Synthesis and spectroscopic studies of binuclear metal complexes of a tetradentate N2O2 Schiff base ligand derived from 4,6-diacetylresorcinol and benzylamine.

PubMed

Shebl, Magdy

2008-09-01

A tetradentate N2O2 donor Schiff base ligand, H2L, was synthesized by the condensation of 4,6-diacetylresorcinol with benzylamine. The structure of the ligand was elucidated by elemental analyses, IR, 1H NMR, electronic and mass spectra. Reaction of the Schiff base ligand with nickel(II), cobalt(II), iron(III), cerium(III), vanadyl(IV) and uranyl(VI) ions in 1:2 molar ratio afforded binuclear metal complexes. Also, reaction of the ligand with several copper(II) salts, including Cl-, NO3-, AcO-, ClO4- and SO42- afforded different metal complexes that reflect the non-coordinating or weakly coordinating power of the ClO(4)(-) anion as compared to the strongly coordinating power of SO42- and Cl- anions. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, 1H NMR, electronic, mass and ESR spectra as well as magnetic susceptibility measurements. The metal complexes exhibited different geometrical arrangements such as square planar, octahedral, square pyramidal and pentagonal bipyramidal arrangements. The variety in the geometrical arrangements depends on the nature of both the anion and the metal ion.

Expanding the remarkable structural diversity of uranyl tellurites: hydrothermal preparation and structures of K[UO(2)Te(2)O(5)(OH)], Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O, beta-Tl(2)[UO(2)(TeO(3))(2)], and Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2).

PubMed

Almond, Philip M; Albrecht-Schmitt, Thomas E

2002-10-21

The reactions of UO(2)(C(2)H(3)O(2))(2).2H(2)O with K(2)TeO(3).H(2)O, Na(2)TeO(3) and TlCl, or Na(2)TeO(3) and Sr(OH)(2).8H(2)O under mild hydrothermal conditions yield K[UO(2)Te(2)O(5)(OH)] (1), Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O (2) and beta-Tl(2)[UO(2)(TeO(3))(2)] (3), or Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2) (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers that are bound by terminal oxo groups and tellurite anions. These UO(6) units span between one-dimensional chains of corner-sharing, square pyramidal TeO(4) polyhedra to create two-dimensional layers. Alternating corner-shared oxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional chains of corner-sharing TeO(4) units found in 1 are also present in 2. However, in 2 there are two distinct chains present, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are unprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional [UO(2)(TeO(3))(2)](2-) chains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ between 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite anions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO(3)(2-) anions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) A, b = 8.7416(6) A, c = 11.4413(8) A, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) A, b = 23.024(2) A, c = 7.9389(6) A, Z = 4; 3, monoclinic, space group P2(1)/n, a = 5.4766(4) A, b = 8.2348(6) A, c = 20.849(3) A, beta = 92.329(1) degrees, Z = 4; 4, monoclinic, space group C2/c, a = 20.546(1) A, b = 5.6571(3) A, c = 13.0979(8) A, beta = 94.416(1) degrees, Z = 4.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andreev, P. V., E-mail: andreev@phys.unn.ru; Somov, N. V.; Kalistratova, O. S.

The newly synthesized triphenylbismuth bis(3-phenylprop-2-enoate) was studied by X-ray diffraction and by IR, UV, and NMR spectroscopy. The crystals are monoclinic, sp. gr. C2/c, Z = 4, a = 13.2820(4) Å, b = 21.3750(2) Å, c = 12.2407(2) Å, β = 119.936(1)°. The coordination polyhedron of the bismuth atom can be described as a distorted pentagonal bipyramid.

On the origin of the cation templated self-assembly of uranyl-peroxide nanoclusters.

PubMed

Miró, Pere; Pierrefixe, Simon; Gicquel, Mickaël; Gil, Adrià; Bo, Carles

2010-12-22

Uranyl-peroxide nanoclusters display different topologies based on square, pentagonal and hexagonal building blocks. Computed complexation energies of different cations (Li(+), Na(+), K(+), Rb(+), and Cs(+)) with [UO(2)(O(2))(H(2)O)](n) (n = 4, 5, and 6) macrocycles suggest a strong cation templating effect. The inherent bent structure of a U-O(2)-U model dimer is demonstrated and justified through the analysis of its electronic structure, as well as of the inherent curvature of the four-, five-, and six-uranyl macrocyles. The curvature is enhaced by cation coordination, which is suggested to be the driving force for the self-assembly of the nanocapsules.

Synthesis, spectral and magnetic studies of mono- and bi-nuclear metal complexes of a new bis(tridentate NO2) Schiff base ligand derived from 4,6-diacetylresorcinol and ethanolamine.

PubMed

Shebl, Magdy

2009-07-15

A new bis(tridentate NO2) Schiff base ligand, H(4)L, was prepared by the reaction of the bifunctional carbonyl compound; 4,6-diacetylresorcinol (DAR) with ethanolamine. The ligand reacted with iron(III), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), cerium(III) and uranyl(VI) ions, in absence and in presence of LiOH, to yield mono- and bi-nuclear complexes with different coordinating sites. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. In absence of LiOH, mononuclear complexes (2, 3 and 5-9) as well as binuclear complexes (1 and 4) were obtained. In mononuclear complexes, the ligand acted as a neutral, mono- and di-basic/bi- and tetra-dentate ligand while in binuclear complexes (1 and 4), the ligand acted as a bis(mono- or di-basic/tridentate) ligand. On the other hand, in presence of LiOH, only binuclear complexes (10-15) were obtained in which the ligand acted as a bis(dibasic tridentate) ligand. The metal complexes exhibited different geometrical arrangements such as octahedral, tetrahedral, square planar, square pyramidal and pentagonal bipyramidal arrangements.

Selective Se-for-S substitution in Cs-bearing uranyl compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Tyumentseva, Olga S.; Krivovichev, Sergey V.

Phase formation in the mixed sulfate-selenate aqueous system of uranyl nitrate and cesium nitrate has been investigated. Two types of crystalline compounds have been obtained and characterized using a number of experimental (single crystal XRD, FTIR, SEM) and theoretical (information-based complexity calculations, topological analysis) techniques. No miscibility gaps have been observed for Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se), which crystallizes in tetragonal system, P-42{sub 1}m, a =9.616(1)–9.856(2), c =8.105(1)–8.159(1) Å, V =749.6(2)–792.5(3) Å{sup 3}. Nine phases with variable amount of S and Se have been structurally characterized. The structures of the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]more » (T= S, Se) compounds are based upon the [(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]{sup 2-} layers of corner-sharing uranyl pentagonal bipyramids and TO{sub 4} tetrahedra. The layers contain two types of tetrahedral sites: T1 (3-connected, i.e. having three O atoms shared by adjacent uranyl polyhedra) and T2 (4-connected). The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded T2 site. Crystallization in the pure Se system starts with the formation of Cs{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) crystals, its subsequent dissolution and formation of Cs{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}]. The information-based structural complexity calculations for these two phases support the rule that more topologically complex structures form at the latest stages of crystallization. - Graphical abstract: Nine phases representing the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) solid solution series with variable amount of S and Se have been prepared by isothermal evaporation from aqueous solutions and characterized using a number of experimental and theoretical techniques. No immiscibility is observed between the pure sulfate and selenate compounds. The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded 4-connected site. - Highlights: • Single crystals of novel mixed sulfate-selenate uranyl oxysalts were prepared by evaporation method. • Topological analysis and information-based complexity calculations were used for structure description. • The selective Se-for-S substitution was observed. • Evolution of phase formation in the aqueous Cs{sup +}–UO{sub 2}{sup 2+}–SO{sub 4}{sup 2–}–SeO{sub 4}{sup 2–} system was analyzed.« less

Syntheses and crystal structures of two topologically related modifications of Cs(2)[(UO(2))(2)(MoO(4))(3)].

PubMed

Krivovichev, S V; Cahill, C L; Burns, P C

2002-01-14

Two polymorphs of Cs(2)(UO(2))(2)(MoO(4))(3) have been synthesized by hydrothermal (alpha-phase) and high-temperature (beta-phase) routes. Both were characterized by single-crystal X-ray diffraction: alpha-Cs(2)(UO(2))(2)(MoO(4))(3), orthorhombic, Pna2(1), a = 20.4302(15) A, b = 8.5552(7) A, c = 9.8549(7) A, Z = 4; beta-Cs(2)(UO(2))(2)(MoO(4))(3), tetragonal, P4(2)/n, a = 10.1367(8) A, c = 16.2831(17) A, Z = 4. The structures of both phases consist of linked UO(7) pentagonal bipyramids and MoO(4) tetrahedra: alpha-Cs(2)(UO(2))(2)(MoO(4))(3) is a framework compound with large channels parallel to the c axis. Two cesium sites are located in these channels and are coordinated by 8 and 10 oxygen atoms. The structure of beta-Cs(2)(UO(2))(2)(MoO(4))(3) contains corrugated [(UO(2))(2)(MoO(4))(3)] sheets that are parallel to (001). The cesium cations are located between the sheets and are coordinated by eight oxygen atoms. The structures are topologically related; both can be described in terms of chains of 5-connected UO(7) pentagonal bipyramids and 3- and 4-connected MoO(4) tetrahedra.

The crystal structure of ianthinite, [U 24+(UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5: a possible phase for Pu 4+ incorporation during the oxidation of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Burns, Peter C.; Finch, Robert J.; Hawthorne, Frank C.; Miller, Mark L.; Ewing, Rodney C.

1997-10-01

Ianthinite, [U 24+(UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5, is the only known uranyl oxide hydrate mineral that contains U 4+, and it has been proposed that ianthinite may be an important Pu 4+-bearing phase during the oxidative dissolution of spent nuclear fuel. The crystal structure of ianthinite, orthorhombic, a = 0.7178(2), b = 1.1473(2), c = 3.039(1) nm, V = 2.5027 nm 3Z = 4, space group P2 1cn, has been solved by direct methods and refined by least-squares methods to an R index of 9.7% and a wR index of 12.6% using 888 unique observed [| F| ≥ 5 σ | F|] reflections. The structure contains both U 4+. The U 6+ cations are present as roughly linear (U 6+O 2) 2+ uranyl ion (Ur) that are in turn coordinated by five O 2- and OH - located at the equatorial positions of pentagonal bipyramids. The U 4+ cations are coordinated by O 2-, OH - and H 2O in a distorted octahedral arrangement. The Ur φ5and U 4+| 6 (φ: O 2-, OH -, H 2O) polyhedra l sharing edges to for two symmetrically distinct sheets at z ≈ 0.0 and z ≈ 0.25 that are parallel to (001). The sheets have the β-U 3O 8 sheet anion-topology. There are five symmetrically distinct H 2O groips located at z ≈ 0.125 between the sheets of U φn polyhedra, and the sheets of U φn polyhedra are linked together only by hydrogen bonding to the intersheet H 2O groups. The crystal-chemical requirements of U 4+ and Pu 4+ are very similar, suggesting that extensive Pu 4+ ↔ U 4+ substitution may occur within the sheets of U φn polyhedra in trh structure of ianthinine.

Uranyl-Peroxide Clusters Incorporating Iron Trimers and Bridging by Bisphosphonate- and Carboxylate-Containing Ligands.

PubMed

Qiu, Jie; Dong, Sining; Szymanowski, Jennifer E S; Dobrowolska, Malgorzata; Burns, Peter C

2017-04-03

A hybrid uranium-iron cage nanocluster, [(UO 2 ) 24 (FeOH) 24 (O 2 ) 24 (PO 4 ) 8 (CH(COO)(PO 3 ) 2 ) 24 ] 96- (U 24 Fe 24 ), was synthesized using bridging ligands containing bisphosphonate and carboxylate groups. U 24 Fe 24 contains six tetramers of uranyl hexagonal bipyramids and eight iron trimers, each of which consists of three corner-sharing Fe 3+ octahedra and is stabilized by in situ formed phosphate and 2,2-bis(phosphonato)acetate (C 2 P 2 ) groups. Tetramers and trimers are bridged by 24 C 2 P 2 groups into a cage cluster. Crystals of U 24 Fe 24 present a paramagnetic-like behavior. X-ray scattering showed that U 24 Fe 24 forms in the reactant solution prior to crystallization and is stable upon dissolution in water.

Infrared spectroscopy of extreme coordination: the carbonyls of U(+) and UO(2)(+).

PubMed

Ricks, Allen M; Gagliardi, Laura; Duncan, Michael A

2010-11-17

Uranium and uranium dioxide carbonyl cations produced by laser vaporization are studied with mass-selected ion infrared spectroscopy in the C-O stretching region. Dissociation patterns, spectra, and quantum chemical calculations establish that the fully coordinated ions are U(CO)(8)(+) and UO(2)(CO)(5)(+), with D(4d) square antiprism and D(5h) pentagonal bipyramid structures. Back-bonding in U(CO)(8)(+) causes a red-shifted CO stretch, but back-donation is inefficient for UO(2)(CO)(5)(+), producing a blue-shifted CO stretch characteristic of nonclassical carbonyls.

Crystal Chemistry of the Potassium and Rubidium Uranyl Borate Families Derived from Boric Acid Fluxes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Shuao; Alekseev, Evgeny V.; Stritzinger, Jared T.

