin-immobilized MS microspheres were then locally packed into the capillary by the application of a strong magnetic field using a magnet. The performance of the method was exemplified with digestion of bovine serum albumin for 5 min at 50 degrees C and the result was comparable to the 12 h in-solution digestion. The ability of regeneration of the prepared on-column microreactor and good reproducibility of microreactor before and after regeneration were also demonstrated. PMID:17577873

  20. 乙二胺螯合细菌纤维素的制备及其吸附Cu2+研究%Preparation of ethylenediamine chelating bacterial cellulose for the adsorption of copper ions

    Institute of Scientific and Technical Information of China (English)

    马波; 孙东平; 朱春林; 刘长生; 牛会君

    2009-01-01

    以细菌纤维素为原料制备乙二胺螯合细菌纤维素.通过红外光谱仪、元素分析仪对产物进行了表征.研究了乙二胺螯合细菌纤维素对铜离子的吸附动力学、等温吸附等特征.结果表明,吸附动力学可用拟二级速度方程来描述,吸附平衡符合Freundlich等温吸附方程,并对其吸附与解吸性能进行了分析.%Ethylenediamine chelating bacterial cellulose has been synthesized by bacterial cellulose. The product is characterized by the infra-red spectroscopy and elemental analyser. Its characteristics, such as adsorption kinetics and adsorption isotherms for copper ions are studied. The results show that the adsorption kinetics can be described by pseudo-second-level velocity equation. The adsorption equilibrium accords with Freundlich isotherm adsorption equation. The adsorption and desorption properties of ethylenediamine chelating bacterial cellulose are also analyzed.

  1. Comments on chelation therapy

    International Nuclear Information System (INIS)

    The primary purpose of actinide chelation is to decrease the risk from radiation-induced cancer. While occupational exposures in the past have mainly involved low specific activity 239Pu, future exposures will increasingly involve high specific activity plutonium, americium, and curium - all of which clear more rapidly from the lung. This will tend to shift the cancer risk from lung to bone and liver. Although therapy with Ca- or Zn-DTPA rapidly removes 241Am from the canine, the sub-human primate, and the human liver, improved methods for removal from bone and lung are needed. DTPA can remove 241Am more easily from the growing skeleton of a child than from the mature skeleton of an adult. Investigators at Karlsruhe are developing chelation agents for oral administration and are investigating the reduction in local dose to bone resulting from chelation therapy

  2. 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)

  3. 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...

  4. 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.)

  5. 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)

  6. 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

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

    Science.gov (United States)

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

    2015-01-01

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

  8. Simultaneous determination of copper, cobalt, and mercury ions in water samples by solid-phase extraction using carbon nanotube sponges as adsorbent after chelating with sodium diethyldithiocarbamate prior to high performance liquid chromatography.

    Science.gov (United States)

    Wang, Lei; Zhou, Jia-Bin; Wang, Xia; Wang, Zhen-Hua; Zhao, Ru-Song

    2016-06-01

    Recently, a sponge-like material called carbon nanotube sponges (CNT sponges) has drawn considerable attention because it can remove large-area oil, nanoparticles, and organic dyes from water. In this paper, the feasibility of CNT sponges as a novel solid-phase extraction (SPE) adsorbent for the enrichment and determination of heavy metal ions (Co(2+), Cu(2+), and Hg(2+)) was investigated for the first time. Sodium diethyldithiocarbamate (DDTC) was used as the chelating agent and high performance liquid chromatography (HPLC) for the final analysis. Important factors which may influence extraction efficiency of SPE were optimized, such as the kind and volume of eluent, volume of DDTC, sample pH, flow rate, etc. Under the optimized conditions, wide range of linearity (0.5-400 μg L(-1)), low limits of detection (0.089~0.690 μg L(-1); 0.018~0.138 μg), and good repeatability (1.27~3.60 %, n = 5) were obtained. The developed method was applied for the analysis of the three metal ions in real water samples, and satisfactory results were achieved. All of these findings demonstrated that CNT sponges will be a good choice for the enrichment and determination of target ions at trace levels in the future. PMID:27108287

  9. 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)].

  10. 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...

  11. Infrared Spectroscopy of Discrete Uranyl Anion Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Gary S. Groenewold; Anita K. Gianotto; Michael E. McIlwain; Michael J. Van Stipdonk; Michael Kullman; Travis J. Cooper; David T. Moore; Nick Polfer; Jos Oomens; Ivan Infante; Lucas Visscher; Bertrand Siboulet; Wibe A. de Jong

    2007-12-01

    The Free-Electron Laser for Infrared Experiments, FELIX, was used to study the wavelength-resolved multiphoton dissociation of discrete, gas phase uranyl (UO22+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The apparent uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was either hydroxide, methoxide or acetate, S was water, ammonia, acetone or acetonitrile, and n = 0-2. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands, and are comparable to solution phase values. This result was surprising because initial DFT calculations using B3LYP predicted values that were 30 – 40 cm-1 higher, consistent with intuition but not with the data. Modification of the basis set and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which resulted only very modest changes to the uranyl frequency, and did not universally shift values lower. DFT calculations for [UO2AS]+ were in accord with trends in the data, and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity.

  12. Infared Spectroscopy of Discrete Uranyl Anion Complexes

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-01-24

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

  13. Infrared Spectroscopy of Discrete Uranyl Anion Complexes

    International Nuclear Information System (INIS)

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

  14. 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)

  15. Binding of uranyl by humic acid

    International Nuclear Information System (INIS)

    The binding of tracer level UO2+2 to a soil humic acid was measured by a solvent extraction technique. The binding is interpreted as involving only the carboxylate groups of the humate and both 1:1 and 1:2 UO2+2:CO2-binding is observed. Estimates based on these values indicate that uranyl complexing by humic and/or fulvic materials is not significant in sea water but may play a role in fresh water systems. Retention of uranyl from ground water by soil humics would be strong. (author)

  16. Intrinsic hydration of monopositive uranyl hydroxide, nitrate, and acetate cations.

    Science.gov (United States)

    Chien, Winnie; Anbalagan, Victor; Zandler, Melvin; Van Stipdonk, Michael; Hanna, Dorothy; Gresham, Garold; Groenewold, Gary

    2004-06-01

    The intrinsic hydration of three monopositive uranyl-anion complexes (UO(2)A)(+) (where A = acetate, nitrate, or hydroxide) was investigated using ion-trap mass spectrometry (IT-MS). The relative rates for the formation of the monohydrates [(UO(2)A)(H(2)O)](+), with respect to the anion, followed the trend: Acetate > or = nitrate > hydroxide. This finding was rationalized in terms of the donation of electron density by the strongly basic OH(-) to the uranyl metal center, thereby reducing the Lewis acidity of U and its propensity to react with incoming nucleophiles, viz., H(2)O. An alternative explanation is that the more complex acetate and nitrate anions provide increased degrees of freedom that could accommodate excess energy from the hydration reaction. The monohydrates also reacted with water, forming dihydrates and then trihydrates. The rates for formation of the nitrate and acetate dihydrates [(UO(2)A)(H(2)O)(2)](+) were very similar to the rates for formation of the monohydrates; the presence of the first H(2)O ligand had no influence on the addition of the second. In contrast, formation of the [(UO(2)OH)(H(2)O)(2)](+) was nearly three times faster than the formation of the monohydrate. PMID:15144967

  17. Comparing potential copper chelation mechanisms in Parkinson's disease protein

    Science.gov (United States)

    Rose, Frisco; Hodak, Miroslav; Bernholc, Jerry

    2011-03-01

    We have implemented the nudged elastic band (NEB) as a guided dynamics framework for our real-space multigrid method of DFT-based quantum simulations. This highly parallel approach resolves a minimum energy pathway (MEP) on the energy hypersurface by relaxing intermediates in a chain-of-states. As an initial application we present an investigation of chelating agents acting on copper ion bound to α -synuclein, whose misfolding is implicated in Parkinson's disease (PD). Copper ions are known to act as highly effective misfolding agents in a-synuclein and are thus an important target in understanding PD. Furthermore, chelation therapy has shown promise in the treatment of Alzheimer's and other neuro-degenerative diseases with similar metal-correlated pathologies. At present, our candidate chelating agents include nicotine, curcumin and clioquinol. We examine their MEP activation barriers in the context of a PD onset mechanism to assess the viability of various chelators for PD remediation.

  18. Selectivity in extraction of copper and indium with chelate extractants

    International Nuclear Information System (INIS)

    Simultaneous extraction of copper and indium with chelate extractants (LIX84 and D2E11PA) was described. Stechiometry of metal-organic complexes examined using the method of equimolar ratios resulted in CuR2 and InR3 forms of hydrophobic extracting species. A linear correlation was obtained between logarithm of distribution coefficients and chelate agents and pH, respectively. Selectivity is generally higher with higher concentrations of chelate agents in the organic phase, and is decreased with increase of concentration of hydrogen ions in feeding phase. (Original)

  19. Sorption efficiency of a new sorbent towards uranyl. Phosphonic acid grafted Merrifield resin

    International Nuclear Information System (INIS)

    A novel sorbent resin consisting of a Phosphonic Acid grafted on Merrifield Resin (PA-MR) for the extraction of uranyl from nitrate media is described. The sorption behaviour of uranyl cation on PA-MR was investigated using batch equilibrium technique. The effects of parameters such as shaking speed, pH levels, contact time, metal concentrations, ionic strength and temperature were reported. The results show that the sorption capacity increases with increasing both initial uranyl ion concentration and temperature and decreases with increasing ionic strength. Therefore, the optimum condition for the present study should be using 6.6 mg adsorbent per 1.0 mg uranyl in solution with pH 3.6 and shaking at 250 rpm for 180 min. The adsorption behavior of the system was also investigated and found to be in line with Langmuir isotherm. The kinetic data was well described by the pseudo second-order. Thermodynamics data leads to endothermic process ΔH = + 31.03 kJ-1 mol-1, ΔS = + 146.64 J mol-1 K-1 and ΔG = -11.96 kJ mol-1 at 20 K. ΔG decreased to negatives values with increasing temperature indicating that the process was more favoured at high temperature. (author)

  20. Archetypes for actinide-specific chelating agents

    International Nuclear Information System (INIS)

    The complexes of uranium and thorium with monomeric hydroxamic acids can serve as archetypes for an optimized macrochelate designed for tetravalent actinides. The eight-coordinate complexes, Th(i-PrN(O)C(O)R)4, where R = tert-butyl or R = neopentyl, have been synthesized and their structures have been determined by x-ray diffraction. The bulky alkyl substituents impart remarkable volatility and hydrocarbon solubility to these complexes, and the steric interactions of these substituents largely determine the structures. When R = tert-butyl, the substituents occupy the corners of a tetrahedron and force the complex into a distorted cubic geometry with crystallographic S4 symmetry. Insertion of a methylene group between the carbonyl carbon and the tert-butyl group relaxes the steric requirements, and the coordination polyhedron of the neopentyl derivative is close to the mmmm isomer of the trigonal-faced dodecahedron. Uranium tetrachloride was quantitatively oxidized via an oxygen transfer reaction with two equivalents of N-phenylbenzohydroxamic acid anion (PBHA) in tetrahydrofuran (THF) to form UO2 Cl(PBHA)(THF)2 and benzanilide. The structure of the uranyl complex has been determined from x-ray diffraction data; the linear uranyl ion is surrounded by a planar pentagonal array composed of two hydroxamate oxygen atoms, a chloride ion and two THF oxygens, such that the chloride ion is opposite the hydroxamate group. That the THF and phenyl rings are twisted from this equatorial plane limits the molecular geometry to that of the C1 point group. Some aspects of the chemistry of hydroxamic acids and of their incorporation into molecules that may serve as precursors of tetravalent actinide specific sequestering agents have also been investigated

  1. The use of new modified poly(acrylamide chelating resin with pendent benzothiazole groups containing donor atoms in the removal of heavy metal ions from aqueous solutions

    Directory of Open Access Journals (Sweden)

    Semmedu Selvaraj Kalaivani

    2014-03-01

    Full Text Available The adsorption studies of poly(6-(ethoxybenzothiazole acrylamide (PEBTA, for Cu(II and Zn(II metal ions removal from an aqueous solution have been investigated, as a function of solution pH, adsorbent dose, contact time, initial metal ion concentration and temperature. The chemical and structural characteristics of the adsorbent were determined by the FT-IR, 1H-NMR, TGA, SEM, and EDAX analysis. The maximum adsorption capacities of the adsorbent for Cu(II and Zn(II ions, as calculated from the Langmuir isotherm model, were 273.5 and 216.4 mg/g, respectively. The adsorption kinetic studies show that the adsorption of Cu(II and Zn(II ions onto PEBTA follows the pseudo second order kinetic model. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were also evaluated, and it has been found that the adsorption process is feasible, spontaneous and exothermic in nature. Desorption studies were carried out using 0.3 N HCl, and it revealed that the adsorbed Cu(II and Zn(II ions can be easily removed. The adsorption–desorption process is reversible, and this indicates that PEBTA is an effective adsorbent for the removal of heavy metal ions from an aqueous medium.

  2. Treatment of uranyl nitrate and flouride solutions

    International Nuclear Information System (INIS)

    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

  3. 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

  4. 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.)

  5. Ternary system uranyl monochloroacetate/water/tri-n-butyl phosphate (ir spectroscopic study)

    Energy Technology Data Exchange (ETDEWEB)

    Baluev, A.V.; Lumpov, A.A.; Suglobova, I.G.

    1986-01-01

    The phase equilibria in the ternary system uranyl monochloroacetate/water/TBP are examined from the standpoint of IR spectroscopic data obtained in the present work for the equilibrium phases in various concentration regions. A number of hypotheses are advanced relative to the composition of the solvated complex of this salt in the organic phases, and also in connection with the relationship between solvation and hydration processes and the electron-donor properties of the haloacetate ions.

  6. Determination of the stability constants of uranyl/polymer complexes by differential pulse polarography

    OpenAIRE

    Leroy, D.; Martinot, Lucien; Jérôme, Christine; Jérôme, Robert

    2001-01-01

    Differential pulse polarography (DPP) allows for the determination of the stability constants (K) and the stoichiometry (n) for the complexation of the UO22+ ion by various monomers and the parent polymers. The experimental observation is the shift of the totally reversible reduction wave UO22++e- UO2+ toward more cathodic potentials when the complexing monomer or polymer is added to an uranyl nitrate aqueous solution. This shift is, however, much greater when the polymer is used rather than ...

