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Sample records for perrhenates

  1. Dimeric uranyl complexes with bridging perrhenates.

    PubMed

    John, Gordon H; May, Iain; Sarsfield, Mark J; Collison, David; Helliwell, Madeleine

    2007-04-28

    The reaction between [UO2(ReO4)2.H(2)O] and two equivalents of either tri-n-butyl phosphine oxide (TBPO) or tri-iso-butyl phosphate (TiBP) results in the formation of [UO2(mu2-ReO4)(ReO4)(TBPO)2]2 (1) and [UO2(mu2-ReO4)(ReO4)(TiBP)2]2 (2) respectively. Both complexes crystallise as two structurally similar centrosymmetric dimers, the cores containing two uranyl moieties linked by bridging perrhenates. Two P=O donor ligands and one monodenatate perrhenate complete the pentagonal bipyramidal coordination sphere at each metal centre. Both complexes have also been characterised in the solid state by vibrational and absorption spectroscopy. Solution spectroscopic characterisation indicates that both perrhenate and phosphine oxide (1) or phosphate (2) remain coordinated, although it is not possible to state conclusively that the dimeric species remain intact. A low resolution structural study of a minor product from the reaction that yielded revealed a monomeric complex with only monodentate perrhenate coordination, [UO2(ReO4)2(H2O)(TiBP)2] (2'). These results represent the first structural evidence for the bridging coordination mode of perrhenate on coordination to an actinide and yields further insight into the possible solvent phase pertechnetate complexes that may exist in PUREX process phosphate rich solvent.

  2. Structure and Thermochemistry of Perrhenate Sodalite and Mixed Guest Perrhenate/Pertechnetate Sodalite.

    PubMed

    Pierce, Eric M; Lilova, Kristina; Missimer, David M; Lukens, Wayne W; Wu, Lili; Fitts, Jeffrey; Rawn, Claudia; Huq, Ashfia; Leonard, Donovan N; Eskelsen, Jeremy R; F Woodfield, Brian; Jantzen, Carol M; Navrotsky, Alexandra

    2017-01-17

    Treatment and immobilization of technetium-99 ((99)Tc) contained in reprocessed nuclear waste and present in contaminated subsurface systems represents a major environmental challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and meso-porous crystalline solids, specifically sodalite. We synthesized and characterized the structure of perrhenate sodalite, Na8[AlSiO4]6(ReO4)2, and the structure of a mixed guest perrhenate/pertechnetate sodalite, Na8[AlSiO4]6(ReO4)2-x(TcO4)x. Perrhenate was used as a chemical analogue for pertechnetate. Bulk analyses of each solid confirm a cubic sodalite-type structure (P4̅3n, No. 218 space group) with rhenium and technetium in the 7+ oxidation state. High-resolution nanometer scale characterization measurements provide first-of-a-kind evidence that the ReO4(-) anions are distributed in a periodic array in the sample, nanoscale clustering is not observed, and the ReO4(-) anion occupies the center of the sodalite β-cage in Na8[AlSiO4]6(ReO4)2. We also demonstrate, for the first time, that the TcO4(-) anion can be incorporated into the sodalite structure. Lastly, thermochemistry measurements for the perrhenate sodalite were used to estimate the thermochemistry of pertechnetate sodalite based on a relationship between ionic potential and the enthalpy and Gibbs free energy of formation for previously measured oxyanion-bearing feldspathoid phases. The results collected in this study suggest that micro- and mesoporous crystalline solids maybe viable candidates for the treatment and immobilization of (99)Tc present in reprocessed nuclear waste streams and contaminated subsurface environments.

  3. Structure and Thermochemistry of Perrhenate Sodalite and Mixed Guest Perrhenate/Pertechnetate Sodalite

    DOE PAGES

    Pierce, Eric M.; Lilova, Kristina; Missimer, David M.; ...

    2016-12-05

    Development of a sustainable fuel cycle, which must include closing the back-end by reprocessing and/or disposing of used nuclear fuel, is a key component of the nuclear energy renaissance. Technetium-99 ( = 293.7 keV, t1/2 = 2.1 105 years), a byproduct of 235U and 239Pu fission, comprises a significant component of radioactive waste (~5% fission yield), and its worldwide inventory has increased steadily. Treatment and immobilization of 99Tc contained in reprocessed nuclear waste represents a major challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and mesoporous crystalline solids, specifically sodalite. We synthesizedmore » and characterized the structure of perrhenate sodalite, Na8[AlSiO4]6(ReO4)2, and the structure of a guest-guest perrhenate/pertechnetate sodalite, Na8[AlSiO4]6(ReO4)2-x(TcO4)x. Perrhenate was used as a chemical analogue for pertechnetate. Bulk analyses of each solid confirm a cubic sodalite-type structure ( 43 , No. 218 space group) with rhenium and technetium in the 7+ oxidation state. High-resolution nanometer scale characterization measurements provide first-of-a-kind evidence that the ReO4- anions are distributed in a periodic array in the sample, nanoscale clustering is not observed, and the ReO4- anion occupies the center of the sodalite -cage in Na8[AlSiO4]6(ReO4)2. We also demonstrate, for the first time, that the TcO4- anion can be incorporated into the sodalite structure. Lastly, thermochemistry measurements for the perrhenate sodalite were used to estimate the thermochemistry of pertechnetate sodalite based on a relationship between ionic potential and the enthalpy and Gibbs free energy of formation for previously measured oxyanion-bearing feldspathoid phases. These results not only provide the data required to evaluate the long-term chemical stability of pertechnetate sodalities, but also an approach to estimate thermodynamic constants for a range of micro

  4. Structure and Thermochemistry of Perrhenate Sodalite and Mixed Guest Perrhenate/Pertechnetate Sodalite

    SciTech Connect

    Pierce, Eric M.; Lilova, Kristina; Missimer, David M.; Lukens, Wayne W.; Wu, Lili; Fitts, Jeffrey P.; Rawn, Claudia; Huq, Ashfia; Leonard, Donovan N.; Eskelsen, Jeremy R.; Jantzen, Carol M.; Navrotsky, Alexandra

    2016-12-05

    Development of a sustainable fuel cycle, which must include closing the back-end by reprocessing and/or disposing of used nuclear fuel, is a key component of the nuclear energy renaissance. Technetium-99 ( = 293.7 keV, t1/2 = 2.1 105 years), a byproduct of 235U and 239Pu fission, comprises a significant component of radioactive waste (~5% fission yield), and its worldwide inventory has increased steadily. Treatment and immobilization of 99Tc contained in reprocessed nuclear waste represents a major challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and mesoporous crystalline solids, specifically sodalite. We synthesized and characterized the structure of perrhenate sodalite, Na8[AlSiO4]6(ReO4)2, and the structure of a guest-guest perrhenate/pertechnetate sodalite, Na8[AlSiO4]6(ReO4)2-x(TcO4)x. Perrhenate was used as a chemical analogue for pertechnetate. Bulk analyses of each solid confirm a cubic sodalite-type structure ( 43 , No. 218 space group) with rhenium and technetium in the 7+ oxidation state. High-resolution nanometer scale characterization measurements provide first-of-a-kind evidence that the ReO4- anions are distributed in a periodic array in the sample, nanoscale clustering is not observed, and the ReO4- anion occupies the center of the sodalite -cage in Na8[AlSiO4]6(ReO4)2. We also demonstrate, for the first time, that the TcO4- anion can be incorporated into the sodalite structure. Lastly, thermochemistry measurements for the perrhenate sodalite were used to estimate the thermochemistry of pertechnetate sodalite based on a relationship between ionic potential and the enthalpy and Gibbs free energy of formation for previously measured oxyanion-bearing feldspathoid phases. These results not only provide the data required to evaluate the long-term chemical stability of pertechnetate sodalities, but also an approach to estimate thermodynamic constants for a range of micro- and

  5. Competitive incorporation of perrhenate and nitrate into sodalite.

    PubMed

    Dickson, Johnbull O; Harsh, James B; Flury, Markus; Lukens, Wayne W; Pierce, Eric M

    2014-11-04

    Nuclear waste storage tanks at the Hanford site in southeastern Washington have released highly alkaline solutions, containing radioactive and other contaminants, into subsurface sediments. When this waste reacts with subsurface sediments, feldspathoid minerals (sodalite, cancrinite) can form, sequestering pertechnetate (99TcO4-) and other ions. This study investigates the potential for incorporation of perrhenate (ReO4-), a chemical surrogate for 99TcO4-, into mixed perrhenate/nitrate (ReO4-/NO3-) sodalite. Mixed-anion sodalites were hydrothermally synthesized in the laboratory from zeolite A in sodium hydroxide, nitrate, and perrhenate solutions at 90 °C for 24 h. The resulting solids were characterized by bulk chemical analysis, X-ray diffraction, scanning electron microscopy, and X-ray absorption near edge structure spectroscopy (XANES) to determine the products' chemical composition, structure, morphology, and Re oxidation state. The XANES data indicated that nearly all rhenium (Re) was incorporated as Re(VII)O4-. The nonlinear increase of the unit cell parameter with ReO4-/NO3- ratios suggests formation of two separate sodalite phases in lieu of a mixed-anion sodalite. The results reveal that the sodalite cage is highly selective toward NO3- over ReO4-. Calculated enthalpy and Gibbs free energy of formation at 298 K for NO3- and ReO4-sodalite suggest that NO3- incorporation into the cage is favored over the incorporation of the larger ReO4-, due to the smaller ionic radius of NO3-. Based on these results, it is expected that NO3-, which is present at significantly higher concentrations in alkaline waste solutions than 99TcO4-, will be strongly preferred for incorporation into the sodalite cage.

  6. Competitive Incorporation of Perrhenate and Nitrate into Sodalite

    DOE PAGES

    Dickson, Johnbull O.; Harsh, James B.; Flury, Markus; ...

    2014-10-03

    Nuclear waste storage tanks at the Hanford site in southeastern Washington have released highly alkaline solutions, containing radioactive and other contaminants, into subsurface sediments. When this waste reacts with subsurface sediments, feldspathoid minerals (sodalite, cancrinite) can form, sequestering pertechnetate (99TcO4–) and other ions. This study investigates the potential for incorporation of perrhenate (ReO4–), a chemical surrogate for 99TcO4–, into mixed perrhenate/nitrate (ReO4–/NO3–) sodalite. Mixed-anion sodalites were hydrothermally synthesized in the laboratory from zeolite A in sodium hydroxide, nitrate, and perrhenate solutions at 90 °C for 24 h. The resulting solids were characterized by bulk chemical analysis, X-ray diffraction, scanning electronmore » microscopy, and X-ray absorption near edge structure spectroscopy (XANES) to determine the products’ chemical composition, structure, morphology, and Re oxidation state. The XANES data indicated that nearly all rhenium (Re) was incorporated as Re(VII)O4–. The nonlinear increase of the unit cell parameter with ReO4–/NO3– ratios suggests formation of two separate sodalite phases in lieu of a mixed-anion sodalite. The results reveal that the sodalite cage is highly selective toward NO3– over ReO4–. Calculated enthalpy and Gibbs free energy of formation at 298 K for NO3- and ReO4-sodalite suggest that NO3– incorporation into the cage is favored over the incorporation of the larger ReO4–, due to the smaller ionic radius of NO3–. In conclusion, based on these results, it is expected that NO3–, which is present at significantly higher concentrations in alkaline waste solutions than 99TcO4–, will be strongly preferred for incorporation into the sodalite cage.« less

  7. Hydrolysis of cellulose catalyzed by quaternary ammonium perrhenates in 1-allyl-3-methylimidazolium chloride.

    PubMed

    Wang, Jingyun; Zhou, Mingdong; Yuan, Yuguo; Zhang, Quan; Fang, Xiangchen; Zang, Shuliang

    2015-12-01

    Quaternary ammonium perrhenates were applied as catalyst to promote the hydrolysis of cellulose in 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The quaternary ammonium perrhenates displayed good catalytic performance for cellulose hydrolysis. Water was also proven to be effective to promote cellulose hydrolysis. Accordingly, 97% of total reduced sugar (TRS) and 42% of glucose yields could be obtained under the condition of using 5mol% of tetramethyl ammonium perrhenate as catalyst, 70μL of water, ca. 0.6mmol of microcrystalline cellulose (MCC) and 2.0g of [Amim]Cl as solvent under microwave irradiation for 30min at 150°C (optimal conditions). The influence of quaternary ammonium cation on the efficiency of cellulose hydrolysis was examined based on different cation structures of perrhenates. The mechanism on perrhenate catalyzed cellulose hydrolysis is also discussed, whereas hydrogen bonding between ReO4 anion and hydroxyl groups of cellulose is assumed to be the key step for depolymerization of cellulose.

  8. Evaluation of Perrhenate Spectrophotometric Methods in Bicarbonate and Nitrate Media.

    PubMed

    Lenell, Brian A; Arai, Yuji

    2016-04-01

    2-pyridyl thiourea and methyl-2-pyridyl ketoxime based perrhenate, Re(VII), UV-vis spectrophotometric methods were evaluated in nitrate and bicarbonate solutions ranging from 0.001 M to 0.5 M. Standard curves at [Re]=2.5-50 mg L(-1) for the Re(IV)-thiourea and the Re ketoxime complexes were constructed at 405 nm and 490 nm, respectively. Detection of limits for N-(2-pyridyl) thiourea and methyl-2-pyridyl ketoxime methods in ultrapure water are 3.06 mg/L and 4.03 mg/L, respectively. Influences of NaHCO3 and NaNO3 concentration on absorbance spectra, absorptivity, and linearity were documented. For both methods, samples in ultrapure water and NaHCO3 have an R(2) value>0.99, indicating strong linear relationships. Statistical analysis supports that NaHCO3 does not affect linearity between standards for either method. NaNO3 causes major interference with the ketoxime method above 0.001 M NaNO3. Data provides information for practical use of Re spectrophotometric methods in environmental media that is high in bicarbonate and nitrate.

  9. Perrhenate extraction studies by Cyphos 101-IL; screening for implementation in technetium removal

    SciTech Connect

    Mark D Ogden; Sarah E. Pepper

    2013-10-01

    The solvent extraction of rhenium (VII) from chloride solutions by Cyphos 101-IL in toluene has been studied. Distribution values for the extraction of perrhenate are extremely high leading to almost quantitative extraction. From slope analysis, an anion exchange extraction mechanism is proposed, with formation of a ReO4 association with one Cyphos IL-101 cation. The extraction kinetics are fast, with complete equilibration occurring within 60 s. Under identical conditions, distribution coefficients for Cyphos 101-IL are greater than for Aliquat-336. Extraction of the perrhenate anion does not seem to be negatively impacted by common environmental contaminants including iron, sulphate and nitrate at the pH values tested.

  10. Influence of substituents on cation-anion contacts in imidazolium perrhenates.

    PubMed

    Reich, Robert M; Cokoja, Mirza; Markovits, Iulius I E; Münchmeyer, Christian J; Kaposi, Marlene; Pöthig, Alexander; Herrmann, Wolfgang A; Kühn, Fritz E

    2015-05-14

    A series of imidazolium perrhenates with different substituents at the imidazolium ring were synthesised and characterised, including single crystal X-ray diffraction. The effect of the substitution pattern on the state of aggregation of the compounds, the charge delocalisation and the ion pairing interaction via hydrogen bonds was studied. Particularly the substitution at the C2 position of the imidazolium ring was shown to be crucial to fine-tune the ion contacts. Fluorinated substituents appear to exhibit enhanced interionic interactions. The ability to tune the degree of contacts of the perrhenate anion allows for adjusting the nucleophilicity of this anion.

  11. Bamboo (Acidosasa edulis) shoot shell biochar: Its potential isolation and mechanism to perrhenate as a chemical surrogate for pertechnetate.

    PubMed

    Hu, Hui; Jiang, Bangqiang; Wu, Huixiong; Zhang, Jubin; Chen, Xiaohui

    2016-12-01

    In this work, a biochar was prepared from bamboo (Acidosasa edulis) shoot shell through slow pyrolysis (under 300-700 °C). Characterization with various tools showed that the biochar surface was highly hydrophobic and also had more basic functional groups. Batch sorption experiments showed that the biochar had strong sorption ability to perrhenate (a chemical surrogate for pertechnetate) with maximum sorption capacity of 46.46 mg/g, which was significantly higher than commercial coconut shell activated carbon and some adsorbents reported previously. Desorption experiments showed that more than 94% of total perrhenate adsorbed could be recovered using 0.1 mol/L KOH as a desorption medium. Pearson correlation analysis showed that the recovery of perrhenate by the biochars was mainly through surface adsorption mechanisms involving both high hydrophobicity and high basic sites of biochar surface.

  12. Raman Analysis of Perrhenate and Pertechnetate in Alkali Salts and Borosilicate Glasses

    SciTech Connect

    Gassman, Paul L.; McCloy, John S.; Soderquist, Chuck Z.; Schweiger, Michael J.

    2014-01-03

    Sodium borosilicate glasses containing various concentrations of rhenium or technetium were fabricated, and their vibrational spectra studied using a Raman microscope. Spectra were interpreted with reference to new high resolution measurements of alkali pertechnetates and perrhenates NaReO4, KReO4, NaTcO4, and KTcO4. At low concentrations of ReO4- or TcO4-, glass spectra show weak peaks superimposed on a dominant spectrum of glass characteristic of silicate and borate network vibrations. At high concentrations, sharp peaks characteristic of crystal field splitting and C4h symmetry dominate the spectra of glasses, indicating alkali nearby tetrahedral Re or Tc. Often peaks indicative of both the K and Na pertechnetates/ perrhenates are evident in the Raman spectrum, with the latter being favored at high additions of the source chemical, since Na is more prevalent in the glass and ion exchange takes place. These results have significance to immobilization of nuclear waste containing radioactive 99Tc in glass for ultimate disposal.

  13. Production of High-Purity Anhydrous Nickel(II) Perrhenate for Tungsten-Based Sintered Heavy Alloys.

    PubMed

    Leszczyńska-Sejda, Katarzyna; Benke, Grzegorz; Kopyto, Dorota; Majewski, Tomasz; Drzazga, Michał

    2017-04-24

    This paper presents a method for the production of high-purity anhydrous nickel(II) perrhenate. The method comprises sorption of nickel(II) ions from aqueous nickel(II) nitrate solutions, using strongly acidic C160 cation exchange resin, and subsequent elution of sorbed nickel(II) ions using concentrated perrhenic acid solutions. After the neutralization of the resulting rhenium-nickel solutions, hydrated nickel(II) perrhenate is then separated and then dried at 160 °C to obtain the anhydrous form. The resulting compound is reduced in an atmosphere of dissociated ammonia in order to produce a Re-Ni alloy powder. This study provides information on the selected properties of the resulting Re-Ni powder. This powder was used as a starting material for the production of 77W-20Re-3Ni heavy alloys. Microstructure examination results and selected properties of the produced sintered heavy alloys were compared to sintered alloys produced using elemental W, Re, and Ni powders. This study showed that the application of anhydrous nickel(II) perrhenate in the production of 77W-20Re-3Ni results in better properties of the sintered alloys compared to those made from elemental powders.

  14. Production of High-Purity Anhydrous Nickel(II) Perrhenate for Tungsten-Based Sintered Heavy Alloys

    PubMed Central

    Leszczyńska-Sejda, Katarzyna; Benke, Grzegorz; Kopyto, Dorota; Majewski, Tomasz; Drzazga, Michał

    2017-01-01

    This paper presents a method for the production of high-purity anhydrous nickel(II) perrhenate. The method comprises sorption of nickel(II) ions from aqueous nickel(II) nitrate solutions, using strongly acidic C160 cation exchange resin, and subsequent elution of sorbed nickel(II) ions using concentrated perrhenic acid solutions. After the neutralization of the resulting rhenium-nickel solutions, hydrated nickel(II) perrhenate is then separated and then dried at 160 °C to obtain the anhydrous form. The resulting compound is reduced in an atmosphere of dissociated ammonia in order to produce a Re-Ni alloy powder. This study provides information on the selected properties of the resulting Re-Ni powder. This powder was used as a starting material for the production of 77W-20Re-3Ni heavy alloys. Microstructure examination results and selected properties of the produced sintered heavy alloys were compared to sintered alloys produced using elemental W, Re, and Ni powders. This study showed that the application of anhydrous nickel(II) perrhenate in the production of 77W-20Re-3Ni results in better properties of the sintered alloys compared to those made from elemental powders. PMID:28772808

  15. Selective perrhenate recognition in pure water by halogen bonding and hydrogen bonding alpha-cyclodextrin based receptors.

    PubMed

    Cornes, Stuart P; Sambrook, Mark R; Beer, Paul D

    2017-03-20

    Alpha-cyclodextrin based anion receptors functionalised with pendant arms containing halogen and hydrogen bond donor motifs display selective association of perrhenate in aqueous media at neutral pH. NMR and ITC anion binding investigations reveal the halogen bonding receptor to be the superior host.