2010-07-19

The reaction of uranyl nitrate with a large excess of molten boric acid in the presence of potassium or rubidium nitrate results in the formation of three new potassium uranyl borates, K{sub 2}[(UO{sub 2}){sub 2}B{sub 12}O{sub 19}(OH){sub 4}]·0.3H{sub 2}O (KUBO-1), K[(UO{sub 2}){sub 2}B{sub 10}O{sub 15}(OH){sub 5}] (KUBO-2), and K[(UO{sub 2}){sub 2}B{sub 10}O{sub 16}(OH){sub 3}]·0.7H{sub 2}O (KUBO-3) and two new rubidium uranyl borates Rb{sub 2}[(UO{sub 2}){sub 2}B{sub 13}O{sub 20}(OH){sub 5}] (RbUBO-1) and Rb[(UO{sub 2}){sub 2}B{sub 10}O{sub 16}(OH){sub 3}]·0.7H{sub 2}O (RbUBO-2). The latter is isotypic with KUBO-3. These compounds share a common structural motif consisting of a linear uranyl, UO{sub 2}{sup 2+},more » cation surrounded by BO{sub 3} triangles and BO{sub 4} tetrahedra to create an UO{sub 8} hexagonal bipyramidal environment around uranium. The borate anions bridge between uranyl units to create sheets. Additional BO{sub 3} triangles extend from the polyborate layers and are directed approximately perpendicular to the sheets. All of these compounds adopt layered structures. With the exception of KUBO-1, the structures are all centrosymmetric. All of these compounds fluoresce when irradiated with long-wavelength UV light. The fluorescence spectrum yields well-defined vibronically coupled charge-transfer features.« less

High pressure synthesis and properties of ternary titanium (III) fluorides in the system KF-TiF 3 containing regular pentagonal bipyramids [TiF 7

NASA Astrophysics Data System (ADS)

Yamanaka, Shoji; Yasuda, Akira; Miyata, Hajime

2010-01-01

Titanium trifluoride TiF 3 has the distorted ReO 3 structure composed of corner sharing TiF 6 octahedra linked with Ti-F-Ti bridges. Potassium fluoride KF was inserted into the bridges using high-pressure and high-temperature conditions (5 GPa, 1000-1200 °C). When the molar ratio KF/TiF 3≥1, a few low dimensional compounds were obtained forming non-bridged F ions. At the composition KF/TiF 3=1/2, a new compound KTi 2F 7 was formed, which crystallizes with the space group Cmmm and the lattice parameters of a=6.371(3), b=10.448(6), c=3.958(2) Å, consisting of edge-sharing pentagonal bipyramids [TiF 7] forming ribbons running along the a axis. The ribbons are linked by corners to construct a three-dimensional framework without forming non-bridged F ions. The compound is antiferromagnetic with the Néel temperature T N=75 K, and the optical band gap was 6.4 eV. A new fluoride K 2TiF 5 (KF/TiF 3=2) with the space group Pbcn and the lattice parameters of a=7.4626(2), b=12.9544(4) and c=20.6906(7) Å was also obtained by the high pressure and high temperature treatment (5 GPa at 1000 °C) of a molar mixture of 2 KF+TiF 3. The compound contains one-dimensional chains of corner-sharing TiF 6 octahedra.

Synthesis of Two New Group 13 Benzoato-Chloro Complexes: A Structural Study of Gallium and Indium Chelating Carboxylates

NASA Technical Reports Server (NTRS)

Duraj, Stan A.; Hepp, Aloysius F.; Woloszynek, Robert; Protasiewicz, John D.; Dequeant, Michael; Ren, Tong

2010-01-01

Two new heteroleptic chelated-benzoato gallium (III) and indium (III) complexes have been prepared and structurally characterized. The molecular structures of [GaCl2(4-Mepy)2(O2CPh)]4-Mepy (1) and [InCl(4-Mepy)2(O2CPh)2]4-Mepy (2) have been determined by single-crystal x-ray diffraction. The gallium compound (1) is a distorted octahedron with cis-chloride ligands co-planar with the chelating benzoate and the 4-methylpyridines trans to each other. This is the first example of a Ga(III) structure with a chelating benzoate. The indium compound (2) is a distorted pentagonal bipyramid with two chelating benzoates, one 4-methylpyridine in the plane and a chloride trans to the other 4-methylpyridine. The indium bis-benzoate is an unusual example of a seven-coordinate structure with classical ligands. Both complexes, which due to the chelates, could also be described as pseudo-trigonal bipyramidal, include a three-bladed motif with three roughly parallel aromatic rings that along with a solvent of crystallization and electron-withdrawing chloride ligand(s) stabilize the solid-state structures.

Mixed-metal uranium(VI) iodates: hydrothermal syntheses, structures, and reactivity of Rb[UO(2)(CrO(4))(IO(3))(H(2)O)], A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K, Rb, Cs), and K(2)[UO(2)(MoO(4))(IO(3))(2)].

PubMed

Sykora, Richard E; McDaniel, Steven M; Wells, Daniel M; Albrecht-Schmitt, Thomas E

2002-10-07

The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensional[UO(2)(CrO(4))(IO(3))(H(2)O)](-) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional [UO(2)(MoO(4))(IO(3))(2)](2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4.

Fast Kinetics of Calcium Signaling and Sensor Design

PubMed Central

Tang, Shen; Reddish, Florence; Zhuo, You; Yang, Jenny J.

2015-01-01

Fast calcium signaling is regulated by numerous calcium channels exhibiting high spatiotemporal profiles which are currently measured by fluorescent calcium sensors. There is still a strong need to improve the kinetics of genetically encoded calcium indicators (sensors) to capture calcium dynamics in the millisecond time frame. In this review, we summarize several major fast calcium signaling pathways and discuss the recent developments and application of genetically encoded calcium indicators to detect these pathways. A new class of genetically encoded calcium indicators designed with site-directed mutagenesis on the surface of beta-barrel fluorescent proteins to form a pentagonal bipyramidal-like calcium binding domain dramatically accelerates calcium binding kinetics. Furthermore, novel genetically encoded calcium indicators with significantly increased fluorescent lifetime change are advantageous in deep-field imaging with high light-scattering and notable morphology change. PMID:26151819

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abugideiri, F.; Kelland, M.A.; Poli, R.

Cp*MoH[sub 5](PMe[sub 3]) has been prepared from Cp*MoCl[sub 2](PMe[sub 3]) and LiAlH[sub 4]. The compound is analogous to the previously reported Cp*WH[sub 5](PMe[sub 3]) and CpWH[sub 5](PMe[sub 3]) (Green, M.L.H.; Parkin, G.J. Chem. Soc., Chem. Commun. 1984, 1467. Schrock, R. R.; et al. Organometallics 1986, 5, 1681) for which structural assignments were not made. A single sharp [sup 1]H-NMR resonance is observed for the five hydrides down to 183 K, consistent with either a static symmetric structure or a highly fluxional structure, either classical or nonclassical. The measured minimum longtudinal relaxation time, T[sub 1], is quite long (780 ms atmore » 400 MHz and 230 K) and consistent with a classical structure based on the pentagonal bipyramid which gives rise to a substantially anisotropic moment of inertia. 14 refs., 1 tab.« less

Structural and electronic investigations of PbTa4O11 and BiTa7O19 constructed from α-U3O8 types of layers

NASA Astrophysics Data System (ADS)

Boltersdorf, Jonathan; Maggard, Paul A.

2015-09-01

The PbTa4O11 and BiTa7O19 phases were prepared by ion-exchange and solid-state methods, respectively, and their structures were characterized by neutron time-of-flight diffraction and Rietveld refinement methods (PbTa4O11, R 3 (No. 146), a=6.23700(2) Å, c=36.8613(1) Å; BiTa7O19, P 6 bar c 2 (No. 188), a=6.2197(2) Å, c=20.02981(9) Å). Their structures are comprised of layers of TaO6 octahedra surrounded by three 7-coordinate Pb(II) cations or two 8-coordinate Bi(III) cations. These layers alternate down the c-axis with α-U3O8 types of single and double TaO7 pentagonal bipyramid layers. In contrast to earlier studies, both phases are found to crystallize in noncentrosymmetric structures. Symmetry-lowering structural distortions within PbTa4O11, i.e. R 3 bar c →R3, are found to be a result of the displacement of the Ta atoms within the TaO7 and TaO6 polyhedra, towards the apical and facial oxygen atoms, respectively. In BiTa7O19, relatively lower reaction temperatures leads to an ordering of the Bi/Ta cations within a lower-symmetry structure, i.e., P63/mcm→ P 6 bar c 2 . In the absence of Bi/Ta site disorder, the Ta-O-Ta bond angles decrease and the Ta-O bond distances increase within the TaO7 double layers. Scanning electron microscopy images reveal two particle morphologies for PbTa4O11, hexagonal rods and finer irregularly-shaped particles, while BiTa7O19 forms as aggregates of irregularly-shaped particles. Electronic-structure calculations confirm the highest-energy valence band states are comprised of O 2p-orbitals and the respective Pb 6s-orbital and Bi 6s-orbital contributions. The lowest-energy conduction band states are composed of Ta 5d-orbital contributions that are delocalized over the TaO6 octahedra and layers of TaO7 pentagonal bipyramids. The symmetry-lowering distortions in the PbTa4O11 structure, and the resulting effects on its electronic structure, lead to its relatively higher photocatalytic activity compared to similar structures without these distortions.

Synthesis, structure and property of diorganotin complexes with chiral N-(5-chlorosalicylidene)valinate ligand

NASA Astrophysics Data System (ADS)

Tian, Laijin; Yao, Yanze; Wang, Yuhua; Liu, Jin

2018-03-01

Six new diorganotin N-[(5-chloro-2-oxyphenyl)methylene]valinates, R2SnL (R = Me, 1; Et, 2; L = 5-Cl-2-OC6H3CH = NCH(i-Pr)COO: (S)-, a; (R)-, b; (RS)-, c), have been synthesized from the reaction of R2SnCl2 with the chiral ligand KHL (potassium salt of HL) in different solvents and characterized by elemental analysis, IR, NMR (1H, 13C and 119Sn) spectra. In benzene, the configuration of the chiral ligand was retained. (S)-Enantiomers (1a and 2a) and (R)-enantiomers (1b and 2b) display discrete molecular structures with distorted trigonal bipyramidal geometries in which two C atoms of organic groups (R) and the imino N atom occupy the equatorial positions and a phenoxide O and an unidentate carboxylate group O atom are in the axial orientation. In the methanol, the chiral ligand was racemized. 1cṡMeOH is a centrosymmetric dimers formed by (R)- and (S)- enantiomers through two Snsbnd OṡṡṡSn bridges. The coordination geometry of the Sn atom can be described as a distorted pentagonal bipyramid with two methyl groups in axial positions. The crystal of 2c is composed of two threefold symmetric trimers, a [Et2SnL-(R)]3 and a [Et2SnL-(S)]3, with a macrocyclic 12-membered ring structure formed by the bidenate bridging coordination of carboxylate group to tin atoms. Each tin atom is six-coordinated in distorted [SnC2NO3] octahedron geometry. The fluorescence properties of ligand KHL and complexes 1 (1a-1c) and 2 (2a-2c) have been measured. The results show the complexes may be explored for potential luminescent materials.

A highly stable l-alanine-based mono(aquated) Mn(ii) complex as a T1-weighted MRI contrast agent.

PubMed

Khannam, Mahmuda; Weyhermüller, Thomas; Goswami, Upashi; Mukherjee, Chandan

2017-08-08

The synthesized lithium (S)-6,6'-(1-carboxyethylazanediyl)bis(methylene)dipicolinate (Li 3 cbda) is a new chiral, alanine-based ligand bearing two picolinate functionalities. The trianionic form of the ligand [(cbda) 3- ] constitutes a seven-coordinate, water-soluble, pentagonal bipyramidal Mn(ii) complex (1). The structural analysis reveals the presence of a water coordinating site in the complex. The complex is thermodynamically very stable, and the stability is not affected by the presence of physiological anions (HCO 3 - , PO 4 3- , and F - ). The pH of the medium exerts a small effect on the stability of the complex. The r 1 relaxivity of 3.02 mM -1 s -1 is exhibited by the complex at 1.41 T, pH ∼7.4, and 25 °C. Phantom images obtained via a clinical MRI BRIVO MR355 system established concentration-dependent signal enhancement by the complex. The cytotoxicity test confirmed complex 1 as a biocompatible potential T 1 -weighted MRI contrast agent.

DFT Analysis of Spin Crossover in Mn(III) Complexes: Is a Two-Electron S = 2 to S = 0 Spin Transition Feasible?

PubMed

Amabilino, Silvia; Deeth, Robert J

2017-03-06

Six-coordinate, rigorously octahedral d 4 Mn(III) spin crossover (SCO) complexes are limited by symmetry to an S = 1 (intermediate spin, IS) to S = 2 (high spin, HS) transition. In order to realize the potential S = 0 to S = 2 transition, a lower symmetry and/or change in coordination number is needed, which we explore here computationally. First, a number of complexes are analyzed to develop a reliable and relatively fast DFT protocol for reproducing known Mn(III) spin state energetics. The hybrid meta-GGA functional TPSSh with a modest split valence plus polarization basis set and an empirical dispersion correction is found to predict correctly the ground spin state of Mn(III) complexes, including true low-spin (LS) S = 0 systems, with a range of donor sets including the hexadentate [N 4 O 2 ] Schiff base ligands. The electronic structure design criteria necessary for realizing a ΔS = 2 SCO transition are described, and a number of model complexes are screened for potential SCO behavior. Five-coordinate trigonal-bipyramidal symmetry fails to yield any suitable systems. Seven-coordinate, approximately pentagonal bipyramidal symmetry is more favorable, and when a known pentadentate macrocyclic donor is combined with π-acceptor axial ligands, a novel Mn(III) complex, [Mn(PABODP)(PF 3 ) 2 ] 3+ (PABODP = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene), is predicted to have the right spin state energetics for an S = 0 to S = 2 transition. Successful synthesis of such a complex could provide the first example of a ΔS = 2 SCO transition for d 4 Mn(III). However, the combination of a rigid macrocycle and a high coordination number dilutes the stereochemical activity of the d electrons, leading to relatively small structural changes between HS and LS systems. It may therefore remain a challenge to realize strong cooperative effects in Mn(III) systems.

Structure of the orthorhombic Al13Co4(100) surface using LEED, STM, and ab initio studies

NASA Astrophysics Data System (ADS)

Shin, Heekeun; Pussi, K.; Gaudry, É.; Ledieu, J.; Fournée, V.; Alarcón Villaseca, S.; Dubois, J.-M.; Grin, Yu.; Gille, P.; Moritz, W.; Diehl, R. D.

2011-08-01

In a combined scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and density functional theory (DFT) study of the surface of Al13Co4(100), all techniques have found that after annealing to 1165 K, the surface structure is consistent with a dense Al-rich plane with surface Co atom depletion. Various structure models were considered, and in the LEED study, the best agreement was found with a model that consists of Al-rich terminating planes with no Co atoms, and otherwise a structure similar to the bulk puckered layers. This structure was also found to be stable in the DFT study. The best-fit structural parameters are presented for the two domains of this structure, which contain bipentagons that can be related to the pentagonal bipyramidal structures in the bulk, plus additional glue atoms between them. These domains are not strictly related to each other by symmetry, as they have different surface relaxations. The STM study found significant differences in the surfaces of samples grown by different methods and is able to explain a different interpretation made in an earlier study.