  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. 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

  9. Conjugates of monoclonal antibodies and chelating polymers

    International Nuclear Information System (INIS)

    The primary purpose of protein modification with chelating polymers is to prepare monoclonal antibodies labeled with heavy metal isotopes (alpha-, beta-, and gamma-emitting metal and paramagnetic ions for NMR tomography). Conventional binding of metals to proteins via chelating agents directly coupled to proteins does not permit binding of a large number of metal atoms per protein molecule without causing alterations in the specific properties of the protein molecules. On the other hand, metal ion binding to proteins via intermediate chelating polymers should permit binding of several dozens of the metal atoms per protein molecule without affect the specific properties adversely. Moreover, the biodistribution and clearance rates can be regulated by varying the polymer properties. Modified antibodies may be used successfully in nuclear and NMR diagnostic applications and in radiotherapy. Possible applications of this approach shall be demonstrated with monoclonal antibody R11D10 for visualization of acute myocardial infarction. Use of this modification with other monoclonal antibodies is also discussed. The chemistry of protein modification with these polymers is presented

  10. 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.

  11. 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

  12. Preparation and characterization of chitosan-grafted-poly(2-amino-4,5-pentamethylene-thiophene-3-carboxylic acid N'-acryloyl-hydrazide) chelating resin for removal of Cu(II), Co(II) and Ni(II) metal ions from aqueous solutions.

    Science.gov (United States)

    Bekheit, M M; Nawar, N; Addison, A W; Abdel-Latif, D A; Monier, M

    2011-05-01

    The graft copolymerization of ethylacrylate (EA) onto chitosan initiated by potassium persulphate and Mohr's salt combined redox initiator system in limited aqueous medium was carried out in heterogeneous media. Moreover, modification of the grafted chitosan was carried out by reaction of the ester group (-COOEt) with 2-amino-4,5-pentamethylene-thiophene-3-carboxylic acid hydrazide which eventually produce chitosan-grafted-poly(2-amino-4,5-pentamethylene-thiophene-3-carboxylic acid N'-acryloyl-hydrazide) (chitosan-g-ATAH) chelating resin. The application of the modified resin for metal ion uptake was studied using Cu(2+), Co(2+) and Ni(2+) ions. The modified chelating resins were characterized using FTIR spectroscopy, SEM and X-ray diffraction. PMID:21277322

  13. Microwave Irradiation-Assisted Synthesis of a Novel Crown Ether Crosslinked Chitosan as a Chelating Agent for Heavy Metal Ions (M+n

    Directory of Open Access Journals (Sweden)

    Ibrahim A. Alsarra

    2010-09-01

    Full Text Available Microwave irradiation was used to obtain a di-Schiff base type crosslinked chitosan dibenzocrown ether (CCdBE via the reaction between the –NH2 and –CHO groups in chitosan and 4,4′-diformyldibenzo-18-c-6, respectively. The structure of the synthesized compound was characterized by elemental analysis, solid state 13C-NMR and FT-IR spectra analysis. The results showed that the mass fraction of nitrogen in the CCdBE derivative was much lower than those of chitosan. The FT-IR spectra of CCdBE revealed the expected chitosan-crown ether structure, as evidenced by the presence of the characteristic C=N and Ar peaks. The adsorption properties of CCdBE for Pd2+ and Hg2+ were investigated and the results demonstrated that the adsorbent has both desirable adsorption properties with a high particular adsorption selectivity for Hg2+ when in the presence of Pb2+ as well as selectivity coefficients for metal ions of KHg2+ /Pb2+ = 8.00 and KHg 2+/Pb2+ = 10.62 at pH values of 4 and 6, respectively. The reusability tests for CCdBE for Pb2+ adsorption showed that complete recovery of the ion was possible with CCdBE after 10-multiple reuses while CTS had no reusability at acidic solution because of its higher dissolution. The studied features of CCdBE suggested that the material could be considered as a new adsorbent. It is envisaged that the crosslinking of CTS into CCdBE would enhance practicality and effectiveness of adsorption in ion separation and removal procedures.

  14. 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.)

  15. Design, synthesis and characterization of new iron and aluminium chelating agents

    OpenAIRE

    Toso, Leonardo

    2014-01-01

    Chelation therapy is widely used for metal-unbalance related diseases, namely those due to disorders on metal metabolism, such as beta-thalassemia, hemochromatosis (Fe), and neurodegenerative diseases (Cu, Fe, Zn and Al). The study of metal chelators for clinical applications, either as chelating therapeutics able to target specific metal ions in the body, or as metal-carriers for therapeutic or imaging purposes, is a topical research area which faces up to urgent medical problems. Meta...

  16. Effect of uranyl intoxication on renal corticomedullary gradient of orthoiodohippurate in laboratory rat

    International Nuclear Information System (INIS)

    The assessment is attempted of the intrarenal distribution (by means of the cortico-medullary gradient and the cortico-pelvic gradient) of a model diagnostic substance (o-125I-hippurate) for the analysis of mechanisms causing damage to the renal function during intoxication induced by uranyl ions (uranyl nitrate). The findings were correlated with other indicators of the renal lesion (creatinine and urea plasma levels). Relative shifts of different gradients, i.e. mutual shifts and shifts in relation to hippurate blood levels, make it possible to describe the stepwise character of functional changes in the damaged kidney. The method used is suitable for investigating the dynamics of substances transport during functional renal changes in particular when combined with the determination the intensity of the uptake of model substances by renal tissue slices. (author)

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

    Science.gov (United States)

    Refat, Moamen S.

    2013-03-01

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

  18. Oxidation of calprotectin by hypochlorous acid prevents chelation of essential metal ions and allows bacterial growth: Relevance to infections in cystic fibrosis.

    Science.gov (United States)

    Magon, Nicholas J; Turner, Rufus; Gearry, Richard B; Hampton, Mark B; Sly, Peter D; Kettle, Anthony J

    2015-09-01

    Calprotectin provides nutritional immunity by sequestering manganese and zinc ions. It is abundant in the lungs of patients with cystic fibrosis but fails to prevent their recurrent infections. Calprotectin is a major protein of neutrophils and composed of two monomers, S100A8 and S100A9. We show that the ability of calprotectin to limit growth of Staphylococcus aureus and Pseudomonas aeruginosa is exquisitely sensitive to oxidation by hypochlorous acid. The N-terminal cysteine residue on S100A9 was highly susceptible to oxidation which resulted in cross-linking of the protein monomers. The N-terminal methionine of S100A8 was also readily oxidized by hypochlorous acid, forming both the methionine sulfoxide and the unique product dehydromethionine. Isolated human neutrophils formed these modifications on calprotectin when their myeloperoxidase generated hypochlorous acid. Up to 90% of the N-terminal amine on S100A8 in bronchoalveolar lavage fluid from young children with cystic fibrosis was oxidized. Oxidized calprotectin was higher in children with cystic fibrosis compared to disease controls, and further elevated in those patients with infections. Our data suggest that oxidative stress associated with inflammation in cystic fibrosis will stop metal sequestration by calprotectin. Consequently, strategies aimed at blocking extracellular myeloperoxidase activity should enable calprotectin to provide nutritional immunity within the airways. PMID:26006104

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

    Science.gov (United States)

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

    2016-04-01

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

  20. Development of a treatment process for the removal of heavy metals from raw water for drinking water supply using chelating ion exchange resins. Subproject 1. Final report; Entwicklung der Verfahrenstechnik zur Eliminierung von Schwermetallen aus Rohwaessern zur Trinkwassergewinnung mit chelatbildenden Kationenaustauscherharzen zur technischen Reife. Teilprojekt 1. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Overath, H.; Stetter, D.; Doerdelmann, O.

    2002-07-01

    Chelating cation exchange resins with iminodiacetic acid group (Lewatit TP 207 and Amberlite IRC 748) were tested for the removal of heavy metals in a drinking water treatment plant. The pilot scale filtration experiments were conducted by varying the operating conditions, such as flow rate and feed concentrations. Heavy metal concentrations (nickel, lead, cadmium, zinc) in the feed were adjusted between 20 and 200 {mu}g/L. Different methods for regeneration and conditioning of the resins were developed and investigated. Finally the ion exchange resins were tested according to German health regulations for ion exchangers in drinking water treatment. (orig.)

  1. Structural variability in uranyl-lanthanide hetero-metallic complexes with DOTA and oxalato ligands

    International Nuclear Information System (INIS)

    Four novel 4f-5f hetero-metallic complexes could be obtained from the reaction of uranyl and lanthanide nitrates with DOTA (H4L) under hydrothermal conditions. In all cases, as in the previous examples reported, additional oxalato ligands are formed in situ. Variations in the stoichiometry of the final products and the presence of hydroxo ions in some cases appear to result in a large structural variability. In the two isomorphous complexes [(UO2)2Ln2(L)2(C2O4)] with Ln = Sm(1) or Eu(2), the lanthanide ion is located in the N4O4 site and is also bound to a carboxylate oxygen atom from a neighbouring unit, to give zigzag chains which are further linked to one another by [(UO2)2(C2O4)]2+ di-cations, resulting in the formation of a 3D framework. In [(UO2)4Gd2(L)2(C2O4)3(H2O)6].2H2O (3), 2D bilayer subunits of the 'double floor' type with uranyl oxalate pillars are assembled into a 3D framework by other, disordered uranyl ions. [(UO2)2Gd(L)(C2O4)(OH)].H2O (4) is a 2D assembly in which cationic {[(UO2)2(C2O4)(OH)]+}n chains are linked to one another by the [Gd(L)]- groups. The most notable feature of this compound is the environment of the 4f ion, which is eight-coordinate and twisted square anti-prismatic (TSA'), instead of nine-coordinate mono-capped square anti-prismatic (SA), as generally observed in DOTA complexes of gadolinium(III) and similarly-sized ions. (author)

  2. Densities concentrations of aqueous of uranyl nitrate solutions

    International Nuclear Information System (INIS)

    The ratio density-concentration of aqueous uranyl nitrate solutions expressed as U3O8 grams/liter, U grams/liter and hexahydrate uranyl nitrate weight percent at different temperatures, are established. Experimental values are graphically correlated and compared whit some published data. (Author) 2 refs

  3. New insights into the acid mediated disproportionation of pentavalent uranyl

    Energy Technology Data Exchange (ETDEWEB)

    Mougel, Victor; Biswas, Biplab; Pecaut, Jacques; Mazzanti, Marinella [Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E 3 CEA-UJF FRE 3200 CNRS, INAC, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France)

    2010-07-01

    The reaction of benzoic acid with the uranyl(V) complex [(UO{sub 2}Py{sub 5})(KI{sub 2}Py{sub 2})] in pyridine leads to immediate disproportionation with formation of a hexa-nuclear U(IV) benzoate cluster, a bis-benzoate complex of uranyl(VI) and water. (authors)

  4. Contribution to the study of the mechanism of extraction of uranyl chloride by long chain aliphatic amines

    International Nuclear Information System (INIS)

    After having studied and developed the mechanisms which may 'a priori' explain the extraction process (co-ordination, ion association or intermediate mechanism), experience shows that ion association only should be taken into consideration. The structure of the organic complex of uranyl chloride has been defined on the basis of the study of the variation of the distribution coefficient of uranium between the two phases at the equilibrium as a function of successively the activity of Cl- ions in the aqueous phase, the concentration of amine salt in the organic phase and finally of the concentration of uranium in the aqueous phase. The plotting of the results in bi-logarithmic co-ordinates enables us to propose the following formula for the extracted compound: UO2Cl4--(NR3H+)2. The calculation of the equilibrium constant of formation of the organic compound of uranyl chloride has been possible in the case of diluted solutions of uranium only. (author)

  5. 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

  6. 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)

  7. Enhanced Sodium Ion Storage Behavior of P2-Type Na(2/3)Fe(1/2)Mn(1/2)O2 Synthesized via a Chelating Agent Assisted Route.

    Science.gov (United States)

    Bai, Ying; Zhao, Lixiang; Wu, Chuan; Li, Hui; Li, Yu; Wu, Feng

    2016-02-01

    On the basis of resource abundance and low cost, high capacity layered P2-type Na2/3Fe1/2Mn1/2O2 material is regarded as a potential cathode material for sodium-ion batteries but suffers from its unstable structure during cycling. In this work, P2-type Na2/3Fe1/2Mn1/2O2 layered materials were synthesized by a chelating agent assisted sol-gel method with NH3·H2O. With the addition of NH3·H2O and the control of the synthesis conditions, highly active material with a more stable structure and better electrochemical performance was obtained. Furthermore, the influences of structure changes during different voltage ranges (1.5-4.0 V and 1.5-4.3 V vs Na(+)/Na) on the Na(+) storage behaviors were also evaluated and compared. It is confirmed that, when being charged to 4.2 V, an OP4-type phase emerges, which can reduce the damage by the gilding of the MeO2 layers but leads to an unstable crystal structure. For long-term cycling, it is preferred to cut off at 4.0 V rather than at 4.3 V. For the optimized P2-type Na2/3Fe1/2Mn1/2O2 calcined at 900 °C, a discharge capacity of 92 mAh/g remains after 40 cycles in the voltage range of 1.5-4.0 V, and the Coulombic efficiency remains 100%. PMID:26732022

  8. The Scientific Basis for Chelation: Animal Studies and Lead Chelation

    OpenAIRE

    Smith, Donald; Strupp, Barbara J.

    2013-01-01

    This presentation summarizes several of the rodent and non-human studies that we have conducted to help inform the efficacy and clinical utility of succimer (meso-2,3-dimercaptosuccincinic acid) chelation treatment. We address the following questions: (1) What is the extent of body lead, and in particular brain lead reduction with chelation, and do reductions in blood lead accurately reflect reductions in brain lead? (2) Can succimer treatment alleviate the neurobehavioral impacts of lead poi...

  9. 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...