  16. A Hexameric Cationic Copper(II) Metallacrown as a Pertechnetate and Perrhenate Scavenger.

    PubMed

    Rodríguez-Hermida, Sabina; Lago, Ana Belén; Pino-Cuevas, Arantxa; Hagenbach, Adelheid; Cañadillas-Delgado, Laura; Carballo, Rosa; Abram, Ulrich; Vázquez-López, Ezequiel M

    2016-01-26

    Materials based on the cationic copper(II) hexanuclear 18-membered metallacrown [18-MCCuII-N(2ph)-6](6+) (2phH=2-piconyl hydrazide) and tetrafluoroborate, perchlorate, nitrate, sulfate, and perrhenate anions were prepared by an easy method in aqueous medium. Single-crystal X-ray characterization of six members of this new family of complexes showed that the anions are attached to the metallacrown by direct coordination to a copper cation or by hydrogen-bonding interaction with the center of the hexamer. The stable cationic nature of the complexes and their ability to bind different anions allows them to adsorb and immobilize environmentally relevant anions such as MO4(-) (M=Tc, Re). The MO4(-) trapping capacities suggest that these materials would be useful in the treatment of oxoanionic contaminants in water. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Zirconium-Based Metal–Organic Framework for Removal of Perrhenate from Water

    SciTech Connect

    Banerjee, Debasis; Xu, Wenqian; Nie, Zimin; Johnson, Lewis E. V.; Coghlan, Campbell; Sushko, Maria L.; Kim, Dongsang; Schweiger, Michael J.; Kruger, Albert A.; Doonan, Christian J.; Thallapally, Praveen K.

    2016-09-06

    Efficient removal of pertechnetate (TcO4-) anions from liquid waste or melter off-gas solution for alternative treatment is one of the promising options to manage 99Tc in legacy nuclear waste. Safe immobilization of 99Tc is of major importance due to its long half-life (t1/2= 2.13 × 105 yrs) and environmental mobility. Different types of inorganic and solid state ion-exchange materials such as layered double hydroxides have been shown to absorb TcO4- anions from water. However, both high capacity and selectivity have yet to be achieved in a single material. Herein, we show that a protonated version of an ultra-stable zirconium based metal-organic framework can adsorb perrhenate (ReO4-) anions, a non-radioactive sur-rogate for TcO4-, from water even in the presence of other common anions. Synchrotron based powder X-ray diffraction and molecular simulations were used to identify the position of the adsorbed ReO4- (surrogate for TcO4-) molecule within the framework.

  18. DETERMINATION OF PERRHENATE ADSORPTION KINETICS FROM HANFORD WASTE SIMULANTS USING SUPERLING 639 RESIN

    SciTech Connect

    Duffey, C.; King, W.; Hamm, L.

    2002-04-02

    This report describes the results of SuperLig{reg_sign} 639 sorption kinetics tests conducted at the Savannah River Technology Center (SRTC) in support of the Hanford River Protection Project - Waste Treatment Plant (RPP-WTP). The RPP-WTP contract was awarded to Bechtel for the design, construction, and initial operation of a plant for the treatment and vitrification of millions of gallons of radioactive waste currently stored in tanks at Hanford, WA. Part of the current treatment process involves the removal of technetium from tank supernate solutions using columns containing SuperLig{reg_sign} 639 resin. This report is part of a body of work intended to quantify and optimize the operation of the technetium removal columns with regard to various parameters (such as liquid flow rate, column aspect ratio, resin particle size, loading and elution temperature, etc.). The tests were conducted using nonradioactive simulants of the actual tank waste samples containing rhenium as a chemical surrogate for the technetium in the actual waste. Previous column tests evaluated the impacts of liquid flow rate, bed aspect ratio, solution temperature and composition upon SuperLig{reg_sign} 639 column performance (King et al., 2000, King et al., 2003). This report describes the results of kinetics tests to determine the impacts of resin particle size, solution composition, and temperature on the rate of uptake of perrhenate ions.

  19. Zirconium Based Metal-Organic Framework for Removal of Perrhenate from Water

    SciTech Connect

    Banerjee, Debasis; Xu, Wenqian; Nie, Zimin; Johnson, Lewis E. V.; Coghlan, Campbell; Sushko, Maria L.; Kim, Dongsang; Schweiger, Michael J.; Kruger, Albert A.; Doonan, Christian J.; Thallapally, Praveen K.

    2016-01-01

    Efficient removal of pertechnetate (TcO4 -) anions from liquid waste or melter off-gas solution for alternative treatment is one of the promising options to manage 99Tc in legacy nuclear waste. Safe immobilization of 99Tc is of major importance due to its long half-life (t1/2= 2.13 × 105 yrs) and environmental mobility. Different types of inorganic and solid state ion-exchange materials such as layered double hydroxides have been shown to absorb TcO4 - anions from water. However, both high capacity and selectivity have yet to be achieved in a single material. Herein, we show that a protonated version of an ultra-stable zirconium based metalorganic framework can adsorb perrhenate (ReO4 -) anions, a non-radioactive surrogate for TcO4 -, from water even in the presence of other common anions. Synchrotron based powder X-ray diffraction and molecular simulations were used to identify the position of the adsorbed ReO4 - (surrogate for TcO4 -) molecule within the framework.

  20. Perrhenate and Pertechnetate Behavior on Iron and Sulfur-Bearing Compounds

    SciTech Connect

    Anderson, B.E.; Becker, U.; Helean, K.B.; Ewing, R.C.

    2007-07-01

    Investigations of the behavior of the element {sup 99}Tc frequently use a stable isotope of rhenium as an analogue. This is based on the elements? similar radii, major oxidation states of +7 and +4, and analogous eH-pH diagrams. However, recent studies [1] have shown this analogy to be imperfect. Therefore, one goal of this study is to compare the behavior of these elements, with an emphasis on the adsorption of perrhenate and pertechnetate (the major forms of Re and Tc in natural waters) onto mineral surfaces. Quantum mechanical calculations were performed for the adsorption of these two anions onto relaxed clusters of the well-characterized sulfide galena (PbS). With these calculations, we have gained insight into differences between the anions adsorption behavior, including geometry, adsorption energies, and electronic structure. Differences between interactions on terraces and step edges, the effects of co-adsorbates such as Na{sup +} and Cl{sup -}, and chloride complexation were also explored. The influence of water was calculated using homogeneous dielectric fluids.As a complement to the calculations, batch sorption tests are in progress involving ReO{sub 4}{sup -}/TcO{sub 4}{sup -} solution in contact with Fe metal, 10% Fe-doped hydroxyapatite, goethite, hematite, magnetite, pyrite, galena, pyrrhotite, and sphalerite. (authors)

  1. Perrhenate and Pertechnetate Behavior on Iron and Sulfur-Bearing Compounds.

    SciTech Connect

    B.E. Anderson; U. Becker; K.B. Helean; R.C. Ewing

    2006-09-15

    Investigations on the behavior of the radioactive element technetium frequently use a stable isotope of rhenium as an analogue. This is justified by citing the elements similar radii and major oxidation states of +7 and +4. However, at least one study [1] has shown this analogy to be imperfect. Therefore, one goal of our study is to compare the adsorption behavior of perrhenate and pertechnetate (the major forms of Re and Tc in natural waters) on a number of different mineral surfaces. Quantum mechanical calculations were performed on the adsorption of these two anions on a series of iron oxides and sulfides. With these calculations, we gain insight into any differences between the anions adsorption behavior, including geometry, adsorption energies, and electronic structure such as density of states and orbital shapes and energies at the adsorption site. Differences between interactions on terraces and step edges, the effects of co-adsorbates such as Na{sup +} or H{sup +}, and possible reduction mechanisms are also explored. The influence of water was calculated using homogeneous dielectric fluids and explicit water molecules. As a complement to the calculations, batch sorption tests are in progress involving ReO{sub 4}{sup -}/TcO{sub 4}{sup -} solution in contact with Fe metal, 10% Fe-doped hydroxyapatite, goethite, hematite, magnetite, pyrite, galena, and sphalerite.

  2. Rhenium volatilisation as caesium perrhenate from simulated vitrified high level waste from a melter crucible

    SciTech Connect

    Taylor, T.A.; Short, R.J.; Gribble, N.R.; Roe, J.I.; Steele, C.J.

    2013-07-01

    The Waste Vitrification Plant (WVP) converts Highly Active Liquor (HAL) from spent nuclear fuel reprocessing into a stable vitrified product. Recently WVP have been experiencing accumulation of solids in their primary off gas (POG) system leading to potential blockages. Chemical analysis of the blockage material via Laser Induced Breakdown Spectroscopy (LIBS) has shown it to exclusively consist of caesium, technetium and oxygen. The solids are understood to be caesium pertechnetate (CsTcO{sub 4}), resulting from the volatilisation of caesium and technetium from the high level waste glass melt. Using rhenium as a chemical surrogate for technetium, a series of full scale experiments have been performed in order to understand the mechanism of rhenium volatilisation as caesium perrhenate (CsReO{sub 4}), and therefore technetium volatilisation as CsTcO{sub 4}. These experiments explored the factors governing volatilisation rates from the melt, potential methods of minimising the amount of volatilisation, and various strategies for mitigating the deleterious effects of the volatile material on the POG. This paper presents the results from those experiments, and discusses potential methods to minimise blockages that can be implemented on WVP, so that the frequency of the CsTcO{sub 4} blockages can be reduced or even eradicated altogether. (authors)

  3. Synthesis and structure determination of copper perrhenate, CuReO 4

    NASA Astrophysics Data System (ADS)

    Mikhailova, D.; Ehrenberg, H.; Fuess, H.

    2006-07-01

    Copper(I) perrhenate, CuReO 4, has been synthesized as a single-phase sample in sealed silica tubes at 500-800 °C, and its structure was determined for the first time by single-crystal X-ray diffraction. CuReO 4 forms a new structure type derived from the diamond-structure and crystallizes in space group I4 1cd with lattice parameters a=13.6965(5) Å and c=7.7729(5) Å, Z=16 (rotation method data acquisition using ω and ϕ scans, R1=0.0191, w R2=0.0403). Cu and Re atoms are tetrahedrally coordinated by O atoms, these tetrahedra are corner-shared, forming spirally twisted rings of 4-6-8-10- MeO 4 like Si xO y-rings in some silicon dioxide modifications or aluminosilicates. According to low-temperature powder X-ray diffraction and differential thermal analysis, CuReO 4 shows no phase transition down to 80 K and up to its melting point, 703 K.

  4. Synthesis of α,β-Unsaturated Acylsilanes via Perrhenate-Catalyzed Meyer-Schuster Rearrangement of 1-Silylalkyn-3-ols.

    PubMed

    Nikolaev, Andrei; Orellana, Arturo

    2015-12-04

    We report the synthesis of α,β-unsaturated acylsilanes via the perrhenate-catalyzed Meyer-Schuster rearrangement of 1-silylalkyn-3-ols. Propargylic alcohols derived from TES-acetylene and substituted benzaldehydes can be converted to acylsilanes using a combination of p-TSA·H(2)O and n-Bu(4)N·ReO(4), or Ph(3)SiOReO(3) in good yields. Some propargylic alcohols derived from ketones, as well as aliphatic and unsaturated aldehydes, can also be converted to acylsilanes; however, they were often prone to side reactions.

  5. Perrhenate uptake by iron and aluminum oxyhydroxides: an analogue for pertechnetate incorporation in Hanford waste tank sludges.

    PubMed

    Wakoff, Bradley; Nagy, Kathryn L

    2004-03-15

    Perrhenate (ReO4-), a nonradioactive surrogate for pertechnetate (99TcO4-), was partitioned during precipitation and aging of iron and aluminum oxyhydroxide solids from aqueous simulants of high-level nuclear waste stored at Hanford, WA. Neutralization of acidic metal nitrate solutions (Al/Fe mole ratio 0.25 and 13.5; 40 ppm Re) to a final pH > 13, followed by aging at 90 degrees C for up to 18 weeks, resulted in substantial amounts of reversibly sorbed Re (approximately 1-10 ppm). Irreversibly sorbed Re increased in the Fe-dominated system with aging, reaching a final value of approximately 83 ppb after 168 h, in a mixture of hematite with minor goethite. Irreversibly sorbed Re in the Al-dominated system generally decreased with time to approximately 30 ppb after 18 weeks in solids dominated by boehmite. Increasing the total amount of Re to 1000 ppm increased the extent of irreversible sorption. The presence of 100 ppm Si prevented transformation of and irreversible Re uptake by ferrihydrite in Fe-dominated systems. In Al-dominated systems, 200 ppm Ni prevented hematite formation but did not affect perrhenate uptake. Results suggest that 5% of the 99Tc inventory in the Hanford waste tanks may be associated with the sludges, and approximately 0.5% incorporated into the solids under oxidizing conditions.

  6. Perrhenate incorporation into binary mixed sodalites: The role of anion size and implications for technetium-99 sequestration

    DOE PAGES

    Dickson, Johnbull O.; Harsh, James B.; Lukens, Wayne W.; ...

    2014-12-20

    Perrhenate (ReO4-), as a TcO4- analogue, was incorporated into mixed-anion sodalites from binary solutions containing ReO4- and a competing anion Xn- (Cl-, CO32-, SO42-, MnO4-, or WO42-). For this study, our objective was to determine the extent of solid solution formation and the dependence of competing ion selectivity on ion size. Using equivalent aqueous concentrations of the anions (ReO4-/Xn- molar ratio = 1:1), we synthesized mixed-anion sodalites from zeolite and NaOH at 90 °C for 96 h. The resulting solids were characterized by bulk chemical analysis, powder X-ray diffraction, scanning electron microscopy, and X-ray absorption near edge structure (XANES) spectroscopymore » to determine crystal structure, chemical composition, morphology, and rhenium (Re) oxidation state. Rhenium in the solid phase occurred predominately as Re(VII)O4- in the sodalites, which have a primitive cubic pattern in the space group P43n. The refined unit-cell parameters of the mixed sodalites ranged from 8.88 to 9.15 Å and showed a linear dependence on the size and mole fraction of the incorporated anion(s). The ReO4- selectivity, represented by its distribution coefficient (Kd), increased in the following order: Cl- < NO3- < MnO4- and CO32- < SO42- < WO42- for the monovalent and divalent anions, respectively. The relationship between the ReO4- distribution coefficient and competing anion size was nonlinear. When the difference in ionic radius (DIR) between ReO4- and Xn - (n = 1 or 2) was greater than ~ 12%, then ReO4- incorporation into sodalite was insignificant. The results imply that anion size is the major factor that determines sodalite anion compositions. Given the similarity in chemical behavior and anion size, ReO4- serves as a suitable analogue for TcO4- under oxidizing conditions where both elements are expected to remain as oxyanions in the + 7 oxidation state.« less

  7. Perrhenate incorporation into binary mixed sodalites: The role of anion size and implications for technetium-99 sequestration

    SciTech Connect

    Dickson, Johnbull O.; Harsh, James B.; Lukens, Wayne W.; Pierce, Eric M.

    2014-12-20

    Perrhenate (ReO4-), as a TcO4- analogue, was incorporated into mixed-anion sodalites from binary solutions containing ReO4- and a competing anion Xn- (Cl-, CO32-, SO42-, MnO4-, or WO42-). For this study, our objective was to determine the extent of solid solution formation and the dependence of competing ion selectivity on ion size. Using equivalent aqueous concentrations of the anions (ReO4-/Xn- molar ratio = 1:1), we synthesized mixed-anion sodalites from zeolite and NaOH at 90 °C for 96 h. The resulting solids were characterized by bulk chemical analysis, powder X-ray diffraction, scanning electron microscopy, and X-ray absorption near edge structure (XANES) spectroscopy to determine crystal structure, chemical composition, morphology, and rhenium (Re) oxidation state. Rhenium in the solid phase occurred predominately as Re(VII)O4- in the sodalites, which have a primitive cubic pattern in the space group P43n. The refined unit-cell parameters of the mixed sodalites ranged from 8.88 to 9.15 Å and showed a linear dependence on the size and mole fraction of the incorporated anion(s). The ReO4- selectivity, represented by its distribution coefficient (Kd), increased in the following order: Cl- < NO3- < MnO4- and CO32- < SO42- < WO42- for the monovalent and divalent anions, respectively. The relationship between the ReO4- distribution coefficient and competing anion size was nonlinear. When the difference in ionic radius (DIR) between ReO4- and Xn - (n = 1 or 2) was greater than ~ 12%, then ReO4- incorporation

  8. Experimental determination of the speciation, partitioning, and release of perrhenate as a chemical surrogate for pertechnetate from a sodalite-bearing multiphase ceramic waste form

    SciTech Connect

    Pierce, Eric M.; Lukens, Wayne W.; Fitts, Jeff. P.; Jantzen, Carol. M.; Tang, G.

    2013-12-01

    A key component to closing the nuclear fuel cycle is the storage and disposition of nuclear waste in geologic systems. Multiphase ceramic waste forms have been studied extensively as a potential host matrix for nuclear waste. Understanding the speciation, partitioning, and release behavior of radionuclides immobilized in multiphase ceramic waste forms is a critical aspect of developing the scientific and technical basis for nuclear waste management. In this study, we evaluated a sodalite-bearing multiphase ceramic waste form (i.e., fluidized-bed steam reform sodium aluminosilicate [FBSR NAS] product) as a potential host matrix for long-lived radionuclides, such as technetium (99Tc). The FBSR NAS material consists primarily of nepheline (ideally NaAlSiO4), anion-bearing sodalites (ideally M8[Al6Si6O24]X2, where M refers to alkali and alkaline earth cations and X refers to monovalent anions), and nosean (ideally Na8[AlSiO4]6SO4). Bulk X-ray absorption fine structure analysis of the multiphase ceramic waste form, suggest rhenium (Re) is in the Re(VII) oxidation state and has partitioned to a Re-bearing sodalite phase (most likely a perrhenate sodalite Na8[Al6Si6O24](ReO4)2). Rhenium was added as a chemical surrogate for 99Tc during the FBSR NAS synthesis process. The weathering behavior of the FBSR NAS material was evaluated under hydraulically unsaturated conditions with deionized water at 90 ?C. The steady-state Al, Na, and Si concentrations suggests the weathering mechanisms are consistent with what has been observed for other aluminosilicate minerals and include a combination of ion exchange, network hydrolysis, and the formation of an enriched-silica surface layer or phase. The steady-state S and Re concentrations are within an order of magnitude of the nosean and perrhenate sodalite solubility, respectively. The order of magnitude difference between the observed and predicted concentration for Re and S may be associated with the fact that the anion

  9. Experimental Determination of the Speciation, Partitioning, and Release of Perrhenate as a Chemical Surrogate for Pertechnetate from a Sodalite-Bearing Multiphase Ceramic Waste Form

    SciTech Connect

    Pierce, Eric M; Lukens, Wayne W; Fitts, Jeffrey P; Tang, Guoping; Jantzen, C M

    2013-01-01

    A key component to closing the nuclear fuel cycle is the storage and disposition of nuclear waste in geologic systems. Multiphase ceramic waste forms have been studied extensively as a potential host matrix for nuclear waste. Understanding the speciation, partitioning, and release behavior of radionuclides immobilized in multiphase ceramic waste forms is a critical aspect of developing the scientific and technical basis for nuclear waste management. In this study, we evaluated a sodalite-bearing multiphase ceramic waste form (i.e., fluidized-bed steam reform sodium aluminosilicate [FBSR NAS] product) as a potential host matrix for long-lived radionuclides, such as technetium (99Tc). The FBSR NAS material consists primarily of nepheline (ideally NaAlSiO4), anion-bearing sodalites (ideally M8[Al6Si6O24]X2, where M refers to alkali and alkaline earth cations and X refers to monovalent anions), and nosean (ideally Na8[AlSiO4]6SO4). Bulk x-ray absorption fine structure analysis of the multiphase ceramic waste form, suggest rhenium (Re) is in the Re(VII) oxidation state and has partitioned to a Re-bearing sodalite phase (most likely a perrhenate sodalite Na8[Al6Si6O24](ReO4)2). Rhenium was added as a chemical surrogate for 99Tc during the FBSR NAS synthesis process. The weathering behavior of the FBSR NAS material was evaluated under hydraulically unsaturated conditions with deionized water at 90 C. The steady-state Al, Na, and Si concentrations suggests the weathering mechanisms are consistent with what has been observed for other aluminosilicate minerals and include a combination of ion exchange, network hydrolysis, and the formation of an enriched-silica surface layer or phase. The steady-state S and Re concentrations are within an order of magnitude of the nosean and perrhenate sodalite solubility, respectively. The order of magnitude difference between the observed and predicted concentration for Re and S may be associated with the fact that the anion

  10. Concentration of perrhenate and pertechnetate solutions

    DOEpatents

    Knapp, Furn F.; Beets, Arnold L.; Mirzadeh, Saed; Guhlke, Stefan

    1998-01-01

    A method of preparing a concentrated solution of a carrier-free radioisotope which includes the steps of: a. providing a generator column loaded with a composition containing a parent radioisotope; b. eluting the generator column with an eluent solution which includes a salt of a weak acid to elute a target daughter radioisotope from the generator column in a first eluate. c. eluting a cation-exchange column with the first eluate to exchange cations of the salt for hydrogen ions and to elute the target daughter radioisotope and a weak acid in a second eluate; d. eluting an anion-exchange column with the second eluate to trap and concentrate the target daughter radioisotope and to elute the weak acid solution therefrom; and e. eluting the concentrated target daughter radioisotope from the anion-exchange column with a saline solution.