A Comparative Study of [CaEDTA](2-) and [MgEDTA](2-): Structural and Dynamical Insights from Quantum Mechanical Charge Field Molecular Dynamics.

PubMed

Tirler, Andreas O; Hofer, Thomas S

2015-07-09

Structure and dynamics of [MgEDTA](2-) and [CaEDTA](2-) complexes in aqueous solution have been investigated via quantum mechanical/molecular mechanical (QM/MM) simulations. While for the first a 6-fold octahedral complex has been observed, the presence of an additional coordinating water ligand has been observed in the latter case. Because of rapidly exchanging water molecules, this 7-fold coordination complex was found to form pentagonal bipyramidal as well as capped trigonal prismatic configurations along the simulation interchanging on the picosecond time scale. Also in the case of [MgEDTA](2-) a trigonal prismatic configuration has been observed for a very short time period of approximately 1 ps. This work reports for the first time the presence of trigonal prismatic structures observed in the coordination sphere of [MgEDTA](2-) and [CaEDTA](2-) complexes in aqueous solution. In addition to the detailed characterization of structure and dynamics of the systems, the prediction of the associated infrared spectra indicates that the ion-water vibrational mode found at approximately 250 cm(-1) provides a distinctive measure to experimentally detect the presence of the coordinating water molecule via low-frequency IR setups.

F-element metalated dipyrrins: synthesis and characterization of a family of uranyl bis(dipyrrinate) complexes.

PubMed

Bolotaulo, Duer; Metta-Magaña, Alejandro; Fortier, Skye

2017-03-07

Using an improved, chromatography-free dipyrrin synthesis, the α,β-unsubstituted dipyrrins [RC(C 4 H 2 N) 2 H] (2) (R = tolyl (2toly l ), p-OMe-C 6 H 4 (2anis), mesityl (2mes), ferrocenyl (2Fc)) were isolated in good to excellent yields. Deprotonation of 2 with Na[N(SiMe 3 ) 2 ] gives the alkali metal salts [Na(DME) n ][RC(C 4 H 2 N) 2 ] (3) which reacts with UO 2 Cl 2 (THF) 3 to give the uranyl bis(dipyrrinates) UO 2 [RC(C 4 H 2 N) 2 ] 2 (L) (L = THF (4R-THF); DMAP (4R-DMAP)) (R = tolyl, p-OMe-C 6 H 4 , mesityl, ferrocenyl). The THF adducts, 4R-THF, are unstable in aromatic and nonpolar solvents and rapidly decompose to 2 and an intractable uranium-containing solid. On the other hand, the DMAP adducts, 4R-DMAP, are indefinitely stable in solution. The solid-state structures of 4R-THF and 4R-DMAP reveal distorted trigonal bipyramidal geometries. In the solid-state, the dipyrrinate ligands exhibit significant distortions including bowing and, in some instances, out-of-plane equatorial N-atom coordination, likely as a consequence of steric crowding and interligand repulsion. The complexes, 4R-DMAP, have been fully characterized by NMR, UV/Vis, and fluorescence spectroscopies, and their electrochemical properties have been investigated through cyclic voltammetry. The cyclic voltammograms of 4R-DMAP display several redox features but present a reversible wave at ca. -1.9 V (vs. Fc 0/+ ) attributable to a ligand centred reduction. Fluorescence measurements of all compounds reveal that only the mesityl derivatives 2mes, 3mes, and 4mes fluoresce with modest Stokes shift that ranges from ca. 30-70 nm, with 4mes displaying the greatest relative emission intensity.

Pyramidal space frame and associated methods

DOEpatents

Clark, Ryan Michael; White, David; Farr, Jr, Adrian Lawrence

2016-07-19

A space frame having a high torsional strength comprising a first square bipyramid and two planar structures extending outward from an apex of the first square bipyramid to form a "V" shape is disclosed. Some embodiments comprise a plurality of edge-sharing square bipyramids configured linearly, where the two planar structures contact apexes of all the square bipyramids. A plurality of bridging struts, apex struts, corner struts and optional internal bracing struts increase the strength and rigidity of the space frame. In an embodiment, the space frame supports a solar reflector, such as a parabolic solar reflector. Methods of fabricating and using the space frames are also disclosed.

Crystalline phase-stability of tantalum pentoxide

NASA Astrophysics Data System (ADS)

Walton, Santiago; Padilha, Antonio; Dalpian, Gustavo; Guillén, Jorge; Dalpian's Research Group Collaboration; Grupo de Estado Solido Collaboration; Gritad Collaboration

2013-03-01

Memristive devices are attractive candidates to provide a paradigm change in memory devices fabrication. These new devices would be faster, denser and less power consuming than those available today. However, the mechanism of memristance is not yet well understood. It is believed that a voltage/current-driven phase transition occurs in the material, which leads to significant changes in the device's conductivity. In the particular case of tantalum-oxide-based devices the relevant crystalline phases are still a matter of debate. Some of these phases are not even completely known and there is no agreement about which model best explains the crystallographic results. In this work we have performed ab-initio DFT based calculations to study the structural properties of different phases (and models) of Ta2O5 - the structure which is believed to exist inside Tantalum Oxide based devices. The equations of state for this material were constructed through first principles total energy calculations and we have also calculated the phonon frequencies at Γ. These results show that the most stable phase of this oxide (B-Ta2O5) is in fact composed of octahedral, instead of pentagonal (as L-Ta2O5) or hexagonal (as δ-Ta2O5) bipyramids. Fapesp, CNPq, Capes,CODI-UdeA

A New Bis(aquated) High Relaxivity Mn(II) Complex as an Alternative to Gd(III)-Based MRI Contrast Agent.

PubMed

Phukan, Bedika; Mukherjee, Chandan; Goswami, Upashi; Sarmah, Amrit; Mukherjee, Subhajit; Sahoo, Suban K; Moi, Sankar Ch

2018-03-05

Disclosed here are a piperazine, a pyridine, and two carboxylate groups containing pentadentate ligand H 2 pmpa and its corresponding water-soluble Mn(II) complex (1). DFT-based structural optimization implied that the complex had pentagonal bipyramidal geometry where the axial positions were occupied by two water molecules, and the equatorial plane was constituted by the ligand ON 3 O donor set. Thus, a bis(aquated) disc-like Mn(II) complex has been synthesized. The complex showed higher stability compared with Mn(II)-EDTA complex [log K MnL = 14.29(3)] and showed a very high r 1 relaxivity value of 5.88 mM -1 s -1 at 1.41 T, 25 °C, and pH = 7.4. The relaxivity value remained almost unaffected by the pH of the medium in the range of 6-10. Although the presence of 200 equiv of fluoride and bicarbonate anions did not affect the relaxivity value appreciably, an increase in the value was noticed in the presence of phosphate anion due to slow tumbling of the complex. Cell viability measurements, as well as phantom MR images using clinical MRI imager, consolidated the possible candidature of complex 1 as a positive contrast agent.

2,6-diacetylpyridine bis(thiosemicarbazones) zinc complexes: synthesis, structure, and biological activity.

PubMed

Rodriguez-Argüelles, M C; Belicchi Ferrari, M; Gasparri Fava, G; Pelizzi, C; Tarasconi, P; Albertini, R; Dall'Aglio, P P; Lunghi, P; Pinelli, S

1995-05-15

The reaction of zinc chloride, acetate, or perchlorate with two bis(thiosemicarbazones) of 2,6-diacetylpyridine [H2daptsc = 2,6-diacetylpyridine bis(thiosemicarbazone) and H2dapipt = 2,6-diacetylpyridine bis(hydrazinopyruvoylthiosemicarbazone)] leads to the formation of four novel complexes that have been characterized by spectroscopic studies (NMR, IR) and biological properties. The crystal structures of the two compounds--[Zn(daptsc)]2.2DMF (1) and [Zn(H2dapipt)(OH2)2](CIO4)2.3H2O (2)--also have been determined by x-ray methods from diffractometer data. Compound (1) is dimeric and the two zinc atoms have a distorted octahedral coordination. The ligand is deprotonated. In compound (2), the coordination geometry about zinc is pentagonal--bipyramidal and the ligand is in the neutral form. The molecular structure of (2) consists of cations [Zn(H2dapipt)(OH2)]2+, CIO4- disordered anions, and three water molecules of solvation. Biological studies have shown that the ligands and the complexes Zn(daptsc).1/2EtOH and Zn(H2daptsc)Cl2 have an effect in vitro on cell proliferation and differentiation (inhibition); both are concentration dependent. [Zn(daptsc)]2.2DMF (1) shows the effects at lower concentration values with respect to other compounds.

Pentagon Force Protection Agency

Science.gov Websites

engage the American public in keeping our country safe and resilient.Story Pentagon Police Badge Pentagon Safe WASHINGTON, May 2, 2011 - On the evening of March 4, 2010, an armed gunman approached the antiterrorism officer with the Pentagon Force Protection Agency. Story Protection Agency Keeps Pentagon Safe

DefenseLink.mil - Special Report - Remembering September 11, 2001

Science.gov Websites

, Survivors Remember at Pentagon Memorial Pentagon Sept. 11 Memorial: A Place to 'Remember, Reflect, Renew ' More Stories » 9/11 Survivor Honors Memory Of Sister Who Died in Pentagon Memorial Designer Reflects On Work as Opening Nears Pentagon Memorial Evokes Emotion as Completion Date Nears Pentagon Force

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures.

PubMed

Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

2012-09-30

This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144×10(3) J mol(-1). The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature. Copyright © 2012 Elsevier B.V. All rights reserved.

Synthesis and chemistry of the open-cage cobaltaheteroborane cluster [{(η(5)-C5Me5)Co}2B2H2Se2]: a combined experimental and theoretical study.

PubMed

Barik, Subrat Kumar; Dorcet, Vincent; Roisnel, Thierry; Halet, Jean-François; Ghosh, Sundargopal

2015-08-28

Reaction of [(η(5)-C5Me5)CoCl]2 with a two-fold excess of [LiBH4·thf] followed by heating with an excess of Se powder produces the dicobaltaselenaborane species [{(η(5)-C5Me5)Co}2B2H2Se2], , in good yield. The geometry of resembles a nido pentagonal [Co2B2Se2] bipyramid with a missing equatorial vertex. It can alternatively be seen as an open cage triple-decker cluster. Isolation of permits its reaction with [Fe2(CO)9] to give heterometallic diselenametallaborane [{(η(5)-C5Me5)Co}Fe(CO)3B2H2Se2], . The geometry of is similar to that of with one of the [(η(5)-C5Me5)Co] groups replaced by the isolobal, two-electron fragment [Fe(CO)3]. Both new compounds have been characterized by mass spectrometry, and by (1)H, (11)B and (13)C NMR spectroscopy. The structural architectures have been unequivocally established by crystallographic analysis. In addition, density functional theory calculations were performed to investigate the bonding and electronic properties. The large HOMO-LUMO gaps computed for both clusters are consistent with their thermodynamic stability. Natural bond order calculations predict the absence of metal-metal bonding interaction.

Size-controlled synthesis of gold bipyramids using an aqueous mixture of CTAC and salicylate anions as the soft template.

PubMed

Yoo, Hyojong; Jang, Min Hoon

2013-08-07

One-dimensional (1D) gold (Au) bipyramids are successfully synthesized through a facile seed-mediated method using cetyltrimethylammonium chloride (CTAC), Au seed nanoparticles, Ag(+) ions, and ascorbic acid. The length and optical properties of the synthesized Au bipyramids are controlled with precision by varying the amount of salicylate anions (Sal(-)) added during the synthesis. The micelles formed from CTA(+)-Sal(-) mixtures in aqueous solutions act as effective templates for the size-controlled synthesis of 1D nanocrystals.

Remembering Sept. 11, 2001

Science.gov Websites

ever during a 9/11 remembrance service at the Pentagon Memorial. Story Panetta, at Pentagon Memorial audience during a 9/11 remembrance ceremony at the Pentagon Memorial. Story Dempsey Memorializes a Hero during a remembrance service at the National 9/11 Pentagon Memorial. Story Winnefeld: Events of 9/11

Pentagon Digital Library

Science.gov Websites

About Us Contact Us Tell Us pentlib logo Pentagon Digital Library Pentagon 703.695.1992 | 703.695.1997 | PLC2 Mark Center 571.372.3613 | Room B1-D13 Ask A Librarian I Need a Library Card Renew WHS 1155 Defense Pentagon Washington DC 20301-1155 Search the Library Intranet Catalog Journals

Formic acid interaction with the uranyl(VI) ion: structural and photochemical characterization.

PubMed

Lucks, Christian; Rossberg, André; Tsushima, Satoru; Foerstendorf, Harald; Fahmy, Karim; Bernhard, Gert

2013-10-07

Complex formation between the uranyl(VI) ion and formic acid was studied by infrared absorption (IR) and X-ray absorption (EXAFS) spectroscopy as well as density functional theory (DFT) calculations. In contrast to the acetate ion which forms exclusively a bidentate complex with uranyl(VI), the formate ion binds to uranyl(VI) in a unidentate fashion. The photochemistry of the uranyl(VI)-formic acid system was explored by DFT calculations and photoreduction of uranyl(VI) in the presence of formic acid was found to occur via an intermolecular process, that is, hydrogen abstraction from hydrogenformate by the photo-excited uranyl(VI). There is no photo-induced decarboxylation of uranyl(VI) formate via an intramolecular process, presumably due to lack of a C=C double bond.

Symmetry and the Golden Ratio in the Analysis of a Regular Pentagon

ERIC Educational Resources Information Center

Sparavigna, Amelia Carolina; Baldi, Mauro Maria

2017-01-01

The regular pentagon had a symbolic meaning in the Pythagorean and Platonic philosophies and a subsequent important role in Western thought, appearing also in arts and architecture. A property of regular pentagons, which was probably discovered by the Pythagoreans, is that the ratio between the diagonal and the side of these pentagons is equal to…

Molten salt flux synthesis and crystal structure of a new open-framework uranyl phosphate Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}: Spectroscopic characterization and cationic mobility studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yagoubi, S., E-mail: said.yagoubi@cea.fr; Renard, C.; Abraham, F.