  10. Uranyl p-toluenesulfonate and its crystal hydrates, synthesis, and dehydration-hydration processes

    International Nuclear Information System (INIS)

    While uranyl benzenesulfonate (UBS) crystallizes from aqueous solutions as monohydrate, uranyl p-toluenesulfonate (UPTS) crystallizes as pentahydrate, UPTS solubility in water is 2.57 mol.kg-1, which is about one-half the solubility of UBS (4.85 mol.kg-1). We synthesized the lowest hydrates of UPTS and the anhydrous salt and studied the hydration of anhydrous UPTS in air at various water vapour pressures. Thermogravimetry and gravimetry in air under standard conditions revealed that the hydrate shell of UPTS.5H2O possess a layer structure. After thorough grinding and storage of the product in air for 3-4 days we obtained stable UPTS.3H20. In conditions of slow crystallization from aqueous solutions, crystals of UO2(CH3C6H4S03)2.5H20 were obtained. Their size was 5 mm x 3 mm, the crystal had regular faces. The coordination of sulfonate ions to uranyl (apparently bidentate) in UPTS and its hydrates is similar to that in UBS

  11. Determination of uranyl incorporation into biogenic manganese oxides using X-ray absorption spectroscopy and scattering

    Science.gov (United States)

    Webb, S.M.; Fuller, C.C.; Tebo, B.M.; Bargar, J.R.

    2006-01-01

    Biogenic manganese oxides are common and an important source of reactive mineral surfaces in the environment that may be potentially enhanced in bioremediation cases to improve natural attenuation. Experiments were performed in which the uranyl ion, UO22+ (U(VI)), at various concentrations was present during manganese oxide biogenesis. At all concentrations, there was strong uptake of U onto the oxides. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) studies were carried out to determine the molecular-scale mechanism by which uranyl is incorporated into the oxide and how this incorporation affects the resulting manganese oxide structure and mineralogy. The EXAFS experiments show that at low concentrations (2 mol % U, >4 ??M U(VI) in solution), the presence of U(VI) affects the stability and structure of the Mn oxide to form poorly ordered Mn oxide tunnel structures, similar to todorokite. EXAFS modeling shows that uranyl is present in these oxides predominantly in the tunnels of the Mn oxide structure in a tridentate complex. Observations by XRD corroborate these results. Structural incorporation may lead to more stable U(VI) sequestration that may be suitable for remediation uses. These observations, combined with the very high uptake capacity of the Mn oxides, imply that Mn-oxidizing bacteria may significantly influence dissolved U(VI) concentrations in impacted waters via sorption and incorporation into Mn oxide biominerals. ?? 2006 American Chemical Society.

  12. Electronic structure and properties of uranyl compounds. Quasi-relativistic calculation of uranyl by the MO LCAO method

    International Nuclear Information System (INIS)

    Matrix elements of non-relativiitic secular equation of MO LCAO method of uranyl and the means to correct molecular integrals included in them, taking account of relativistic effects, are described. In the bais 7ssub(1/2), 6dsub(5/2), 6dsub(3/2), 5fsub(7/2), 5fsub(5/2), 6psub(3/2), 6psub(1/2), 6ssub(1/2)-AO of uranium and 2ssub(1/2), 2psub(1/2), and 2psub(3/2)-AO of of oxygen the calculations of quasirelativistic MO of uranyl and clusters, modelling real compounds of uranyl, are made. On the basis of analysis of the chemical bonding nature a conclusion is drawn that in uranyl the contribution of internal 6p-AO of uranium into population of OUO bonds can reach 40% of total population of uranyl MO

  13. Adsorption of Uranyl ions on Amine-functionalization of MIL-101(Cr) Nanoparticles by a Facile Coordination-based Post-synthetic strategy and X-ray Absorption Spectroscopy Studies

    Science.gov (United States)

    Zhang, Jian-Yong; Zhang, Na; Zhang, Linjuan; Fang, Yongzheng; Deng, Wei; Yu, Ming; Wang, Ziqiang; Li, Lina; Liu, Xiyan; Li, Jingye

    2015-09-01

    By a facile coordination-based post-synthetic strategy, the high surface area MIL-101(Cr) nanoparticles was functionallized by grafting amine group of ethylenediamine (ED) on coordinatively unsaturated Cr(III) centers, yielding a series of ED-MIL-101(Cr)-based adsorbents and their application for adsorption of U(VI) from aqueous solution were also studied. The obtained ED-functionallized samples with different ED contents were characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), FTIR, elemental analysis (EA) and N2 adsorption and desorption isothermal. Compared with the pristine MIL-101(Cr) sorbents, the ED-functionallized MIL-101(Cr) exhibits significantly higher adsorption capacity for U(VI) ions from water with maximum adsorption capacities as high as 200 mg/g (corresponding to 100% extraction rate) at pH of 4.5 with ED/Cr ratio of 0.68 and the sorbed U(VI) ions can easily be desorbed at lower pH (pH ≤ 2.0). The adsorption mode of U(VI) ions and effects of grafted ED on the MIL-101(Cr) frameworks were also been studied by X-ray absorption spectroscopy (XAS). We believe that this work establishes a simple and energy efficient route to a novel type of functional materials for U(VI) ions extraction from solution via the post-synthetic modification (PSM) strategy.

  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. 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

  16. Overview of current chelation practices

    OpenAIRE

    Aydinok, Y.

    2011-01-01

    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 ...

  17. Bifunctional Chelates for Metal Nuclides

    OpenAIRE

    Brechbiel, Martin W.

    2007-01-01

    The use of “non-standard” metallic radionuclides continues to be an expanding field of investigation. Radiolabeling small molecules, peptides, proteins, and up to nano-particles are all areas of active investigation for both diagnostic and therapeutic applications. All require a common variable – the need for appropriate chelation chemistry for adequate sequestration of the metallic radionuclide that is equal to the intended application. A brief overview of the array of the chelation chemistr...

  18. A new chiral uranyl phosphonate framework consisting of achiral building units generated from ionothermal reaction: structure and spectroscopy characterizations.

    Science.gov (United States)

    Zheng, Tao; Gao, Yang; Chen, Lanhua; Liu, Zhiyong; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2015-11-01

    The ionothermal reactions of uranyl nitrate and 1,3-pbpH4 (1,3-pbpH4 = 1,3-phenylenebis(phosphonic acid) ligand in ionic liquids of [C4mim][Dbp], [C4mpyr][Br], and [Etpy][Br], respectively, afforded three new uranyl phosphonates, namely [C4mim][(UO2)2(1,3-pbpH)(1,3-pbpH)·Hmim] (1), [UO2(1,3-pbpH2)H2O·mpr] (2), and [Etpy][UO2(1,3-pbpH2)F] (3). Compound 1 exhibits a rare example of a chiral uranyl phosphonate 3D framework structure built from achiral building units of tetragonal bipyramidal uranium polyhedra and 1,3-pbp ligands. The structure adopts a network with channels extending along the b axis, which are filled with C4mim(+) and protonated 1-methylimidazole. In sharp contrast, compounds 2 & 3 both show pillared topology composed of uranyl pentagonal bipyramid polyhedra and phosphonate ligands. The layers are neutral in compound 2 with N-methylpyrrole molecules in the interlayer space, while compound 3 adopts anionic layer, and the charge is compensated with N-ethyl-pyridinium cations between the layers. Although compounds 1, 2, and 3 were synthesized under identical conditions with sole variation of the ionic liquid species, the resulting structures show a rich diversity in the local coordination environment of uranyl ions, the protonation of the phosphonate ligand, the conformation of ionic liquid ions, and the overall arrangement of the structure. All compounds were characterized by absorption, temperature dependent fluorescence, as well as infrared and Raman spectroscopies. PMID:26419426

  19. 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.)

  20. 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

  1. 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

  2. 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

  3. Uranyl tris-(carbohydrazide) nitrate [UO2((N2H3)2CO)3](NO3)2. Synthesis, structure and properties

    International Nuclear Information System (INIS)

    Uranyl tris-(carbohydrazide) nitrate [UO2((N2H3)2CO)3](NO3)2 was prepared by the reaction of water solution of dioxouranium(VI) nitrate UO2(NO3)2(H2O)6 with ethanol solution of carbohydrazide (N2H3)2CO in a molar ratio of 1 to 3 in an neutral medium. The substance was characterized by elemental, thermal analysis and IR and 15N 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 Aa3, Z = 4, SG = Cc. The type of carbohydrazide coordination was additionally confirmed by 15N MAS CP NMR and IR spectroscopy. In the complex ion [UO2((N2H3)2CO)3]2+ three carbohydrazide ligands coordinate to UO22+ 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 [UO2((N2H3)2CO)3]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 [UO2((N2H3)2CO)3](NO3)2 is thermally stable up to 215 C and then decomposes with an explosion.

  4. Determination of formation constants of uranyl(VI complexes with a hydrophilic SO3-Ph-BTP ligand, using liquid-liquid extraction

    Directory of Open Access Journals (Sweden)

    Steczek Lukasz

    2015-12-01

    Full Text Available Complex formation between uranyl ion, UO22+, and a hydrophilic anionic form of SO3-Ph-BTP4- ligand, L4-, in water was studied by liquid-liquid extraction experiments performed over a range of the ligand and HNO3 concentrations in the aqueous phase, at a constant concentration of nitrate anions at 25°C . The competition for UO22+ ions between the lipophilic TODGA extractant and the hydrophilic L4- ligand leads to the decrease in the uranyl distribution ratios, D, with an increasing L4- concentration. The model of the solvent extraction process used accounts - apart from uranyl complexation by TODGA and SO3-Ph-BTP4- - also for uranyl complexation by nitrates and for the decrease in the concentration of the free L4- ligand in the aqueous phase, due to its protonation, bonding in the uranyl complex and the distribution between the two liquid phases. The unusually strong dependence of the D values on the acidity, found in the experiment, could hardly be explained as due to L4- protonation merely. Three hypotheses were experimentally tested, striving to interpret the data in terms of additional extraction to the organic phase of ion associates of protonated TODGA cation with either partly protonated anionic L4- ligands or anionic UO22+ complexes with NO3 - or L4-. None of them has been confirmed. The analysis of the results, based on the formal correction of free ligand concentrations, points to the formation of 1 : 1 and 1 : 2 uranyl - SO3-Ph-BTP complexes in the aqueous phase. The conditional formation constant of the 1:1 complex has been determined, logßL,1 = 2.95 ± 0.15.

  5. 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)

  6. 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.

  7. Behind adhesion of uranyl onto montmorillonite surface: A molecular dynamics study

    International Nuclear Information System (INIS)

    Highlights: • We investigated the adsorption of uranyl onto Montmorillonite surface. • We studied the surface energy between layered Montmorillonite sheets. • We studied the work of adhesion between radionuclide and charged Montmorillonite. -- Abstract: We have performed molecular dynamics simulations to investigate the adsorption of radionuclide elements species onto substituted Montmorillonite (001) surface in the presence of different counterions. The structure and the dynamics of uranyl ion as well as its aquo, chloride ion, and carbonate complexes are analyzed. In addition, we have studied the surface energy between layered Montmorillonite sheets and the work of adhesion between radionuclide and charged Montmorillonite. The clay model used here is a Wyoming-type Montmorillonite with 0.75e negative charge per unit cell resulting from substitutions in Octahedral and Tetrahedral sheets. The system model was constructed based on CLAYFF force field potential model. To evaluate the thermodynamic work of adhesion, each surface and clay layer regions are converted to a thin film model. One and two species of radionuclide elements (UO2(H2O)5,UO2CO3(H2O)5, and UO2Cl2(H2O)5) were deposited near the clay surface in a pseudo-two-dimensional periodic cell. Analysis shows that the uranyl ion structure is preserved with two axial oxygen atoms detected at 1.8 Å. Radial distribution functions results indicate that average U-Ow distances are 2.45–2.61 Å, and 2.29–2.40 Å for U-Oc distance. Average U-Cl distances are 2.78–3.08 Å, which is relatively larger than that of Uranium atom-Oxygen atom because of electrostatic factors

  8. Complexes of uranyl chloride and uranyl nitrate with neutral oxygen-containing bases

    International Nuclear Information System (INIS)

    Conditions of complex preparation from uranyl chloride and nitrate crystallohydrates with various neutral organic bases, such as dimethyl sulfoxide, diethyl sulfoxide, dimethylformamide, acetonitrile, acetone, diethyl ether are studied. It is shown that the composition of the products formed depends on organic molecule basicity: with its increase neutral ligand is able to replace water from uranyl crystallohydrate. Absorption frequencies ν(UO22+) and ν(X=0), responsible for the complexing, are analyzed. It is shown that the values ν3(UO22+) do not manifest linear dependence on donor ability of organic base. Thermal stability of the products prepared is studied. Complexes of the composition UO2X2x2L are shown to decompose in two stages with splitting off of organic base molecule and destruction of monosolvate. Increase in the temperatures of the above- mentioned processes with an increase in the base donor ability is detected

  9. Chelating regularities in the series of chelating polymer sorbents and their complexes with vanadium, manganese, and chromium

    International Nuclear Information System (INIS)

    Physicochemical properties of new synthesized polymer chelation sorbents - substituted polystyrene-azo-salicylic acid are investigated. Correlations between pKCOOH of functional groups of sorbents with chelation pH50 and vanadium, manganese and chromium lgstab are established with the aim of studying interactions in the ion of element - sorbent system. Established correlations suggest physicochemical properties of the sorbents and sorption parameters of cations of metals with the aim of concentration and separation of V(5), Mn(2) and Cr(3) microamounts from natural and technical objects including environmental ones

  10. Equilibrium study of the complex formation of some trivalent metal ion chelates of Schiff bases derived from 2-hydroxy-3-phenyl benzaldehyde and evaluation of these reagents from their anticoagulant activity

    International Nuclear Information System (INIS)

    Potentiometric studies have been carried out on metal chelates of La3+, Pr3+, Gd3+, Tb3+, Dy3+, Er3+ and Yb3+ with N-(2-hydroxy-3-phenylbenz ylidene)-aniline and N-(2-hydroxy-3-phenylbenzylidene)-3, 4, 5 trimethoxyaniline. The dissociatio n constants of the reagents and formation constants of their metal chelates have been determine d by Calvin-Bjerrum pH titration technique as adopted by Irving and Rossotti and at 28 ± 0.1degC at ionic strength 0.1 M in 75:25 (v/v) dioxane-water mediium. (author). 7 figs., 5 refs

  11. Investigation of some uranyl halogenoacetates and their crystalohydrates using the method of thermogravimetry

    International Nuclear Information System (INIS)