  11. Concentration of perrhenate and pertechnetate solutions

    DOEpatents

    Knapp, F.F.; Beets, A.L.; Mirzadeh, S.; Guhlke, S.

    1998-03-17

    A method is described for preparing a concentrated solution of a carrier-free radioisotope which includes the steps of: (a) providing a generator column loaded with a composition containing a parent radioisotope; (b) eluting the generator column with an eluent solution which includes a salt of a weak acid to elute a target daughter radioisotope from the generator column in a first eluate; (c) eluting a cation-exchange column with the first eluate to exchange cations of the salt for hydrogen ions and to elute the target daughter radioisotope and a weak acid in a second eluate; (d) eluting an anion-exchange column with the second eluate to trap and concentrate the target daughter radioisotope and to elute the weak acid solution therefrom; and (e) eluting the concentrated target daughter radioisotope from the anion-exchange column with a saline solution. 1 fig.

  12. Synthesis and Structure of Perrhenate Sodalite

    SciTech Connect

    Mattigod, Shas V.; McGrail, B. PETER; McCready, David E.; Wang, Li Q.; Parker, Kent E.; Young, James S.

    2006-04-15

    Na8(AlSiO4)6(ReO4)2 sodalite was synthesized using a hydrothermal method, and its crystal structure was determined from Rietveld refinement of experimental X-ray powder diffraction data. The refinement showed that this compound adopts the cubic sodalite structure (Space Group, No.218) with a = 9.1528 (1) ?. Raman spectroscopic measurements confirm the presence of tetrahedral ReO4- groups. Broadening of the asymmetric stretching and bending vibrational modes suggests the tetrahedra are slightly distorted from ideal Td symmetry in the sodalite lattice. MAS NMR of 29Si and 27Al nuclei showed single intense peaks at ?iso = -92.4 ppm and ?iso = 57.5 ppm, respectively, confirming the alternating Si, Al tetrahedral ordering in sodalite deduced from the structural data. Chemical shifts for 29Si and 27Al calculated using correlative structural parameters (56.6 ? 0.8 ppm and -92.3 ? 0.9 ppm) showed good agreement with measured data indicating the validity of data derived from the Rietveld structural refinement.

  13. The structural and spectroscopic characterisation of three actinyl complexes with coordinated and uncoordinated perrhenate: [UO2(ReO4)2(TPPO)3], [[(UO2)(TPPO)3]2(mu2-O2)][ReO4]2 and [NpO2(TPPO)4][ReO4].

    PubMed

    John, Gordon H; May, Iain; Sarsfield, Mark J; Steele, Helen M; Collison, David; Helliwell, Madeleine; McKinney, James D

    2004-03-07

    The first structural characterization of an actinide complex with coordinated perrhenate is reported, [UO2(ReO4)2(TPPO)3] (1). In this [UO2]2+ complex two [ReO4]- anions and three TPPO (triphenylphosphine oxide) P=O donor ligands are coordinated in the equatorial plane in a cisoid arrangement. This bonding arrangement, and apparent strain observed in the equatorially bonded ligands, is attributed to the solid state packing in adjacent molecules in which hydrophobic TPPO ligands form an effective "shell" around a hydrophilic core of two UO2(ReO4)2 moieties. Solid state vibrational spectroscopy (infrared and Raman), 31P CP MAS NMR and elemental analysis are also consistent with the formula of 1. Solution state vibrational spectroscopy and 31P NMR measurements in EtOH indicate the lability of the TPPO and [ReO4]- groups. The photolytic generation of peroxide in EtOH solutions of 1 leads to the formation of trace quantities of [[(UO2)(TPPO)3]2(mu2-O2)][ReO4]2, 2, in which the coordinated [ReO4]- groups of 1 have been displaced by bridging O2(2-), derived from atmospheric O2. Finally, attempts to synthesise a [NpO2]+ analogue of have resulted only in the formation of [NpO2(TPPO)4][ReO4], 3, in which [ReO4]- acts solely as a counter anion. From these results it can be concluded that [ReO4]- will bond to [UO2]2+, but will be readily displaced by a more strongly coordinating ligand (e.g. peroxide) and will not coordinate to an actinyl cation with a lower charge, [NpO2]+, under the same reaction conditions.

  14. Tungsten-188/carrier-free rhenium-188 perrhenic acid generator system

    DOEpatents

    Knapp, F.F. Jr.; Lisic, E.C.; Mirzadeh, S.; Callahan, A.P.

    1993-02-16

    A generator system for providing a carrier-free radioisotope in the form of an acid comprises a chromatography column in tandem fluid connection with an ion exchange column, the chromatography column containing a charge of a radioactive parent isotope. The chromatography column, charged with a parent isotope, is eluted with an alkali metal salt solution to generate the radioisotope in the form of an intermediate solution, which is passed through the ion-exchange column to convert the radioisotope to a carrier-free acid form.

  15. Tungsten-188/carrier-free rhenium-188 perrhenic acid generator system

    DOEpatents

    Knapp, Jr., Furn F.; Lisic, Edward C.; Mirzadeh, Saed; Callahan, Alvin P.

    1994-01-01

    A generator system for providing a carrier-free radioisotope in the form of an acid comprises a chromatography column in tandem fluid connection with an ion exchange column, the chromatography column containing a charge of a radioactive parent isotope. The chromatography column, charged with a parent isotope, is eluted with an alkali metal salt solution to generate the radioisotope in the form of an intermediate solution, which is passed through the ion-exchange column to convert the radioisotope to a carrier-free acid form.

  16. Tungsten-188/carrier-free rhenium-188 perrhenic acid generator system

    DOEpatents

    Knapp, Jr., Furn F.; Lisic, Edward C.; Mirzadeh, Saed; Callahan, Alvin P.

    1993-01-01

    A generator system for providing a carrier-free radioisotope in the form of an acid comprises a chromatography column in tandem fluid connection with an ion exchange column, the chromatography column containing a charge of a radioactive parent isotope. The chromatography column, charged with a parent isotope, is eluted with an alkali metal salt solution to generate the radioisotope in the form of an intermediate solution, which is passed through the ion-exchange column to convert the radioisotope to a carrier-free acid form.

  17. Tungsten-188/carrier-free rhenium-188 perrhenic acid generator system

    DOEpatents

    Knapp, F.F. Jr.; Lisic, E.C.; Mirzadeh, S.; Callahan, A.P.

    1994-01-04

    A generator system has been invented for providing a carrier-free radioisotope in the form of an acid comprises a chromatography column in tandem fluid connection with an ion exchange column, the chromatography column containing a charge of a radioactive parent isotope. The chromatography column, charged with a parent isotope, is eluted with an alkali metal salt solution to generate the radioisotope in the form of an intermediate solution, which is passed through the ion-exchange column to convert the radioisotope to a carrier-free acid form. 1 figure.

  18. A mono-diazenide complex from perrhenate: toward a new core for rhenium radiopharmaceuticals.

    PubMed

    Cowley, Andrew R; Dilworth, Jonathan R; Donnelly, Paul S

    2003-02-24

    A new method for the synthesis of low to intermediate oxidation state rhenium complexes containing a bifunctional ligand has been developed. Reaction of [ReO(4)](-) with substituted phenylhydrazines and triphenylphosphine in acetonitrile in the presence of HCl allows the isolation of [ReCl(2)(NNC(6)H(4)-4-R)(NCCH(3))(PPh(3))(2)] (where R = OCH(3), Cl, or CO(2)CH(3)). The substituted hydrazine acts as both a reductant and source of a monodentate diazenide ligand. The compounds have all been characterized in the solid state by X-ray crystallography and in the solution state by NMR, electrospray mass spectrometry, and HPLC. Cyclic voltammetry measurements show that the mono-diazenide complexes undergo a reversible oxidation.

  19. Crystal structure of the high-temperature modification of ytterbium perrhenate Yb(ReO{sub 4}){sub 3}

    SciTech Connect

    Khrustalev, V.N.; Varfolomeev, M.B.; Shamrai, N.B.; Struchkov, Yu.T.; Pisarevskii, A.P. |

    1993-11-01

    Yb(ReO{sub 4}){sub 3} obtained by the slow crystallization of its melt in air is investigated by X-ray diffraction (298 K, 329 reflections, R = 0.083, R{sub w} = 0.102). Crystals are hexagonal, a = 9.999(4) {angstrom}, c = 6.070(2) {angstrom}, Z = 2, space group P6{sub 3}/m. The structure is related to the CdTh(MoO{sub 4}){sub 3} type and consists of columns of Yb polyhedra (three-cap trigonal prisms) and of Re tetrahedra. The correlation of the structures of Yb(ReO{sub 4}){sub 3} and apatite is discussed.

  20. Copper(II) perrhenate Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2}: Synthesis from isopropanol and CuReO{sub 4}, structure and properties

    SciTech Connect

    Mikhailova, D.; Engel, J.M.; Schmidt, M.; Tsirlin, A.A.; Ehrenberg, H.

    2015-12-15

    The crystal structure of Cu{sup +}Re{sup 7+}O{sub 4} is capable of a quasi-reversible incorporation of C{sub 3}H{sub 7}OH molecules. A room-temperature reaction between CuReO{sub 4} and C{sub 3}H{sub 7}OH under oxidizing conditions leads to the formation of a novel metal-organic hybrid compound Cu{sup 2+}(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2}. Upon heating under reducing conditions, this compound transforms back into CuReO{sub 4}, albeit with ReO{sub 2} and metallic Cu as by-products. The crystal structure of Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} solved from single-crystal X-ray diffraction (Pbca, a=10.005(3) Å, b=7.833(2) Å, and c=19.180(5) Å) reveals layers of corner-sharing CuO{sub 6}-octahedra and ReO{sub 4}-tetrahedra, whereas isopropyl groups are attached to both sides of these layers, thus providing additional connections within the layers through hydrogen bonds. Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} is paramagnetic down to 4 K because the spatial arrangement of the Cu{sup 2+} half-filled orbitals prevents magnetic superexchange. The paramagnetic effective moment of 2.0(1) μ{sub B} is slightly above the spin-only value and typical for Cu{sup 2+} ions. - Highlights: • Novel Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} compound has a sequence of inorganic and organic layers. • Hydrogen bonds provide an additional bonding Isopropanol molecules serve as a reducing agent during decomposition. • No direct Cu-O-Re-O-Cu connections via d{sub x2-y2} orbital of Cu{sup 2+} explain paramagnetism. • Hydrogen bonds provide an additional bonding. • Isopropanol molecules serve as a reducing agent during decomposition.

  1. Copper(II) perrhenate Cu(C3H7OH)2(ReO4)2: Synthesis from isopropanol and CuReO4, structure and properties

    NASA Astrophysics Data System (ADS)

    Mikhailova, D.; Engel, J. M.; Schmidt, M.; Tsirlin, A. A.; Ehrenberg, H.

    2015-12-01

    The crystal structure of Cu+Re7+O4 is capable of a quasi-reversible incorporation of C3H7OH molecules. A room-temperature reaction between CuReO4 and C3H7OH under oxidizing conditions leads to the formation of a novel metal-organic hybrid compound Cu2+(C3H7OH)2(ReO4)2. Upon heating under reducing conditions, this compound transforms back into CuReO4, albeit with ReO2 and metallic Cu as by-products. The crystal structure of Cu(C3H7OH)2(ReO4)2 solved from single-crystal X-ray diffraction (Pbca, a=10.005(3) Å, b=7.833(2) Å, and c=19.180(5) Å) reveals layers of corner-sharing CuO6-octahedra and ReO4-tetrahedra, whereas isopropyl groups are attached to both sides of these layers, thus providing additional connections within the layers through hydrogen bonds. Cu(C3H7OH)2(ReO4)2 is paramagnetic down to 4 K because the spatial arrangement of the Cu2+ half-filled orbitals prevents magnetic superexchange. The paramagnetic effective moment of 2.0(1) μB is slightly above the spin-only value and typical for Cu2+ ions.

  2. Experimental Ion Exchange Column With SuperLig 639 And Simulant Formulation

    SciTech Connect

    Morse, Megan; Nash, C.

    2013-08-26

    SuperLig®639 ion exchange resin was tested as a retrieval mechanism for pertechnetate, through decontamination of a perrhenate spiked 5M Simple Average Na{sup +} Mass Based Simulant. Testing included batch contacts and a three-column ion exchange campaign. A decontamination of perrhenate exceeding 99% from the liquid feed was demonstrated. Analysis of the first formulation of a SBS/WESP simulant found unexpectedly low concentrations of soluble aluminum. Follow-on work will complete the formulation.

  3. Binding of ReO[subscript 4];#8722; with an engineered MoO[subscript 4 superscript 2];#8722;-binding protein: towards a new approach in radiopharmaceutical applications

    SciTech Connect

    Aryal, Baikuntha P.; Brugarolas, Pedro; He, Chuan

    2012-05-25

    Radiolabeled biomolecules are routinely used for clinical diagnostics. {sup 99m}Tc is the most commonly used radioactive tracer in radiopharmaceuticals. {sup 188}Re and {sup 186}Re are also commonly used as radioactive tracers in medicine. However, currently available methods for radiolabeling are lengthy and involve several steps in bioconjugation processes. In this work we present a strategy to engineer proteins that may selectively recognize the perrhenate (ReO{sub 4}{sup -}) ion as a new way to label proteins. We found that a molybdate (MoO{sub 4}{sup 2-})-binding protein (ModA) from Escherichia coli can bind perrhenate with high affinity. Using fluorescence and isothermal titration calorimetry measurements, we determined the dissociation constant of ModA for ReO{sub 4}{sup -} to be 541 nM and we solved a crystal structure of ModA with a bound ReO{sub 4}{sup -}. On the basis of the structure we created a mutant protein containing a disulfide linkage, which exhibited increased affinity for perrhenate (K{sub d} = 104 nM). High-resolution crystal structures of ModA (1.7 {angstrom}) and A11C/R153C mutant (2.0 {angstrom}) were solved with bound perrhenate. Both structures show that a perrhenate ion occupies the molybdate binding site using the same amino acid residues that are involved in molybdate binding. The overall structure of the perrhenate-bound ModA is unchanged compared with that of the molybdate-bound form. In the mutant protein, the bound perrhenate is further stabilized by the engineered disulfide bond.

  4. Binding of ReO4(-) with an engineered MoO4(2-)-binding protein: towards a new approach in radiopharmaceutical applications.

    PubMed

    Aryal, Baikuntha P; Brugarolas, Pedro; He, Chuan

    2012-01-01

    Radiolabeled biomolecules are routinely used for clinical diagnostics. (99m)Tc is the most commonly used radioactive tracer in radiopharmaceuticals. (188)Re and (186)Re are also commonly used as radioactive tracers in medicine. However, currently available methods for radiolabeling are lengthy and involve several steps in bioconjugation processes. In this work we present a strategy to engineer proteins that may selectively recognize the perrhenate (ReO(4)(-)) ion as a new way to label proteins. We found that a molybdate (MoO(4)(2-))-binding protein (ModA) from Escherichia coli can bind perrhenate with high affinity. Using fluorescence and isothermal titration calorimetry measurements, we determined the dissociation constant of ModA for ReO(4)(-) to be 541 nM and we solved a crystal structure of ModA with a bound ReO(4)(-). On the basis of the structure we created a mutant protein containing a disulfide linkage, which exhibited increased affinity for perrhenate (K(d) = 104 nM). High-resolution crystal structures of ModA (1.7 Å) and A11C/R153C mutant (2.0 Å) were solved with bound perrhenate. Both structures show that a perrhenate ion occupies the molybdate binding site using the same amino acid residues that are involved in molybdate binding. The overall structure of the perrhenate-bound ModA is unchanged compared with that of the molybdate-bound form. In the mutant protein, the bound perrhenate is further stabilized by the engineered disulfide bond.

  5. Removal of Pertechnetate-Related Oxyanions from Solution Using Functionalized Hierarchical Porous Frameworks

    SciTech Connect

    Banerjee, Debasis; Elsaidi, Sameh K.; Aguila, Briana; Li, Baiyan; Kim, Dongsang; Schweiger, Michael J.; Kruger, Albert A.; Doonan, Christian J.; Ma, Shengqian; Thallapally, Praveen K.

    2016-10-20

    Efficient and cost-effective removal of radioactive pertechnetate anions from nuclear waste is a key challenge to mitigate long-term nuclear waste storage issues. Traditional materials such as resins and layered double hydroxides (LDHs) were evaluated for their pertechnetate or perrhenate (the non-radioactive surrogate) removal capacity, but there is room for improvement in terms of capacity, selectivity and kinetics. A series of functionalized hierarchical porous frameworks were evaluated for their perrhenate removal capacity in the presence of other competing anions.

  6. Elution of Re-188 from W-188/Re-188 generators with salts of weak acids permits efficient concentration to low volumes using a new tandem cation/anion exchange system

    SciTech Connect

    Guhlke, S. |; Beets, A.L.; Knapp, F.F. Jr.

    1997-05-01

    Re-188, available from a W-188/Re-188 generator, is an important therapeutic radioisotope for bone pain palliation, cancer therapy and intravascular brachytherapy, etc. Because of the relatively low specific activity of reactor-produced W-188 (ORNL HFIR, 296-370 MBq mCi/mg W-186 for 2 cycles), methods of concentrating the Re-188 bolus (10-12 mL) from clinical scale (18.5-37 BGq W-188) generators (5-6 gm alumina) are thus very important. We demonstrate for the first time a new strategy of generator elution with salts of weak acids and specific perrhenate anion {open_quotes}trapping{close_quotes} with QMA anion columns. Re-188 perrhenate is efficiently eluted (65-75%) from the alumina-based generator with 0.15-0.3 M ammonium acetate. An acetic acid solution of Re-188 perrhenic acid is obtained by subsequent on-line passage of the generator eluant through a DOWEX AG 50Wx8 (200-400 mesh, H{sup +} form) column. Since acetic acid is not ionized (< 0.001%) at this pH (< pK{sub a} = 4.76) the perrhenate anion is then specifically trapped on a QMA {open_quotes}Light{close_quotes} anion extraction column. QMA elution with 0.9% NaCl, provides Re-188 perrhenate solution in <1 mL. Concentration of 10-20 mL of Re-188 solution (> 15 BGq) in <1 mL has been demonstrated using this simple new approach, which is also effective for concentration of Tc-99m from low specific activity Mo-99 (n,y) generators. The cation/anion tandem system is inexpensive and disposable and use can be easily automated. The availability of this very simple, efficient system is important for broad use of rhenium-188.

  7. Rhenium(VII) Catalysis of Prins Cyclization Reactions

    PubMed Central

    Tadpetch, Kwanruthai; Rychnovsky, Scott D.

    2009-01-01

    The rhenium(VII) complex O3ReOSiPh3 are particularly effective catalyst for Prins cyclizations using aromatic and α,β-unsaturated aldehydes. The reaction conditions are mild and the highly substituted 4-hydroxy tetrahydropyran products are formed stereoselectively. Rhenium(VII) complexes appear to spontaneously form esters with alcohols and to directly activate electron rich alcohols for solvolysis. Re2O7 and perrhenic acid were equally effective in catalyzing these cyclizations. PMID:18816133

  8. Corrosion Behavior of Nuclear Waste Storage Canister Materials

    NASA Astrophysics Data System (ADS)

    Grant, John

    The nature of interaction of mild steel nuclear waste storage containers with technetium ions is not fully known. Technetium is formed during nuclear processing and some of this technetium has leaked at the Hanford nuclear waste storage site in Washington State. It is often found as highly oxidized pertechnetate (TeO4-) anions at these storage sites which also happen to be highly alkaline and contain a significant amount of nitrate. Theoretically, pertechnetate anions can act as electron acceptors and interact with the mild steel containers and accelerate the oxidation (corrosion) of steel. It is of interest to identify if pertechnetate anions pose a corrosion hazard to the mild steel nuclear waste storage tanks, under the conditions of the storage sites, as that can accelerate the degradation of the tanks and lead to further contamination. In this thesis, the interaction of two relevant container materials, namely, steel alloys A285 and A537 with a technetium surrogate, rhenium was studied. Perrhenate was used as an analog for pertechnetate. As all isotopes of technetium are radioactive, rhenium was chosen as the experimental surrogate due to its chemical similarity to technetium. Electrochemical behavior was evaluated using potentiodynamic polarization tests, and the surface morphology was studied using optical microscopy and scanning electron microscopy. Potentiodynamic polarization tests were conducted in 1.0M NaNO3 + 0.1M NaOH and 1.0M NaNO3 + 0.1M NaOH + 0.02M NaReO4. Tests were performed at three different temperatures, namely, (i) room temperature, (ii) 50°C and (iii) 80°C to study the effect of higher temperatures found in the storage sites. Corrosion current, corrosion potential, anodic and cathodic Tafel slopes, polarization resistance and corrosion rates were obtained from electrochemical testing and evaluated. Increasing temperatures was found to lead to increasing corrosion rates for all samples. The data also revealed increased corrosion from

  9. Ion Exchange Column Tests Supporting Technetium Removal Resin Maturation

    SciTech Connect

    Nash, C.; McCabe, D.; Hamm, L.; Smith, F.; Morse, M.