2013-04-15

The reaction of triuranyl diphosphate tetrahydrate precursor (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4} with a CsI flux at 750 °C yields a yellow single crystals of new compound Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}. The crystal structure (monoclinic, space group C2/c, a=13.6261 (13) Å, b=8.1081(8) Å, c=12.3983(12) Å, β=114.61(12)°, V=1245.41(20) Å{sup 3} with Z=4) has been solved using direct methods and Fourier difference techniques. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R1=0.028 and wR2=0.071 for 79 parameters and 1352 independent reflections with I≥2σ(I) collected on a BRUKER AXS diffractometer with MoKα radiation and a charge-coupledmore » device detector. The crystal structure is built by two independent uranium atoms in square bipyramidal coordination, connected by two opposite corners to form infinite chains {sup 1}{sub ∞}[UO{sub 5}] and by one phosphorus atom in a tetrahedral environment PO{sub 4}. The two last entities {sup 1}{sub ∞}[UO{sub 5}] and PO{sub 4} are linked by sharing corners to form a three-dimensional structure presenting different types of channels occupied by Cs{sup +} alkaline cations. Their mobility within the tunnels were studied between 280 and 800 °C and compared with other tunneled uranyl minerals. The infrared spectrum shows a good agreement with the values inferred from the single crystal structure analysis of uranyl phosphate compound. - Graphical abstract: Arrhenius plot of the electrical conductivity of tunneled compounds Cs{sub 3}U{sub 2}PO{sub 10} and CsU{sub 2}Nb{sub 2}O{sub 11.5}. Highlights: ► The reaction of (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4} in excess of molten CsI leads to single-crystals of new tunneled compound Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}. ► Ionic conductivity measurements and crystal structure analysis indicate a strong connection of the Cs{sup +} cations to the tunnels. ► A low symmetry in Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2} is the cause of IR activation and splitting of the bands in the IR spectrum.« less

Trigonal bipyramidal 5d-4f molecules with SMM behavior.

PubMed

Saber, Mohamed R; Dunbar, Kim R

2014-02-28

A family of trigonal bipyramidal (TBP) 5d-4f cyanide bridged aggregates were synthesized that exhibit slow relaxation of the magnetization below 4 K as indicated by a signal in the out-of-phase ac susceptibility data under zero field.

Analysis of Doppler Lidar Data Acquired During the Pentagon Shield Field Campaign

DTIC Science & Technology

2011-04-01

two coherent Doppler lidars deployed during the Pentagon Shield field campaign are analyzed in conjunction with other sensors to characterize the...Observations from two coherent Doppler lidars deployed during the Pentagon Shield field campaign are analyzed in conjunction with other sensors to... coherent Doppler lidars deployed during the Pentagon Shield field campaign are analyzed in conjunction with other sensors to characterize the overall

Photochemical water oxidation and origin of nonaqueous uranyl peroxide complexes.

PubMed

McGrail, Brendan T; Pianowski, Laura S; Burns, Peter C

2014-04-02

Sunlight photolysis of uranyl nitrate and uranyl acetate solutions in pyridine produces uranyl peroxide complexes. To answer longstanding questions about the origin of these complexes, we conducted a series of mechanistic studies and demonstrate that these complexes arise from photochemical oxidation of water. The peroxo ligands are easily removed by protonolysis, allowing regeneration of the initial uranyl complexes for potential use in catalysis.

Enhanced magnetoelectric effect in M-type hexaferrites by Co substitution into trigonal bi-pyramidal sites

NASA Astrophysics Data System (ADS)

Beevers, J. E.; Love, C. J.; Lazarov, V. K.; Cavill, S. A.; Izadkhah, H.; Vittoria, C.; Fan, R.; van der Laan, G.; Dhesi, S. S.

2018-02-01

The magnetoelectric effect in M-type Ti-Co doped strontium hexaferrite has been studied using a combination of magnetometry and element specific soft X-ray spectroscopies. A large increase (>×30) in the magnetoelectric coefficient is found when Co2+ enters the trigonal bi-pyramidal site. The 5-fold trigonal bi-pyramidal site has been shown to provide an unusual mechanism for electric polarization based on the displacement of magnetic transition metal (TM) ions. For Co entering this site, an off-centre displacement of the cation may induce a large local electric dipole as well as providing an increased magnetostriction enhancing the magnetoelectric effect.

Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

NASA Astrophysics Data System (ADS)

Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.; Fendorf, Scott; Kumar, Naresh; Lowry, Gregory V.; Brown, Gordon E.

2017-10-01

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O22+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0-835 ppm) or Suwanee River Fulvic Acid (SRFA) (0-955 ppm). No evidence was found for reduction of uranyl by either form of NOM after 24 h of exposure. The following three size fractions were considered in this study: (1) ≥0.2 μm (Fh-NOM aggregates), (2) 0.02-0.2 μm (dispersed Fh nanoparticles and NOM macro-molecules), and (3) <0.02 μm (dissolved). The extent to which U(VI) is sorbed in aggregates or dispersed as colloids was assessed by comparing U, Fe, and NOM concentrations in these three size fractions. Partitioning of uranyl between Fh and NOM was determined in size fraction (1) using X-ray absorption spectroscopy (XAS). Uranyl sorption on Fh-NOM aggregates was affected by the presence of NOM in different ways depending on pH and type of NOM (ESHA vs. SRFA). The presence of ESHA in the uranyl-Fh-NOM ternary system at pH 4.6 enhanced uranyl uptake more than the presence of SRFA. In contrast, neither form of NOM affected uranyl sorption at pH 7.0 over most of the NOM concentration range examined (0-500 ppm); at the highest NOM concentrations (500-955 ppm) uranyl uptake in the aggregates was slightly inhibited at pH 7.0, which is interpreted as being due to the dispersion of Fh aggregates. XAS at the U LIII-edge was used to characterize molecular-level changes in uranyl complexation as a result of sorption to the Fh-NOM aggregates. In the absence of NOM, uranyl formed dominantly inner-sphere, mononuclear, bidentate sorption complexes on Fh. However, when NOM concentration was increased at pH 4.6, the proportion of uranyl-Fh inner-sphere sorption complexes decreased relative to uranyl-ESHA or uranyl-SRFA complexes, which comprised up to ∼60% of the total uranyl in the systems studied. At pH 7.0, uranyl-NOM complexes were also present in the Fh-NOM aggregates in the concentration ranges of ESHA or SRFA considered; however, the proportion of these complexes was smaller at pH 7.0 than at pH 4.6 and did not increase significantly with increasing NOM concentration.

Water structure and aqueous uranyl(VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: results from molecular simulations.

PubMed

Greathouse, Jeffery A; Cygan, Randall T

2006-06-15

Molecular dynamics simulations were performed to provide a systematic study of aqueous uranyl adsorption onto the external surface of 2:1 dioctahedral clays. Our understanding of this key process is critical in predicting the fate of radioactive contaminants in natural groundwaters. These simulations provide atomistic detail to help explain experimental trends in uranyl adsorption onto natural media containing smectite clays. Aqueous uranyl concentrations ranged from 0.027 to 0.162 M. Sodium ions and carbonate ions (0.027-0.243 M) were also present in the aqueous regions to more faithfully model a stream of uranyl-containing groundwater contacting a mineral system comprised of Na-smectite. No adsorption occurred near the pyrophyllite surface, and there was little difference in uranyl adsorption onto the beidellite and montmorillonite, despite the difference in location of clay layer charge between the two. At low uranyl concentration, the pentaaquouranyl complex dominates in solution and readily adsorbs to the clay basal plane. At higher uranyl (and carbonate) concentrations, the mono(carbonato) complex forms in solution, and uranyl adsorption decreases. Sodium adsorption onto beidellite occurred both as inner- and outer-sphere surface complexes, again with little effect on uranyl adsorption. Uranyl surface complexes consisted primarily of the pentaaquo cation (85%) and to a lesser extent the mono(carbonato) species (15%). Speciation diagrams of the aqueous region indicate that the mono(carbonato)uranyl complex is abundant at high ionic strength. Oligomeric uranyl complexes are observed at high ionic strength, particularly near the pyrophyllite and montmorillonite surfaces. Atomic density profiles of water oxygen and hydrogen atoms are nearly identical near the beidellite and montmorillonite surfaces. Water structure therefore appears to be governed by the presence of adsorbed ions and not by the location of layer charge associated with the substrate. The water oxygen density near the pyrophyllite surface is similar to the other cases, but the hydrogen density profile indicates reduced hydrogen bonding between adsorbed water molecules and the surface.

Stepwise Construction of Heterobimetallic Cages by an Extended Molecular Library Approach.

PubMed

Hardy, Matthias; Struch, Niklas; Topić, Filip; Schnakenburg, Gregor; Rissanen, Kari; Lützen, Arne

2018-04-02

Two novel heterobimetallic complexes, a trigonal-bipyramidal and a cubic one, have been synthesized and characterized using the same C 3 -symmetric metalloligand, prepared by a simple subcomponent self-assembly strategy. Adopting the molecular library approach, we chose a mononuclear, preorganized iron(II) complex as the metalloligand capable of self-assembly into a trigonal-bipyramidal or a cubic aggregate upon coordination to cis-protected C 2 -symmetric palladium(II) or unprotected tetravalent palladium(II) ions, respectively. The trigonal-bipyramidal complex was characterized by NMR and UV-vis spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray diffraction. The cubic structure was characterized by NMR and UV-vis spectroscopy and ESI-MS.

Regular Pentagons and the Fibonacci Sequence.

ERIC Educational Resources Information Center

French, Doug

1989-01-01

Illustrates how to draw a regular pentagon. Shows the sequence of a succession of regular pentagons formed by extending the sides. Calculates the general formula of the Lucas and Fibonacci sequences. Presents a regular icosahedron as an example of the golden ratio. (YP)

Theoretical, biological and in silico studies of pendant-armed heteroleptic copper(II) phenolate complexes

NASA Astrophysics Data System (ADS)

Arthi, P.; Mahendiran, D.; Shobana, S.; Srinivasan, P.; Rahiman, A. Kalilur

2018-06-01

A new series of pendant-armed heteroleptic copper(II) phenolate complexes of the type [CuL1-3(diimine)] (1-6) have been synthesized by the reaction of pendant-armed ligands 2,2'-(benzoyliminodiethylene)bissalicylidene (H2L1), 2,2'-(4-nitrobenzoyliminodiethylene)bissalicylidene (H2L2) or 2,2'-(3,5-dinitrobenzoyliminodiethylene)bissalicylidene (H2L3) with coligands (diimine; 2,2‧-bipyridyl (bpy) or 1,10-phenanthroline (phen)) in the presence of copper(II) chloride, and characterized by spectroscopic techniques. The seven coordinated pentagonal-bipyramidal geometry around the copper(II) center was inferred from the electronic spectra of the complexes. The bond length, bond angle and HOMO-LUMO energy gap calculations were carried out by DFT studies, using Gaussian 03 program. Electrochemical studies of the mononuclear complexes evidenced one-electron irreversible reduction wave in the cathodic region (Epc = -0.61 to -0.65 V). Experimental and in silico molecular docking studies support groove mode of binding with DNA. Further, the molecular docking studies of complexes with B-DNA indicate the binding of the guanine-cytosine residues in the minor groove of the DNA. Molecular docking studies also revealed the interaction of complexes with protein ERK2 kinase and significant topoisomerase (Topo-I) inhibitory activity. All the complexes display pronounced cleavage activity against supercoiled pBR322 DNA in the presence of H2O2. In vitro cytotoxicity of the complexes was tested against liver cancer cell line (HepG2) by MTT reduction assay.

Polyoxometal cations within polyoxometalate anions. Seven-coordinate uranium and zirconium heteroatom groups in [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- and [Zr4(μ3-O)2(μ2-OH)2(H2O)4 (P2W16O59)2]14-

NASA Astrophysics Data System (ADS)

Gaunt, Andrew J.; May, Iain; Collison, David; Travis Holman, K.; Pope, Michael T.

2003-08-01

Two new composite polyoxotungstate anions with unprecedented structural features, [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- (1) and [Zr4(μ3-O)2(μ2-OH)2(H2O)4 (P2W16O59)2]14- (2) contain polyoxo-uranium and -zirconium clusters as bridging units. The anions are synthesized by reaction of Na12[P2W15O56] with solutions of UO2(NO3)2 and ZrCl4. The structure of 1 in the sodium salt contains four [P2W15O56]12- anions assembled into an overall tetrahedral cluster by means of trigonal bridging groups formed by three equatorial-edge-shared UO7 pentagonal bipyramids. The structure of anion 2 consists of a centrosymmetric assembly of two [P2W16O59]12- anions linked by a {Zr4O2(OH)2(H2O)4}10+ cluster. Both complexes in solution yield the expected two-line 31P-NMR spectra with chemical shifts of -2.95, -13.58 and -6.45, -13.69 ppm, respectively.

Synthesis and crystal structure of Cd-based metal-organic framework for removal of methyl-orange from aqueous solution

NASA Astrophysics Data System (ADS)

Tella, Adedibu C.; Olawale, Margaret D.; Neuburger, Markus; Obaleye, Joshua A.

2017-11-01

A novel [Cd(INA)2(H2O)]. ISB (1) (INA = isonicotinate; ISB = isobutanol) was synthesized through the reaction between the isonicotinic acid ligand and cadmium (II) salt and characterized by elemental analysis, FTIR and UV-Visible spectroscopies, SEM and Single crystal X-ray diffraction. The crystal is orthorhombic, space group Pbca, a = 12.24(10) Å, b = 15.4646(13) Å, c = 18.8445(17) Å, V = 3569(3) Å3, Z = 8. The pentagonal bipyramid (seven coordinate) around the cadmium (II) ion is of the form CdN2O5 coordinating to four oxygen atoms from carboxylates, one oxygen atom from water molecule and two nitrogen atoms of pyridine. The structure of compound is stabilized by two hydrogen bonds namely intermolecular (O-H-O) and intramolecular type C-H-O accounting for polymeric nature of the metal-organic frameworks. 1 was studied for adsorptive removal of methyl orange (MO) from aqueous solution. Equilibrium isotherm study reveals that Langmuir model gave a better fitting result than the Freundlich model. The pseudo-second order model could be used to interpret adsorption kinetics. The maximum adsorption capacity calculated by Langmuir was 166 mg/g at 300 K. These results indicate the adsorption of MO on 1 is partly due to electrostatic interaction between methyl orange and the adsorbent. 1 could be used as adsorbent to remove methyl orange from aqueous solution.