    The method of thermogravimetry is used to study thermal stability of uranyl trichloro-, trifluoro-, and monochloroacetate and their crystallohydrates. It is established that dehydration temperature coordinated to a cation of water rises with decreasing electron-donor ability of halogenacetate-ion. The results obtained and the data of spectroscopy permit to assume that heat stability of hydrates in the salt series considered is mainly determined by the strength of water uranium-oxygen bond. Hydrogen bonds with anion play a less significant role in the process of dehydration

  12. 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

  13. Solid solutions of hydrogen uranyl phosphate and hydrogen uranyl arsenate. A family of luminescent, lamellar hosts

    International Nuclear Information System (INIS)

    Hydrogen uranyl phosphate, HUO2PO4 x 4H2O (HUP), and hydrogen uranyl arsenate, HUO2AsO4 x 4H2O (HUAs), form solid solutions of composition HUO2(PO4)1-x(AsO4)x (HUPAs), representing a family of lamellar, luminescent solids that can serve as hosts for intercalation chemistry. The solids are prepared by aqueous precipitation reactions from uranyl nitrate and mixtures of phosphoric and arsenic acids; thermogravimetric analysis indicates that the phases are tetrahydrates, like HUP and HUAs. Powder x-ray diffraction data reveal the HUPAs solids to be single phases whose lattice constants increase with X, in rough accord with Vegard's law Spectral shifts observed for the HUPAs samples. Emission from the solids is efficient (quantum yields of ∼ 0.2) and long-lived (lifetimes of ∼ 150 μs), although the measured values are uniformly smaller than those of HUP and HUAs; unimolecular radiative and nonradiative rate constants for excited-state decay of ∼ 1500 and 5000 s-1, respectively, have been calculated for the compounds. 18 refs., 5 figs., 2 tabs

  14. 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)

  15. Adsorption of uranyl in SiO2 porous glass

    International Nuclear Information System (INIS)

    Vitreous SiO2 porous matrices can be used in many applications involving the uptake of chemical species on its solid surface. In this work, vitreous silica sponges were prepared from a sodium borosilicate glass manufactured in our laboratory. The product obtained was then separated into phases with subsequent leaching of the soluble phase rich in B and Na. The resulting porous matrices have a specific surface of 35 m2/gr. Adsorption of uranyl ions onto the SiO2 porous surface was studied to evaluate the use of this material as a filter for treatment of uranium containing water. The effects of contact time, adsorbent mass and equilibrium concentration of solution were studied. The porous adsorbent exhibits a pseudo-second-order kinetic behavior. The sponges with adsorbed uranium were thermally sealed as a way of U immobilization. Retention of uranium was confirmed during the matrix sealing by TGA. Uranium concentration before and after adsorption tests were made by means of ICP-OES. For uranium concentration of 800 ppm, 72 hours contact time and pH of 3.5, the amount of uranium adsorbed was 21.06 ± 0.02 mg U per gram of vitreous porous SiO2. (author)

  16. Europium(III)-chelates embedded in nanoparticles are protected from interfering compounds present in assay media

    International Nuclear Information System (INIS)

    Lanthanide chelates are excellent labels in ligand binding assays due to their long lifetime fluorescence, which enables efficient background reduction using time-resolved measurement. In separation-free homogeneous assays, however, some compounds in the sample may cause quenching of the lanthanide fluorescence and extra steps are required before these samples can be measured. In this study we have evaluated whether europium chelates packed inside a polystyrene nanoparticle are better protected from the environment than individual Eu(III)-chelates, and do these particles have higher tolerance against known interfering compounds (bivalent metal ions and variation of pH). We also tested whether metal ions had any effect on a fluorescence resonance energy transfer (FRET) based detection of a bioaffinity binding reaction. The presence of metal ions or variation of pH did not affect the fluorescence of the Eu(III)-chelate dyed nanoparticles, while significant decrease of the fluorescence was detected with a 9-dentate Eu(III)-chelate. Metal ions also decreased the fluorescence lifetime of the 9-dentate Eu(III)-chelate from 0.960 to 0.050 ms. Coloured metal ions caused a minor decrease in sensitised emission generated by FRET when Eu(III)-chelate dyed nanoparticles were used as donor labels. The decreased signal was due to the absorption of the sensitised emission by the coloured metal ions, since the metal ions had no effect on the lifetime of the sensitised emission. Thus the Eu(III)-chelate dyed nanoparticles are preferred labels in homogeneous bioaffinity assays, when interfering compounds are known to be present

  17. 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)

  18. Structural study of the uranyl and rare earth complexation functionalized by the CMPO

    International Nuclear Information System (INIS)

    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)

  19. Evaluation of genotoxicity induced by hydrogen peroxide in the presence of ions chelator Fe{sup 2+} (2,2'-dipyridyl) and of Cu{sup 2+}(neocuproine), in Escherichia coli: involvement of DNA repair mechanisms in the bacteria survival; Avaliacao da genotoxicidade induzida pelo peroxido de hidrogenio na presenca dos quelantes de ions Fe{sup 2+} (2,2'-dipiridil) e de ions Cu{sup 2+} (neocuproina), em Escherichia coli: envolvimento de mecanismos de reparo de DNA na sobrevivencia bacteriana

    Energy Technology Data Exchange (ETDEWEB)

    Almeida, Carlos Eduardo Bonacossa de

    1998-07-01

    Prior incubation of the E. coli cultures with the iron ions chelator 2,2'-dipyridyl (1 mM) caused an intensification of the lethality and the mutagenesis induced by the hydrogen peroxide, mainly at high concentrations (20 mM). It was also detected an enhancement of DNA strand breaks in this condition. The addition of the copper ions chelator neocuproine blocked partially this phenomenon. The enzymes XthA and Nfo act alternatively in the repair of the lesions induced by H{sub 2}O{sub 2} in the presence of 2,2'-dipyridyl. H{sub 2}O{sub 2} can act synergistically with neocuproine in killing E. coli, causing an enhancement in DNA strand breaks. The recombinational repair, the UvrABC excinuclease and Fpg function appeared to participate in the repair of the synergistic lesions. (author)

  20. Determination of trace metal ions via on-line separation and preconcentration by means of chelating Sepharose beads in a sequential injection lab-on-valve (SI-LOV) system coupled to electrothermal atomic absorption spectrometric detection

    DEFF Research Database (Denmark)

    Long, Xiangbao; Hansen, Elo Harald; Miró, Manuel

    2005-01-01

    The analytical performance of an on-line sequential injection lab-on-valve (SI-LOV) system using chelating Sepharose beads as sorbent material for the determination of ultra trace levels of Cd(II), Pb(II) and Ni(II) by electrothermal atomic absorption spectrometry (ETAAS) is described and discussed...

  1. Some thermodynamic characteristics of uranyl haloacetates and their crystal hydrates

    International Nuclear Information System (INIS)

    Data on values of standard formation enthalpies for some uranyl carboxylates, acetates, chloroacetates, trichloroacetates and trifluoroacetates, their crystal hydrates and respective acids and their anions in gaseous state are presented. Thermochemical cycle is suggested, and calculation for lattice enthalpies of mentioned uranyl carboxylates is made. Errors of key and obtained values are discussed. It is shown, that the basic contribution into lattice enthalpies changing in the series considered is determined by anion electrodonor ability changing

  2. 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)

  3. 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.

  4. 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

  5. In Vitro Ion Chelating, Antioxidative Mechanism of Extracts from Fruits and Barks of Tetrapleura tetraptera and Their Protective Effects against Fenton Mediated Toxicity of Metal Ions on Liver Homogenates

    Directory of Open Access Journals (Sweden)

    Bruno Moukette Moukette

    2015-01-01

    Full Text Available The aim of the present study was to investigate the antioxidant activity and protective potential of T. tetraptera extracts against ion toxicity. The antioxidant activity of the extracts was investigated spectrophotometrically against several radicals (1,1-diphenyl-2-picrylhydrazyl (DPPH•, 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid (ABTS•, hydroxyl radical (HO•, and nitric oxide (NO•, followed by the ferric reducing power, total phenols, flavonoid, and flavonol contents. The effects of the extracts on catalase (CAT, superoxide dismutase (SOD, and peroxidase activities were also determined using the standard methods as well as the polyphenol profile using HPLC. The results showed that the hydroethanolic extract of T. tetraptera (CFH has the lowest IC50 value with the DPPH, ABTS, OH, and NO radicals. The same extract also exhibited the significantly higher level of total phenols (37.24 ± 2.00 CAE/g dried extract; flavonoids (11.36 ± 1.88 QE/g dried extract; and flavonols contents (3.95 ± 0.39 QE/g dried extract. The HPLC profile of T. tetraptera revealed that eugenol (958.81 ± 00 mg/g DW, quercetin (353.78 ± 00 mg/g DW, and rutin (210.54 ± 00 mg/g DW were higher in the fruit than the bark extracts. In conclusion, extracts from T. tetraptera may act as a protector against oxidative mediated ion toxicity.

  6. Iron chelation and multiple sclerosis

    Directory of Open Access Journals (Sweden)

    Kelsey J. Weigel

    2014-01-01

    Full Text Available Histochemical and MRI studies have demonstrated that MS (multiple sclerosis patients have abnormal deposition of iron in both gray and white matter structures. Data is emerging indicating that this iron could partake in pathogenesis by various mechanisms, e.g., promoting the production of reactive oxygen species and enhancing the production of proinflammatory cytokines. Iron chelation therapy could be a viable strategy to block iron-related pathological events or it can confer cellular protection by stabilizing hypoxia inducible factor 1α, a transcription factor that normally responds to hypoxic conditions. Iron chelation has been shown to protect against disease progression and/or limit iron accumulation in some neurological disorders or their experimental models. Data from studies that administered a chelator to animals with experimental autoimmune encephalomyelitis, a model of MS, support the rationale for examining this treatment approach in MS. Preliminary clinical studies have been performed in MS patients using deferoxamine. Although some side effects were observed, the large majority of patients were able to tolerate the arduous administration regimen, i.e., 6–8 h of subcutaneous infusion, and all side effects resolved upon discontinuation of treatment. Importantly, these preliminary studies did not identify a disqualifying event for this experimental approach. More recently developed chelators, deferasirox and deferiprone, are more desirable for possible use in MS given their oral administration, and importantly, deferiprone can cross the blood–brain barrier. However, experiences from other conditions indicate that the potential for adverse events during chelation therapy necessitates close patient monitoring and a carefully considered administration regimen.

  7. Oxidation of 2-propanol ligands during collision-induced dissociation of a gas-phase uranyl complex

    Science.gov (United States)

    van Stipdonk, Michael J.; Chien, Winnie; Anbalagan, Victor; Gresham, Garold L.; Groenewold, Gary S.

    2004-10-01

    We demonstrate, by way of multi-stage tandem mass spectrometry and extensive deuterium labeling, that 2-propanol is converted to acetone, and 2-propoxide to acetaldehyde, when monopositive 2-propanol-coordinated uranyl-ligand cations are subjected to collision-induced dissociation in the gas-phase environment of an ion trap mass spectrometer. A species with formula [(UO2OCH(CH3)2)(HOCH(CH3)2)]+, derived from dissociation of the gas-phase precursor [(UO2NO3)(HOCH(CH3)2)3]+ eliminates two H atoms and CH3 in consecutive stages to generate a monopositive complex composed of the U(V) species UO2+ coordinated by acetone and acetaldehyde, i.e. [UO2+(OC(CH3)2)(OC(H)CH3)]. Dissociation of this latter ion resulted in elimination of the two coordinating carbonyl ligands in two consecutive dissociation stages to leave UO2+. Analogous reactions were not observed for uranyl complexes containing 1-propanol or 2-methyl-2-propanol, or for cationic complexes with divalent metals such as Ni2+, Co2+, Pb2+ and Ca2+. One explanation for these reactions is bond insertion by the metal center in the bis-ligated uranyl complex, which would be expected to have an LUMO consisting of unoccupied 6d-orbitals that would confer transition metal-like behavior on the complex.

  8. Preparation, Spectroscopic Investigation and Biological Activity of New Mixed Ligand Chelates

    International Nuclear Information System (INIS)

    Preparation and investigation of new Co(II), Ni(II), Zn(II) and Cr(III) chelates with mixed ligands including Schiff base (L1) formed from the condensation of 4-dimethylaminobenzaldehyde with 2-aminophenol and anthranilic acid (L2) were studied. The obtained Schiff base and mixed ligand chelates were subjected to several physiochemical techniques, in terms of CHN elemental analyses, molar conductivity, magnetic moment measurements, infrared, proton nuclear magnetic resonance, electronic and mass spectra. The analytical data showed the formation of the Schiff base compound and the ratio of metal to ligands of the chelates are 1:1:1(M:L1:L2). The infrared spectral data exhibited that the used ligands behaving as bidentate ligands towards the metal ions. The proton nuclear magnetic resonance spectral data showed the signals of the active groups in the ligands which entered in chelation with Zn(II) metal ion. The electronic spectral results showed the existence of pie (phenyl ring) and n = pie (C=N) of the ligands and suggested the geometrical structures of the chelates. Meanwhile, the mass spectral data revealed the fragmentations of the Schiff base, anthranilic acid and their Ni(II) mixed ligand chelate has been preformed the only chelate conducted for justification. All the prepared mixed chelates were non-electrolyte in nature. The antibacterial activity of the Schiff base, anthranilic acid, metal salts and mixed ligand chelates were studied and found to be that mixed ligand chelates have the most biological activity in comparison to the free ligands and salts. (author)

  9. Uranyl hydrogel leaching as one of technological nodes of sol-gel process. Part 3

    International Nuclear Information System (INIS)

    The process of leaching is described of the fine fraction of uranyl hydrogel prepared by internal gelation from aqueous solutions of uranyl nitrate under the action of urea and urotropin. For preparing the dispersion a two-liquid jet was used which provided a polydispersion mixture with mean particle size of around 300 μm. Leaching took place in a 0.5 to 2 molar aqueous solution of ammonia at the solid:liquid phase ratio in the range of 1:10 to 1:2 with the addition of a wetting agent in extraction containers for a period of 5 to 60 mins. The effect of the said parameters was studied on the uranium content - the residual content of nitrate ions, carbon and the content of adsorbed NH4OH in the solid phase and the content of leached nitrate ions and uranium in the leaching solution. The leaching process was so rapid that after 5 mins steady state was achieved and further leaching for over 60 mins affected the composition of neither the solid nor the liquid phase. Under the conditions the optimal arrangement of the experiment appears to be leaching with ca. 1 M agueous solution of ammonia at a s:l ratio of 1:5 over 10 mins. The kinetics of leaching carbonaceous substances was evaluated by previously verified equations and the diffusion mechanism of the formation of a stabilized skeleton of ammonium polyuranate was confirmed. (author)