    2013-12-20

    The primary treatment of the tank waste at the DOE Hanford site will be done in the Waste Treatment and Immobilization Plant, currently under construction. The baseline plan for this facility is to treat the waste, splitting it into High Level Waste (HLW) and Low Activity Waste (LAW). Both waste streams are then separately vitrified as glass and sealed in canisters. The LAW glass will be disposed on site. There are currently no plans to treat the waste to remove technetium, so its disposition path is the LAW glass. Due to the soluble properties of pertechnetate and long half-life of 99Tc, effective management of 99Tc is important. Options are being explored to immobilize the supplemental LAW portion of the tank waste, as well as to examine the volatility of 99Tc during the vitrification process. Removal of 99Tc, followed by off-site disposal has potential to reduce treatment and disposal costs. A conceptual flow sheets for supplemental LAW treatment and disposal that could benefit from technetium removal will specifically examine removing 99Tc from the LAW feed stream to supplemental immobilization. SuperLig® 639 is an elutable ion exchange resin. In the tank waste, 99Tc is predominantly found in the tank supernate as pertechnetate (TcO4-). Perrhenate (ReO4-) has been shown to be a good non-radioactive surrogate for pertechnetate in laboratory testing for this ion exchange resin. This report contains results of experimental ion exchange distribution coefficient and column resin maturation kinetics testing using the resin SuperLig® 639a to selectively remove perrhenate from simulated LAW. This revision includes results from testing to determine effective resin operating temperature range. Loading tests were performed at 45°C, and the computer modeling was updated to include the temperature effects. Equilibrium contact testing indicated that this batch of

  10. Low temperature heat capacity and thermodynamic functions of anion bearing sodalities Na8Al6Si6O24X2 (X = SO4, ReO4, Cl, I)

    DOE PAGES

    Schliesser, Jacob; Lilova, Kristina; Pierce, Eric M.; ...

    2017-06-01

    Heat capacities of sulfate, perrhenate, chloride, and iodide sodalites with the ideal formula Na8Al6Si6O24X2 (X = SO4, ReO4, Cl, I) were measured from 2 K to 300 K using a Quantum Design Physical Property Measurement System (PPMS). From the heat capacity data, the standard thermodynamic functions were determined. All four sodalites undergo a phase transition below room temperature for which thermodynamic parameters were determined. Additionally, the heat capacity of one of the constituent compounds (NaReO4) was measured.

  11. Low temperature heat capacity and thermodynamic functions of anion bearing sodalites Na8Al6Si6O24X2 (X = SO4, ReO4, Cl, I)

    DOE PAGES

    Schliesser, Jacob; Lilova, Kristina; Pierce, Eric M.; ...

    2017-06-01

    Heat capacities of sulfate, perrhenate, chloride, and iodide sodalites with the ideal formula Na8Al6Si6O24X2 (X = SO4, ReO4, Cl, I) were measured from 2 K to 300 K using a Quantum Design Physical Property Measurement System (PPMS). From the heat capacity data, the standard thermodynamic functions were determined. All four sodalites undergo a phase transition below room temperature for which thermodynamic parameters were determined. Additionally, the heat capacity of one of the constituent compounds (NaReO4) was measured.

  12. New Gel-Like Polymers as Selective Weak-Base Anion Exchangers

    PubMed Central

    Gierczyk, Błażej; Cegłowski, Michał; Zalas, Maciej

    2015-01-01

    A group of new anion exchangers, based on polyamine podands and of excellent ion-binding capacity, were synthesized. The materials were obtained in reactions between various poly(ethyleneamines) with glycidyl derivatives of cyclotetrasiloxane. The final polymeric, strongly cross-linked materials form gel-like solids. Their structures and interactions with anions adsorbed were studied by spectroscopic methods (CP-MAS NMR, FR-IR, UV-Vis). The sorption isotherms and kinetic parameters were determined for 29 anions. Materials studied show high ion capacity and selectivity towards some important anions, e.g., selenate(VI) or perrhenate. PMID:25946220

  13. Vibrational spectroscopy of the double complex salt Pd(NH3)4(ReO4)2, a bimetallic catalyst precursor

    NASA Astrophysics Data System (ADS)

    Thompson, Simon T.; Lamb, H. Henry; Delley, Bernard; Franzen, Stefan

    2017-02-01

    Tetraamminepalladium(II) perrhenate, a double complex salt, has significant utility in PdRe catalyst preparation; however, the vibrational spectra of this readily prepared compound have not been described in the literature. Herein, we present the infrared (IR) and Raman spectra of tetraamminepalladium(II) perrhenate and several related compounds. The experimental spectra are complemented by an analysis of normal vibrational modes that compares the experimentally obtained spectra with spectra calculated using DFT (DMol3). The spectra are dominated by features due to the ammine groups and the Resbnd O stretch in Td ReO4-; lattice vibrations due to the D4h Pd(NH3)42+ are also observed in the Raman spectrum. Generally, we observe good agreement between ab initio calculations and experimental spectra. The calculated IR spectrum closely matches experimental results for peak positions and their relative intensities. The methods for calculating resonance Raman intensities are implemented using the time correlator formalism using two methods to obtain the excited state displacements and electron-vibration coupling constants, which are the needed inputs in addition to the normal mode wave numbers. Calculated excited state energy surfaces of Raman-active modes correctly predict relative intensities of the peaks and Franck-Condon activity; however, the position of Raman bands are predicted at lower frequencies than observed. Factor group splitting of Raman peaks observed in spectra of pure compounds is not predicted by DFT.

  14. Purification of alkaline solutions and wastes from actinides and technetium by coprecipitation with some carriers using the method of appearing reagents: Final Report

    SciTech Connect

    Peretrukhin, V.F.; Silin, V.I.; Kareta, A.V.; Gelis, A.V.; Shilov, V.P.; German, K.E.; Firsova, E.V.; Maslennikov, A.G.; Trushina, V.E.

    1998-09-01

    The coprecipitation of transuranium elements (TRU) and technetium from alkaline solutions and from simulants of Hanford Site tank wastes has been studied in reducing and oxidizing conditions on uranium(IV,VI) hydroxocompounds, tetraalkylammonium perrhenate and perchlorate, and on hydroxides of Fe(III), Co(III), Mn(II), and Cr(III) using the method of appearing reagents (MAR). Coprecipitations in alkaline solution have been shown to give high decontamination factors (DF) at low content of carrier and in the presence of high salt concentrations. Uranium(IV) hydroxide in concentrations higher than 3 {times} 10{sup {minus}3} M coprecipitates Pu and Cm in any oxidation state from 0.2 to 4 M NaOH with DFs of 110 to 1000 and Np and Tc with DFs of 51 to 176. Technetium (VII) coprecipitates with (5 to 8) {times} 10{sup {minus}4} M tetrabutylammonium (TBA) perrhenate in 0.01 to 0.02 M TBA hydroxide from 0.5 to 1.5 M NaOH to give DFs of 150 to 200. Coprecipitations of Np and Pu with Co(OH){sub 3}, Fe(OH){sub 3}, Cr(OH){sub 3}, and Mn(OH){sub 2} obtained by the MAR from precursors in the range from pH 10.5 to 0.4 M NaOH give DFs from 80 to 400.

  15. Bolometric Bounds on the Antineutrino Mass

    NASA Astrophysics Data System (ADS)

    Arnaboldi, C.; Brofferio, C.; Cremonesi, O.; Fiorini, E.; Lo Bianco, C.; Martensson, L.; Nucciotti, A.; Pavan, M.; Pessina, G.; Pirro, S.; Previtali, E.; Sisti, M.; Giuliani, A.; Margesin, B.; Zen, M.

    2003-10-01

    High statistics calorimetric measurements of the β spectrum of 187Re are being performed with arrays of silver perrhenate crystals operated at low temperature. After a substantial modification of the experimental setup, a new measurement with ten silver perrhenate microbolometers has been running since July 2002. The crystals have masses around 300 μg and their average FWHM energy resolution is of 28.3eV at the β end point. The Kurie plot collected during 4485 h×mg effective running time has an end-point energy of 2466.1±0.8stat±1.5syst eV, while the half lifetime of the decay is found to be 43.2±0.2stat±0.1syst Gy. These values are the most precise obtained so far for 187Re. The best fit value for m2ν¯e is 147±237stat±90syst eV2, which corresponds to an upper limit for the electron antineutrino mass mν¯e≤21.7 eV at 90%C.L.

  16. Study of the structure of PyHReO{sub 4} under high pressure

    SciTech Connect

    Kichanov, S. E. Kozlenko, D. P.; Wasicki, J. W.; Czarnecki, P.; Glazkov, V. P.; Nawrocik, W.; Savenko, B. N.; Lathe, C.

    2007-05-15

    The structure of deuterated pyridinium perrhenate (d{sub 5}PyH)ReO{sub 4} (C{sub 5}D{sub 5}NHReO{sub 4}) is studied by X-ray diffraction at room temperature and pressures up to 3.5 GPa and by neutron diffraction in the temperature range 10-293 K and at pressures up to 2.0 GPa. Under normal conditions, this compound belongs to the orthorhombic space group Cmc2{sub 1} (ferroelectric phase II). At room temperature and pressures above P > 0.7 GPa, a transition to an orthorhombic phase (paraelectric phase II) is observed. This paraelectric phase is described by the space group Cmcm. At a pressure as high as P = 2.0 GPa, phase I remains stable at temperatures down to 10 K. This fact indicates that the high pressure suppresses the ferroelectric state in deuterated pyridinium perrhenate (d{sub 5}PyH)ReO{sub 4}.

  17. Column Performance Testing of Superlig 639 Resin with Simulated Hanford Waste Supernates: Identification of the Primary Sorbing Species and Detailed Characterization of their Desorption Profiles

    SciTech Connect

    King, WD

    2003-11-10

    Several bench-scale column tests (resin bed volume less than or equal to 75 mL) have been conducted with SuperLig 639 resin and simulated Hanford waste supernates. Rhenium (surrogate for technetium in actual waste samples) breakthrough profiles were determined for three simulant compositions which are representative of the basic waste categories requiring treatment in the Hanford River Protection Project Waste Treatment Plant. Considerable loading performance variability was observed between the three waste types, although the resin is effective at rhenium removal from each solution. Careful and frequent analysis during elution studies conducted at the conclusion of the column loading tests confirmed that sodium nitrate and sodium perrhenate ion pairs are primary sorbing species on SuperLig 639 resin. Furthermore, it was discovered that potassium nitrate and potassium perrhenate salts are significant competitors for sorption sites on the resin. Successive desorption profiles were identified for all four salt species during elution tests. Integration of the desorption profiles revealed that the resin is selective for removal of the potassium salts over the sodium salts.

  18. Vibrational spectroscopy of the double complex salt Pd(NH3)4(ReO4)2, a bimetallic catalyst precursor.

    PubMed

    Thompson, Simon T; Lamb, H Henry; Delley, Bernard; Franzen, Stefan

    2017-02-15

    Tetraamminepalladium(II) perrhenate, a double complex salt, has significant utility in PdRe catalyst preparation; however, the vibrational spectra of this readily prepared compound have not been described in the literature. Herein, we present the infrared (IR) and Raman spectra of tetraamminepalladium(II) perrhenate and several related compounds. The experimental spectra are complemented by an analysis of normal vibrational modes that compares the experimentally obtained spectra with spectra calculated using DFT (DMol(3)). The spectra are dominated by features due to the ammine groups and the ReO stretch in Td ReO4(-); lattice vibrations due to the D4h Pd(NH3)4(2+) are also observed in the Raman spectrum. Generally, we observe good agreement between ab initio calculations and experimental spectra. The calculated IR spectrum closely matches experimental results for peak positions and their relative intensities. The methods for calculating resonance Raman intensities are implemented using the time correlator formalism using two methods to obtain the excited state displacements and electron-vibration coupling constants, which are the needed inputs in addition to the normal mode wave numbers. Calculated excited state energy surfaces of Raman-active modes correctly predict relative intensities of the peaks and Franck-Condon activity; however, the position of Raman bands are predicted at lower frequencies than observed. Factor group splitting of Raman peaks observed in spectra of pure compounds is not predicted by DFT.

  19. Pyrazole complexes as anion receptors: effects of changing the metal, the pyrazole substitution pattern, and the number of pyrazole ligands.

    PubMed

    Nieto, Sonia; Pérez, Julio; Riera, Lucía; Riera, Víctor; Miguel, Daniel; Golen, James A; Rheingold, Arnold L

    2007-04-16

    Compound cis,fac-[Mo(eta3-allyl)(CO)2(Hdmpz)3]BAr'4 (1) (Hdmpz = 3,5-dimethylpyrazole, Ar' = 3,5-bis(trifluoromethyl)phenyl) undergoes rapid substitution of one of the pyrazole ligands by anions, including the low nucleophilic ReO4-, a reaction that afforded [Mo(OReO3)(eta3-allyl)(CO)2(Hdmpz)2] (2), structurally characterized by X-ray diffraction. The new compounds fac-[Mn(CO)3(Hdmpz)3]BAr'4 (4a) and fac-[Mn(CO)3(HtBupz)3]BAr'4 (4b) (HtBupz = 3(5)-tert-butylpyrazole) also undergo pyrazole substitution with most anions, and the product from the reaction with nitrate was crystallographically characterized. Compounds 4a,b were found to be substitutionally stable toward perrhenate, and the adducts [Mn(CO)3(Hdmpz)3].[ReO4] (7a) and [Mn(CO)3(HtBupz)3].[ReO4].[Bu4N].[BAr'4] (7b), crystallographically characterized, display hydrogen bonds between one of the perrhenate oxygens and the N-H groups of two of the pyrazole ligands. The structurally similar adduct [Re(CO)3(Hdmpz)3].[ReO4] (8) was found to result from the interaction of [Re(CO)3(Hdmpz)3]BAr'4 with perrhenate. The reaction of [Re(OTf)(CO)5] with 3,5-dimethylpyrazole (Hdmpz) afforded [Re(CO)5(Hdmpz)]OTf (9). The reaction of 9 with Hdmpz and NaBAr'4 yielded [Re(CO)4(Hdmpz)2]BAr'4 (10), which was found to be unstable toward chloride anion. In contrast, the new compound fac,cis-[Re(CO)3(CNtBu)(Hdmpz)2]BAr'4 (11) is stable in solution in the presence of different anions. Binding constants for 11 with chloride, bromide, and nitrate are 1-2 orders of magnitude lower than those found for these anions and rhenium tris(pyrazole) hosts, indicating that the presence of the third pyrazole ligand is crucial. Compounds fac-[Re(CO)3(HPhpz)3]BAr'4 (14) (HPhpz = 3(5)-phenylpyrazole) and fac-[Re(CO)3(HIndz)3]BAr'4 (15) (HIndz = indazole) are, in terms of anion binding strength and selectivity, inferior to those with dimethylpyrazole or tert-butylpyrazole ligands.

  20. Intraarterial irradiation with rhenium-188 for inhibition of restenosis after PTCA - strategy and evaluation of Re-188-species for rapid urinary excretion

    SciTech Connect

    Knapp, F.F. Jr.; Guhlke, S.; Beets, A.L.

    1997-05-01

    Estimated costs for coronary restenosis therapy after PTCA are > $ 1 billion (U.S.). Radiation is a simple and effective tool for inhibition of neointimal proliferation an important component of restenosis. We propose use of Re-188 (t{sub {1/2}} 16.9 h, 2.1 MeV {beta}), obtained from decay of W-188 (T{sub {1/2}} 69 d). Our alumina-based W-188/Re-188 generator has a shelf-life of several months and we have developed an on-line tandem cation/anion exchange column system to concentrate to > 18.5 BGq/mL. Estimates for targeted regional dose of 8.4 rad/37 MBq/min/mL, which is > 1,400 cGy for about 370 MBq Re-188 for 5 min. Balloon inflation with Re-188 solutions is a new approach for more uniform vascular dose distribution as an alternative to use of radioactive wires or other linear sources. Rapid urinary excretion kinetics are important in the unlikely event of balloon rupture (<0.1%). We have therefore evaluated relative excretion kinetics of Re-188-perrhenate and -MAG3 in rats; Re-188-perrhenate was obtained from generator elution with 0.9% NaCl and re-188-MAG3 was prepared be reaction of the ligand with Sn(II)-reduced perrhenate. Fischer rats (n=4-5/group) were injected i.v. and urine and feces collected every 2 h for 12 h and then daily for 5 d. Both agents excreted > 90% in urine; biodistribution studies showed low organ uptake with intestines as the major site. Rhenium-188-MAG3 excreted more rapidly (2 h = 59.6{+-}18.5%) then Re-188-MAG3 excreted more rapidly (2 h = 68.3{+-}13.5%) in same model. Both Re-188 species are thus good candidates for balloon inflation. Studies are in progress in a swine model to evaluate the effectiveness of Re-188 for inhibition of restenosis.

  1. Sodalite as a vehicle to increase Re retention in waste glass simulant during vitrification

    SciTech Connect

    Luksic, Steven A.; Riley, Brian J.; Parker, Kent E.; Hrma, Pavel

    2016-10-01

    Technetium retention during Hanford waste vitrification can be increased by inhibiting technetium volatility from the waste glass melter. Incorporating technetium into a mineral phase, such as sodalite, is one way to achieve this. Rhenium-bearing sodalite was tested as a vehicle to transport perrhenate (ReO4-), a nonradioactive surrogate for pertechnetate (TcO4-), into high-level (HLW) and low-activity waste (LAW) glasses. After melting feeds of these two glasses, the retention of rhenium was measured and compared with the rhenium retention in glass prepared from a feed containing Re2O7 as a standard. The rhenium retention was 21% higher for HLW glass and 85% higher for LAW glass when added to samples in the form of sodalite as opposed to when it was added as Re2O7, demonstrating the efficacy of this type of an approach.

  2. Aqueous biphasic systems for metal separations : a microcalorimetric analysis of polymer/salt interactions.

    SciTech Connect

    Chaiko, D. J.; Hatton, T. A.; Zaslavsky, B.

    1999-05-03

    Certain radionuclide ions (e.g., TcO{sub 4}{sup 16}) exhibit unusually strong Affinities toward the polymer-rich phase in aqueous biphase systems generated by combinations of salt solutions with polymers such as poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG). Thus, aqueous polymer phases could potentially be used to selectively extract these ions during pretreatment of radioactive tank wastes at Hanford. To help develop a fundamental understanding of the interactions between various ions and polymers in aqueous solution, interaction enthalpies between sodium perrhenate and a random copolymer of PEG and PPG (UCON-50) were measured by microcalorimetric titration. An entropy compensation effect was observed in this system in which changes in enthalpic interactions were balanced by entropy changes such that the interaction free energy remained constant and approximately equal to zero.

  3. Crystallization and rhenium MAD phasing of the acyl-homoserinelactone synthase EsaI

    SciTech Connect

    Watson, W.T.; Murphy IV, Frank V.; Gould, Ty A.; Jambeck, Per; Val, Dale L.; Cronan, Jr., John E.; Beck von Bodman, Susan; Churchill, Mair E.A.

    2009-04-22

    Acyl-homoserine-L-lactones (AHLs) are diffusible chemical signals that are required for virulence of many Gram-negative bacteria. AHLs are produced by AHL synthases from two substrates, S-adenosyl-L-methionine and acyl-acyl carrier protein. The AHL synthase EsaI, which is homologous to the AHL synthases from other pathogenic bacterial species, has been crystallized in the primitive tetragonal space group P4{sub 3}, with unit-cell parameters a = b = 66.40, c = 47.33 {angstrom}. The structure was solved by multiple-wavelength anomalous diffraction with a novel use of the rhenium anomalous signal. The rhenium-containing structure has been refined to a resolution of 2.5 {angstrom} and the perrhenate ion binding sites and liganding residues have been identified.

  4. Methods for the separation of rhenium, osmium and molybdenum applicable to isotope geochemistry

    USGS Publications Warehouse

    Morgan, J.W.; Golightly, D.W.; Dorrzapf, A.F.

    1991-01-01

    Effective methods are described for the chemical separation of rhenium, osmium and molybdenum. The methods are based on distillation and anion-exchange chromatography, and have been the basis for rhenium-osmium isotope studies of ore deposits and meteorites. Successful anion-exchange separation of osmium requires both recognition and careful control of the osmium species in solution; thus, distillation of osmium tetroxide from a mixture of sulfuric acid and hydrogen peroxide is preferred to anion-exchange. Distribution coefficients measured for perrhenate in sulfuric acid media are sufficiently high (Kd > 500) for rhenium to be directly loaded onto an ion-exchange column from a distillation residue and subsequently eluted with nitric acid. Polymerization of molybdenum species during elution is prevented by use of a solution that is 1M in hydrochloric acid and 1M in sodium chloride. ?? 1991.