JSF: JOINT STRIKE FIGHTER OR JUST SIMPLE FAILURE ANALYZING THE F-35S JOINT ACQUISITION MODEL

DTIC Science & Technology

2016-02-01

41 Rosen, Armin and Macias, Amanda, This is What Regret Looks Like for the Pentagon, Yahoo ! Finance, 1 Feb 2016. http://finance.yahoo.com/news/regret...Like for the Pentagon, Yahoo ! Finance, 1 Feb 2016. http://finance.yahoo.com/news/regret-looks-pentagon-032341164.html 45 Government Accountability...City, New York: Doubleday & Company, Inc. 1971. Rosen, Armin and Macias, Amanda, This is What Regret Looks Like for the Pentagon, Yahoo ! Finance, 1

Comparative study of uranyl(VI) and -(V) carbonato complexes in an aqueous solution.

PubMed

Ikeda, Atsushi; Hennig, Christoph; Tsushima, Satoru; Takao, Koichiro; Ikeda, Yasuhisa; Scheinost, Andreas C; Bernhard, Gert

2007-05-14

Electrochemical, complexation, and electronic properties of uranyl(VI) and -(V) carbonato complexes in an aqueous Na2CO3 solution have been investigated to define the appropriate conditions for preparing pure uranyl(V) samples and to understand the difference in coordination character between UO22+ and UO2+. Cyclic voltammetry using three different working electrodes of platinum, gold, and glassy carbon has suggested that the electrochemical reaction of uranyl(VI) carbonate species proceeds quasi-reversibly. Electrolysis of UO22+ has been performed in Na2CO3 solutions of more than 0.8 M with a limited pH range of 11.7 < pH < 12.0 using a platinum mesh electrode. It produces a high purity of the uranyl(V) carbonate solution, which has been confirmed to be stable for at least 2 weeks in a sealed glass cuvette. Extended X-ray absorption fine structure (EXAFS) measurements revealed the structural arrangement of uranyl(VI) and -(V) tricarbonato complexes, [UO2(CO3)3]n- [n = 4 for uranyl(VI), 5 for uranyl(V)]. The bond distances of U-Oax, U-Oeq, U-C, and U-Odist are determined to be 1.81, 2.44, 2.92, and 4.17 A for the uranyl(VI) complex and 1.91, 2.50, 2.93, and 4.23 A for the uranyl(V) complex, respectively. The validity of the structural parameters obtained from EXAFS has been supported by quantum chemical calculations for the uranyl(VI) complex. The uranium LI- and LIII-edge X-ray absorption near-edge structure spectra have been interpreted in terms of electron transitions and multiple-scattering features.

Micro-SHINE Uranyl Sulfate Irradiations at the Linac

DOE Office of Scientific and Technical Information (OSTI.GOV)

Youker, Amanda J.; Kalensky, Michael; Chemerisov, Sergey

2016-08-01

Peroxide formation due to water radiolysis in a uranyl sulfate solution is a concern for the SHINE Medical Technologies process in which Mo-99 is generated from the fission of dissolved low enriched uranium. To investigate the effects of power density and fission on peroxide formation and uranyl-peroxide precipitation, uranyl sulfate solutions were irradiated using a 50-MeV electron linac as part of the micro-SHINE experimental setup. Results are given for uranyl sulfate solutions with both high and low enriched uranium irradiated at different linac powers.

Composition for detecting uranyl

DOEpatents

Baylor, Lewis C.; Stephens, Susan M.

1995-01-01

A composition for detecting the presence and concentration of a substance such as uranyl, comprising an organohalide covalently bonded to an indicator for said substance. The composition has at least one active OH site for forming a complex with the substance to be detected. The composition is made by reacting equimolar amounts of the indicator and the organohalide in a polar organic solvent. The absorbance spectrum of the composition-uranyl complex is shifted with respect to the absorbance spectrum of the indicator-uranyl complex, to provide better spectral resolution for detecting uranyl.

Precipitation characteristics of uranyl ions at different pHs depending on the presence of carbonate ions and hydrogen peroxide.

PubMed

Kim, Kwang-Wook; Kim, Yeon-Hwa; Lee, Se-yoon; Lee, Jae-Won; Joe, Kih-Soo; Lee, Eil-Hee; Kim, Jong-Seung; Song, Kyuseok; Song, Kee-Chan

2009-04-01

This work studied the dissolution of uranium dioxide and precipitation characteristics of uranyl ions in alkaline and acidic solutions depending on the presence of carbonate ions and H2O2 in the solutions at different pHs controlled by adding HNO3 or NaOH in the solution. The chemical structures of the precipitates generated in different conditions were evaluated and compared by using XRD, SEM, TG-DT, and IR analyses together. The sizes and forms of the precipitates in the solutions were evaluated, as well. The uranyl ions were precipitated in the various forms, depending on the solution pH and the presences of hydrogen peroxide and carbonate ions in the solution. In a 0.5 M Na2CO3 solution with H2O2, where the uranyl ions formed mixed uranyl peroxy-carbonato complexes, the uranyl ions were precipitated as a uranium peroxide of UO4(H20)4 at pH 3-4, and precipitated as a clarkeite of Na2U2Ox(OH)y(H2O)z above pH 13. In the same carbonate solution without H2O2, where the uranyl ions formed uranyl tris-carbonato complex, the uranyl ions were observed to be precipitated as a different form of clarkeite above pH 13. The precipitate of uranyl ions in a nitrate solution without carbonate ions and H2O2 at a high pH were studied together to compare the precipitate forms in the carbonate solutions.

Defense.gov Special Report: Travels with Carter - September 2013

Science.gov Websites

Indian officials during a visit, Pentagon Press Secretary George Little said. Story Success of India Pakistani government and defense officials, Pentagon Press Secretary George Little said. Story After Readout of Deputy Secretary Carter's Visit to India Statement by Pentagon Press Secretary George Little on

Constructing I[subscript h] Symmetrical Fullerenes from Pentagons

ERIC Educational Resources Information Center

Gan, Li-Hua

2008-01-01

Twelve pentagons are sufficient and necessary to form a fullerene cage. According to this structural feature of fullerenes, we propose a simple and efficient method for the construction of I[subscript h] symmetrical fullerenes from pentagons. This method does not require complicated mathematical knowledge; yet it provides an excellent paradigm for…

Pentagon Spending on Research Sees Largest Increase in a Decade.

ERIC Educational Resources Information Center

Brainard, Jeffrey

1999-01-01

Examines trends in Pentagon support of campus-based military research and reports that lawmakers gave the Defense Department a science budget 11 percent higher in 2000 than in 1999. Notes critics' concerns about Pentagon priorities versus the nation's science needs and lobbying by university and industry groups in the Coalition for National…

Effects of aqueous uranyl speciation on the kinetics of microbial uranium reduction

DOE PAGES

Belli, Keaton M.; DiChristina, Thomas J.; Van Cappellen, Philippe; ...

2015-02-16

The ability to predict the success of the microbial reduction of soluble U(VI) to highly insoluble U(IV) as an in situ bioremediation strategy is complicated by the wide range of geochemical conditions at contaminated sites and the strong influence of aqueous uranyl speciation on the bioavailability and toxicity of U(VI) to metal-reducing bacteria. In order to determine the effects of aqueous uranyl speciation on uranium bioreduction kinetics, incubations and viability assays with Shewanella putrefaciens strain 200 were conducted over a range of pH and dissolved inorganic carbon (DIC), Ca 2+, and Mg 2+ concentrations. A speciation-dependent kinetic model was developedmore » to reproduce the observed time series of total dissolved uranium concentration over the range of geochemical conditions tested. The kinetic model yielded the highest rate constant for the reduction of uranyl non-carbonate species (i.e., the ‘free’ hydrated uranyl ion, uranyl hydroxides, and other minor uranyl complexes), indicating that they represent the most readily reducible fraction of U(VI) despite being the least abundant uranyl species in solution. In the presence of DIC, Ca 2+, and Mg 2+ is suppressed during the formation of more bioavailable uranyl non-carbonate species and resulted in slower bioreduction rates. At high concentrations of bioavailable U(VI), however, uranium toxicity to S. putrefaciens inhibited bioreduction, and viability assays confirmed that the concentration of non-carbonate uranyl species best predicts the degree of toxicity. The effect of uranium toxicity was accounted for by incorporating the free ion activity model of metal toxicity into the bioreduction rate law. These results demonstrate that, in the absence of competing terminal electron acceptors, uranium bioreduction kinetics can be predicted over a wide range of geochemical conditions based on the bioavailability and toxicity imparted on U(VI) by solution composition. Finally, these findings also imply that the concentration of uranyl non-carbonate species, despite being extremely low, is a determining factor controlling uranium bioreduction at contaminated sites.« less

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

PubMed

Rodríguez-Jeangros, Nicolás; Seminario, Jorge M

2014-03-01

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

Matrix pentagons

NASA Astrophysics Data System (ADS)

Belitsky, A. V.

2017-10-01

The Operator Product Expansion for null polygonal Wilson loop in planar maximally supersymmetric Yang-Mills theory runs systematically in terms of multi-particle pentagon transitions which encode the physics of excitations propagating on the color flux tube ending on the sides of the four-dimensional contour. Their dynamics was unraveled in the past several years and culminated in a complete description of pentagons as an exact function of the 't Hooft coupling. In this paper we provide a solution for the last building block in this program, the SU(4) matrix structure arising from internal symmetry indices of scalars and fermions. This is achieved by a recursive solution of the Mirror and Watson equations obeyed by the so-called singlet pentagons and fixing the form of the twisted component in their tensor decomposition. The non-singlet, or charged, pentagons are deduced from these by a limiting procedure.

Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase

DOE PAGES

Abergel, Rebecca J.; de Jong, Wibe A.; Deblonde, Gauthier J. -P.; ...

2017-10-11

Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U 6+ chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidence d by CID, using deuterium and 18O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theorymore » (DFT) computations predict that the overall reaction requires only 132 kJ/mol, with the first oxygen activation entailing about 107 kJ/mol. Here, combined with analysis of similar, but unreactive ligands, these results shed light on the chelation-driven mechanism of uranyl oxo bond cleavage, demonstrating its dependence on the presence of ligand hydroxyl protons available for direct interactions with the uranyl oxygens.« less

Remembering Sept. 11, 2001. We will never forget.

Science.gov Websites

who died at the Pentagon on Sept. 11, 2001, gathered at the Pentagon Memorial on the ninth anniversary Americans," he said at a White House news conference. Story We Honor Their Sacrifice 9/11 Memorial Memorial Fund. Story Pentagon Plans Private 9/11 Remembrance WASHINGTON, Sept. 9, 2010 - President Barack

Remembering September 11

Science.gov Websites

disabilities experiencing difficulties accessing content on archive.defense.gov, please use the DoD Section 508 side of the Pentagon. The crash killed all 59 people on board and 125 Pentagon personnel. Shanksville killed 2,606 people at the World Trade Center, 40 people in Pennsylvania and 184 people at the Pentagon

EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

DOEpatents

Furman, N.H.; Mundy, R.J.

1957-12-10

An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2016-06-24

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

A Uranyl Peroxide Dimer in the Gas Phase

DOE PAGES

Dau, Phuong D.; Dau, Phuong V.; Rao, Linfeng; ...

2017-03-14

For this study, the gas-phase uranyl peroxide dimer, [(UO 2) 2(O2)(L) 2] 2+ where L = 2,2'-trifluoroethylazanediyl)bis(N,N'-dimethylacetamide), was synthesized by electrospray ionization of a solution of UO 2 2+ and L. Collision-induced dissociation of this dimer resulted in endothermic O atom elimination to give [(UO 2) 2(O)(L) 2] 2+, which was found to spontaneously react with water via exothermic hydrolytic chemisorption to yield [(UO 2) 2(OH) 2(L) 2] 2+. Density functional theory computations of the energies for the gas-phase reactions are in accord with observations. The structures of the observed uranyl dimer were computed, with that of the peroxide ofmore » particular interest, as a basis to evaluate the formation of condensed phase uranyl peroxides with bent structures. The computed dihedral angle in [(UO 2) 2(O 2)(L) 2] 2+ is 145°, indicating a substantial deviation from the planar structure with a dihedral angle of 180°. Energies needed to induce bending in the most elementary gas-phase uranyl peroxide complex, [(UO 2) 2(O 2)] 2+, were computed. It was found that bending from the lowest-energy planar structure to dihedral angles up to 140° required energies of <10 kJ/mol. The gas-phase results demonstrate the inherent stability of the uranyl peroxide moiety and support the notion that the uranyl-peroxide-uranyl structural unit is intrinsically planar, with only minor energy perturbations needed to form the bent structures found in studtite and uranyl peroxide nanostructures.« less

URANIUM PURIFICATION PROCESS

DOEpatents

Ruhoff, J.R.; Winters, C.E.

1957-11-12

A process is described for the purification of uranyl nitrate by an extraction process. A solution is formed consisting of uranyl nitrate, together with the associated impurities arising from the HNO/sub 3/ leaching of the ore, in an organic solvent such as ether. If this were back extracted with water to remove the impurities, large quantities of uranyl nitrate will also be extracted and lost. To prevent this, the impure organic solution is extracted with small amounts of saturated aqueous solutions of uranyl nitrate thereby effectively accomplishing the removal of impurities while not allowing any further extraction of the uranyl nitrate from the organic solvent. After the impurities have been removed, the uranium values are extracted with large quantities of water.

A Solution-Based Approach for Mo-99 Production: Considerations for Nitrate versus Sulfate Media

DOE PAGES

Youker, Amanda J.; Chemerisov, Sergey D.; Kalensky, Michael; ...