  10. Determination of halogens, silicon, phosphorus, carbon, sulfur, tributyl phosphate and of free acid in uranyl nitrate solutions

    International Nuclear Information System (INIS)

    High-purity uranium compounds are widely used in nuclear field in the form of uranyl nitrate or uranium oxides. In production of uranium material the estimation and the control of products quality is necessary and very important. Halogens was separated from uranium compounds by steam distillation and they were later determined by high performance liquid chromatography (HPLC) for Cl- , Br- , I- ions. Br- was also determined by spectrophotometric and iodide by the individual pulse polarography. Silicon and phosphorus in uranyl nitrate solutions were determined by the photometric method. Sulfur was determined as sulfate form by the measurement of turbidity by the titrimetry. TBP in kerosene and free acid in aqueous solution were determined by the titration. (author)

  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. 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

  13. Synthesis and Characterization of polyacrylamide Chelating Resin with Thenoyltrifluoroacetone for Separation of Thorium from Uranium

    International Nuclear Information System (INIS)

    New effective chelating resin is synthesized by immobilization of Thenoyltrifluoroacetone (HTTA) on cross linked polyacrylamide. The chelating exchanger is used for separation of uranium (UO22+) and thorium(Th4+). The analyzed metal ions were quantitatively measured by ion chromatographic technique coupled with UV/V is detector and derivatization reaction of Arsenazo(III) at wavelength 660 nm. Different factors affecting the metal ions uptake and hence the separation efficient c y of the chelating polyacrylamide resin were investigated. Optimization of conditions showed that maximum uptake of UO22+ and Th4+ are at ph 4.0 and 3.0 respectively. Isothermal capacity shows a relatively high capacity of the chelating resin towards divalent uranium more than that of tetravalent thorium. The capacity of the chelating resin for UO22+ and Th4+ was found to be 0.05 and 0.034 mmol/gm, respectively. Separation of UO22+ and Th4+ was successively performed using column chromatographic technique loaded with the chelating resin. The retained metal ions were sequentially separated by i socratic elution using 0.1 M HNO3

  14. Behavior of the extraction of metallic ions in carbonate medium, using N-benzoylphenylhydroxylamine (BPHA) - benzene

    International Nuclear Information System (INIS)

    The possibility of separating quantitatively trace impurities like Cu, Fe, In and Pb, present in uranium base materials of nuclear grade, is demonstrated. A solvent extraction is employed which makes use of -benzoylphenylhydroxylamine(BPHA)-benzene solution and separation is effected in a medium containing 252 moles per liter of sodium-uranyl tricarbonate at pH of 9,0. Carbonate ions under such conditions inhibit uranium extraction by masking uranyl ion-BPHA reaction. The uranyl ions show a demasking action, releasing, thereby, Pb(II) ions which are being extracted from carbonate medium. The Atomic Absorption Spectrophometry technique is used to obtain the experimental data

  15. Synthesis and Characterization of Templated Ion Exchange Resins for the Selective Complexation of Actinide Ions

    Energy Technology Data Exchange (ETDEWEB)

    Uy, O. Manual

    2001-03-01

    The purpose of this research is to develop a polymeric extractant for the selective complexation of uranyl ions (and subsequently other actinyl and actinide ions) from aqueous solutions (lakes, streams, waste tanks and even body fluids). Chemical insights into what makes a good complexation site will be used to synthesize reagents tailor-made for the complexation of uranyl and other actinide ions. These insights, derived from studies of molecular recognition include ion coordination number and geometry, ionic size and ionic shape, as well as ion to ligand thermodynamic affinity. Selectivity for a specific actinide ion will be obtained by providing the polymers with cavities lined with complexing ligands so arranged as to match the charge, coordination number, coordination geometry, and size of the actinide metal ion. These cavity-containing polymers will be produced by using a specific ion (or surrogate) as a template around which monomeric complexing ligands will be polymerized. The complexing ligands will be ones containing functional groups known to form stable complexes with a specific ion and less stable complexes with other cations. Prior investigator's approaches for making templated resins for metal ions have had marginal success. We have extended and amended these methodologies in our work with Pb(II) and uranyl ion, by changing the order of the steps, by the inclusion of sonication, by using higher complex loading, and the selection of functional groups with better complexation constants. This has resulted in significant improvements to selectivity. The unusual shape of the uranyl ion suggests that this approach will result in even greater selectivities than already observed for Pb(II). Preliminary data obtained for uranyl templated polymers shows unprecedented selectivity and has resulted in the first ion selective electrode for uranyl ion.

  16. Ion exchange properties of crystalline bismuth molybdenum hydrous oxide and its intercalates. Equilibrium and kinetics of UO22+ ions on the crystals

    International Nuclear Information System (INIS)

    The sorption of uranyl ions on crystalline bismuth molybdenum hydrous oxide and its intercalates were investigated from point of view of both equilibrium and kinetics. Ion exchange isotherms of uranyl ions on the crystals were obtained, and ionic sieve effect was employed to describe the characteristics of ion exchange isotherms. The best fitting for sorption of uranyl ions on BMHO was achieved by means of the Langmuir isotherm, while the Freundlich isotherm appeared to best fit for its intercalates. The slightly negative free-energy change indicates that, thermodynamically, the crystals behave less favourable for uranyl ions. The equation derived from SN2 chemical reactions was proved to fit the rate curves, and the rate constants were determined. The comparison between the calculated and observed pH values as a function of time further verified the chemical reaction mechanism. (author)

  17. 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.

  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. 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

  20. 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)

  1. Iron chelation and multiple sclerosis

    OpenAIRE

    Kelsey J. Weigel; Sharon G. Lynch; Steven M. LeVine

    2014-01-01

    Histochemical and MRI studies have demonstrated that MS (multiple sclerosis) patients have abnormal deposition of iron in both gray and white matter structures. Data is emerging indicating that this iron could partake in pathogenesis by various mechanisms, e.g., promoting the production of reactive oxygen species and enhancing the production of proinflammatory cytokines. Iron chelation therapy could be a viable strategy to block iron-related pathological events or it can confer cellular prote...

  2. Some Linguistic Detail on Chelation

    Science.gov (United States)

    Haworth, Daniel T.

    1998-01-01

    The term chelate was first applied by Morgan and Drew in 1920 to describe the heterocyclic rings formed from bidentate ligands bonding to a central atom. The history of the word ch_l_ is traced from its original Greek meaning through the Latin language to its anglicized form, chela. This word has a very rich history and has been cited by both Greek (Aristotle) and Latin (Cicero, Vergil) philosophers and poets.

  3. 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

  4. Analysis of hydrosoluble organic chelating agents. Potentialities of capillary electrophoresis and ionic chromatography

    International Nuclear Information System (INIS)

    Capillary electrophoresis and ion exchange chromatography are good techniques for the determination of organic chelating agents as mono or poly-carboxylates. Ion exchange chromatography allows to obtain very high sensitivities (a few μg/L). Capillary electrophoresis generates practically none analytical waste; this technique is then very interesting for nuclear industry. This microanalysis technique has been here carried out for the determination of organic chelating agents in leaching water of an old waste for which an important release rate of radio-toxic metals had been found. Thus, formate and especially acetate ions have been correlated with this unusual behaviour

  5. Photostimulated oxygen exchange of uranyl in aqueous-ethanol solutions

    International Nuclear Information System (INIS)

    Uranyl oxygen exchange (18O/16O) in solution 1 mol/l HClO4 in the presence of ethanol small additions (up to 0.4 mol/l) when irradiated by the light with λmax=400 nm is investigated. Quantum yield of the exchange increases rapidly with an increase in ethanol concentration and reaches the limiting value of ∼ 3500 at ethanol concentrations of ∼ 0.2 mol/l. The conclusion is made that in similar soltuons ethanol oxidation by excited uranyl proceeds mainly with one electron transfer in the unit event. The rate constant of uranyl extinction by ethanol is evaluated to be ∼ 5x107 lxmol-1xs-1

  6. 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

  7. 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).

  8. Some thermodynamic characteristics of uranyl haloacetates and their crystal hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Baluev, A.V.

    1988-11-01

    Data on the values of the standard heats of formation of a number of uranyl carboxylates and their crystal hydrates, as well as the corresponding acids and their anions in the gaseous state, have been presented. A thermochemical cycle has been proposed, and a calculation of the lattice heats of the uranyl carboxylates indicated has been carried out. The errors of the tabulated values and the values obtained have been discussed. It has been shown that the main contribution to the changes in the lattice heats in the series under consideration is determined by the changes in the electron-donor ability of the anion.

  9. 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.

  10. 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

  11. Status of chelation research: a review

    International Nuclear Information System (INIS)

    The current status of research on the removal of actinide elements from the body is reviewed. Items occurring prior to 1980 include evidence for fetal toxicity from Ca-DTPA, the FDA approval of Zn-DTPA for human therapy, the mixed ligand fiasco, and the abrupt wipeout of chelation funding. New concepts that should be explored include improvements in removing radioactivity from lung and bone, the effectiveness of DTPA inside cells, simultaneous therapy with mobilizing agents and chelating agents, prolonging the retention of chelating agents within the body, the oral administration of chelating agents, the effectiveness of LICAM and other new chelating agents, the safety of decorporation procedures, and the effectiveness of chelation therapy on reducing the risk from radionuclide-induced cancer. Some physicians give DTPA by intravenous injection, a safe procedure that should be officially sanctioned

  12. Copper and Zinc Chelation as a Treatment of Alzheimer's Disease

    Science.gov (United States)

    Hodak, Miroslav; Bernholc, Jerry

    2014-03-01

    Alzheimer's disease (AD) is a neurodegenerative disorder affecting millions of people in the U.S. The cause of the disease remains unknown, but amyloid- β (A β), a short peptide, is considered causal its pathogenesis. At cellular level, AD is characterized by deposits mainly composed of A β that also contain elevated levels of transition metals ions. Targeting metals is a promising new strategy for AD treatment, which uses moderately strong metal chelators to sequester them from A β or the environment. PBT2 is a chelating compound that has been the most promising in clinical trials. In our work, we use computer simulations to investigate complexes of a close analog of PBT2 with Cu2+ and Zn2+ ions. The calculations employ KS/FD DFT method, which combines Kohn-Sham DFT with the frozen-density DFT to achieve efficient description of explicit solvent beyond the first solvation shell. Our work is based on recent experiments and examines both 1:1 and 2:1 chelator-metal stochiometries detected experimentally. The results show that copper attaches more strongly than zinc, find that 1:1 complexes involve water in the first coordination shell and determine which one of several possible 2:1 geometries is the most preferable.

  13. 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.

  14. Effects of calcium chelators on calcium distribution and protein solubility in rennet casein dispersions.

    Science.gov (United States)

    McIntyre, Irene; O' Sullivan, Michael; O' Riordan, Dolores

    2016-04-15

    This study investigated the effects of calcium chelating salts on calcium-ion activity (ACa(++)), calcium distribution, and protein solubility in model CaCl2 solutions (50 mmol L(-1)) or rennet casein dispersions (15 g/100 g). Disodium phosphate and trisodium citrate at concentrations of 10 and 30 mmol L(-1) and at ratios of 1:0, 2:1, 1:1, 1:2 and 0:1 were added to both systems. The CaCl2 system, despite its simplicity, was a good indicator of chelating salt-calcium interactions in rennet casein dispersions. Adding trisodium citrate either alone or as part of a mixed chelating salt system resulted in high levels of dispersed "chelated" calcium; conversely, disodium phosphate addition resulted in lower levels, while the ACa(++) decreased with increasing concentration of both chelating salts. Neither chelating salt produced high levels of soluble protein. Thus calcium chelating salts may play a more subtle role in modulating hydration during manufacture of casein-based matrices than simply solubilising calcium or protein. PMID:26616945

  15. Iron Chelation Therapy in Myelodysplastic Syndromes

    OpenAIRE

    Giuseppe Saglio; Daniela Cilloni; Emanuela Messa

    2010-01-01

    Myelodysplastic syndromes (MDS) are a heterogeneous disorder of the hematopoietic stem cells, frequently characterized by anemia and transfusion dependency. In low-risk patients, transfusion dependency can be long lasting, leading to iron overload. Iron chelation therapy may be a therapeutic option for these patients, especially since the approval of oral iron chelators, which are easier to use and better accepted by the patients. The usefulness of iron chelation in MDS patients is still unde...

  16. Beliefs about chelation among thalassemia patients

    OpenAIRE

    Trachtenberg Felicia L; Mednick Lauren; Kwiatkowski Janet L; Neufeld Ellis J; Haines Dru; Pakbaz Zahra; Thompson Alexis A; Quinn Charles T; Grady Robert; Sobota Amy; Olivieri Nancy; Horne Robert; Yamashita Robert

    2012-01-01

    Abstract Background Understanding patients’ views about medication is crucial to maximize adherence. Thalassemia is a congenital blood disorder requiring chronic blood transfusions and daily iron chelation therapy. Methods The Beliefs in Medicine Questionnaire (BMQ) was used to assess beliefs in chelation in thalassemia patients from North America and London in the Thalassemia Longitudinal Cohort (TLC) of the Thalassemia Clinical Research Network (TCRN). Chelation adherence was based on patie...

  17. 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.