  5. Extraction of Perchlorate Using Porous Organosilicate Materials

    PubMed Central

    Johnson, Brandy J.; Leska, Iwona A.; Melde, Brian J.; Siefert, Ronald L.; Malanoski, Anthony P.; Moore, Martin H.; Taft, Jenna R.; Deschamps, Jeffrey R.

    2013-01-01

    Sorbent materials were developed utilizing two morphological structures, comprising either hexagonally packed pores (HX) or a disordered pore arrangement (CF). The sorbents were functionalized with combinations of two types of alkylammonium groups. When capture of perchlorate by the sorbents was compared, widely varying performance was noted as a result of differing morphology and/or functional group loading. A material providing improved selectivity for perchlorate over perrhenate was synthesized with a CF material using N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride. Materials were applied in batch and column formats. Binding isotherms followed the behavior expected for a system in which univalent ligands of varying affinity compete for immobilized sites. Performance of the sorbents was also compared to that of commercial Purolite materials. PMID:28809217

  6. Amplification of anion sensing by disulfide functionalized ferrocene and ferrocene-calixarene receptors adsorbed onto gold surfaces.

    PubMed

    Cormode, David P; Evans, Andrew J; Davis, Jason J; Beer, Paul D

    2010-07-28

    A disulfide functionalized bis-ferrocene urea acyclic receptor and disulfide functionalized mono- and bis-ferrocene amide and urea appended upper rim calix[4]arene receptors were prepared for the fabrication of SAM redox-active anion sensors. 1H NMR and diffusive voltammetric anion recognition investigations revealed each receptor to be capable of complexing and electrochemically sensing anions via cathodic perturbations of the respective receptor's ferrocene/ferrocenium redox couple. SAMs of a ferrocene urea receptor 3 and ferrocene urea calixarene receptor 17 exhibited significant enhanced magnitudes of cathodic response upon anion addition as compared to observed diffusive perturbations. SAMs of 17 were demonstrated to sense the perrhenate anion in aqueous solutions.

  7. Interventional Therapy of Head and Neck Cancer with Lipid Nanoparticle-Carried Rhenium-186 Radionuclide

    PubMed Central

    French, J. Tyler; Goins, Beth; Saenz, Marcela; Li, Shihong; Garcia-Rojas, Xavier; Phillips, William T.; Otto, Randal A.; Bao, Ande

    2010-01-01

    Purpose Minimally invasive interventional cancer therapy of drug-carrying lipid nanoparticles (liposomes) via convection enhanced delivery generally applied by the use of an infusion pump can increase intratumoral drug concentration and retention while facilitating broad distribution throughout solid tumors. We investigated the utility of liposome-carrying β-emitting radionuclides to treat head and neck cancer in nude rats by direct intratumoral infusion. Methods Four groups of nude rats were subcutaneously inoculated with human tongue cancer cells. After tumors reached an average size of 1.6 cm3, the treatment group received an intratumoral infusion of liposomal rhenium-186 (186Re) (185 MBq (5 mCi)/cm3 tumor). Three control groups were intratumorally infused with either, 1) unlabeled liposomes, 2) unencapsulated 186Re-perrhenate, or 3) unencapsulated intermediate 186Re-compound (186Re-BMEDA). In vivo distribution of 186Re-activity was measured by planar gamma camera imaging. Tumor therapy and toxicity were assessed by measurements of tumor size, body weight, and hematology. Results Average tumor volume of the 186Re-liposome group on post-treatment day-14 decreased to 87.7±20.1%, while tumor volumes increased to 395.0% - 514.4% on average in other three groups (P<0.001 vs 186Re-liposome group). 186Re-liposomes provided much higher intratumoral retention of 186Re-activity, resulting in an average tumor radiation absorbed dose of 526.3±93.3 Gy, whereas 186Re-perrhenate and 186Re-BMEDA groups had only 3.3±1.2 and 13.4±9.2 Gy tumor doses respectively. No systemic toxicity was observed. Conclusion Liposomal 186Re effectively treated the head and neck cancer with minimal side effects after convection enhanced interventional delivery. These results suggest the potential of liposomal 186Re for clinical application in interventional therapy of cancer. PMID:20478719

  8. Efficient Removal of Anionic Radioactive Pollutant from Water Using Ordered Urea-Functionalized Mesoporous Polymeric Nanoparticle.

    PubMed

    Shen, Jian; Chai, Wei; Wang, Kaixuan; Zhang, Fang

    2017-07-12

    A urea-functionalized ordered mesoporous polymeric nanoparticle for removing the perrhenate anion ReO4(-) as the surrogate of the particularly intractable anion radioactive pollutant TcO4(-) was demonstrated in the present study. This nanomaterial (denoted as urea-MPN) was produced for the first time by a surfactant-directed urea-phenol-formaldehyde resol oligomers self-assembly protocol under hydrothermal condition. The obtained urea-MPN possessed the uniform nanosized spherical morphology with a 3D interconnected ordered cubic mesoporous structure. Also, the urea functional groups were succefully embedded in the polymer framework without the alteration of the molecular configuration. Meanwhile, it exhibited excellent β radiation resistance up to 200 kGy dose. We employed the perrhenate anion ReO4(-) to test its potential for the removal of anionic radioactive pollutant TcO4(-) from water. Interestingly, the optimized urea-MPN nanocomposite achieved the high removal efficiency at a low concentration of 0.25 mM within a short contact time of 30 min. The control experimental results revealed that the short nanoscale pore channels and the hydrophobic mesopore surface facilitated the hydrogen-bonding interaction between the charge-diffuse ReO4(-) tetrahedral oxoanion and the urea moieties in the framework of urea-MPN, accounting for the rapid and effective removal performance in pure water. Importantly, it can selectively capture ReO4(-) in the presence of different competitive anions including NO3(-), CO3(2-), SO4(2-), and PO4(3-). This attractive capability of this unique nanosized mesoporous polymeric sorbent will pave the way for the diverse applications in the decontamination of nuclear wastes in a more economical and sustainable manner.

  9. Interventional therapy of head and neck cancer with lipid nanoparticle-carried rhenium 186 radionuclide.

    PubMed

    French, J Tyler; Goins, Beth; Saenz, Marcela; Li, Shihong; Garcia-Rojas, Xavier; Phillips, William T; Otto, Randal A; Bao, Ande

    2010-08-01

    Minimally invasive interventional cancer therapy with drug-carrying lipid nanoparticles (ie, liposomes) via convection-enhanced delivery by an infusion pump can increase intratumoral drug concentration and retention while facilitating broad distribution throughout solid tumors. The authors investigated the utility of liposome-carrying beta-emitting radionuclides to treat head and neck cancer by direct intratumoral infusion in nude rats. Four groups of nude rats were subcutaneously inoculated with human tongue cancer cells. After tumors reached an average size of 1.6 cm(3), the treatment group received an intratumoral infusion of liposomal rhenium-186 ((186)Re) (185 MBq [5 mCi]/cm(3) tumor). Three control groups were intratumorally infused with unlabeled liposomes, unencapsulated (186)Re-perrhenate, or unencapsulated intermediate (186)Re compound ((186)Re-N,N-bis[2-mercaptoethyl]-N',N'-diethyl-ethylenediamine [BMEDA]). In vivo distribution of (186)Re activity was measured by planar gamma-camera imaging. Tumor therapy and toxicity were assessed by tumor size, body weight, and hematology. Average tumor volume in the (186)Re-liposome group on posttreatment day 14 decreased to 87.7% +/- 20.1%, whereas tumor volumes increased to 395.0%-514.4% on average in the other three groups (P< .001 vs (186)Re-liposome). The (186)Re-liposomes provided much higher intratumoral retention of (186)Re activity, resulting in an average tumor radiation absorbed dose of 526.3 Gy +/- 93.3, whereas (186)Re-perrhenate and (186)Re-BMEDA groups had only 3.3 Gy +/- 1.2 and 13.4 Gy +/- 9.2 tumor doses, respectively. No systemic toxicity was observed. Liposomal (186)Re effectively treated head and neck cancer with minimal side effects after convection-enhanced interventional delivery. These results suggest the potential of liposomal (186)Re for clinical application in interventional therapy of cancer. Copyright (c) 2010 SIR. Published by Elsevier Inc. All rights reserved.

  10. Development of in situ forming thermosensitive hydrogel for radiotherapy combined with chemotherapy in a mouse model of hepatocellular carcinoma.

    PubMed

    Peng, Cheng-Liang; Shih, Ying-Hsia; Liang, Kuo-Sheng; Chiang, Ping-Fang; Yeh, Chung-Hsin; Tang, I-Chang; Yao, Cheng-Jung; Lee, Shin-Yi; Luo, Tsai-Yueh; Shieh, Ming-Jium

    2013-05-06

    This study evaluated a system for local cancer radiotherapy combined with chemotherapy. The delivery system is a thermosensitive hydrogel containing a therapeutic radionuclide ((188)Re-Tin colloid) and a chemotherapeutic drug (liposomal doxorubicin). The thermosensitive PCL-PEG-PCL copolymer was designed to spontaneously undergo a sol-gel phase transition in response to temperature, remaining liquid at room temperature and rapidly forming a gel at body temperature. A scanning electron microscope was used to observe the microstructure of the fully loaded hydrogel. Release of radionuclide and doxorubicin from the hydrogel was slow, and the system tended to remain stable for at least 10 days. After the intratumoral administration of Lipo-Dox/(188)Re-Tin hydrogel in mice with hepatocellular carcinoma (HCC), its retention by the tumor, spatiotemporal distribution, and therapeutic effect were evaluated. The residence time in the tumor was significantly longer for (188)Re-Tin loaded hydrogel than for Na (188)Re perrhenate (Na (188)ReO4). The hydrogel after thermal transition kept the radionuclide inside the tumor, whereas free (188)Re perrhenate ((188)ReO4) diffused quickly from the tumor. The tumor growth was more profoundly inhibited by treatment with Lipo-Dox/(188)Re-Tin hydrogel (with up to 80% regression of well-established tumors on day 32) than treatment with either (188)Re-Tin hydrogel or Lipo-Dox hydrogel. Therefore, this injectable and biodegradable hydrogel may offer the advantage of focusing radiotherapy and chemotherapy locally to maximize their effects on hepatocellular carcinoma.

  11. Ion Exchange Distribution Coefficient Tests and Computer Modeling at High Ionic Strength Supporting Technetium Removal Resin Maturation

    SciTech Connect

    Nash, Charles A.; Hamm, L. Larry; Smith, Frank G.; McCabe, Daniel J.

    2014-12-19

    The primary treatment of the tank waste at the DOE Hanford site will be done in the Waste Treatment and Immobilization Plant (WTP) that is currently under construction. The baseline plan for this facility is to treat the waste, splitting it into High Level Waste (HLW) and Low Activity Waste (LAW). Both waste streams are then separately vitrified as glass and poured into canisters for disposition. The LAW glass will be disposed onsite in the Integrated Disposal Facility (IDF). There are currently no plans to treat the waste to remove technetium, so its disposition path is the LAW glass. Due to the water solubility properties of pertechnetate and long half-life of 99Tc, effective management of 99Tc is important to the overall success of the Hanford River Protection Project mission. To achieve the full target WTP throughput, additional LAW immobilization capacity is needed, and options are being explored to immobilize the supplemental LAW portion of the tank waste. Removal of 99Tc, followed by off-site disposal, would eliminate a key risk contributor for the IDF Performance Assessment (PA) for supplemental waste forms, and has potential to reduce treatment and disposal costs. Washington River Protection Solutions (WRPS) is developing some conceptual flow sheets for supplemental LAW treatment and disposal that could benefit from technetium removal. One of these flowsheets will specifically examine removing 99Tc from the LAW feed stream to supplemental immobilization. To enable an informed decision regarding the viability of technetium removal, further maturation of available technologies is being performed. This report contains results of experimental ion exchange distribution coefficient testing and computer modeling using the resin SuperLig® 639a to selectively remove perrhenate from high ionic strength simulated LAW. It is advantageous to operate at higher concentration in order to treat the waste

  12. Use of the Oak Ridge National Laboratory tungsten-188/rhenium-188 generator for preparation of the rhenium-188 HDD/lipiodol complex for trans-arterial liver cancer therapy.

    PubMed

    Jeong, Jae Min; Knapp, F F Russ

    2008-03-01

    This work describes the installation, use, and quality control (QC) of the alumina-based tungsten-188 ((188)W)/rhenium-188 ((188)Re) generators provided by the Oak Ridge National Laboratory (ORNL). In addition, methods used for concentration of the (188)Re-perrhenate bolus and preparation of (188)Re-labeled HDD (4-hexadecyl-2,2,9,9-tetramethyl-4,7-diaza-1,10-decanethiol) for trans-arterial administration for therapy of nonresectable liver cancer also are described. The (188)W/(188)Re generator has a long useful shelf-life of several months and is a convenient on-site (188)Re production system. (188)Re has excellent therapeutic and imaging properties (T(1/2) 16.9 hours; E(betamax) 2.12 MeV; 155-keV gamma ray, 15%) and is cost effectively obtained on demand by saline elution of the generator. The clinical efficacy of a variety of (188)Re-labeled agents has been demonstrated for several therapeutic applications. Because of the favorable physical properties of (188)Re, several (188)Re-labeled agents are being developed and evaluated for the treatment of nonresectable/refractory liver cancer. (188)Re-labeled HDD has been the most widely studied of these agents for this application and has been introduced into clinical trials at a number of institutions. The trans-arterial administration of (188)Re-labeled agents for treatment of inoperable liver cancer requires use of high-level (1-2 Ci) (188)W/(188)Re generators. The handling of such high levels of (188)Re imposes radiological precautions normally not encountered in a radiopharmacy and adequate care and ALARA (ie, "As Low As Reasonably Achievable") principles must be followed. The ORNL generator provides consistently high (188)Re yields (>75%) and low (188)W parent breakthrough (<10(-3)%) over an extended shelf-life of several months. However, the high elution volumes (20-40 mL for 1-2 Ci generators) can require concentration of the (188)Re bolus by postelution passage through silver cation chloride trapping columns

  13. 188Re-loaded lipid nanocapsules as a promising radiopharmaceutical carrier for internal radiotherapy of malignant gliomas

    PubMed Central

    Allard, Emilie; Hindré, François; Passirani, Catherine; Lemaire, Laurent; Lepareur, Nicolas; Noiret, Nicolas; Menei, Philippe; Benoit, Jean-Pierre

    2008-01-01

    Purpose Lipid nanocapsules (LNC) entrapping lipophilic complexes of 188Re (188Re(S3CPh)2(S2CPh) [188Re-SSS]) were investigated as a novel radiopharmaceutical carrier for internal radiation therapy of malignant gliomas. The present study was designed to evaluate the efficacy of intracerebral administration of 188Re-SSS LNC by means of convection-enhanced delivery (CED) on a 9L rat brain tumour model. Methods Female Fischer rats with 9L glioma were treated with a single injection of 188Re-SSS LNC by CED 6 days after cell implantation. Rats were put into random groups according to the dose infused: 12, 10, 8, and 3 Gy in comparison with blank LNC, perrhenate solution (4Gy) and non-treated animals. The radionuclide brain retention level was evaluated by measuring 188Re elimination in faeces and urine over 72h after the CED injection. The therapeutic effect of 188Re-SSS LNC was assessed based on animal survival. Results CED of 188Re perrhenate solution resulted in rapid drug clearance with a brain T1/2 of 7h. In contrast, when administered in LNC, 188Re tissue retention was greatly prolonged, with only 10% of the injected dose being eliminated at 72h. Rat median survival was significantly improved for the group treated with 8Gy 188Re-SSS LNC compared to the control group and blank-LNC treated animals. The increase in the median survival time (ISTmedian) was about 80% compared to the control group; 33% of the animals were long-term survivors. The dose of 8Gy proved to be a very effective dose, between toxic (10–12Gy) and ineffective (3–4Gy) doses. Conclusions These findings show that CED of Rhenium-188-loaded lipid nanocapsules is a safe and potent antitumour system for treating malignant gliomas. Our data are the first to show the in vivo efficacy of Rhenium-188 internal radiotherapy for the treatment of brain malignancy. PMID:18465130

  14. SIMS analysis: Development and evaluation 1995 summary report

    SciTech Connect

    Groenewold, G.S.; Appelhans, A.D.; Ingram, J.C.; Delmore, J.E.; Dahl, D.A.

    1995-10-01

    Secondary ion mass spectrometry (SIMS) was evaluated for characterizing Hg salts. It was found that sulfate and chloride species could be identified directly without sample preparation. Mercuric oxide could be identified by complexation with formic acid. Hg nitrates could be identified by complexation with cyclohexylamine (CHA). Laser desorption ion trap MS was evaluated for characterizing EDTA on environmental samples. No intact EDTA ions were observed, but a series of EDTA fragment ions were visible, particularly on basalt and soil. An ion trap SIMS was developed: a perrhenate ion gun was interfaced to a Teledyne ion trap spectrometer, and the entire device was mounted on a cart. The technology was demonstrated using a prototype ion trap SIMS instrument for detecting Hg{center_dot}CHA complexes formed from nitrate salts. Intensity of the ion gun was improved, and the surface damage of the particle was small, and ion gun technology transfer to Phi-Evans, Inc. is being considered. Two technology end users are at INEL`s Central Facilities Area 674 pond and acid pit of the Radioactive Waste Management Complex; target problem at both sites is the need for Hg speciation on soil samples.

  15. Crystallization of rhenium salts in a simulated low-activity waste borosilicate glass

    SciTech Connect

    Riley, Brian J.; McCloy, John S.; Goel, Ashutosh; Liezers, Martin; Schweiger, Michael J.; Liu, Juan; Rodriguez, Carmen P.; Kim, Dong-Sang

    2013-04-01

    This study presents a new method for looking at the solubility of volatile species in simulated low-activity waste glass. The present study looking at rhenium salts is also applicable to real applications involving radioactive technetium salts. In this synthesis method, oxide glass powder is mixed with the volatiles species, vacuum-sealed in a fused quartz ampoule, and then heat-treated under vacuum in a furnace. This technique restricts the volatile species to the headspace above the melt but still within the sealed ampoule, thus maximizing the volatile concentration in contact with the glass. Various techniques were used to measure the solubility of rhenium in glass and include energy dispersive spectroscopy, wavelength dispersive spectroscopy, laser ablation inductively-coupled plasma mass spectroscopy, and inductively-coupled plasma optical emission spectroscopy. The Re-solubility in this glass was determined to be ~3004 parts per million Re atoms. Above this concentration, the salts separated out of the melt as inclusions and as a low viscosity molten salt phase on top of the melt observed during and after cooling. This salt phase was analyzed with X-ray diffraction, scanning electron microscopy as well as some of the other aforementioned techniques and identified to be composed of alkali perrhenate and alkali sulfate.

  16. Upgrade to Ion Exchange Modeling for Removal of Technetium from Hanford Waste Using SuperLig® 639 Resin

    SciTech Connect

    Hamm, L.; Smith, F.; Aleman, S.; McCabe, D.

    2013-05-16

    This report documents the development and application of computer models to describe the sorption of pertechnetate [TcO₄⁻], and its surrogate perrhenate [ReO₄⁻], on SuperLig® 639 resin. Two models have been developed: 1) A thermodynamic isotherm model, based on experimental data, that predicts [TcO₄⁻] and [ReO₄⁻] sorption as a function of solution composition and temperature and 2) A column model that uses the isotherm calculated by the first model to simulate the performance of a full-scale sorption process. The isotherm model provides a synthesis of experimental data collected from many different sources to give a best estimate prediction of the behavior of the pertechnetate-SuperLig® 639 system and an estimate of the uncertainty in this prediction. The column model provides a prediction of the expected performance of the plant process by determining the volume of waste solution that can be processed based on process design parameters such as column size, flow rate and resin physical properties.

  17. Structural and magnetic properties of quasi-1 and 2D pyrazine-containing spin-1/2 antiferromagnets.

    SciTech Connect

    Manson, J. L.; Connor, M. M.; Schlueter, J. A.; Hyzer, K. A.; Kykeem, A.; Materials Science Division; Eastern Washington Univ.

    2007-06-01

    Aqueous reaction of Cu(BF{sub 4}){sub 2}, NH{sub 4}HF{sub 2}, and pyrazine leads to formation of a novel 3D framework, [Cu(HF{sub 2})(pyz){sub 2}]BF{sub 4} (1), where 2D [Cu(pyz){sub 2}]{sup 2+} square layers are connected via HF{sub 2}{sup -}. A second compound, Cu(ReO{sub 4}){sub 2}(H{sub 2}O){sub 2}(pyz) (2), was the result of our attempt to create the perrhenate analog of 1; a linear chain compound consisting of CuO{sub 4}N{sub 2} octahedra linked through pyrazine ligands formed instead. Both compounds exhibit extensive hydrogen bonding interactions where bifluoride, F...H...F{sup -}, and O-H...O link layers and chains together in 1 and 2, respectively. Broad maxima indicative of short-range magnetic ordering (SRO) were observed in the magnetic susceptibility at 5.5 (1) and 7.7 K (2) while no evidence for the transition to long-range magnetic ordering (LRO) was detected above 2 K.