2013-01-01

Molybdenum-99 is the parent of Technetium-99m, which is used in nearly 80% of all nuclear medicine procedures. The medical community has been plagued by Mo-99 shortages due to aging reactors, such as the NRU (National Research Universal) reactor in Canada. There are currently no US producers of Mo-99, and NRU is scheduled for shutdown in 2016, which means that another Mo-99 shortage is imminent unless a potential domestic Mo-99 producer fills the void. Argonne National Laboratory is assisting two potential domestic suppliers of Mo-99 by examining the effects of a uranyl nitrate versus a uranyl sulfate target solution configuration onmore » Mo-99 production. Uranyl nitrate solutions are easier to prepare and do not generate detectable amounts of peroxide upon irradiation, but a high radiation field can lead to a large increase in pH, which can lead to the precipitation of fission products and uranyl hydroxides. Uranyl sulfate solutions are more difficult to prepare, and enough peroxide is generated during irradiation to cause precipitation of uranyl peroxide, but this can be prevented by adding a catalyst to the solution. A titania sorbent can be used to recover Mo-99 from a highly concentrated uranyl nitrate or uranyl sulfate solution; however, different approaches must be taken to prevent precipitation during Mo-99 production.« less

A geometric constraint, the head-to-tail exclusion rule, may be the basis for the isolated-pentagon rule in fullerenes with more than 60 vertices

PubMed Central

Schein, Stan; Friedrich, Tara

2008-01-01

Carbon atoms self-assemble into the famous soccer-ball shaped Buckminsterfullerene (C60), the smallest fullerene cage that obeys the isolated-pentagon rule (IPR). Carbon atoms self-assemble into larger (n > 60 vertices) empty cages as well—but only the few that obey the IPR—and at least 1 small fullerene (n ≤ 60) with adjacent pentagons. Clathrin protein also self-assembles into small fullerene cages with adjacent pentagons, but just a few of those. We asked why carbon atoms and clathrin proteins self-assembled into just those IPR and small cage isomers. In answer, we described a geometric constraint—the head-to-tail exclusion rule—that permits self-assembly of just the following fullerene cages: among the 5,769 possible small cages (n ≤ 60 vertices) with adjacent pentagons, only 15; the soccer ball (n = 60); and among the 216,739 large cages with 60 < n ≤ 84 vertices, only the 50 IPR ones. The last finding was a complete surprise. Here, by showing that the largest permitted fullerene with adjacent pentagons is one with 60 vertices and a ring of interleaved hexagons and pentagon pairs, we prove that for all n > 60, the head-to-tail exclusion rule permits only (and all) fullerene cages and nanotubes that obey the IPR. We therefore suggest that self-assembly that obeys the IPR may be explained by the head-to-tail exclusion rule, a geometric constraint. PMID:19050075

Probing cluster surface morphology by cryo spectroscopy of N2 on cationic nickel clusters

NASA Astrophysics Data System (ADS)

Dillinger, Sebastian; Mohrbach, Jennifer; Niedner-Schatteburg, Gereon

2017-11-01

We present the cryogenic (26 K) IR spectra of selected [Nin(N2)m]+ (n = 5-20, m = 1 - mmax), which strongly reveal n- and m-dependent features in the N2 stretching region, in conjunction with density functional theory modeling of some of these findings. The observed spectral features allow us to refine the kinetic classification [cf. J. Mohrbach, S. Dillinger, and G. Niedner-Schatteburg, J. Chem. Phys. 147, 184304 (2017)] and to define four classes of structure related surface adsorption behavior: Class (1) of Ni6+, Ni13+, and Ni19+ are highly symmetrical clusters with all smooth surfaces of equally coordinated Ni atoms that entertain stepwise N2 adsorption up to stoichiometric N2:Nisurface saturation. Class (2) of Ni12+ and Ni18+ are highly symmetrical clusters minus one. Their relaxed smooth surfaces reorganize by enhanced N2 uptake toward some low coordinated Ni surface atoms with double N2 occupation. Class (3) of Ni5+ and Ni7+ through Ni11+ are small clusters of rough surfaces with low coordinated Ni surface atoms, and some reveal semi-internal Ni atoms of high next-neighbor coordination. Surface reorganization upon N2 uptake turns rough into rough surface by Ni atom migration and turns octahedral based structures into pentagonal bipyramidal structures. Class (4) of Ni14+ through Ni17+ and Ni20+ are large clusters with rough and smooth surface areas. They possess smooth icosahedral surfaces with some proximate capping atom(s) on one hemisphere of the icosahedron with the other one largely unaffected.

DefenseLink.mil - Pentagon Memorial Dedication

Science.gov Websites

Dept. photo by Army Staff Sgt. Michael J. Carden An entry stone at the Pentagon Memorial lists the their lives during the Sept. 11 terrorist attack on the Pentagon. Photo by Staff Sgt. Michael J. Carden Staff Sgt. Michael J. Carden A member of The United States Air Force Band practices before the start of

Shaping Strategic Defense: The Air Force Nuclear Mission

DTIC Science & Technology

2009-01-01

Strike Command. Washington DC: Department of the Air Force. Kall , Rob. June 20, 2008. “Pentagon: Over 1000 Nuclear Weapons Parts Missing?” http...www.huffingtonpost.com/rob- kall /pentagon-over-1000-nuclea_b_108225.html (accessed December 16, 2008). Rolfsen, B. November 6, 2007. http...16, 2008). 6 Schlesinger. 7 Kall , Rob. June 20, 2008. “Pentagon: Over 1000 Nuclear Weapons Parts Missing?” http://www.huffingtonpost.com/rob- kall

Outsourcing & Privatization of Defense Infrastructure

DTIC Science & Technology

1997-03-01

Pentagon organizes and prepares to fight. Left out of this equation will be how the Pentagon manages the day to day business of national defense. This...Pentagon initiatives in official travel management and military family housing, show how far the Department has come and what remains to be done. Both...to be in the housing business at all. To succeed, we recommend a decidedly private sector approach to housing servicemembers and their families

Computer Security: the Achilles’ Heel of the Electronic Air Force?

DTIC Science & Technology

2013-02-01

commercials not enough. In the Pentagon a General Electric system called “GCOS” provided classified (secret) com- putation for the Air Staff and others...necessary computer function. January–February 2013 Air & Space Power Journal | 169 Historical Highlight Government designers not perfect. After the Pentagon ...laboratory computer to evaluate Multics as a potential multilevel secure computer for the Pentagon . Although it had the best security design of any system

Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

DOE PAGES

Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.; ...

2017-07-14

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O 2 2+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0–835 ppm) or Suwanee River Fulvic Acid (SRFA) (0–955 ppm). Here, no evidence was found for reduction of uranyl by either form of NOM aftermore » 24 h of exposure.« less

Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O 2 2+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0–835 ppm) or Suwanee River Fulvic Acid (SRFA) (0–955 ppm). Here, no evidence was found for reduction of uranyl by either form of NOM aftermore » 24 h of exposure.« less

Uranyl interaction with the hydrated (001) basal face of gibbsite: a combined theoretical and spectroscopic study.

PubMed

Veilly, Edouard; Roques, Jérôme; Jodin-Caumon, Marie-Camille; Humbert, Bernard; Drot, Romuald; Simoni, Eric

2008-12-28

The sorption of uranyl cations and water molecules on the basal (001) face of gibbsite was studied by combining vibrational and fluorescence spectroscopies together with density functional theory (DFT) computations. Both the calculated and experimental values of O-H bond lengths for the gibbsite bulk are in good agreement. In the second part, water sorption with this surface was studied to take into account the influence of hydration with respect to the uranyl adsorption. The computed water configurations agreed with previously published molecular dynamics studies. The uranyl adsorption in acidic media was followed by time-resolved laser-induced fluorescence spectroscopy and Raman spectrometry measurements. The existence of only one kind of adsorption site for the uranyl cation was then indicated in good agreement with the DFT calculations. The computation of the uranyl adsorption has been performed by means of a bidentate interaction with two surface oxygen atoms. The optimized structures displayed strong hydrogen bonds between the surface and the -yl oxygen of uranyl. The uranium-surface bond strength depends on the protonation state of the surface oxygen atoms. The calculated U-O(surface) bond lengths range between 2.1-2.2 and 2.6-2.7 A for the nonprotonated and protonated surface O atoms, respectively.

Solving fully fuzzy transportation problem using pentagonal fuzzy numbers

NASA Astrophysics Data System (ADS)

Maheswari, P. Uma; Ganesan, K.

2018-04-01

In this paper, we propose a simple approach for the solution of fuzzy transportation problem under fuzzy environment in which the transportation costs, supplies at sources and demands at destinations are represented by pentagonal fuzzy numbers. The fuzzy transportation problem is solved without converting to its equivalent crisp form using a robust ranking technique and a new fuzzy arithmetic on pentagonal fuzzy numbers. To illustrate the proposed approach a numerical example is provided.

Design of modified pentagonal patch antenna on defective ground for Wi-Max/WLAN application

NASA Astrophysics Data System (ADS)

Rawat, Sanyog; Sharma, K. K.

2016-04-01

This paper presents the design and performance of a modified pentagonal patch antenna with defective ground plane. A pentagonal slot is inserted in the pentagonal patch and slot loaded ground through optimized dimensions is used in the antenna to resonate it at dual frequency. The geometry operates at two resonant frequencies (2.5 GHz and 5.58 GHz) and offers impedance bandwidth of 864 MHz and 554 MHz in the two bands of interest. The proposed antenna covers the lower band (2.45 to 2.484/2.495 to 2.695 GHz) and upper band (5.15 to 5.825 GHz/5.25 to 5.85 GHz) allocated for Wi-Max and WLAN communication systems.

Preparation of U.sub.3 O.sub.8

DOEpatents

Johnson, David R.

1980-01-01

A method is described for the preparation of U.sub.3 O.sub.8 nuclear fuel material by direct precipitation of uranyl formate monohydrate from uranyl nitrate solution. The uranyl formate monohydrate precipitate is removed, dried and calcined to produce U.sub.3 O.sub.8 having a controlled particle size distribution.

Structure and Reactivity of X-ray Amorphous Uranyl Peroxide, U 2O 7

DOE PAGES

Odoh, Samuel O.; Shamblin, Jacob; Colla, Christopher A.; ...

2016-03-14

Recent accidents resulting in worker injury and radioactive contamination occurred due to pressurization of uranium yellowcake drums produced in the western USA. The drums contained an unexpected X-ray amorphous reactive form of uranium oxide, U 2O7. Heating hydrated uranyl peroxides produced during in situ mining unintentionally produced U 2O 7. It is a hygroscopic anhydrous uranyl peroxide that reacts rapidly with water to release O 2 gas and form metaschoepite, a uranyl-oxide hydrate. Quantum chemical calculations indicate that the most stable U 2O 7 conformer consists of two bent (UO 2) 2+ uranyl ions bridged by a peroxide group bidentatemore » and parallel to each uranyl ion, and a μ2-O atom, resulting in charge neutrality. A pair distribution function from neutron total scattering supports this structural model. The reactivity of U 2O 7 in water and with water in air is much higher than other uranium oxides, and this can be both hazardous and potentially advantageous in the nuclear fuel cycle.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

WANG,YIFENG; XU,HUIFANG

Correctly identifying the possible alteration products and accurately predicting their occurrence in a repository-relevant environment are the key for the source-term calculation in a repository performance assessment. Uraninite in uranium deposits has long been used as a natural analog to spent fuel in a repository because of their chemical and structural similarity. In this paper, a SEM/AEM investigation has been conducted on a partially alternated uraninite sample from a uranium ore deposit of Shinkolobwe of Congo. The mineral formation sequences were identified: uraninite {yields} uranyl hydrates {yields} uranyl silicates {yields} Ca-uranyl silicates or uraninite {yields} uranyl silicates {yields} Ca-uranyl silicates.more » Reaction-path calculations were conducted for the oxidative dissolution of spent fuel in a representative Yucca Mountain groundwater. The predicted sequence is in general consistent with the SEM observations. The calculations also show that uranium carbonate minerals are unlikely to become major solubility-controlling mineral phases in a Yucca Mountain environment. Some discrepancies between model predictions and field observations are observed. Those discrepancies may result from poorly constrained thermodynamic data for uranyl silicate minerals.« less

Size-Dependent Coherent-Phonon Plasmon Modulation and Deformation Characterization in Gold Bipyramids and Nanojavelins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirschner, Matthew S.; Lethiec, Clotilde M.; Lin, Xiao-Min

2016-04-04

Localized surface plasmon resonances (LSPRs) arising from metallic nanoparticles offer an array of prospective applications that range from chemical sensing to biotherapies. Bipyramidal particles exhibit particularly narrow ensemble LSPR resonances that reflect small dispersity of size and shape but until recently were only synthetically accessible over a limited range of sizes with corresponding aspect ratios. Narrow size dispersion offers the opportunity to examine ensemble dynamical phenomena such as coherent phonons that induce periodic oscillations of the LSPR energy. Here, we characterize transient optical behavior of a large range of gold bipyramid sizes, as well as higher aspect ratio nanojavelin ensemblesmore » with specific attention to the lowest-order acoustic phonon mode of these nanoparticles. We report coherent phonon-driven oscillations of the LSPR position for particles with resonances spanning 670 to 1330 nm. Nanojavelins were shown to behave similarly to bipyramids but offer the prospect of separate control over LSPR energy and coherent phonon oscillation period. We develop a new methodology for quantitatively measuring mechanical expansion caused by photogenerated coherent phonons. Using this method, we find an elongation of approximately 1% per photon absorbed per unit cell and that particle expansion along the lowest frequency acoustic phonon mode is linearly proportional to excitation fluence for the fluence range studied. These characterizations provide insight regarding means to manipulate phonon period and transient mechanical deformation.« less

Uranyl sulfate irradiations at the Van de Graaff: A means to combat uranyl peroxide precipitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Youker, Amanda J.; Kalensky, Michael; Quigley, Kevin J.

As part of an effort to support SHINE Medical Technologies in developing a process to produce Mo-99 by neutron-induced fission, a series of irradiation experiments was performed with a 3 MeV Van de Graaff accelerator to generate high radiation doses in 0.5–2 mL uranyl sulfate solutions. The purpose was to determine what conditions result in uranyl peroxide precipitation and what can be done to prevent its formation. The effects of temperature, dose rate, uranium concentration, and the addition of known catalysts for the destruction of peroxide were determined.