  18. Isolation of Uranyl Dicyanamide Complexes from N-Donor Ionic Liquids.

    Science.gov (United States)

    Kelley, Steven P; Rogers, Robin D

    2015-11-01

    An ionic liquid (IL) approach for soft-donor f-element chemistry has been demonstrated by the isolation of several new uranyl dicyanamide complexes through reactions of UO2(NO3)2·6H2O with dicyanamide ([N(CN)2](-))-containing ILs. The [N(CN)2](-) ions are able to rapidly substitute uranium's O-donor ligands, as evidenced by single-crystal X-ray diffraction studies on two anhydrous adducts of UO2(NO3)2 with [N(CN)2](-) ILs as well as by IR and NMR spectroscopic studies on solutions of UO2(NO3)2 in these ILs. By contrast, the slow reaction of UO2(OAc)2·2H2O with a nitrile-functionalized imidazolium dicyanamide IL in solvent and the reaction of UO2(NO3)2·6H2O with NaN(CN)2 at elevated temperature resulted in irreversible hydrolysis. The reaction of UO2SO4 with [N(CN)2](-) ions in an acidified aqueous solution resulted in the crystallization of a [UO2](2+) complex with biuret, a N(CN)2](-) hydrolysis product. [N(CN)2](-) ions in the form of ILs react rapidly with [UO2](2+) at room temperature, allowing ligand substitution with [N(CN)2](-) to out-compete the slower hydrolysis reaction, enabling the isolation of uranyl dicyanamide complexes and challenging assumptions regarding the affinity of uranium for O-donors. PMID:26479078

  19. Environmental biogeochemistry of chelating agents and recommendations for the disposal of chelated radioactive wastes

    International Nuclear Information System (INIS)

    The environmental chemistry of the three most common aminopolycarboxylic acid chelating agents, NTA (nitrilotriacetic acid), EDTA (ethylenediaminetetraacetic acid), and DTPA (diethylenetriaminepentaacetic acid) is reviewed. This review includes information on their persistence in the environment, as well as their tendency to form complexes with actinides. Data on the sorption of chelated actinides by geologic substrates and on the uptake of chelated actinides by plants are also presented. Three different technical options for disposing chelated low-level radioactive wastes are proposed: bind the solidified chelated waste in some kind of solid matrix that has a slow leach rate and bury the waste in a ''dry'' disposal site; substitute biodegradable chelating agents in the decontamination reagent for the chelating agents that are persistent in the environment; chemically or thermally degrade the chelating agents in the waste prior to disposal. The relative advantages and disadvantages of each of these options are discussed. 81 refs

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

    Science.gov (United States)

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

    2016-06-01

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

  1. 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.

  2. 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

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

    International Nuclear Information System (INIS)

    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 Å. 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

  4. 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

  5. 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

  6. Three-component system of uranyl monochloracetate - water - tri-n-butyl phosphate (IR-spectroscopic investigation)

    International Nuclear Information System (INIS)

    Phase equilibria in the three-component system of uranyl monochloracetate-water-TBP(tri-n-butyl phosphate) are analyzed from the standpoint of IR-spectroscopic data for equilibrium phases in different concentration regions obtained in the work. A number af assumptions in regard to the composition of a solvated complex of the studied salt in the organic phases is made as well as in regard to the relation of solvation and hydration processes with electron-donor properties of halogenacetate-ions

  7. 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

  8. Gas phase reactions of uranyl with α-hydroxyisobutyric acid using electrospray ionization mass spectrometry and density functional theory

    International Nuclear Information System (INIS)

    Electrospray ionization mass spectrometry (ESI-MS) technique was used to find out the type of species of uranyl with a-hydroxyisobutyric acid in positive and negative ion modes. It was found that the singly charged monomeric and doubly charged dimeric species were present in soft ionization conditions. The molecular level understanding on the structures and energetics were investigated using density functional theory based calculations. It was found that ML3, the most intense species observed in ESI-MS were energetically more favorable as compared to ML1 and ML2. (author)

  9. Synthesis of alumina nano-sheets via supercritical fluid technology with high uranyl adsorptive capacity

    International Nuclear Information System (INIS)

    Supercritical carbon dioxide is beneficial to the synthesis of superior ultrafine and uniform materials due to its high chemical stability, low viscosity, high diffusivity, and 'zero' surface tension. γ-Alumina nano-sheets were obtained by a simple hydrothermal route in the presence of supercritical carbon dioxide. XRD, FTIR, SEM, TEM and nitrogen sorption isotherm were employed to characterize the samples. Alumina as-prepared has a high specific surface area of up to 200 ± 6 m2 g-1, which presents a high adsorption capacity (4.66 ± 0.02 mg g-1) for uranyl ions from aqueous solution. Furthermore, the adsorption process was found to be endothermic and spontaneous in nature. (authors)

  10. Ion exchange separation for decontamination of centrifuge enrichment plant

    International Nuclear Information System (INIS)

    Ion exchange separation of uranyl ion (UO22+) from metal cations has been carried out by the columnar operation using ion exchange resins in 0.1 mol/dm3 sulfuric acid medium. Uranyl ion was adsorbed in an anion exchange resin and the rest metal cations, Fe(III), Al(III), Cr(III), Ni(II) and Cu(II) ions, were adsorbed in a cation exchange resin in this system. Desorption of uranyl ion and metal cations adsorbed in the resins were tested by 2 mol/dm3 sulfuric acid solution. Desorbed elements were confirmed to be precipitated by appropriate alkaline solutions. On the basis of the results obtained, a concept was made on a decontamination system for uranium-contaminated waste solution from centrifuge enrichment plant. (author)

  11. Removal of iron by chelation with molecularly imprinted supermacroporous cryogel.

    Science.gov (United States)

    Çimen, Duygu; Göktürk, Ilgım; Yılmaz, Fatma

    2016-06-01

    Iron chelation therapy can be used for the selective removal of Fe(3+) ions from spiked human plasma by ion imprinting. N-Methacryloyl-(L)-glutamic acid (MAGA) was chosen as the chelating monomer. In the first step, MAGA was complexed with the Fe(3+) ions to prepare the precomplex, and then the ion-imprinted poly(hydroxyethyl methacrylate-N-methacryloyl-(L)-glutamic acid) [PHEMAGA-Fe(3+)] cryogel column was prepared by cryo-polymerization under a semi-frozen temperature of - 12°C for 24 h. Subsequently, the template, of Fe(3+) ions was removed from the matrix by using 0.1 M EDTA solution. The values for the specific surface area of the imprinted PHEMAGA-Fe(3+) and non-imprinted PHEMAGA cryogel were 45.74 and 7.52 m(2)/g respectively, with a pore size in the range of 50-200 μm in diameter. The maximum Fe(3+) adsorption capacity was 19.8 μmol Fe(3+)/g cryogel from aqueous solutions and 12.28 μmol Fe(3+)/g cryogel from spiked human plasma. The relative selectivity coefficients of ion-imprinted cryogel for Fe(3+)/Ni(2+) and Fe(3+)/Cd(2+) were 1.6 and 4.2-fold greater than the non-imprinted matrix, respectively. It means that the PHEMAGA-Fe(3+) cryogel possesses high selectivity to Fe(3+) ions, and could be used many times without significantly decreasing the adsorption capacity. PMID:25727711

  12. Preparation and characterization of the spherical mesoporous silica (MCM-41) for recovery of uranium ions from sea water

    International Nuclear Information System (INIS)

    MCM-41 materials were synthesized using alkyl (decosane, dodecyl and eicosane) trimethyl ammonium bromide as structure directing surfactants. X ray diffraction (XRD) analysis and nitrogen adsorption measurements reveal that the pores are hexagonal with tunable textural properties through the choice of surfactant and experimental condition. MCM-41 materials suit for application as adsorbent. Studies on sorption of uranyl ion were N2--adsorption measurements, XRD and FTIR spectroscopic analysis of uranyl ion loaded MCM-41 confirm the entrapment of uranyl ion in the pores of MCM-41. (author)

  13. Importance of iron chelation therapy

    OpenAIRE

    A. Varoğlu

    2011-01-01

    It is necessary to remember that today patients have different options of chelation treatment, as desferrioxamine, deferiprone and deferasirox are available. However, a patient has to be compliant with treatments. They have always to remember that too much iron causes different complications and could be a barrier for a definitive cure from thalassemia. 由于出现了去铁胺、去铁酮和去铁斯若等药物,病人现在可以选择不同的螯合治疗方式。 然而,病人必须适应这几种治疗方式。 他们必须时刻记住太多的铁元素会引发多种并发症,并对地中海贫血的彻底治疗造成阻碍。...

  14. 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

  15. Temperature effect on uranium retention onto Zr{sub 2}O(PO{sub 4}){sub 2} surface; Effet de la temperature sur les mecanismes d'interaction entre l'ion uranyle et l'oxophosphate de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Almazan Torres, M.G

    2007-03-15

    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(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: (ZrOH){sub 2}UO{sub 2}{sup 2+} and (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 (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 (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 associated to the retention processes. (author)

  16. 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.

  17. Phase equilibria in the ternary uranyl trichloroacetate -water - methylisobutylketone system at 25 deg C

    International Nuclear Information System (INIS)

    Results of investigation into mutual solubility within uranyl trichloroacetate - water - methylisobutylketone (MIBK) ternary system under 25 ged C, are presented. The obtained phase diagram is considered from the point of available data on uranyl nitrate - water - organic solvents systems including MIBK, as well as, on similar systems with uranyl trichloroacetonate. Occurrences of anion effects at extraction based on hydrate-solvate mechanism result mainly from the properties of extractants

  18. Uranyl sorption by smectites: spectroscopic assessment of thermodynamic modeling.

    Science.gov (United States)

    Chisholm-Brause, C J; Berg, J M; Little, K M; Matzner, R A; Morris, D E

    2004-09-15

    Batch sorption experiments and thermodynamic modeling of the interaction of UO2(2+) and its hydrolysis products with two smectitic clay minerals, the reference material SWy-1 [McKinley et al., Clays Clay Miner. 43 (1995) 586] and the soil isolate LK-1 [Turner et al., Geochim. Cosmochim. Acta 30 (1996) 3399], have established a conceptual framework for uranyl/smectite surface complexation based on general reactions between aqueous uranyl species and the reactive sites on the mineral surfaces. In this report, we have formulated and spectroscopically tested a set of hypotheses based on this conceptual framework using samples prepared under similar or identical conditions to evaluate the agreement between surface complexation/speciation as enumerated by spectroscopic characterization and that elaborated by the surface complexation model. Both steady-state and time-resolved optical emission spectral data are presented for uranyl on both smectite minerals as well as on the analogue phases SiO2 and Al(OH)3 spanning the pH range from approximately 4 to 8 and the background electrolyte concentrations from approximately 0.001 to 0.1 M. The spectral data enable the explicit identification of an outer-sphere exchange-site population of the hydrated cation [UO2(OH2)5(2+) ] in SWy-1. Spectral data also clearly establish the existence of inner-sphere surface complexes on the analogue phases and on the amphoteric clay crystallite edge sites [aluminol (>Al-OH) and silanol (>Si-OH)]. Based on the spectral characteristics of these uranyl edge-site populations, it is possible to readily infer for the SiO2, Al(OH)3, and SWy-1 samples the evolution in surface speciation with increasing pH to more hydrolyzed uranyl-surface complexes consistent with the conceptual model. The spectral domain characteristics of the edge-site populations on LK-1 with increasing pH suggest that there is no change in the hydrolysis of the uranyl-surface species. However, emission lifetime data are interpreted

  19. Evaluation of uranyl nitrate crystallization for spent nuclear fuel separations

    International Nuclear Information System (INIS)

    Previous work in Germany and Japan has indicated that crystallization of uranyl nitrate at low temperatures from nitric acid solution could be a useful process for removing most of the uranium from spent LWR fuel after the fuel is dissolved in nitric acid. The crystallization process potentially could reduce the cost of LWR fuel partitioning because it provides a selective and compact process for removing most of the uranium which is about 96% of the LWR spent fuel mass. Subsequent separation processes would only need to handle the smaller volume of remaining actinides and the fission products. We are evaluating an approach to separating uranyl nitrate that uses a continuous adiabatic reduced-pressure crystallizer to concentrate and cool a nitric acid solution from dissolution of spent fuel. Initial work to define the process flowsheet and obtain data on optimum crystallization conditions and the purity of the uranium product will be presented. (authors)

  20. 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)

  1. In vitro dissolution of uranyl acetate using different methods

    International Nuclear Information System (INIS)

    The dissolution rate of a material in the lung is an important parameter in evaluating the risk to humans following accidental inhalation of a substance and is also a parameter that may be useful in characterizing particles for nuclear forensics analysis. Conventional methods of measuring dissolution rates in vitro involve exposing the material or particles to a solvent, such as water, saline, or solutions that simulate lung fluid, and measuring the fraction of material that dissolves with time. A new device for measuring dissolution rates for small samples, especially individual particles, was evaluated that incorporates a regenerated cellulose dialysis membrane fixed to the bottom of a small, 2 mL plastic cup that fits into the top of a 50 mL plastic centrifuge tube. The cup is easily transferred among a series of tubes containing solvent to measure rate of dissolution. The dialysis membrane has a diffusion rating of 20 kDa molecular weight cut off which greatly exceeds the size of the dissolved uranium molecule. The performance of the dialysis cup device was evaluated by measuring the dissolution rate of uranyl acetate in distilled water, phosphate buffered saline (PBS), and simulated lung fluid (SLF). These results were compared to the dissolution rate measured using the traditional filter sandwich method in which a sample is sealed between two hydrophilic membranes. Although the majority of uranyl acetate dissolved in SLF within 30 min using the filter sandwich method, most of the uranyl acetate was undissolved in PBS and SLF using the dialysis membrane device. Reactions between the dissolved uranyl acetate, solvent, and the dialysis membrane likely caused the membrane to swell, shrinking the pore size, and thus reducing the transport of dissolved uranium across the membrane. Use of the dialysis cup device for evaluating dissolution rates for uranium-bearing materials in solvents containing a high concentration of salts is therefore not recommended. (author)

  2. Tritium gettering from air with hydrogen uranyl phosphate

    International Nuclear Information System (INIS)

    Hydrogen uranyl phosphate (HUP), a solid proton electrolyte, getters tritium gas and water vapor from air by DC electrical action. We have reduced the formation of residual tritiated water to less than 2%, and demonstrated that HUP can clean a 5.5 m3 working glove box. Data are presented to illustrate the parameters of the gettering and a model is derived. Two other tritium gettering electrolytes have been discovered. 9 refs., 5 figs., 3 tabs

  3. 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.)

  4. Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes

    International Nuclear Information System (INIS)

    Tris-carboxylate complexes of the uranyl (UO2)2+ cation with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transformion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetatouranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric -CO2 stretches of both the monodentate and bidentate acetate, CH3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate, and two bidentate benzoate ligands.

  5. Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Groenewold, G. S.; De Jong, Wibe A.; Oomens, Jos; Van Stipdonk, Michael J.

    2010-05-01

    Tris-carboxylate complexes of the uranyl [UO2]2+ cation with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transformion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetatouranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric -CO2 stretches of both the monodentate and bidentate acetate, CH3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate, and two bidentate benzoate ligands.