  18. Root Absorption and Transport Behavior of Technetium in Soybean 1

    PubMed Central

    Cataldo, Dominic A.; Wildung, Raymond E.; Garland, Thomas R.

    1983-01-01

    The absorption characteristics and mechanisms of pertechnetate (TcO4−) uptake by hydroponically grown soybean seedlings (Glycine max cv Williams) were determined. Absorption from 10 micromolar solutions was linear for at least 6 hours, with 30% of the absorbed TcO4− being transferred to the shoot. Evaluation of concentration-dependent absorption rates from solutions containing 0.02 to 10 micromolar TcO4− shows the presence of multiphasic absorption isotherms with calculated Ks values of 0.09, 8.9, and 54 micromolar for intact seedlings. The uptake of TcO4− was inhibited by a 4-fold concentration excess of sulfate, phosphate, selenate, molybdate, and permanganate; no reduction was noted with borate, nitrate, tungstate, perrhenate, iodate, or vanadate. Analyses of the kinetics of interaction between TcO4− and inhibiting anions show permanganate to be a noncompetitive inhibitor, while sulfate, phosphate, and selenate, and molybdate exhibit characteristics of competitive inhibitors of TcO4− transport suggesting involvement of a common transport process. PMID:16663311

  19. Root absorption and transport behavior of technetium in soybean.

    PubMed

    Cataldo, D A; Wildung, R E; Garland, T R

    1983-11-01

    The absorption characteristics and mechanisms of pertechnetate (TcO(4) (-)) uptake by hydroponically grown soybean seedlings (Glycine max cv Williams) were determined. Absorption from 10 micromolar solutions was linear for at least 6 hours, with 30% of the absorbed TcO(4) (-) being transferred to the shoot. Evaluation of concentration-dependent absorption rates from solutions containing 0.02 to 10 micromolar TcO(4) (-) shows the presence of multiphasic absorption isotherms with calculated K(s) values of 0.09, 8.9, and 54 micromolar for intact seedlings. The uptake of TcO(4) (-) was inhibited by a 4-fold concentration excess of sulfate, phosphate, selenate, molybdate, and permanganate; no reduction was noted with borate, nitrate, tungstate, perrhenate, iodate, or vanadate. Analyses of the kinetics of interaction between TcO(4) (-) and inhibiting anions show permanganate to be a noncompetitive inhibitor, while sulfate, phosphate, and selenate, and molybdate exhibit characteristics of competitive inhibitors of TcO(4) (-) transport suggesting involvement of a common transport process.

  20. Characterization of rhenium oxide films and their application to liquid crystal cells

    NASA Astrophysics Data System (ADS)

    Cazzanelli, E.; Castriota, M.; Marino, S.; Scaramuzza, N.; Purans, J.; Kuzmin, A.; Kalendarev, R.; Mariotto, G.; Das, G.

    2009-06-01

    Rhenium trioxide exhibits high electronic conductivity, while its open cubic crystal structure allows an appreciable hydrogen intercalation, generating disordered solid phases, with protonic conductivity. Rhenium oxide thin films have been obtained by thermal evaporation of ReO3 powders on different substrates, maintained at different temperatures, and also by reactive magnetron sputtering of a Re metallic target. A comparative investigation has been carried out on these films, by using micro-Raman spectroscopy and x-ray diffraction. Two basic types of solid phases appear to grow in the films: a red metallic HxReO3 compound, with distorted perovskite structures, like in the bulk material, and ordered HReO4 crystals based on tetrahedral perrhenate ions. Because of its conduction properties, the electrical and electro-optical behaviors of ReO3 films deposited on standard indium tin oxide/glass substrate have been tested inside asymmetric nematic liquid crystal cells, showing an appreciable capability of rectification of their electro-optical response, in similar way to tungsten trioxide.

  1. MARE-l in Milan: Status and Perspectives

    NASA Technical Reports Server (NTRS)

    Ferri, E.; Arnaboldi, C.; Ceruti, G.; Faverzani, M.; Gatti, C.; Giachero, A.; Gotti, C.; Kilbourne, C.; Kraft-Bermuth, S.; Nucciotti, A.; Pessini, G.; Schaeffer, D.; Sisti, M.

    2012-01-01

    The international project MARE (Microcalorimeter Array for a Rhenium Experiment) aims at the direct and calorimetric measurement of the electron neutrino mass with sub-eV sensitivity. Although the baseline of the MARE project consists in a large array of rhenium based thermal detectors, a different option for the isotope is also being considered. The different option is Ho-163. The potential of using Re-187 for a calorimetric neutrino mass experiment has been already demonstrated. On the contrary, no calorimetric spectrum of Ho-163 has been so far measured with the precision required to set a useful limit on the neutrino mass. The first phase of the project (MARE-1) is a collection of activities with the aim of sorting out both the best isotope and the most suited detector technology to be used for the final experiment. One of the MARE-1 activities is carried out in Milan by the group of Milano-Bicocca in collaboration with NASA/GSFC and Wisconsin groups. The Milan MARE-l arrays are based on semiconductor thermistors, provided by the NASA/GSFC group, with dielectric silver perrhenate absorbers, AgReO4. The experiment, which is presently being assembled, is designed to host up to 8 arrays.

  2. A new paradigm for anion trapping in high capacity and selectivity: crystal-to-crystal transformation of cationic materials.

    PubMed

    Fei, Honghan; Bresler, Marc R; Oliver, Scott R J

    2011-07-27

    We describe a new methodology to the selective trapping of priority pollutants that occur inherently as oxo-anions (e.g., perchlorate, chromate, arsenate, pertechnetate, etc.) or organic anions (e.g., salicylate, pharmaceuticals, and their metabolites, which are often chlorinated into potentially more harmful compounds). The typical approach to trapping anions is exchange into cationic hosts such as resins or layered double hydroxides. Both capacity and selectivity are limited by the equilibrium of the process and moreover are often subject to interference, e.g. by carbonate that is always present in water from atmospheric CO(2). Our approach takes advantage of the metastability of our cationically charged materials to instead trap by recrystallization to a new structure. Exceptionally high adsorption capacities for permanganate and perrhenate--studied as models for pertechnetate--were found for a Ag(I)-based cationic extended framework. The exchange capacity reached 292 and 602 mg/g, respectively, over five times the exchange capacity compared to conventional layered double hydroxides. Our cationic material can also selectively trap these and other toxic oxo-anions when nontoxic anions (e.g., nitrate, carbonate) were present in an over 100-fold excess concentration.

  3. Lipid Nanocapsules Loaded with Rhenium-188 Reduce Tumor Progression in a Rat Hepatocellular Carcinoma Model

    PubMed Central

    Vanpouille-Box, Claire; Lacoeuille, Franck; Roux, Jérôme; Aubé, Christophe; Garcion, Emmanuel; Lepareur, Nicolas; Oberti, Frédéric; Bouchet, Francis; Noiret, Nicolas; Garin, Etienne; Benoît, Jean-Pierre; Couturier, Olivier; Hindré, François

    2011-01-01

    Background Due to their nanometric scale (50 nm) along with their biomimetic properties, lipid nanocapsules loaded with Rhenium-188 (LNC188Re-SSS) constitute a promising radiopharmaceutical carrier for hepatocellular carcinoma treatment as its size may improve tumor penetration in comparison with microspheres devices. This study was conducted to confirm the feasibility and to assess the efficacy of internal radiation with LNC188Re-SSS in a chemically induced hepatocellular carcinoma rat model. Methodology/Principal Findings Animals were treated with an injection of LNC188Re-SSS (80 MBq or 120 MBq). The treated animals (80 MBq, n = 12; 120 MBq, n = 11) were compared with sham (n = 12), blank LNC (n = 7) and 188Re-perrhenate (n = 4) animals. The evaluation criteria included rat survival, tumor volume assessment, and vascular endothelial growth factor quantification. Following treatment with LNC188Re-SSS (80 MBq) therapeutic efficiency was demonstrated by an increase in the median survival from 54 to 107% compared with control groups with up to 7 long-term survivors in the LNC188Re-SSS group. Decreased vascular endothelial growth factor expression in the treated rats could indicate alterations in the angiogenesis process. Conclusions/Significance Overall, these results demonstrate that internal radiation with LNC188Re-SSS is a promising new strategy for hepatocellular carcinoma treatment. PMID:21408224

  4. Sodalite as a vehicle to increase Re retention in waste glass simulant during vitrification

    NASA Astrophysics Data System (ADS)

    Luksic, Steven A.; Riley, Brian J.; Parker, Kent E.; Hrma, Pavel

    2016-10-01

    Technetium (Tc) retention during Hanford waste vitrification can be increased if the volatility can be controlled. Incorporating Tc into a thermally stable mineral phase, such as sodalite, is one way to achieve increased retention. Here, rhenium (Re)-bearing sodalite was tested as a vehicle to transport perrhenate (ReO4-), a nonradioactive surrogate for pertechnetate (TcO4-), into high-level (HLW) and low-activity waste (LAW) glass simulants. After melting HLW and LAW simulant feeds, the retention of Re in the glass was measured and compared with the Re retention in glass prepared from a feed containing Re2O7. Phase analysis of sodalite in both these glasses across a profile of temperatures describes the durability of Re-sodalite during the feed-to-glass transition. The use of Re sodalite improved the Re retention by 21% for HLW glass and 85% for LAW glass, demonstrating the potential improvement in Tc-retention if TcO4- were to be encapsulated in a Tc-sodalite prior to vitrification.

  5. Non-Complexing Anions for Quantitative Speciation Studies Using Raman Spectroscopy in Fused Silica High-Pressure Optical Cells Under Hydrothermal Conditions.

    PubMed

    Applegarth, Lucas M S G A; Alcorn, Christopher; Bissonette, Katherine; Noël, John; Tremaine, Peter R

    2015-08-01

    This paper reports methods for obtaining time-dependent reduced isotropic Raman spectra of aqueous species in quartz capillary high-pressure optical cells under hydrothermal conditions, as a means of determining quantitative speciation in hydrothermal fluids. The methods have been used to determine relative Raman scattering coefficients and to examine the thermal decomposition kinetics of the non-complexing anions bisulfate (HSO4(-)), perchlorate (CIO4(-)), perrhenate (ReO4(-)), and trifluoromethanesulfonate, or "triflate" (CF3SO3(-)) in acidic and neutral solutions at temperatures up to 400°C and 30 MPa. Arrhenius expressions for calculating the thermal decomposition rate constants are also reported. Thermal stabilities in the acidic solutions followed the order HSO4(-) (stable) > ReO4(-) > CIO4(-) > CF3SO3(-), with half-lives (t1/2) > 7 h at 300°C. In neutral solutions, the order was HSO4(-) (stable) > CF3SO3(-) > ReO4(-) > CIO4(-), with t1/2 > 8 h at 350°C. CF3SO3(-) was extremely stable in neutral solutions, with t1/2 > 11 h at 400°C.

  6. Pyrazole complexes as anion receptors.

    PubMed

    Nieto, Sonia; Pérez, Julio; Riera, Lucía; Riera, Víctor; Miguel, Daniel

    2006-03-01

    The behavior of the receptors [Re(CO)3(Hdmpz)3]BAr'4 (Hdmpz = 3,5-dimethylpyrazole) (1) and [Re(CO)3(HtBupz)3]BAr'4 (HtBupz = 3(5)-tert-butylpyrazole) (2; Ar' = 3,5-bis(trifluoromethyl)phenyl) toward the anions fluoride, chloride, bromide, iodide, hydrogensulfate, dihydrogenphosphate, nitrate, and perrhenate was studied in CD3CN solution. In most cases, the receptors were stable. Anion exchange was fast, and binding constants were calculated from the NMR titration profiles. The structure of the adduct [Re(CO)3(HtBupz)3] x NO3 (3) was determined by X-ray diffraction. Two pyrazole moieties are hydrogen-bonded to one nitrate oxygen atom, and the third pyrazole moiety is hydrogen-bonded to an oxygen atom of an adjacent nitrate, leading to infinite chains. The structure of the adduct [Re(CO)3(Hdmpz)3]BAr'4acetone (4), also determined by X-ray diffraction, showed a similar interaction of two pyrazole N-H groups with the acetone oxygen atom. F- and H2PO4(-) deprotonate the receptors, and HSO4(-) decomposed 1. The structure of one of the decomposition products (5), determined by X-ray diffraction, is consistent with pyrazole protonation and substitution by sulfate.

  7. Separation of technetium from nuclear waste stream simulants. Final report

    SciTech Connect

    Strauss, S.H.

    1995-09-11

    The author studied liquid anion exchangers, such as Aliquat-336 nitrate, various pyridinium nitrates, and related salts, so that they may be applied toward a specific process for extracting (partitioning) and recovering {sup 99}TcO{sub 4}{sup {minus}} from nuclear waste streams. Many of the waste streams are caustic and contain a variety of other ions. For this reason, the author studied waste stream simulants that are caustic and contain appropriate concentrations of selected, relevant ions. Methods of measuring the performance of the exchangers and extractant systems included contact experiments. Batch contact experiments were used to determine the forward and reverse extraction parameters as a function of temperature, contact time, phase ratio, concentration, solvent (diluent), and other physical properties. They were also used for stability and competition studies. Specifically, the author investigated the solvent extraction behavior of salts of perrhenate (ReO{sub 4}{sup {minus}}), a stable (non-radioactive) chemical surrogate for {sup 99}TcO{sub 4}{sup {minus}}. Results are discussed for alternate organic solvents; metalloporphyrins, ferrocenes, and N-cetyl pyridium nitrate as alternate extractant salts; electroactive polymers; and recovery of ReO{sub 4}{sup {minus}} and TcO{sub 4}{sup {minus}}.

  8. Characterization of rhenium oxide films and their application to liquid crystal cells

    SciTech Connect

    Cazzanelli, E.; Castriota, M.; Marino, S.; Scaramuzza, N.; Purans, J.; Kuzmin, A.; Kalendarev, R.; Mariotto, G.; Das, G.

    2009-06-01

    Rhenium trioxide exhibits high electronic conductivity, while its open cubic crystal structure allows an appreciable hydrogen intercalation, generating disordered solid phases, with protonic conductivity. Rhenium oxide thin films have been obtained by thermal evaporation of ReO{sub 3} powders on different substrates, maintained at different temperatures, and also by reactive magnetron sputtering of a Re metallic target. A comparative investigation has been carried out on these films, by using micro-Raman spectroscopy and x-ray diffraction. Two basic types of solid phases appear to grow in the films: a red metallic H{sub x}ReO{sub 3} compound, with distorted perovskite structures, like in the bulk material, and ordered HReO{sub 4} crystals based on tetrahedral perrhenate ions. Because of its conduction properties, the electrical and electro-optical behaviors of ReO{sub 3} films deposited on standard indium tin oxide/glass substrate have been tested inside asymmetric nematic liquid crystal cells, showing an appreciable capability of rectification of their electro-optical response, in similar way to tungsten trioxide.

  9. Intratumoral Injection of 188Re labeled Cationic Polyethylenimine Conjugates: A Preliminary Report

    PubMed Central

    Kim, Eun-Mi; Heo, Young-Jun; Moon, Hyung-Bae; Bom, Hee-Seung; Kim, Chang-Guhn

    2004-01-01

    188Re(Rhenium) is easily obtained from an in-house 188W/188Re generator that is similar to the current 99Mo/99mTc generator, making it very convenient for clinical use. This characteristic makes this radionuclide a promising candidate as a therapeutic agent. Polyethylenimine (PEI) is a cationic polymer and has been used as a gene delivery vector. Positively charged materials interact with cellular blood components, vascular endothelium, and plasma proteins. In this study, the authors investigated whether intratumoral injection of 188Re labeled transferrin (Tf)-PEI conjugates exert the effect of radionuclide therapy against the tumor cells. When the diameters of the Ramos lymphoma (human Burkitt's lymphoma) xenografted tumors reached approximately 1 cm, 3 kinds of 188Re bound compounds (HYNIC-PEI-Tf, HYNIC-PEI, 188Re perrhenate) were injected directly into the tumors. There were increases in the retention of 188Re inside the tumor when PEI was incorporated with 188Re compared to the use of free 188Re. The 188Re HYNIC-Tf-PEI showed the most retention inside the tumor (retention rate=approximately 97%). H&E stain of isolated tumor tissues showed that 188Re labeled HYNIC-PEI-Tf caused extensive tumor necrosis. These results support 188Re HYNIC-PEI-Tf as being a useful radiopharmaceutical agent to treat tumors when delievered by intratumoral injection. PMID:15483337

  10. Use of a new tandem cation/anion exchange system with clinical-scale generators provides high specific volume solutions of technetium-99m and rhenium-188

    SciTech Connect

    Knapp, F.R. Jr.; Beets, A.L.; Mirzadeh, S.; Guhlke, S. |

    1998-03-01

    In this paper the authors describe the first application of a simple and inexpensive post elution tandem cation-anion exchange column system which is based on generator elution with salts of weak acids such as ammonium acetate instead of saline solution to provide very high specific volume solutions of technetium-99m and rhenium-188 from clinical scale molybdenum-99/technetium-99m generator prepared from low specific activity (n,y) molybdenum-99, and tungsten-188/rhenium-188 generators, respectively. Initial passage of the bolus through a strong cation exchange cartridge converts the ammonium acetate to acetic acid which is essentially not ionized at the acidic pH, allowing specific subsequent amine type (QMA SepPak{trademark}) anion exchange cartridge column trapping of the microscopic levels of the pertechnetate or perrhenate. Subsequent elution of the anion cartridge with a small volume (< 1 mL) of saline then provides high specific volume solutions of technetium-99m by concentration of the high eluant volumes obtained by elution of clinical-scale (1 Ci) generators. This new approach also works very effectively to obtain high specific volume solutions of rhenium-188 (> 500 mCi/mL) from the alumina-based tungsten-188/rhenium-188 generator.

  11. Rhenium Radioisotopes for Therapeutic Radiopharmaceutical Development

    SciTech Connect

    Beets, A.L.; Knapp, F.F., Jr.; Kropp, J.; Lin, W.-Y.; Pinkert, J.; Wang, S.-Y.

    1999-01-18

    The availability of therapeutic radioisotopes at reasonable costs is important for applications in nuclear medicine, oncology and interventional cardiology, Rhenium-186 (Re-186) and rhenium-1 88 (Re-188) are two reactor-produced radioisotope which are attractive for a variety of therapeutic applications, Rhenium-186 has a half-life of 90 hours and decays with emission of a &particle with a maximum energy of 1.08 MeV and a 135 keV (9Yo) gamma which permits imaging. In contrast, Re- 188 has a much shorter half-life of 16.9 hours and emits a p-particle with a much higher energy of 2.12 MeV (Em=) and a 155 keV gamma photon (15Yo) for imaging. While Re-186 is unavailable from a generator system and must be directly produced in a nuclear reactor, Re-188 can also be directly produced in a reactor with high specific activity, but is more conveniently and cost-effectively available as carrier-free sodium perrhenate by saline elution of the alumina-based tungsten-188 (W1 88)/Re-l 88 generator system [1-2]. Since a comprehensive overviewofRe-186 and Re-188 therapeutic agents is beyond the scope of this &tended Abstrac4 the goal is to provide key examples of various agents currently in clinical use and those which are being developed for important clinical applications.

  12. Rhenium solubility in borosilicate nuclear waste glass: implications for the processing and immobilization of technetium-99.

    PubMed

    McCloy, John S; Riley, Brian J; Goel, Ashutosh; Liezers, Martin; Schweiger, Michael J; Rodriguez, Carmen P; Hrma, Pavel; Kim, Dong-Sang; Lukens, Wayne W; Kruger, Albert A

    2012-11-20

    The immobilization of technetium-99 ((99)Tc) in a suitable host matrix has proven to be a challenging task for researchers in the nuclear waste community around the world. In this context, the present work reports on the solubility and retention of rhenium, a nonradioactive surrogate for (99)Tc, in a sodium borosilicate glass. Glasses containing target Re concentrations from 0 to 10,000 ppm [by mass, added as KReO(4) (Re(7+))] were synthesized in vacuum-sealed quartz ampules to minimize the loss of Re from volatilization during melting at 1000 °C. The rhenium was found as Re(7+) in all of the glasses as observed by X-ray absorption near-edge structure. The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) using inductively coupled plasma optical emission spectroscopy. At higher rhenium concentrations, additional rhenium was retained in the glasses as crystalline inclusions of alkali perrhenates detected with X-ray diffraction. Since (99)Tc concentrations in a glass waste form are predicted to be <10 ppm (by mass), these Re results implied that the solubility should not be a limiting factor in processing radioactive wastes, assuming Tc as Tc(7+) and similarities between Re(7+) and Tc(7+) behavior in this glass system.

  13. Influence of rhenium speciation on the stability and activity of Re/Pd bimetal catalysts used for perchlorate reduction.