Theoretical insights into the uranyl adsorption behavior on vanadium carbide MXene

NASA Astrophysics Data System (ADS)

Zhang, Yu-Juan; Zhou, Zhang-Jian; Lan, Jian-Hui; Ge, Chang-Chun; Chai, Zhi-Fang; Zhang, Peihong; Shi, Wei-Qun

2017-12-01

Remediation of the contamination by long-lived actinide wastes is extremely important but also challenging. Adsorption based techniques have attracted much research attention for their potential as low-cost and effective methods to reduce the radioactive waste from solution. In this work, we have investigated the adsorption behavior of uranyl species [with the general form UO2(L1)x(L2)y(L3)z, where L1, L2 and L3 stand for ligands H2O, OH and CO3, respectively] on hydroxylated vanadium carbide V2C(OH)2 MXene nanosheets using density functional theory based simulation methods We find that all studied uranyl species can stably bond to hydroxylated MXene with binding energies ranging from -3.3 to -4.6 eV, suggesting that MXenes could be effective adsorbers for uranyl ions. The strong adsorption is achieved by forming two Usbnd O bonds with the hydroxylated Mxene. In addition, the axial oxygen atoms from the uranyl ions form hydrogen bonds with the hydroxylated V2C, further strengthening the adsorption. We have also investigated the effects of F termination on the uranyl adsorption properties of V2C nanosheets. Usbnd F bonds are in general weaker than Usbnd O bonds on the adsorption site, suggesting that F terminated Mexne is less favorable for uranyl adsorption applications.

Self-assembly of silver nanoparticles as high active surface-enhanced Raman scattering substrate for rapid and trace analysis of uranyl(VI) ions

NASA Astrophysics Data System (ADS)

Wang, Shaofei; Jiang, Jiaolai; Wu, Haoxi; Jia, Jianping; Shao, Lang; Tang, Hao; Ren, Yiming; Chu, Mingfu; Wang, Xiaolin

2017-06-01

A facile surface-enhanced Raman scattering (SERS) substrate based on the self-assembly of silver nanoparticles on the modified silicon wafer was obtained, and for the first time, an advanced SERS analysis method basing on this as-prepared substrate was established for high sensitive and rapid detection of uranyl ions. Due to the weakened bond strength of Odbnd Udbnd O resulting from two kinds of adsorption of uranyl species (;strong; and ;weak; adsorption) on the substrate, the ν1 symmetric stretch vibration frequency of Odbnd Udbnd O shifted from 871 cm- 1 (normal Raman) to 720 cm- 1 and 826 cm- 1 (SERS) along with significant Raman enhancement. Effects of the hydrolysis of uranyl ions on SERS were also investigated, and the SERS band at 826 cm- 1 was first used to approximately define the constitution of uranyl species at trace quantity level. Besides, the SERS intensity was proportional to the variable concentrations of uranyl nitrate ranging from 10- 7 to 10- 3 mol L- 1 with an excellent linear relation (R2 = 0.998), and the detection limit was 10- 7 mol L- 1. Furthermore, the related SERS approach involves low-cost substrate fabrication, rapid and trace analysis simultaneously, and shows great potential applications for the field assays of uranyl ions in the nuclear fuel cycle and environmental monitoring.

Equatorial coordination of uranyl: Correlating ligand charge donation with the O yl-U-O yl asymmetric stretch frequency

DOE PAGES

Gibson, John K.; de Jong, Wibe A.; van Stipdonk, Michael J.; ...

2017-10-14

In uranyl coordination complexes, UO 2(L) n 2+, uranium in the formally dipositive [O=U=O] 2+ moiety is coordinated by n neutral organic electron donor ligands, L. The extent of ligand electron donation, which results in partial reduction of uranyl and weakening of the U=O bonds, is revealed by the magnitude of the red-shift of the uranyl asymmetric stretch frequency, ν 3 . This phenomenon appears in gas-phase complexes in which uranyl is coordinated by electron donor ligands: the ν 3 red-shift increases as the number of ligands and their proton affinity (PA) increases. Because PA is a measure of themore » enthalpy change associated with a proton-ligand interaction, which is much stronger and of a different nature than metal ion-ligand bonding, it is not necessarily expected that ligand PAs should reliably predict uranyl-ligand bonding and the resulting ν 3 red-shift. In this study, ν 3 was measured for uranyl coordinated by ligands with a relatively broad range of PAs, revealing a surprisingly good correlation between PA and ν 3 frequency. From computed ν 3 frequencies for bare UO 2 cations and neutrals, it is inferred that the effective charge of uranyl in UO 2(L) n 2+ complexes can be reduced to near zero upon ligation by sufficiently strong charge-donor ligands. The basis for the correlation between ν 3 and ligand PAs, as well as limitations and deviations from it, are considered. It is demonstrated that the correlation evidently extends to a ligand that exhibits polydentate metal ion coordination.« less

Surface complexation model of uranyl sorption on Georgia kaolinite

USGS Publications Warehouse

Payne, T.E.; Davis, J.A.; Lumpkin, G.R.; Chisari, R.; Waite, T.D.

2004-01-01

The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3-10), total U (1 and 10 ??mol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uranium was preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO2, its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite. ?? 2004 Elsevier B.V. All rights reserved.

Fiber optic detector and method for using same for detecting chemical species

DOEpatents

Baylor, Lewis C.; Buchanan, Bruce R.

1995-01-01

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

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

DOE PAGES

Munasinghe, P. Sumudu; Elwood Madden, Megan E.; Brooks, Scott C.; ...

2015-04-17

We report that natural examples demonstrate uranyl-phosphate minerals can maintain extremely low levels of aqueous uranium in groundwaters due to their low solubility. Thus, greater understanding of the geochemical factors leading to uranyl phosphate precipitation may lead to successful application of phosphate-based remediation methods. However, the solubility of uranyl phosphate phases varies over >3 orders of magnitude, with the most soluble phases typically observed in lab experiments. To understand the role of common soil/sediment mineral surfaces in the nucleation and transformation of uranyl phosphate minerals under environmentally relevant conditions, we carried out batch experiments with goethite and mica at pHmore » 6 in mixed electrolyte solutions ranging from 1–800 μM U and 1–800 μM P. All experiments ended with uranium concentrations below the USEPA MCL for U, but with 2–3 orders of magnitude difference in uranium concentrations.« less

Structural link between giant molybdenum oxide based ions and derived Keggin structure: modular assemblies based on the [BW11O39]9- ion and pentagonal {M'M5} units (M' = W; M = Mo,W).

PubMed

Leclerc-Laronze, Nathalie; Marrot, Jérôme; Thouvenot, René; Cadot, Emmanuel

2009-01-01

Linked to the Pentagon: The addition of molybdate to [HBW(11)O(39)](8-) ions leads to the formation of mixed pentagonal units {W(Mo(5))} and {W(WMo(4))} trapped as linkers in the resulting modular assemblies, thus establishing the first link between the conventional Keggin ion derivatives and the giant molybdenum oxide and keplerate ions.

Stakeholder Analysis of Integrating Women Into Ground Combat Units

DTIC Science & Technology

2014-06-01

article posted on SaukValley.com titled “Sources: Pentagon Rules Shift on Women in Combat,” Lolita C. Baldor cites Bhagwati regarding news about plans...Jan-13 AP Sources: Pentagon Open Combat Roles to Women Lolita C. Baldor Associated Press 17-Jan-14 Military Women in Combat Nancy Carol Squidoo...Security Journal 9-Feb-12 Sources: Pentagon rules shift on women in combat Lolita C. Baldor SaukValley.com 24-Oct-13 A Voice for Men None named

75 FR 36701 - Issuance of Environmental Assessment and Finding of No Significant Impact for Modification of...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-28

... in the form of highly water soluble uranyl fluoride. EnergySolutions also proposed the addition of...; the concentration of residual uranyl fluoride in the K-25 piping waste in the railcars would likely... soluble uranyl fluoride in quantities in excess of the limits in Condition 4 of the 2006 Order (i.e., up...

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide.

PubMed

Kirkegaard, Marie C; Miskowiec, Andrew; Ambrogio, Michael W; Anderson, Brian B

2018-05-21

We have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novel UP formation mechanism.

METHOD OF INHIBITING CORROSION IN URANYL SULFATE SOLUTIONS

DOEpatents

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

1960-08-23

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

Contrasting coordination behavior of Group 12 perchlorate salts with an acyclic N3O2 donor ligand by X-ray crystallography and (1)H NMR.

PubMed

Tice, Daniel B; Pike, Robert D; Bebout, Deborah C

2016-08-09

An unbranched N3O2 ligand 2,6-bis[((2-pyridinylmethyl)oxy)methyl]pyridine (L1) was used to prepare new mononuclear heteroleptic Group 12 perchlorate complexes characterized by IR, (1)H NMR and X-ray crystallography. Racemic complexes with pentadentate L1 and one to four oxygens from either water or perchlorate bound to a metal ion were structurally characterized. Octahedral [Zn(L1)(OH2)](ClO4)2 (1) and pentagonal bipyramidal [Cd(L1)(OH2)(OClO3)]ClO4 (2) structures were found with lighter congeners. The polymorphic forms of [Hg(L1)(ClO4)2] characterized (3 in P1[combining macron] and 4 in P21/c) had a mix of monodentate, anisobidentate and bidentate perchlorates, providing the first examples of a tricapped trigonal prismatic Hg(ii) coordination geometry, as well as additional examples of a rare square antiprismatic Hg(ii) coordination geometry. Solution state (1)H NMR characterization of the Group 12 complexes in CD3CN indicated intramolecular reorganization remained rapid under conditions where intermolecular M-L1 exchange was slow on the chemical shift time scale for Zn(ii) and on the J(M(1)H) time scale for Cd(ii) and Hg(ii). Solution studies with more than one equivalent of ligand also suggested that a complex with a 1 : 2 ratio of M : L1 contributed significantly to solution equilibria with Hg(ii) but not the other metal ions. The behavior of related linear pentadentate ligands with Group 12 perchlorate salts is discussed.

Table of periodic properties of fullerenes based on structural parameters.

PubMed

Torrens, Francisco

2004-01-01

The periodic table (PT) of the elements suggests that hydrogen could be the origin of everything else. The construction principle is an evolutionary process that is formally similar to those of Darwin and Oparin. The Kekulé structure count and permanence of the adjacency matrix of fullerenes are related to structural parameters involving the presence of contiguous pentagons p, q and r. Let p be the number of edges common to two pentagons, q the number of vertices common to three pentagons, and r the number of pairs of nonadjacent pentagon edges shared between two other pentagons. Principal component analysis (PCA) of the structural parameters and cluster analysis (CA) of the fullerenes permit classifying them and agree. A PT of the fullerenes is built based on the structural parameters, PCA and CA. The periodic law does not have the rank of the laws of physics. (1) The properties of the fullerenes are not repeated; only, and perhaps, their chemical character. (2) The order relationships are repeated, although with exceptions. The proposed statement is the following: The relationships that any fullerene p has with its neighbor p + 1 are approximately repeated for each period.

Expanding the Library of Uranyl Amide Derivatives: New Complexes Featuring the tert-Butyldimethylsilylamide Ligand.

PubMed

Pattenaude, Scott A; Coughlin, Ezra J; Collins, Tyler S; Zeller, Matthias; Bart, Suzanne C

2018-04-16

New uranyl derivatives featuring the amide ligand, -N(SiHMe 2 ) t Bu, were synthesized and characterized by X-ray crystallography, multinuclear NMR spectroscopy, and absorption spectroscopies. Steric properties of these complexes were also quantified using the computational program Solid-G. The increased basicity of the free ligand -N(SiHMe 2 ) t Bu was demonstrated by direct comparison to -N(SiMe 3 ) 2 , a popular supporting ligand for uranyl. Substitutional lability on a uranyl center was also demonstrated by exchange with the -N(SiMe 3 ) 2 ligand. The increased basicity of this ligand and diverse characterization handles discussed here will make these compounds useful synthons for future reactivity.

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirkegaard, Marie C.; Miskowiec, Andrew J.; Ambrogio, Michael W.

Here, we have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novelmore » UP formation mechanism.« less

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide

DOE PAGES

Kirkegaard, Marie C.; Miskowiec, Andrew J.; Ambrogio, Michael W.; ...

2018-05-10

Here, we have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novelmore » UP formation mechanism.« less

Iron (III) Matrix Effects on Mineralization and Immobilization of Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cynthia-May S. Gong; Tyler A. Sullens; Kenneth R. Czerwinski

2006-01-01

Abstract - A number of models for the Yucca Mountain Project nuclear waste repository use studies of actinide sorption onto well-defined iron hydroxide materials. In the case of a waste containment leak, however, a complex interaction between dissolved waste forms and failed containment vessel components can lead to immediate precipitation of migratory iron and uranyl in the silicate rich near-field environment. Use of the Fe(III) and UO22+ complexing agent acetohydroxamic acid (AHA) as a colorimetric agent for visible spectrophotometry is well-known. Using the second derivative of these spectra a distinct shift in iron complexation in the presence of silicate ismore » seen that is not seen with uranyl or alone. Silica also decreases the ability of uranyl and ferric solutions to absorb hydroxide, hastening precipitation. These ferric silicate precipitates are highly amorphous and soluble. Precipitates formed in the presence of uranyl below ~1 mol% exhibit lower solubility than precipitates from up to 50 mol % and of uranyl silicates alone.« less

Potential New Ligand Systems for Binding Uranyl Ions in Seawater Environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arnold, John

2014-12-13

Work began this quarter on a new project involving a combined computational and biosynthetic approach to selective recognition of uranyl ion in aqueous solution. This project exploits the results of computational studies to discover new ligand classes. Synthetic studies will follow to generate target systems for uranyl binding and determination of binding constants. The process will be iterative, with results from computation informing synthesis, and vice versa. The theme of the ligand classes to be examined initially will be biologically based. New phosphonate-containing α-amino acid N-carboxyanhydride (NCA) monomers were used recently to prepare well-defined phosphonate-containing poly-peptides and block copolypeptides. Ourmore » first approach is to utilize these phosphate- and phosphonate-containing NCAs for the coordination of uranyl. The work includes the laboratory-scale preparation of a series of NCAs and the full thermodynamic and spectroscopic characterization of the resulting uranyl complexes. We are also evaluating the sequestering activity in different physiological and environmental conditions of these copolymers as well as their biodegradability.« less

Synthesis and characterization of heterometallic uranyl pyridinedicarboxylate compounds

NASA Astrophysics Data System (ADS)

Jayasinghe, Ashini S.; Payne, Maurice K.; Forbes, Tori Z.