  6. 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)

  7. Synthesis and characterization of some new lanthanide(III) chelates with 1,4-bis-(2'-hydroxyphenylazomethine) phenylene

    International Nuclear Information System (INIS)

    The chelates formed between 1,4-bis(2'-hydroxyphenylazomethine) phenylene with La, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, and Lu ions have been investigated in solution using conductometric, potentiometric, and spectrophotometric methods. The studies revealed the formation of M2L and ML complexes. The solid chelates have been characterized by elemental and thermal analysis, molar conductance, IR, 1H NMR (for La and Lu chelates), and electronic spectra. The bonding takes place through the coordination of nitrogen in the -CH=N- group and the oxygen of the hydroxyl group by proton displacement. (author)

  8. Cation-Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Mougel, Victor; Horeglad, Pawel; Nocton, Gregory; Pecaut, Jacques; Mazzanti, Marinella [CEA, INAC, SCIB, Laboratoire de Reconnaissance Ionique et Chimie de Coordination, CEA-Grenoble, 38054 GRENOBLE, Cedex 09 (France)

    2010-07-01

    Three new cation cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO{sub 2}py{sub 5})-(KI{sub 2}py{sub 2})]{sub n} (1) with the Schiff base ligands salen{sup 2-}, acacen{sup 2-}, and salophen{sup 2-} (H{sub 2}salen N, N'-ethylene-bis(salicylidene-imine), H{sub 2}acacen=-N, N'-ethylenebis(acetylacetone-imine), H{sub 2}salophen=N, N'-phenylene-bis(salicylidene-imine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen{sup 2-} in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetra-nuclear complexes ([UO{sub 2}-(acacen)]{sub 4}[{mu}{sub 8}-]{sub 2}[K([18]C-6)(py)]{sub 2}) (3) and ([UO{sub 2}(acacen)](4)[{mu}{sub 8}-]).2[K([222])(py)] (4) ([UO{sub 2}(salophen)](4)[{mu}{sub 8}-K]{sub 2}[mu(5)-KI]{sub 2}[(K([18]C-6)]).2 [K([18]C-6)-(thf){sub 2}].2I (5), and ([UO{sub 2}(salen)(4)][{mu}{sub 8}-Rb]{sub 2}[Rb([18]C-6)]{sub 2}) (9) ([222] = [222]cryptand, py =pyridine), presenting a T-shaped cation cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetra-nuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U{sup V}O{sub 2}(salen)(py)][Cp*{sub 2}Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation cation complexes. The nature of the cation plays a key role in the preparation of stable cation cation complexes. Stable tetra-nuclear complexes form in the presence of K

  9. Synthesis and characterization of ion-imprinted resin based on carboxymethyl cellulose for selective removal of UO₂²⁺.

    Science.gov (United States)

    Monier, M; Abdel-Latif, D A

    2013-09-12

    In this work, the surface ion-imprinting technique was employed for the preparation of surface ion-imprinted chelating microspheres resin based on modified salicylaldehyde-carboxymethyl cellulose (U-CMC-SAL) in presence of uranyl ions as a template and formaldehyde as a cross-linker. Various instrumental techniques such as elemental analysis, scanning electron microscope (SEM), FTIR and X-ray diffraction spectra were utilized for full characterization of the prepared polymeric samples. The prepared resin exhibited a higher capability for selective removal of UO₂²⁺ when compared to the non-imprinted resin (N-CMC-SAL). Also, different important parameters such as pH, temperature, time and initial metal ion concentration were examined in order to evaluate the optimum condition for the adsorption process. The results indicated that pH 5 was the best for the UO₂²⁺ uptake, in addition, the adsorption was exothermic in nature, follows the second-order kinetics and the adsorption isotherm showed the best fit with Langmuir isotherm model with maximum adsorption capacity of 180 ± 1 and 97 ± 1 mg/g for both U-CMC-SAL and N-CMC-SAL respectively. Desorption and regeneration were carried out using 0.5M HNO3 solution and the results confirmed that the resin keeps about 92% of its original efficiency after five consecutive adsorption-desorption operations. PMID:23911510

  10. 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)

  11. Elution of uranyl carbonate from a strong base resin with a mixed carbonate eluant in a fluidized system. Report of investigations 1979

    International Nuclear Information System (INIS)

    The Bureau of Mines evaluated the elution of uranyl carbonate from a strong base resin with a mixed carbonate eluant in a fluidized system. The system consisted of a multiple-compartment ion-exchange (MCIX) elution column with a continuous flow of solution, except for short periods when the resin increments were withdrawn. The exchange of uranyl carbonate from the mill-loaded strong base resin with an eluant composed of 1.0 M Na2CO3 plus 1.0 M NH4HCO3 was studied. The effects of solution flow rate, aqueous-to-resin flow ratio, column diameter, compartment height, initial resin concentration, and column length were examined. The experimental data indicate that for the eluant examined, a resin residence time of 240 minutes is necessary to attain 90-percent elution efficiency. Also provided is a technique for sizing an elution MCIX column from pilot plant experimental data

  12. Flavonoids function as antioxidants: By scavenging reactive oxygen species or by chelating iron?

    Science.gov (United States)

    Wuguo, Deng; Xingwang, Fang; Jilan, Wu

    1997-09-01

    Flavonoids have been reported to exhibit strong antioxidative activity. In the present work, a systematic mechanistic study has been performed on five flavonoids (baicalin, hesperidin, naringin, quercetin and rutin) selected according to their structural characteristics. The experimental results reveal that flavonoids function as antioxidant mainly by chelating iron ions and by scavenging peroxyl radicals whereas their OH radical scavenging effect is much less important.

  13. Kinetic Studies on Forming Iso-nuclear -type Chelates of Rare Earths with p-Sulphoaminobromophosphonazo

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The kinetic behavior of forming the iso-nuclear b -type chelates of rare earth ions (RE3+) with p-sulphoaminobromophosphonazo (BPA-pSN) in ClCH2COOH-CH3COONa buffer solutions were studied by a spectrophotometric method.

  14. Chelation therapy after the Trial to Assess Chelation Therapy: results of a unique trial

    OpenAIRE

    Maria D. Avila; Escolar, Esteban; Lamas, Gervasio A.

    2014-01-01

    Purpose of review EDTA chelation therapy has been in off-label use for the treatment of atherosclerosis. We review the results of the first large-scale randomized trial of this treatment. Recent findings The trial to assess chelation therapy was a $30 million National Institutes of Health-funded study of the safety and efficacy of EDTA-based chelation infusions in 1708 post-myocardial infarction (MI) patients. The trial to assess chelation therapy demonstrated a significant (P = 0.035) 18% re...

  15. 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.)

  16. The preparation and characterization of novel human-like collagen metal chelates

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Chenhui; Sun, Yan [Shaanxi Key Laboratory of Degradable Biomedical Materials, School of Chemical Engineering Northwest University, Xi' an 710069 (China); Shaanxi R and D Center of Biomaterials and Fermentation Engineering, Xi' an 710069 (China); Wang, Yaoyu [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Xi' an 710069 (China); Luo, Yane, E-mail: luoyane@nwu.edu.cn [Shaanxi Key Laboratory of Degradable Biomedical Materials, School of Chemical Engineering Northwest University, Xi' an 710069 (China); Shaanxi R and D Center of Biomaterials and Fermentation Engineering, Xi' an 710069 (China); Fan, Daidi, E-mail: fandaidi@nwu.edu.cn [Shaanxi Key Laboratory of Degradable Biomedical Materials, School of Chemical Engineering Northwest University, Xi' an 710069 (China); Shaanxi R and D Center of Biomaterials and Fermentation Engineering, Xi' an 710069 (China)

    2013-07-01

    In order to develop the nutritional trace elements which could be absorbed and utilized effectively, protein chelates were adopted. Calcium, copper and manganese were considered based on their physiological functions, and the new chelates of HLC-Ca, HLC-Cu and HLC-Mn were formed in MOPS or MES buffer and purified by gel chromatography, and then freeze-dried. And they were detected and analyzed by atomic absorption spectrophotometry, ultraviolet–visible absorption (UV–vis) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, fluorescence quenching method, circular dichroism (CD) and differential scanning calorimetry (DSC). The results showed that some chemical reactions happened between HLC and the three metal ions to form new chemical compounds. The thermodynamic parameters, ∆H, ∆G and ∆S, showed that the chelation process between HLC and metal ions was performed spontaneously. Fluorescence quenching spectra of HLC indicated that the quenching mechanism was static in nature. According to the data of DSC, the new chelates were more stable than the free HLC. And HLC-metal complex was non-toxic to the BHK21 cell through MTT assay. - Highlights: ► HLC-Ca, HLC-Cu and HLC-Mn were new chemical compounds and different to free HLC. ► Possible sites for Ca{sup 2+}, Cu{sup 2+} and Mn{sup 2+} to bind with HLC were presented. ► The chelation process between HLC and metal ions was performed spontaneously. ► The thermodynamic stability of the new chelates was higher than that of free HLC.

  17. The preparation and characterization of novel human-like collagen metal chelates

    International Nuclear Information System (INIS)

    In order to develop the nutritional trace elements which could be absorbed and utilized effectively, protein chelates were adopted. Calcium, copper and manganese were considered based on their physiological functions, and the new chelates of HLC-Ca, HLC-Cu and HLC-Mn were formed in MOPS or MES buffer and purified by gel chromatography, and then freeze-dried. And they were detected and analyzed by atomic absorption spectrophotometry, ultraviolet–visible absorption (UV–vis) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, fluorescence quenching method, circular dichroism (CD) and differential scanning calorimetry (DSC). The results showed that some chemical reactions happened between HLC and the three metal ions to form new chemical compounds. The thermodynamic parameters, ∆H, ∆G and ∆S, showed that the chelation process between HLC and metal ions was performed spontaneously. Fluorescence quenching spectra of HLC indicated that the quenching mechanism was static in nature. According to the data of DSC, the new chelates were more stable than the free HLC. And HLC-metal complex was non-toxic to the BHK21 cell through MTT assay. - Highlights: ► HLC-Ca, HLC-Cu and HLC-Mn were new chemical compounds and different to free HLC. ► Possible sites for Ca2+, Cu2+ and Mn2+ to bind with HLC were presented. ► The chelation process between HLC and metal ions was performed spontaneously. ► The thermodynamic stability of the new chelates was higher than that of free HLC

  18. 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.

  19. 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.)

  20. Current Use of Chelation in American Health Care

    OpenAIRE

    Wax, Paul M.

    2013-01-01

    The National Center for Health Statistics estimates that more than 100,000 Americans receive chelation each year, although far fewer than 1 % of these cases are managed by medical toxicologists. Unfortunately, fatalities have been reported after inappropriate chelation use. There are currently 11 FDA-approved chelators available by prescription although chelation products may also be obtained through compounding pharmacies and directly over the internet. Promotion of chelation training is pro...

  1. Complexes of quinone-functionalized chelating ligands for multiple electron/proton transfer reduction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Durfee, W.S.; Pierpont, C.G. (Univ. of Colorado, Boulder (United States))

    1993-03-03

    Quinone-functionalized chelating ligands may be used to effect sequential electron/proton transfer steps necessary for the reduction of substrate molecules coordinated to a complexed metal ion. The chelating ligand (NQ)[sub 2]en has been synthesized by condensing 2 equiv of 2-hydroxy-3-acetyl-1,4-naphthoquinone with ethylenediamine. Complexes of Cu(II) and Ni(II) have been prepared and characterized. Electrochemical properties of the complexes show that, in the fully reduced bis(hydroquinone) form, the ligand would be able to provide four electrons and protons to a coordinated substrate molecule at strongly negative potentials. 8 refs., 2 figs.

  2. Synthesis and Analytical Study of New Chelating Resin Containing Sulfadiazine Drug

    OpenAIRE

    Madher N. Abdulla

    2010-01-01

    A new chelating resin was prepared by mixing sulfadiazine drug and TMP (trimethylolphenol). It was polymerized by heating to 90 °C then it was post cured to 100 °C after that it was grinded. The chelating behavior was examined against Cu2+, Ni2+ using patch method in deferent conditions like treatment time and pH at room temperature. The resin show a good loading capacity toward Cu2+ (in treatment time = 3 h & pH=4) = 0.2174 mg ion / 100 mg resin and it show good loading capacity toward Ni2+ ...

  3. Development of a dipodal Schiff base ligand with N-imine and O-naphtholate donors: A potential chelator towards Cu(II) metal ion established through potentiometric and spectrophotometric studies

    Energy Technology Data Exchange (ETDEWEB)

    Baral, Minati, E-mail: minatib@gmail.com; Gupta, Amit [Department of Chemistry, National Institute of Technology, Kurukshetra, Haryana (India); Kanungo, B. K. [Department of Chemistry, Sant Longowal Institute of Engineering and Technology, Longowal, Punjab (India)

    2015-08-28

    A novel hydroxynaphthaldehyde derived Schiff base ligand N,N’-bis-[2-[(2-hydroxy-1-naphthyl)methyleneamino]ethyl]propanediamide (DOTA2HNAP) containing nitrogen and oxygen donor atoms has been developed. The lowest energy molecular structure of DOTA2HNAP and its complexes with Cu (II) metal ion were examined by molecular mechanics using MM+ force which later was re-optimized by semi-empirical method. The theoretical IR and UV spectra of the ligand were obtained using semi empirical/ZINDO/PM3 and were compared with the experimental ones. The coordinating ability of DOTA2HNAP with H{sup +} and Cu(II) ions was investigated in 1:99 (DMSO: water) binary solvent mixture at 25±1°C by potentiometric and spectrophotometric method. The electronic spectra of the ligand show three distinct peaks (253nm, 320nm and 360nm) implicating existence of the Schiff base in quinone form that was well supported by theoretical spectral studies. Out of various complex species forming in solution, all the metal ions show higher stability of complexes when in 1:1 metal-ligand stoichiometry, binding through two N-imine and two O-naphtholate groups.