    PubMed

    Choe, Jong Kwon; Shapley, John R; Strathmann, Timothy J; Werth, Charles J

    2010-06-15

    Recent work demonstrates reduction of aqueous perchlorate by hydrogen at ambient temperatures and pressures using a novel rhenium-palladium bimetal catalyst immobilized on activated carbon (Re/Pd-AC). This study examines the influence of Re speciation on catalyst activity and stability. Rates of perchlorate reduction are linearly dependent on Re content from 0-6 wt %, but no further increases are observed at higher Re contents. Surface-immobilized Re shows varying stability and speciation both in oxic versus H(2)-reducing environments and as a function of Re content. In oxic solutions, Re immobilization is dictated by sorption of the Re(VII) precursor, perrhenate (ReO(4)(-)), to activated carbon via electrostatic interactions. Under H(2)-reducing conditions, Re immobilization is significantly improved and leaching is minimized by ReO(4)(-) reduction to more reduced species on the catalyst surface. X-ray photoelectron spectroscopy shows two different Re binding energy states under H(2)-reducing conditions that correspond most closely to Re(V)/Re(IV) and Re(I) reference standards, respectively. The distribution of the two redox states varies with Re content, with the latter predominating at lower Re contents where catalyst activity is more strongly dependent on Re content. Results demonstrate that both lower Re contents and the maintenance of H(2)-reducing conditions are key elements in stabilizing the active Re surface species that are needed for sustained catalytic perchlorate treatment.

  14. Anion inhibitors of the β-carbonic anhydrase from the pathogenic bacterium responsible of tularemia, Francisella tularensis.

    PubMed

    Del Prete, Sonia; Vullo, Daniela; Osman, Sameh M; AlOthman, Zeid; Donald, William A; Winum, Jean-Yves; Supuran, Claudiu T; Capasso, Clemente

    2017-09-01

    A β-class carbonic anhydrase (CA, EC 4.2.1.1) from the pathogenic bacterium Francisella tularensis (FtuβCA) was cloned and purified, and the anion inhibition profile was investigated. Based on the measured kinetic parameters for the enzyme catalyzed CO2 hydration reaction (kcat of 9.8×10(5)s(-1) and a kcat/KM of 8.9×10(7)M(-1)s(-1)), FtuβCA is a highly effective enzyme. The activity of FtuβCA was not inhibited by a range of anions that do not typically coordinate Zn(II) effectively, including perchlorate, tetrafluoroborate, and hexafluorophosphate. Surprisingly, some anions which generally complex well with many cations, including Zn(II), also did not effectively inhibit FtuβCA, e.g., fluoride, cyanide, azide, nitrite, bisulphite, sulfate, tellurate, perrhenate, perrhuthenate, and peroxydisulfate. However, the most effective inhibitors were in the range of 90-94µM (sulfamide, sulfamic acid, phenylarsonic and phenylboronic acid). N,N-Diethyldithiocarbamate (KI of 0.31mM) was a moderately potent inhibitor. As Francisella tularensis is the causative agent of tularemia, the discovery of compounds that can interfere with the life cycle of this pathogen may result in novel opportunities to fight antibiotic drug resistance. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Comparison of the anion inhibition profiles of the β- and γ-carbonic anhydrases from the pathogenic bacterium Burkholderia pseudomallei.

    PubMed

    Del Prete, Sonia; Vullo, Daniela; di Fonzo, Pietro; Carginale, Vincenzo; Supuran, Claudiu T; Capasso, Clemente

    2017-03-15

    We report the cloning, purification and characterization of BpsβCA, a β-class carbonic anhydrase (CA, EC 4.2.1.1) from the pathogenic bacterium Burkholderia pseudomallei, the etiological agent of melioidosis, and compare its activity and inhibition with those of the γ-CA from the same organism, BpsγCA, recently investigated by our groups. BpsβCA showed a significant catalytic activity for the physiologic, CO2 hydration reaction, with the following kinetic parameters, kcat of 1.6×10(5)s(-1) and kcat/Km of 3.4×10(7)M(-1)×s(-1). The inhibition of BpsβCA with a group of anions and small molecules was also investigated. The best inhibitors were sulfamide, sulfamic acid and phenylarsonic acid, which showed KIs in the range of 83-92µM, whereas phenylboronic acid, fluoride, cyanide, azide, bisulfite, tetraborate, perrhenate, perruthenate, peroxydisulfate, perchlorate, tetrafluoroborate, fluorosulfonate and hexafluorophosphate showed KIs>100mM. Other inhibitors of this new enzyme were bicarbonate, trithiocarbonate, some complex inorganic anions and N,N-diethyldithiocarbamate, which had inhibition constants of 0.32-8.6mM. As little is known of the life cycle and virulence of this bacterium, this type of study may bring information of interest for the development of novel strategies to fight bacterial infection and drug resistance to commonly used antibiotics. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Anion inhibition profiles of the γ-carbonic anhydrase from the pathogenic bacterium Burkholderia pseudomallei responsible of melioidosis and highly drug resistant to common antibiotics.

    PubMed

    Del Prete, Sonia; Vullo, Daniela; Di Fonzo, Pietro; Osman, Sameh M; AlOthman, Zeid; Supuran, Claudiu T; Capasso, Clemente

    2017-01-15

    Burkholderia pseudomallei is a Gram-negative saprophytic bacterium responsible of melioidosis, an endemic disease of tropical and sub-tropical regions of the world. A recombinant γ-CA (BpsγCA) identified in the genome of this bacterium was cloned and purified. Its catalytic activity and anion inhibition profiles were investigated. The enzyme was an efficient catalyst for the CO2 hydration showing a kcat of 5.3×10(5)s(-1) and kcat/Km of 2.5×10(7)M(-1)×s(-1). The best BpsγCA inhibitors were sulfamide, sulfamic acid, phenylboronic acid and phenylarsonic acid, which showed KI in the range of 49-83μM (these inhibitors showed millimolar inhibition constant against hCA II), followed by diethyldithiocarbamate, selenate, tellurate, perrhenate, selenocyanate, trithiocarbonate, tetraborato, pyrophosphate, stannate, carbonate, bicarbonate, azide, cyanide, thiocyanate and cyanate with KIs in the range of 0.55-9.1mM. In our laboratories, work is in progress to resolve the X-ray crystal structures of BpsγCA, which may allow the development of small molecule inhibitors with desired properties for targeting and inhibiting specifically the bacterial over the human CAs, considering the fact that B. pseudomallei is involved in a serious bacterial disease. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. 188Rhenium-induced cell death and apoptosis in a panel of tumor cell lines

    NASA Astrophysics Data System (ADS)

    Antoccia, Antonio; Banzato, Alessandra; Bello, Michele; Bollini, Dante; De Notaristefani, Francesco; Giron, Cecilia; Mazzi, Ulderico; Alafort, Laura Melendez; Moschini, Giuliano; Nadali, Anna; Navarria, Francesco; Perrotta, Andrea; Rosato, Antonio; Tanzarella, Caterina; Uzunov, Nikolay

    2007-02-01

    Assessment of "in vitro" tumor growth inhibition and radiobiological effects, such as apoptosis, have been evaluated in human neoplastic cells of different histotypes (H460 lung cancer cells, U87 glioblastoma, LnCaP prostate tumor cells) treated using solutions of 188Rhenium-perrhenate. The MTT assay, which measures mitochondrial metabolism in the entire cell culture is a recognized test for cytotoxicity and was used in cells exposed 48-72 h to specific activities ranged from 37 to 148 GBq/l. Whereas H460 and LnCaP were particularly sensitive to treatment, U87 glioblastoma cells behaved as radioresistant ones. However, evaluation of 188Re-induced apoptosis indicated that this kind of cell death contributed only marginally to the reduction in cell viability of H460 and LNCaP lines, suggesting the existence of protective mechanisms against apoptosis. In this respect, the membrane receptor, CD44, whose expression is dysregulated in most malignant cell types has proven to alter the response of cancer cells to apoptotic stimuli, including ionizing radiation. Cell samples decorated with a FITC-labelled CD44 antibody indicated, that in H460 and U87 cells the CD44(+) correlated well with an apoptosis-resistant response. Conversely, LnCap cells proven as CD44(-) did not display however sensitivity to radio-induced apoptosis.

  18. Radiant{trademark} Liquid Radioisotope Intravascular Radiation Therapy System

    SciTech Connect

    Eigler, N.; Whiting, J.; Chernomorsky, A.; Jackson, J.; Knapp, F.F., Jr.; Litvack, F.

    1998-01-16

    RADIANT{trademark} is manufactured by United States Surgical Corporation, Vascular Therapies Division, (formerly Progressive Angioplasty Systems). The system comprises a liquid {beta}-radiation source, a shielded isolation/transfer device (ISAT), modified over-the-wire or rapid exchange delivery balloons, and accessory kits. The liquid {beta}-source is Rhenium-188 in the form of sodium perrhenate (NaReO{sub 4}), Rhenium-188 is primarily a {beta}-emitter with a physical half-life of 17.0 hours. The maximum energy of the {beta}-particles is 2.1 MeV. The source is produced daily in the nuclear pharmacy hot lab by eluting a Tungsten-188/Rhenium-188 generator manufactured by Oak Ridge National Laboratory (ORNL). Using anion exchange columns and Millipore filters the effluent is concentrated to approximately 100 mCi/ml, calibrated, and loaded into the (ISAT) which is subsequently transported to the cardiac catheterization laboratory. The delivery catheters are modified Champion{trademark} over-the-wire, and TNT{trademark} rapid exchange stent delivery balloons. These balloons have thickened polyethylene walls to augment puncture resistance; dual radio-opaque markers and specially configured connectors.

  19. Syntheses and structural characterization of rhenium-bis-hydrazinopyrimidine core complexes with thiolate and Schiff base coligands.

    PubMed

    Femia, Frank J; Chen, Xiaoyuan; Maresca, Kevin P; Babich, John W; Zubieta, Jon

    2000-12-15

    The reaction of perrhenate with 2-hydrazinopyrimidine in MeOH-HCl yields [ReCl(3)(eta(1)-NNC(4)H(3)N(2)H)(eta(2)-HNNC(4)H(3)N(2))] (1). The analogous reaction with Na(2)MoO(4) yields [MoCl(3)(eta(1)-NNC(4)H(3)N(2)H)(eta(2)-HNNHC(4)H(3)N(2))] (1a). The reaction of 1 with pyrimidine-2-thiol and triethylamine produces [Re(eta(1)-C(4)H(3)N(2)S)(eta(2)-C(4)H(3)N(2)S)(eta(1)-NNC(4)H(3)N(2))(eta(2)-HNNC(4)H(3)N(2))] (2), while reaction of 1 with the Schiff base HSC(6)H(4)N=C(H)C(6)H(4)OH provides [Re(eta(3)-SC(6)H(4)N=C(H)C(6)H(4)O)(eta(1)-NNC(4)H(3)N(2))(eta(2)-C(6)H(4)O)(eta(1)-NNC(5)H(4)N)(eta(2)-HNNC(5)H(4)N)] (4), was also synthesized by reacting [ReCl(3)(eta(1)-NNC(5)H(4)NH)(eta(2)-HNNC(5)H(4)N)] with HSC(6)H(4)N=C(H)C(6)H(4)OH. The crystal structures of 1-4 have been determined.

  20. Synthesis and properties of pyrazine-pillared Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7} and AgReO{sub 4} layered phases

    SciTech Connect

    Lin Haisheng; Yan Bangbo; Boyle, Paul D.; Maggard, Paul A. . E-mail: Paul_Maggard@ncsu.edu

    2006-01-15

    The new pyrazine-pillared solids, AgReO{sub 4}(C{sub 4}H{sub 4}N{sub 2}) (I) and Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7}(C{sub 4}H{sub 4}N{sub 2}){sub 3} (C{sub 4}H{sub 4}N{sub 2}=pyrazine, pyz) (II), were synthesized by hydrothermal methods at 150 deg. C and characterized using single crystal X-ray diffraction (I-P2{sub 1} /c, No. 14, Z=4, a=7.2238(6) A, b=7.4940(7) A, c=15.451(1) A, {beta}=92.296(4){sup o}; II-P2/n, No. 13, Z=2, a=7.6465(9) A, b=7.1888(5) A, c=19.142(2) A, {beta}=100.284(8){sup o}), thermogravimetric analysis, UV-Vis diffuse reflectance, and photoluminescence measurements. Individual Ag(pyz) chains in I are bonded to three perrhenate ReO{sub 4} {sup -} tetrahedra per layer, while each layer in II contains sets of three edge-shared Ag(pyz) chains ({pi}-{pi} stacked) that are edge-shared to four Mo{sub 2}O{sub 4}F{sub 7} {sup 3-} dimers. A relatively small interlayer spacing results from the short length of the pyrazine pillars, and which can be removed at just slightly above their preparation temperature, at >150-175 deg. C, to produce crystalline AgReO{sub 4} for I, and Ag{sub 2}MoO{sub 4} and an unidentified product for II. Both pillared solids exhibit strong orange-yellow photoemission, at 575 nm for I and 560 nm for II, arising from electronic excitations across (charge transfer) band gaps of 2.91 and 2.76 eV in each, respectively. Their structures and properties are analyzed with respect to parent 'organic free' silver perrhenate and molybdate solids which manifest similar photoemissions, as well as to the calculated electronic band structures. -- Graphical abstract: Two new pyrazine-pillared hybrid solids have been synthesized under hydrothermal conditions, Ag{sub 3}Mo{sub 2}O{sub 4}F{sub 7}(pyz){sub 3} (shown) and AgReO{sub 4}(pyz). These solids are novel examples of layered structures containing pillaring Ag(pyz) chains and also the unique Mo{sub 2}O{sub 4}F{sub 7} {sup 3-} dimer in the former. Both exhibit orange-yellow photoluminescence, and

  1. RHENIUM SOLUBILITY IN BOROSILICATE NUCLEAR WASTE GLASS IMPLICATIONS FOR THE PROCESSING AND IMMOBILIZATION OF TECHNETIUM-99 (AND SUPPORTING INFORMATION WITH GRAPHICAL ABSTRACT)

    SciTech Connect

    AA KRUGER; A GOEL; CP RODRIGUEZ; JS MCCLOY; MJ SCHWEIGER; WW LUKENS; JR, BJ RILEY; D KIM; M LIEZERS; P HRMA

    2012-08-13

    The immobilization of 99Tc in a suitable host matrix has proved a challenging task for researchers in the nuclear waste community around the world. At the Hanford site in Washington State in the U.S., the total amount of 99Tc in low-activity waste (LAW) is {approx} 1,300 kg and the current strategy is to immobilize the 99Tc in borosilicate glass with vitrification. In this context, the present article reports on the solubility and retention of rhenium, a nonradioactive surrogate for 99Tc, in a LAW sodium borosilicate glass. Due to the radioactive nature of technetium, rhenium was chosen as a simulant because of previously established similarities in ionic radii and other chemical aspects. The glasses containing target Re concentrations varying from 0 to10,000 ppm by mass were synthesized in vacuum-sealed quartz ampoules to minimize the loss of Re by volatilization during melting at 1000 DC. The rhenium was found to be present predominantly as Re7 + in all the glasses as observed by X-ray absorption near-edge structure (XANES). The solubility of Re in borosilicate glasses was determined to be {approx}3,000 ppm (by mass) using inductively coupled plasma-optical emission spectroscopy (ICP-OES). At higher rhenium concentrations, some additional material was retained in the glasses in the form of alkali perrhenate crystalline inclusions detected by X-ray diffraction (XRD) and laser ablation-ICP mass spectrometry (LA-ICP-MS). Assuming justifiably substantial similarities between Re7 + and Tc 7+ behavior in this glass system, these results implied that the processing and immobilization of 99Tc from radioactive wastes should not be limited by the solubility of 99Tc in borosilicate LAW glasses.

  2. Ambient aging of rhenium filaments used in thermal ionization mass spectrometry: Growth of oxo-rhenium crystallites and anti-aging strategies.

    PubMed

    Mannion, Joseph M; Wellons, Matthew S; Shick, Charles R; Fugate, Glenn A; Powell, Brian A; Husson, Scott M

    2017-01-01

    Degassing is a common preparation technique for rhenium filaments used for thermal ionization mass spectrometric analysis of actinides, including plutonium. Although optimization studies regarding degassing conditions have been reported, little work has been done to characterize filament aging after degassing. In this study, the effects of filament aging after degassing were explored to determine a "shelf-life" for degassed rhenium filaments, and methods to limit filament aging were investigated. Zone-refined rhenium filaments were degassed by resistance heating under high vacuum before exposure to ambient atmosphere for up to 2 months. After degassing the nucleation and preferential growth of oxo-rhenium crystallites on the surface of polycrystalline rhenium filaments was observed by atomic force microscopy and scanning electron microscopy (SEM). Compositional analysis of the crystallites was conducted using SEM-Raman spectroscopy and SEM energy dispersive X-ray spectroscopy, and grain orientation at the metal surface was investigated by electron back-scatter diffraction mapping. Spectra collected by SEM-Raman suggest crystallites are composed primarily of perrhenic acid. The relative extent of growth and crystallite morphology were found to be grain dependent and affected by the dissolution of carbon into filaments during annealing (often referred to as carbonization or carburization). Crystallites were observed to nucleate in region specific modes and grow over time through transfer of material from the surface. Factors most likely to affect the rates of crystallite growth include rhenium substrate properties such as grain size, orientation, levels of dissolved carbon, and relative abundance of defect sites; as well as environmental factors such as length of exposure to oxygen and relative humidity. Thin (∼180 nm) hydrophobic films of poly(vinylbenzyl chloride) were found to slow the growth of oxo-rhenium crystallites on the filament surfaces and may serve as

  3. Design and construction of a imaging instrument for studying ion emission from pure ion emitters

    SciTech Connect

    Olson, John E.

    1993-09-01

    The development of new ion sources is important in the area of surface analysis to make it easier to perform more sensitive and accurate analyses. In surface analysis a primary ion beam composed of a single species can help when predicting and interpreting the results. Therefore, much interest and effort has been focused on producing pure ion emitters. An instrument has been designed and constructed to view the current densities of the ions being emitted from pure ion emitters. The instrument electrostatically accelerates and focuses the ion beam onto a microchannel plate detector equipped with a phosphor screen for viewing the images. These images are used to identify areas of enhanced ion emission. Once these areas are identified, the investigator can use other instruments to analyze them, and hopefully develop a better understanding of the chemistry and physics involved in the ion emission process. A computer based control system has been integrated into the system to simplify the operation of the instrument and provide safety features to protect the hardware from damage. A closed-circuit video camera system is used to allow the images to be remotely viewed during imaging procedures. Experiments show that the instrument has a lower detection limit of 7.45 x 103 ions/sec/mm2 and a spatial resolution of approximately 3 - 4 μm. Results from imaging cesium zeolite and perrhenate ion sources indicate that the ions are primarily being emitted from the surface of the sources and not from the interfacial region between the substrate and the emitter material.

  4. Evaluation of 188Re-DTPA-deoxyglucose as a potential cancer radiopharmaceutical.

    PubMed

    Chen, Yue; Xiong, Qing-Feng; Yang, Xi-Qun; He, Ling; Huang, Zhan-Wen

    2010-03-01

    We aimed to synthesize diethylenetriamine pentaacetic acid-deoxyglucose (DTPA-DG) radiolabeled with (188)Re and to evaluate its biologic characteristics using mammary tumor-bearing mice. The biodistribution of the radiolabeled compound was determined by tissue counting at 3, 12, and 24 hours after injection in experimental animals. Scintigraphic examinations of nude mice bearing breast cancer (MCF-7 cells) were performed after (188)Re-DTPA-DG (18.5 MBq) was injected in the tail vein. For the tumor inhibitory portion of this work, tumor volumes were measured and recorded every 3 days until the 21st day after injection. The radiochemical purity of (188)Re-DTPA-DG was 95.0%. Based on biodistribution measurements, (188)Re-DTPA-DG was taken up at high levels by the tumor. The mean tumoral percent injected dosages per gram (% ID/g) were 1.98 +/- 0.29 (SD), 2.89 +/- 0.43, and 0.42 +/- 0.06 % ID/g at 3, 12, and 24 hours, respectively, after injection. In the (188)Re-DTPA-DG scintigraphic examinations, the tumors were clearly delineated on the images recorded 2, 4, 8, 12, and 24 hours after injection. In the tumor inhibitory evaluations, the tumor volume of the (188)Re-DTPA-DG-treated group increased more slowly than that of the control groups, which were treated with (188)Re-perrhenate or saline (p < 0.01). Rhenium-188-DTPA-DG showed excellent tumor targeting and tumor growth suppression properties on MCF-7 tumor cells. Rhenium-188-DTPA-DG may be a potential agent for the diagnosis and radiotherapy of tumors.

  5. Ultra-small rhenium nanoparticles immobilized on DNA scaffolds: An excellent material for surface enhanced Raman scattering and catalysis studies.