  4. Development of a dipodal Schiff base ligand with N-imine and O-naphtholate donors: A potential chelator towards Cu(II) metal ion established through potentiometric and spectrophotometric studies

    International Nuclear Information System (INIS)

    A novel hydroxynaphthaldehyde derived Schiff base ligand N,N’-bis-[2-[(2-hydroxy-1-naphthyl)methyleneamino]ethyl]propanediamide (DOTA2HNAP) containing nitrogen and oxygen donor atoms has been developed. The lowest energy molecular structure of DOTA2HNAP and its complexes with Cu (II) metal ion were examined by molecular mechanics using MM+ force which later was re-optimized by semi-empirical method. The theoretical IR and UV spectra of the ligand were obtained using semi empirical/ZINDO/PM3 and were compared with the experimental ones. The coordinating ability of DOTA2HNAP with H+ and Cu(II) ions was investigated in 1:99 (DMSO: water) binary solvent mixture at 25±1°C by potentiometric and spectrophotometric method. The electronic spectra of the ligand show three distinct peaks (253nm, 320nm and 360nm) implicating existence of the Schiff base in quinone form that was well supported by theoretical spectral studies. Out of various complex species forming in solution, all the metal ions show higher stability of complexes when in 1:1 metal-ligand stoichiometry, binding through two N-imine and two O-naphtholate groups

  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. 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)

  7. Two uranyl-organic frameworks with pyridinecarboxylate ligands. A novel hetero-metallic uranyl-copper(II) complex with a cation-cation interaction

    International Nuclear Information System (INIS)

    Reaction of uranyl nitrate with pyridine-2-carboxylic acid (HL1) under hydrothermal conditions gives the complex [(UO2)3(L1)4(NO3)2], 1, which differs from the previously reported molecular complex, obtained at room temperature, by the absence of water, coordinated and free, and the extended carboxylate bridging. Although the tri-metallic basic unit is similar in both cases, 1 crystallizes as a two-dimensional assembly. A hetero-metallic complex results from the reaction of uranyl nitrate and copper(II) trifluoromethanesulfonate with nicotinic acid (pyridine-3-carboxylic acid, HL2), [UO2Cu(L2)2(NO3)2], 2, in which copper nicotinate two-dimensional subunits are bridged by uranyl nitrate groups to give a three-dimensional framework. The copper atom environment geometry is elongated octahedral. with one of the axial donors being a uranyl oxo group (cation-cation interaction). (author)

  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. Solution thermodynamic evaluation of hydroxypyridinonate chelators 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO) for UO{sub 2}(VI) and Th(IV) decorporation

    Energy Technology Data Exchange (ETDEWEB)

    Sturzbecher-Hoehne, M.; Deblonde, G.J.P.; Abergel, R.J. [Lawrence Berkeley National Laboratory, CA (United States). Chemical Sciences Div.

    2013-08-01

    Solution thermodynamic studies were performed to characterize the coordination of U(VI) and Th(IV) by the multidentate hydroxypyridinonate chelating agents 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO). Species distribution and conditional stability pM profiles were calculated based on the determined formation constants, showing that both ligands form extremely stable uranyl and thorium complexes in solution. At physiological pH, the formation of 1:1 ligand:uranyl complexes is favored for both ligands, while a 2:1 ligand:thorium complex is predominant with the tetradentate 5-LIO(Me-3,2-HOPO). Comparisons with functionally similar bidentate ligands as well as with the common actinide chelator diethylenetriamine pentaacetic acid emphasized the superior affinity for U(VI) and Th(IV) of both experimental compounds over a wide pH range. These analytical results corroborate the in vivo chelation efficacy of 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO) and validate their selection for further development as therapeutic actinide decorporation agents. (orig.)

  10. Crystal structure of an eight-coordinate terbium(III) ion chelated by N,N′-bis(2-hydroxybenzyl)-N,N′-bis(pyridin-2-ylmethyl)ethylenediamine (bbpen2−) and nitrate

    OpenAIRE

    Thaiane Gregório; André Luis Rüdiger; Nunes, Giovana G.; Soares, Jaísa F.; Hughes, David L.

    2015-01-01

    The reaction of terbium(III) nitrate pentahydrate in acetonitrile with N,N′-bis(2-hydroxybenzyl)-N,N′-bis(pyridin-2-ylmethyl)ethylenediamine (H2bbpen), previously deprotonated with triethylamine, produced the mononuclear compound [N,N′-bis(2-oxidobenzyl-κO)-N,N′-bis(pyridin-2-ylmethyl-κN)ethylenediamine-κ2N,N′](nitrato-κ2O,O′)terbium(III), [Tb(C28H28N4O2)(NO3)]. The molecule lies on a twofold rotation axis and the TbIII ion is eight-coordinate with a slightly distorted dodecahedral coordinati...

  11. Mineral replacement reactions in naturally occurring hydrated uranyl phosphates from the Tarabau deposit: Examples in the Cu–Ba uranyl phosphate system

    OpenAIRE

    Pinto, André Filipe Jorge; Conçalves, Mário A.; Praceres, Cátia; Astilleros García-Monge, José Manuel; Batista, Maria Joao

    2012-01-01

    Uranyl phosphates are a mineral group which include a wide range of different species, each containing specific cations within the hydrated interlayer, and often display a geochemical/mineralogical relationship with Fe(III) oxy-hydroxides. The environmental relevance of these U-phases arises from their low solubility at most surface and groundwater conditions, where they can ultimately control aqueous U levels. In the present work, samples of naturally occurring uranyl phosphates ...

  12. Mixed Intramolecular Hydrogen Bonding in Dihydroxythiophene-based Units and Boron and Technetium Chelation

    International Nuclear Information System (INIS)

    Three novel potential metal ion chelating units have been synthesized and characterized: 5-hexylcarbamoyl- 3,4-dihydroxythiophene-2-carboxylic acid methyl ester (5), 3-benzyloxy-4-hydroxythiophene-2,5-dicarboxylic acid bis-hexylamide (6), and 3,4-dihydroxythiophene-2,5-dicarboxylic acid bis-hexylamide (7). The crystal structure of 6 was obtained and suggests the presence of three distinct intramolecular hydrogen bonds, namely [Namide-H···O] [O-H···Oamide] and [Namide-H···S]. Boron chelation with 5, 6 and 7 through the use of BF3, B(OH)3 or B(OMe)3 was probed by 1H, 11B, and 13C NMR spectroscopy. Technetium (I) chelation with 5, 6 and 7 was also studied via HPLC elutions using [99mTc(CO)3(OH2)3]+

  13. REVIEW ARTICLE:Future of Lead Chelation – Distribution and Treatment

    Directory of Open Access Journals (Sweden)

    Venkatesh Thuppil

    2012-01-01

    Full Text Available Lead is the major environmental toxin resulting in the ill health and deleterious effect on almost all organs in the human body in a slow and effective manner. The best treatment for lead poisoning is chelation therapy which is next only to prevention. The authors describe the disruption of homeostasis of the human body by lead in various tissues like blood, bones, liver, kidneys and brain; and the ability of lead to enter the cell using calcium channels and calcium receptors like Ca++ dependant K+ ion channels, transient receptor potential channels, T-tubules, calmodulin receptors, inositol trisphosphate receptors and ryanodine receptors. We report a few novel chelating agents like ionophores, decadentate ligands, picolinate ligands, octadentate ligand, allicin, thiamine, that show good potential for being used in chelation therapy. Future of leadpoisoning is a challenge to all and it needs to be meticulously studies to have an economic and health approach.

  14. Existence, characterization and decomposition of uranyl difluoride hydrates

    International Nuclear Information System (INIS)

    The heart of a pressurized water nuclear reactor is composed of assemblies of fuel rods of principally uranium dioxide powder. The 'pyro-hydrolysis process' is currently a preferred route for the preparation of UO2 from enriched uranyl hexafluoride UF6. In this technology, the reaction is carried out under flow of dihydrogen (for its reducing function) and in the presence of water. Between the gaseous fluoride UF6 and the ceramic UO2, uranyl difluoride, UO2F2, is the solid intermediate, that contains the oxygen, but in which uranium is not yet reduced. The study of the interactions between this intermediate and water is of academic interest but is clearly of importance to the industrial process. The aim of this work was to specify the conditions of existence of the hydrates of uranyl fluoride and the reaction mechanism leading from the hydrates to anhydrous UO2F2, precursor in the industrial reaction. The study has been performed using a combination of X-ray diffraction as a function of hygrometry, temperature or pressure and gravimetric analysis. Several hydrated phases have been characterized: two solid solutions, the compositions of which can vary respectively between UO2F2.5 H2O and UO2F2. 4 H2O and between UO2F2. 2.5 H2O and UO2F2.1.6 H2O and one hydrate of defined composition UO2F2.3.5 H2O. Thermal dehydration from the higher hydrates shows the existence of a new phase termed δ, the structure of which is similar to that of UO2F2.3.5 H2O. Hydration of the anhydrous compound under a controlled atmosphere enables us to observe this phase and confirms the strongly lamellar character of these hydrates. (authors)

  15. Copper Chelation in Alzheimer's Disease Protein

    Science.gov (United States)

    Rose, Frisco; Hodak, Miroslav; Bernholc, Jerry

    2013-03-01

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

  16. Spectroscopy and Photochemistry in Single Crystals of Uranyl Formate Monohydrate.

    Science.gov (United States)

    Cox, Jack Neal

    1982-03-01

    UO(,2)CH(OO)(,2)(.)H(,2)O, (UFM) is an orthorhombic crystal (Fdd2, C(,2v)('19)) with two uranyls per unit cell. Above 210(DEGREES)K, when uranyl is excited by visible light, a two-step reaction occurs. The primary photochemical step is. U(VI)O(,2)('++) + HCOO('-) (--->) U(V) + (HCOO(.) or CO(,2)('-)). (1). A study of UFM in the oriented solid explores one of the most basic chemical reactions--the redox reaction. High resolution, polarized absorption and excitation specta were taken on single crystals at liquid helium temperatures. Eight electronic origins are identified, each split into doublets by factor group interactions. Uranyl (a)symmetric stretch vibronic progressions (do not) preserve the factor group splittings and polarizations of their origins. The spectrum of UFM lies closer to the (omega)-(omega) limit, as opposed to Russell-Saunders, than Cs(,2)UO(,2)Cl(,4). Low site symmetry depolarizes the B-symmetry components of the origins. Below 2(DEGREES)K, where UFM exhibits non-single exponential luminescence decay, migration to traps is limited. By 20(DEGREES)K, where the curves become single exponential and drop tenfold in the value of the lifetime, emission is occurring from UFM in thermal equilibrium with a population of killer traps. Above 70(DEGREES)K, the lifetime slowly rises. It peaks at 135(DEGREES)K, and then drops steeply, falling below detectability by 210(DEGREES)K. The drop is accompanied by the onset of photoreactivity. The rise in emission is attributed either to a decrease in trapping efficiency or to a hindered migration to traps due to a thermal population of bound (DELTA)(,g) excitons. ESR studies show that a signal at g = 2.0 observed at 77(DEGREES)K is from surface radicals. Below 20(DEGREES)K, a signal near g = 2.1 is due to organic radicals in the bulk generated by the photochemical step. Studies on a single crystal resolve these signals into components that reflect the crystallographic symmetry elements. A signal near g = 3.4 is

  17. 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

  18. Intracellular reduction/activation of a disulfide switch in thiosemicarbazone iron chelators

    Science.gov (United States)

    Akam, Eman A.; Chang, Tsuhen M.; Astashkin, Andrei V.

    2014-01-01

    Iron scavengers (chelators) offer therapeutic opportunities in anticancer drug design by targeting the increased demand for iron in cancer cells as compared to normal cells. Prochelation approaches are expected to avoid systemic iron depletion as chelators are liberated under specific intracellular conditions. In the strategy described herein, a disulfide linkage is employed as a redox-directed switch within the binding unit of an antiproliferative thiosemicarbazone prochelator, which is activated for iron coordination following reduction to the thiolate chelator. In glutathione redox buffer, this reduction event occurs at physiological concentrations and half-cell potentials. Consistent with concurrent reduction and activation, higher intracellular thiol concentrations increase cell susceptibility to prochelator toxicity in cultured cancer cells. The reduction of the disulfide switch and intracellular iron chelation are confirmed in cell-based assays using calcein as a fluorescent probe for paramagnetic ions. The resulting low-spin Fe(III) complex is identified in intact Jurkat cells by EPR spectroscopy measurements, which also document a decreased concentration of active ribonucleotide reductase following exposure to the prochelator. Cell viability and fluorescence-based assays show that the iron complex presents low cytotoxicity and does not participate in intracellular redox chemistry, indicating that this antiproliferative chelation strategy does not rely on the generation of reactive oxygen species. PMID:25100578

  19. Intracellular reduction/activation of a disulfide switch in thiosemicarbazone iron chelators.

    Science.gov (United States)

    Akam, Eman A; Chang, Tsuhen M; Astashkin, Andrei V; Tomat, Elisa

    2014-10-01

    Iron scavengers (chelators) offer therapeutic opportunities in anticancer drug design by targeting the increased demand for iron in cancer cells as compared to normal cells. Prochelation approaches are expected to avoid systemic iron depletion as chelators are liberated under specific intracellular conditions. In the strategy described herein, a disulfide linkage is employed as a redox-directed switch within the binding unit of an antiproliferative thiosemicarbazone prochelator, which is activated for iron coordination following reduction to the thiolate chelator. In glutathione redox buffer, this reduction event occurs at physiological concentrations and half-cell potentials. Consistent with concurrent reduction and activation, higher intracellular thiol concentrations increase cell susceptibility to prochelator toxicity in cultured cancer cells. The reduction of the disulfide switch and intracellular iron chelation are confirmed in cell-based assays using calcein as a fluorescent probe for paramagnetic ions. The resulting low-spin Fe(III) complex is identified in intact Jurkat cells by EPR spectroscopy measurements, which also document a decreased concentration of active ribonucleotide reductase following exposure to the prochelator. Cell viability and fluorescence-based assays show that the iron complex presents low cytotoxicity and does not participate in intracellular redox chemistry, indicating that this antiproliferative chelation strategy does not rely on the generation of reactive oxygen species. PMID:25100578

  20. Chelating Tendencies of Bioactive Aminophosphonates

    OpenAIRE

    Kiss, Tamas; Lázár, István; Kafarski, Pawel

    1994-01-01

    The metal-binding abilities of a wide variety of bioactive aminophosphonates, from the simple aminoethanephosphonic acids to the rather large macrocyclic polyaza derivatives, are discussed with special emphasis on a comparison of the analogous carboxylic acid and phosphonic acid systems. Examples are given of the biological importance of metal ion – aminophosphonate interactions in living systems, and also of their actual and potential applicability in medicine.