    PubMed

    Anantharaj, S; Sakthikumar, K; Elangovan, Ayyapan; Ravi, G; Karthik, T; Kundu, Subrata

    2016-12-01

    Highly Sensitive and ultra-small Rhenium (Re) metal nanoparticles (NPs) were successfully stabilized in water by the staging and fencing action of the versatile biomolecule DNA that resulted in two distinct aggregated chain-like morphologies with average grain sizes of 1.1±0.1nm and 0.7±0.1nm for the very first time within a minute of reaction time. Re NPs are formed by the borohydride reduction of ammonium perrhenate (NH4ReO4) in the presence of DNA at room temperature (RT) under stirring. The morphologies were controlled by carefully monitoring the molar ratio of NH4ReO4 and DNA. The synthesized material was employed in two potential applications: as a substrate for surface enhanced Raman scattering (SERS) studies and as a catalyst for the reduction of aromatic nitro compounds. SERS study was carried out by taking methylene blue (MB) as the probe and the highest SERS enhancement factor (EF) of 2.07×10(7) was found for the aggregated chain-like having average grain size of 0.7±0.1nm. Catalytic reduction of 4-nitro phenol (4-NP), 2-nitro phenol (2-NP) and 4-nitroaniline (4-NA) with a rate constant value of 6×10(-2)min(-1), 33.83×10(-2)min(-1) and 37.4×10(-2)min(-1) have testified the excellent catalytic performance of our Re NPs immobilized on DNA. The overall study have revealed the capability of DNA in stabilizing the highly reactive Re metal at nanoscale and made them applicable in practice. The present route can also be extended to prepare one dimensional (1-D), self-assembled NPs of other reactive metals, mixed metals or even metal oxides for specific applications in water based solutions. Copyright © 2016 Elsevier Inc. All rights reserved.

  6. Palliation and Survival After Repeated Re-188-HEDP Therapy of Hormone-Refractory Bone Metastases of Prostate Cancer: A Retrospsective Analysis

    SciTech Connect

    Knapp Jr, Russ F

    2011-01-01

    This retrospective study compared the effects of single and multiple administrations of {sup 186}Re-hydroxyethylidenediphosphonate (186Re-HEDP) on palliation and survival of prostate cancer patients presenting with more than 5 skeletal metastases. Methods: A total of 60 patients were divided into 3 groups. Group A (n = 19) consisted of patients who had received a single injection; group B (n = 19), patients who had 2 injections; and group C (n = 22), patients who had 3 or more successive injections. The {sup 188}Re-HEDP was prepared using non-carrier-added {sup 188}Re obtained from an in-house {sup 188}W/{sup 188}Re generator after dilution with carrier perrhenate. Patients data available from the referring physicians - including prostate-specific antigen levels - were entered into a Windows-based matrix and analyzed using a statistical program. The Gleason scores were similar for all 3 groups. Results: Mean survival from the start of treatment was 4.50 {+-} 0.81 mo (95% confidence interval [CI], 2.92-6.08) for group A, 9.98 {+-} 2.21 mo (95% CI, 5.65-14.31) for group B, and 15.66 {+-} 3.23 (95% CI, 9.33-22.0) for group C. Although the 3 groups did not differ in Gleason score, the number of lost life-years was significantly lower in group C than in groups A and B. Pain palliation was achieved in 89.5% of group A, 94.7% of group B, and 90.9% of group C. Conclusion: Posttreatment overall survival could be improved from 4.50 to 15.66 mo by multiple-injection bone-targeted therapy with {sup 188}Re-HEDP, when compared with a single injection. Significant pain palliation was common and independent of administration frequency.

  7. Electrically switched cesium ion exchange. FY 1997 annual report

    SciTech Connect

    Lilga, M.A.; Orth, R.J.; Sukamto, J.P.H.

    1997-09-01

    This paper describes the Electrically Switched Ion Exchange (ESIX) separation technology being developed as an alternative to ion exchange for removing radionuclides from high-level waste. Progress in FY 1997 for specific applications of ESIX is also outlined. The ESIX technology, which combines ion exchange and electrochemistry, is geared toward producing electroactive films that are highly selective, regenerable, and long lasting. During the process, ion uptake and elution can be controlled directly by modulating the potential of an ion exchange film that has been electrochemically deposited onto a high surface area electrode. This method adds little sodium to the waste stream and minimizes the secondary wastes associated with traditional ion exchange techniques. Development of the ESIX process is well underway for cesium removal using ferrocyanides as the electroactive films. Films having selectivity for perrhenate (a pertechnetate surrogate) over nitrate also have been deposited and tested. Based on the ferrocyanide film capacity, stability, rate of uptake, and selectivity shown during performance testing, it appears possible to retain a consistent rate of removal and elute cesium into the same elution solution over several load/unload cycles. In batch experiments, metal hexacyanoferrate films showed high selectivities for cesium in concentrated sodium solutions. Cesium uptake was unaffected by Na/Cs molar ratios of up to 2 x 10{sup 4} , and reached equilibrium within 18 hours. During engineering design tests using 60 pores per inch, high surface area nickel electrodes, nickel ferrocyanide films displayed continued durability. losing less than 20% of their capacity after 1500 load/unload cycles. Bench-scale flow system studies showed no change in capacity or performance of the ESIX films at a flow rate up to 13 BV/h, the maximum flow rate tested, and breakthrough curves further supported once-through waste processing. 9 refs., 24 figs.

  8. DOE FG02-03ER63557: Final Technical Report: Reactivity of Primary Soil Minerals and Secondary Precipitates Beneath Leaking Hanford Waste Tanks

    SciTech Connect

    Kathryn L. Nagy

    2009-05-04

    The purpose of the project was to investigate rates and mechanisms of reactions between primary sediment minerals and key components of waste tank solutions that leaked into the subsurface at the Hanford Site. Results were expected to enhance understanding of processes that cause (1) changes in porosity and permeability of the sediment and resultant changes in flow paths of the contaminant plumes, (2) formation of secondary precipitates that can take up contaminants in their structures, and (3) release of mineral components that can drive redox reactions affecting dissolved contaminant mobility. Measured rates can also be used directly in reactive transport models. Project tasks included (1) measurement of the dissolution rates of biotite mica from low to high pH and over a range of temperature relevant to the Hanford subsurface, (2) measurement of dissolution rates of quartz at high pH and in the presence of dissolved alumina, (3) measurement of the dissolution rates of plagioclase feldspar in high pH, high nitrate, high Al-bearing solutions characteristic of the BX tank farms, (4) incorporation of perrhenate in iron-oxide minerals as a function of pH, and (5) initiation of experiments to measure the formation of uranium(VI)-silicate phases under ambient conditions. Task 2 was started under a previous grant from the Environmental Management Science Program and Task 4 was partially supported by a grant to the PI from the Geosciences Program, Office of Basic Energy Sciences. Task 5 was continued under a subsequent grant from the Environmental Remediation Sciences Program, Office of Biological and Environmental Research.

  9. Technetium (VII) Co-precipitation with Framework Aluminosilicates

    SciTech Connect

    Harsh, James B.; Dickson, Johnbull Otah; Pierce, Eric M.; Bargar, John

    2015-07-13

    Technetium-99 (99Tc), a long-lived radionuclide, is one of the most widespread contaminants within the Hanford subsurface. At some depths, it is only extractable with strong acids, suggesting incorporation into a solid phase. We hypothesized that Tc may have coprecipitated with feldspathoid aluminosilicates under waste tanks that had leaked caustic solutions into the vadose zone. Our objectives were to determine if Tc could be incorporated into the feldspathoids cancrinite and sodalite and under what conditions coprecipitation could occur. Our hypothesis was that sodalite was more likely to incorporate and retain Tc. Our approach was to use known methods of feldspathoid formation in solutions resembling those in Hanford waste tanks contacting sediments in terms of major ion (Na, NO3, OH, Al(OH)4, and Si(OH)4 concentrations. In some cases, Al and Si were supplied from zeolite. We used perrhenate (ReO4) as a surrogate for pertechnetate (TcO4) to avoid the radioactivity. The major findings of this study were 1) ReO4 could be incorporated into either sodalite or cancrinite but the concentration in the solid was < 1% of the competing ion Cl, NO3, or NO2. 2) The small amount of ReO4 incorporated was not exchangeable with NO3 or NO2. 3) In sodalite, NO3 was highly preferred over ReO4 but significant Re-sodalite was formed when the mole fraction in solution (Re/Re+N) exceeded 0.8. 4) A nonlinear relation between the unit cell parameter and amount of Re incorporated suggested that a separate Re-sodalite phase was formed rather than a solid solution. 5) We determined that sodalite preference for sodalite in the presence of different anions increased with the ionic size of the competing anion: Cl < CO3 < NO3 < SO4 < MnO4 < WO4 and significant incorporation did not occur unless the difference in anion radii was less than 12%. 6) Re(VII) was not significantly reduced to Re(IV) under the conditions of this experiment and Re appeared to be a good surrogate for Tc under oxidizing

  10. Preparation and initial characterization of fluidized bed steam reforming pure-phase standards

    SciTech Connect

    Missimer, D. M.; Rutherford, R. L.

    2013-03-21

    Hanford is investigating the Fluidized Bed Steam Reforming (FBSR) process for their Low Activity Waste. The FBSR process offers a low-temperature continuous method by which liquid waste can be processed with the addition of clay into a sodium aluminosilicate (NAS) waste form. The NAS waste form is mainly comprised of nepheline (NaAlSiO{sub 4}), sodalite (Na{sub 8}[AlSiO{sub 4}]{sub 6}Cl{sub 2}), and nosean (Na{sub 8}[AlSiO{sub 4}]{sub 6}SO{sub 4}). Anions such as perrhenate (ReO{sub 4}{sup -}), pertechnetate (TcO{sub 4}{sup -}), and iodine (I{sup -}) are expected to replace sulfate in the nosean structure and/or chloride in the sodalite mineral structure (atomically bonded inside the aluminosilicate cages that these mineral structures possess). In the FBSR waste form, each of these phases can exist in a variety of solid solutions that differ from the idealized forms observed in single crystals in nature. The lack of understanding of the durability of these stoichiometric or idealized mineral phases complicates the ability to deconvolute the durability of the mixed phase FBSR product since it is a combination of different NAS phases. To better understand the behavior, fabrication and testing of the individual phases of the FBSR product is required. Analytical Development (AD) of the Science and Technology directorate of the Savannah River National Laboratory (SRNL) was requested to prepare the series of phase-pure standards, consisting of nepheline, nosean, and Cl, Re, and I sodalite. Once prepared, X-ray Diffraction (XRD) analyses were used to confirm the products were phase pure. These standards are being used for subsequent characterization studies consisting of the following: single-pass flow-through (SPFT) testing, development of thermodynamic data, and x-ray diffraction (XRD) calibration curves. In addition to the above mentioned phase-pure standards, AD was tasked with fabricating a mixed Tc-Re sodalite.

  11. Interaction between anions and cationic metal complexes containing tridentate ligands with exo-C-H groups: complex stability and hydrogen bonding.

    PubMed

    Martínez-García, Héctor; Morales, Dolores; Pérez, Julio; Puerto, Marcos; del Río, Ignacio

    2014-05-05

    [Re(CO)3 ([9]aneS3 )][BAr'4 ] (1), prepared by reaction of ReBr(CO)5 , 1,4,7-trithiacyclononane ([9]aneS3 ) and NaBAr'4 , forms stable, soluble supramolecular adducts with chloride (2), bromide, methanosulfonate (3) and fluoride (4) anions. These new species were characterized by IR, NMR spectroscopy and, for 2 and 3, also by X-ray diffraction. The results of the solid state structure determinations indicate the formation of CH⋅⋅⋅X hydrogen bonds between the anion (X) and the exo-CH groups of the [9]aneS3 ligand, in accord with the relatively large shifts found by (1) H NMR spectroscopy in dichloromethane solution for those hydrogens. The stability of the chloride adduct contrasts with the lability of the [9]aneS3 ligand in allyldicarbonyl molybdenum complexes recently studied by us. With fluoride, in dichloromethane solution, a second, minor neutral dimeric species 5 is formed in addition to 4. In 4, the deprotonation of a CH group of the [9]aneS3 ligand, accompanied by CS bond cleavage and dimerization, afforded 5, featuring bridging thiolates. Compounds [Mo(η(3) -methallyl)(CO)2 (TpyN)][BAr'4 ] (6) and [Mo(η(3) -methallyl)(CO)2 (TpyCH)][BAr'4 ] (7) were synthesized by the reactions of [MoCl(η(3) -methallyl)(CO)2 (NCMe)2 ], NaBAr'4 and tris(2-pyridyl)amine (TpyN) or tris(2-pyridyl)methane (TpyCH) respectively, and characterized by IR and (1) H and (13) C NMR spectroscopy in solution, and by X-ray diffraction in the solid state. Compound 6 undergoes facile substitution of one of the 2-pyridyl groups by chloride, bromide, and methanosulfonate anions. Stable supramolecular adducts were formed between 7 and chloride, bromide, iodide, nitrate, and perrhenate anions. The solid state structures of these adducts (12-16) were determined by X-ray diffraction. Binding constants in dichloromethane were calculated from (1) H NMR titration data for all the new supramolecular adducts. The signal of the bridgehead CH group is the one that undergoes a

  12. Tc and Re behavior in borosilicate waste glass vapor hydration tests.

    PubMed

    McKeown, David A; Buechele, Andrew C; Lukens, Wayne W; Shuh, David K; Pegg, Ian L

    2007-01-15

    Technetium, found in some nuclear wastes (such as those generated from spent fuel reprocessing), is of particular concern with regard to long-term waste storage because of its long half-life (2.13 x 10(5) years) and high mobility in the environment. One method of stabilization of such waste is through vitrification to produce a durable borosilicate glass matrix. The fate of Tc under hydrothermal conditions in the vapor hydration test (VHT) was studied to assess and possibly predict the long-term rate of release of Tc from borosilicate waste glass. For comparison, the fate of rhenium, the preferred nonradioactive surrogate for Tc, was similarly studied. X-ray absorption spectroscopy (XAS) and scanning electron microscopy (SEM) measurements were made on each original borosilicate glass and the corresponding sample after the VHT. Tc K-edge XAS indicates that, despite starting with different Tc(IV) and Tc(VII) distributions in each glass, both corresponding VHT samples contain 100% Tc(IV). The Tc reduction within the VHT samples may be driven by the low-oxygen atmosphere compounded by oxygen depletion from corrosion of the surrounding stainless steel vessel. From SEM analyses, both of the Tc-containing VHT samples show complete alteration of the original glass, significant Tc enrichment near the sample surface, and nearly complete depletion of Tc toward the sample center. XAS indicates Tc(IV)O6 octahedra, possibly within gel-like amorphous silicates in both VHT samples, where Tc-Tc correlations are observed in the higher Tc-content VHT sample. Re L(II)-edge XAS and SEM indicate quite different behavior for Re under VHT conditions. The Re oxidation state appears to be invariant with respect to the VHT treatment, where perrhenate (Re(VII)) species are dominant in all Re-containing samples investigated; Re2O7 concentrations are low near the sample surface and increase to approach that of the unreacted glass toward the sample center.

  13. Synthesis and Characterization of Organohydrazino Complexes of Technetium, Rhenium, and Molybdenum with the {M(eta(1)-H(x)()NNR)(eta(2)-H(y)()NNR)} Core and Their Relationship to Radiolabeled Organohydrazine-Derivatized Chemotactic Peptides with Diagnostic Applications.

    PubMed

    Rose, David J.; Maresca, Kevin P.; Nicholson, Terrence; Davison, Alan; Jones, Alun G.; Babich, John; Fischman, Alan; Graham, Wendy; DeBord, Jeffery R. D.; Zubieta, Jon

    1998-06-01

    The reduction of perrhenate, molybdate and pertechnetate with 2-hydrazinopyridine dihydrochloride in methanol has led to the preparation of a class of complexes containing the {M(eta(1)-NNC(5)H(4)NH(x)())(eta(2)-HNNH(y)()C(5)H(4)N)} core, represented by [TcCl(3)(NNC(5)H(4)NH)(HNNC(5)H(4)N)] (2), [ReCl(3)(NNC(5)H(4)NH)(HNNC(5)H(4)N)] (3), and [MoCl(3)(NNC(5)H(4)NH)(HNNHC(5)H(4)N)] (6). The reaction of 3 with NEt(3) results in the formation of [HNEt(3)][[ReCl(3)(NNC(5)H(4)N)(HNNC(5)H(4)N)].H(2)O (4) by deprotonation of the pyridine nitrogen site. Similarly, the reduction of perrhenate with 2-hydrazino-2-imidazoline hydrobromide has led to the preparation of the analogous [ReCl(3)(NNC(3)H(4)N(2)H)(HNNHC(3)H(4)N(2)H)] (5). Reaction of 3 with pyridine-2-thiol and pyrimidine-2-thiol yields two structurally characterized derivatives with a modified {Re(eta(1)-NNC(5)H(4)N)(eta(2)-HNNC(5)H(4)N)} core, [Re(C(5)H(4)NS)(2)(NNC(5)H(4)N)(HNNC(5)H(4)N)] (8) and [Re(C(4)H(3)N(2)S)(2)(NNC(5)H(4)N)(HNNC(5)H(4)N)] (9), respectively. Reaction of 6 with pyrimidine-2-thiol led to the isolation of the analogous [Mo(C(4)H(3)N(2)S)(2)(NNC(5)H(4)N)(HNNHC(5)H(4)N)] (11) and the seven-coordinate monohydrazine core complex [Mo(C(4)H(3)N(2)S)(3)(NNC(5)H(4)N)].CH(2)Cl(2) (12). In similar fashion, the reaction of 2 with pyridine-2-thiol yielded a complex structurally analogous to 8, [Tc(C(5)H(4)NS)(2)(NNC(5)H(4)N)(HNNC(5)H(4)N)] (7). Crystal data for 3, C(10)H(10)Cl(3)N(6)Re: triclinic, P&onemacr;, a = 7.527(2) Å, b = 7.599(2) Å, c = 13.118(3) Å, alpha = 106.55(3) degrees, beta = 90.28(3) degrees, gamma = 93.83(3) degrees, V = 717.4(4) Å(3), Z = 2. For 4, C(16)H(27)Cl(3)N(7)ORe: orthorhombic, P2(1)2(1)2(1), a = 7.503(2) Å, b = 10.3643(2) Å, c = 30.1590(5) Å, V = 2345.20(6) Å(3), Z = 2. For 5, C(6)H(12)Cl(3)N(8)Re: monoclinic, P2(1)/n, a = 9.093(2) Å, b = 11.105(2) Å, c = 14.295(3) Å, beta = 94.71(3) degrees, V = 1438.6(7) Å(3), Z = 4. For 6, C(10)H(11)Cl(3)N(6)Mo: monoclinic, P2(1)/c

  14. Substitution features in the isomorphous replacement series for metal-organic compounds (Nb{sub x}Ta{sub 1-x}){sub 4}O{sub 2}(OMe){sub 14}(ReO{sub 4}){sub 2}, x=0.7, 0.5, 0.3-Single-source precursors of complex oxides with organized porosity

    SciTech Connect

    Nikonova, Olesya A.; Kessler, Vadim G.; Seisenbaeva, Gulaim A.

    2008-12-15

    Trimetallic oxoalkoxide complexes (Nb{sub 0.7}Ta{sub 0.3}){sub 4}O{sub 2}(OMe){sub 14}(ReO{sub 4}){sub 2} (I), (Nb{sub 0.3}Ta{sub 0.7}){sub 4}O{sub 2}(OMe){sub 14}(ReO{sub 4}){sub 2} (II) and (Nb{sub 0.5}Ta{sub 0.5}){sub 4}O{sub 2}(OMe){sub 14}(ReO{sub 4}){sub 2} (III) were obtained by the interaction of rhenium heptoxide (VII) Re{sub 2}O{sub 7} with niobium and tantalum alkoxides M{sub 2}(OMe){sub 10} (M=Nb, Ta) in toluene. The centrosymmetric molecules (I)-(III) can be considered as a product of condensation of two M{sub 2}(OMe){sub 9}(OReO{sub 3}) molecules with the formation of two oxo-bridges. The specific feature of the structure is the uneven distribution of metal atoms in the crystallographic positions, where one symmetry-independent position, connected via {mu}-O with a perrhenate ReO{sub 4}{sup -} group, is predominantly occupied by niobium atoms, while the other one connected via alkoxide groups has a higher tantalum content. The distribution of Nb and Ta in the structure is truly even only for compound III. The niobium and tantalum content is varied to a different extent for I (less) and for II (more), which is apparently due to small differences in the sizes of these two cations, resulting in preferences for packing of different molecules in the structures. Thermal decomposition of (Nb{sub 1-x}Ta{sub x}){sub 4}O{sub 2}(OMe){sub 14}(ReO{sub 4}){sub 2} (x=0.3, 0.5, 0.7) in air leads to the formation of crystalline species of solid solutions based on tantalum and niobium oxides displaying semi-ordered pores with the size of 100-250 nm. In the dry nitrogen atmosphere, the decomposition leads to the amorphous complex oxides containing rhenium, niobium and tantalum. - Graphical abstract: Thermal decomposition of (Nb{sub 1-x}Ta{sub x}){sub 4}O{sub 2}(OMe){sub 14}(ReO{sub 4}){sub 2} (x=0.3, 0.5, 0.7), single-source complex precursors, in air leads to the formation of crystalline solid solutions based on tantalum and niobium oxides, displaying semi