2017-10-01

The incorporation of transition metals into hybrid uranyl materials can result in more diverse structural topologies and variations in physical and chemical properties. To explore the impact of transition metals on the uranyl cation, five uranium containing bimetallic chain compounds, [(UO2)M(PDC)2(H2O)4]·4(H2O) (PDC = 2,6 pyridinedicarboxylate; M = Ni2+, Co2+, Fe2+, Zn2+, and Cu2+) were synthesized by evaporation of aqueous solutions at room temperature. The uranyl cation is complex by two PDC ligands and the transition metal cations bond to the complex to form a one-dimensional chain topology. The presence of the transition metal leads to the presence of a stronger uranyl oxo bonds as shown by the single-crystal X-ray diffraction data and the Raman spectra. Solid state diffuse reflectance UV/Visible spectra confirmed the presence of the transition metals in the structure by the broad bands that appeared at relevant wavelengths.

First Cationic Uranyl-Organic Framework with Anion-Exchange Capabilities.

PubMed

Bai, Zhuanling; Wang, Yanlong; Li, Yuxiang; Liu, Wei; Chen, Lanhua; Sheng, Daopeng; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

2016-07-05

By controlling the extent of hydrolysis during the self-assembly process of a zwitterionic-based ligand with uranyl cations, we observed a structural evolution from the neutral uranyl-organic framework [(UO2)2(TTTPC)(OH)O(COOH)]·1.5DMF·7H2O (SCU-6) to the first cationic uranyl-organic framework with the formula of [(UO2)(HTTTPC)(OH)]Br·1.5DMF·4H2O (SCU-7). The crystal structures of SCU-6 and SCU-7 are layers built with tetranuclear and dinuclear uranyl clusters, respectively. Exchangeable halide anions are present in the interlaminar spaces balancing the positive charge of layers in SCU-7. Therefore, SCU-7 is able to effectively remove perrhenate anions from aqueous solution. Meanwhile, the H2PO4(-)-exchanged SCU-7 material exhibits a moderate proton conductivity of 8.70 × 10(-5) S cm(-1) at 50 °C and 90% relative humidity, representing nearly 80 times enhancement compared to the original material.

Defense.gov Special Report: Parade Honors Robert M. Gates

Science.gov Websites

Medal of Freedom WASHINGTON - At his Armed Forces Farewell Tribute on the Pentagon's parade field Pentagon farewell ceremony at which Gates was awarded the Presidential Medal of Freedom. Story Mullen Lauds

URANIUM EXTRACTION

DOEpatents

Harrington, C.D.; Opie, J.V.

1958-07-01

The recovery of uranium values from uranium ore such as pitchblende is described. The ore is first dissolved in nitric acid, and a water soluble nitrate is added as a salting out agent. The resulting feed solution is then contacted with diethyl ether, whereby the bulk of the uranyl nitrate and a portion of the impurities are taken up by the ether. This acid ether extract is then separated from the aqueous raffinate, and contacted with water causing back extractioa of the uranyl nitrate and impurities into the water to form a crude liquor. After separation from the ether extract, this crude liquor is heated to about 118 deg C to obtain molten uranyl nitrate hexahydratc. After being slightly cooled the uranyl nitrate hexahydrate is contacted with acid free diethyl ether whereby the bulk of the uranyl nitrate is dissolved into the ethcr to form a neutral ether solution while most of the impurities remain in the aqueous waste. After separation from the aqueous waste, the resultant ether solution is washed with about l0% of its volume of water to free it of any dissolved impurities and is then contacted with at least one half its volume of water whereby the uranyl nitrate is extracted into the water to form an aqueous product solution.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalistratova, O. S., E-mail: Olga.Kalistratova@yandex.ru; Andreev, P. V.; Gushchin, A. V.

Bis[(2E)-3-(2-furyl)prop-2-enoato]triphenylantimony Ph{sub 3}Sb[O{sub 2}CCH=CH(C{sub 4}H{sub 3}O)]{sub 2} is obtained for the first time by the reaction of triphenylantimony, hydrogen peroxide, and 2-furylpropene acid. The X-ray diffraction data show that the central atom of antimony is coordinated in the shape of a distorted trigonal bipyramid. The base of the bipyramid is formed by carbon atoms of phenyl ligands, and the apical vertices are occupied by acid residues. The IR and NMR spectra agree with the composition and structure of the compound.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibson, John K.; de Jong, Wibe A.; van Stipdonk, Michael J.

In uranyl coordination complexes, UO 2(L) n 2+, uranium in the formally dipositive [O=U=O] 2+ moiety is coordinated by n neutral organic electron donor ligands, L. The extent of ligand electron donation, which results in partial reduction of uranyl and weakening of the U=O bonds, is revealed by the magnitude of the red-shift of the uranyl asymmetric stretch frequency, ν 3 . This phenomenon appears in gas-phase complexes in which uranyl is coordinated by electron donor ligands: the ν 3 red-shift increases as the number of ligands and their proton affinity (PA) increases. Because PA is a measure of themore » enthalpy change associated with a proton-ligand interaction, which is much stronger and of a different nature than metal ion-ligand bonding, it is not necessarily expected that ligand PAs should reliably predict uranyl-ligand bonding and the resulting ν 3 red-shift. In this study, ν 3 was measured for uranyl coordinated by ligands with a relatively broad range of PAs, revealing a surprisingly good correlation between PA and ν 3 frequency. From computed ν 3 frequencies for bare UO 2 cations and neutrals, it is inferred that the effective charge of uranyl in UO 2(L) n 2+ complexes can be reduced to near zero upon ligation by sufficiently strong charge-donor ligands. The basis for the correlation between ν 3 and ligand PAs, as well as limitations and deviations from it, are considered. It is demonstrated that the correlation evidently extends to a ligand that exhibits polydentate metal ion coordination.« less

DFT study of uranyl peroxo complexes with H2O, F-, OH-, CO3(2-), and NO3(-).

PubMed

Odoh, Samuel O; Schreckenbach, Georg

2013-05-06

The structural and electronic properties of monoperoxo and diperoxo uranyl complexes with aquo, fluoride, hydroxo, carbonate, and nitrate ligands have been studied using scalar relativistic density functional theory (DFT). Only the complexes in which the peroxo ligands are coordinated to the uranyl moiety in a bidentate mode were considered. The calculated binding energies confirm that the affinity of the peroxo ligand for the uranyl group far exceeds that of the F(-), OH(-), CO3(2-), NO3(-), and H2O ligands. The formation of the monoperoxo complexes from UO2(H2O)5(2+) and HO2(-) were found to be exothermic in solution. In contrast, the formation of the monouranyl-diperoxo, UO2(O2)2X2(4-) or UO2(O2)2X(4-/3-) (where X is any of F(-), OH(-), CO3(2-), or NO3(-)), complexes were all found to be endothermic in aqueous solution. This suggests that the monoperoxo species are the terminal monouranyl peroxo complexes in solution, in agreement with recent experimental work. Overall, we find that the properties of the uranyl-peroxo complexes conform to well-known trends: the coordination of the peroxo ligand weakens the U-O(yl) bonds, stabilizes the σ(d) orbitals and causes a mixing between the uranyl π- and peroxo σ- and π-orbitals. The weakening of the U-O(yl) bonds upon peroxide coordination results in uranyl stretching vibrational frequencies that are much lower than those obtained after the coordination of carbonato or hydroxo ligands.

The qualitative scoring MMSE pentagon test (QSPT): a new method for differentiating dementia with Lewy Body from Alzheimer's disease.

PubMed

Caffarra, Paolo; Gardini, Simona; Dieci, Francesca; Copelli, Sandra; Maset, Laura; Concari, Letizia; Farina, Elisabetta; Grossi, Enzo

2013-01-01

The differential diagnosis across different variants of degenerative diseases is sometimes controversial. This study aimed to validate a qualitative scoring method for the pentagons copy test (QSPT) of Mini-Mental State Examination (MMSE) based on the assessment of different parameters of the pentagons drawing, such as number of angles, distance/intersection, closure/opening, rotation, closing-in, and to verify its efficacy to differentiate dementia with Lewy Body (DLB) from Alzheimer's disease (AD). We established the reliability of the qualitative scoring method through the inter-raters and intra-subjects analysis. QSPT was then applied to forty-six AD and forty-six DLB patients, using two phases statistical approach, standard and artificial neural network respectively. DLB patients had significant lower total score in the copy of pentagons and number of angles, distance/intersection, closure/opening, rotation compared to AD. However the logistic regression did not allow to establish any suitable modeling, whereas using Auto-Contractive Map (Auto-CM) the DLB was more strongly associated with low scores in some qualitative parameters of pentagon copying, i.e. number of angles and opening/closure and, for the remaining subitems of the MMSE, in naming, repetition and written comprehension, and for demographic variables of gender (male) and education (6-13 years). Twist system modeling showed that the QSPT had a good sensitivity (70.29%) and specificity (78.67%) (ROC-AUC 0.74). The proposed qualitative method of assessment of pentagons copying used in combination with non-linear analysis, showed to be consistent and effective in the differential diagnosis between Lewy Body and Alzheimer's dementia.

Solid state and aqueous behavior of uranyl peroxide cage clusters

NASA Astrophysics Data System (ADS)

Pellegrini, Kristi Lynn

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

URANIUM PURIFICATION PROCESS

DOEpatents

Winters, C.E.

1957-11-12

A method for the preparation of a diethyl ether solution of uranyl nitrate is described. Previously the preparation of such ether solutions has been difficult and expensive, since crystalline uranyl nitrate hexahydrate dissolves very slowly in ether. An improved method for effecting such dissolution has been found, and it comprises adding molten uranyl nitrate hexahydrate at a temperature of 65 to 105 deg C to the ether while maintaining the temperature of the ether solvent below its boiling point.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bennett, Megan E.; Bowers, Delbert L.; Vandegrift, George F.

2015-09-01

During FY 2012 and 2013, a process was developed to convert the SHINE Target Solution (STS) of irradiated uranyl sulfate (140 g U/L) to uranyl nitrate. This process is necessary so that the uranium solution can be processed by the UREX (Uranium Extraction) separation process, which will remove impurities from the uranium so that it can be recycled. The uranyl sulfate solution must contain <0.02 M SO 4 2- so that the uranium will be extractable into the UREXsolvent. In addition, it is desired that the barium content be below 0.0007 M, as this is the limit in the Resourcemore » Conservation and Recovery Act (RCRA).« less

The Pentagon: The First Fifty Years

DTIC Science & Technology

1992-01-01

Secretary of War Stimson reviewed it. Initially "skeptical," Stimson finally concurrcd. He wrote in his diary that "it will cost a lot of money, but it will...wrote in his diary : "It struck me as so fantastic that I did not express myself to him, but I told Somervell afterwards... I should absolutely refuse to...8217l Jill10 i"Il LtW ILI il Ih( "IM Ol*110 II )’(1 ol11 ,(\\ o n u l tl,1 + Rivci Eqttancc At ’M AyA I’wP e Pentagon Lore The Pentagon entered into

Walter Reed Army Medical Center's mental health response to the Pentagon attack.

PubMed

Cozza, Stephen J; Huleatt, William J; James, Larry C

2002-09-01

The September 11 terrorist attack on the Pentagon captured the attention and concern of America as well as the world. Given the extent of devastation, and the number of deaths at the Pentagon, it was believed that the uniformed mental health services would serve a pivotal role in the recovery and relief efforts. This article provides a synopsis of the complex and multidisciplinary mental health services provided by Walter Reed Army Medical Center in the wake of the September 11 attack on the Pentagon. This article offers an overview of the functions and roles of mental health team members, describes a constellation of services rendered, and describes how missions differed inside and outside of the Pentagon. Additionally, the authors provide the reader with how services were provided at the Family Assistance Center to family members of those killed during the attack. Liaison with civilian medical, mental health, and relief agencies and facilities will be discussed as well. The mental health response was an intensive and complicated experience and has yielded many lesson learned. To this end, the authors will provide the reader with an understanding of how the lessons learned during this mission may assist mental health commanders and leaders in planning and responding to similar deployments in the future.

Behavior of Colorado Plateau uranium minerals during oxidation

USGS Publications Warehouse

Garrels, Robert Minard; Christ, C.L.

1956-01-01

Uranium occurs as U(VI) and U(IV) in minerals of the Colorado Plateau ores. The number of species containing U(VI) is large, but only two U(IV) minerals are known from the Plateau: uraninite, and oxide, and coffinite, a hydroxy-silicate. These oxidize to yield U(VI) before reacting significantly with other mineral constituents. Crystal-structure analysis has shown that U(VI) invariable occurs as uranyl ion, UO2+2. Uranyl ion may form complex carbonate or sulfate ions with resulting soluble compounds, but only in the absence of quinquevalent vanadium, arsenic, or phosphorous. In the presence of these elements in the +5 valence state, the uranyl ion is fixed in insoluble layer compounds formed by union of uranyl ion with orthovanadate, orthophosphate, or orthoarsenate. Under favorable conditions UO2+2 may react to form the relatively insoluble rutherfordine, UO2CO3, or hydrated uranyl hydroxides. These are rarely found on the Colorado Plateau as opposed to their excellent development in other uraniferous areas, a condition which is apparently related to the semiarid climate and low water table of the Plateau. Uranium may also be fixed as uranyl silicate, but little is known about minerals of this kind. In the present study emphasis has been placed on a detailing of the chemical and crystal structural changes which occur in the oxidation paragenetic sequence.

32 CFR 234.1 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Number 2, the Pentagon heating and sewage treatment plants, and other related facilities are located... Washington County, Maryland, and other related facilities. The Pentagon Reservation shall include all..., by compressed gas, or by spring power; any bow and arrow, crossbow, blowgun, spear gun, hand-thrown...

32 CFR 234.1 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Number 2, the Pentagon heating and sewage treatment plants, and other related facilities are located... Washington County, Maryland, and other related facilities. The Pentagon Reservation shall include all..., by compressed gas, or by spring power; any bow and arrow, crossbow, blowgun, spear gun, hand-thrown...

32 CFR 234.1 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Number 2, the Pentagon heating and sewage treatment plants, and other related facilities are located... Washington County, Maryland, and other related facilities. The Pentagon Reservation shall include all..., by compressed gas, or by spring power; any bow and arrow, crossbow, blowgun, spear gun, hand-thrown...

32 CFR 234.1 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Number 2, the Pentagon heating and sewage treatment plants, and other related facilities are located... Washington County, Maryland, and other related facilities. The Pentagon Reservation shall include all..., by compressed gas, or by spring power; any bow and arrow, crossbow, blowgun, spear gun, hand-thrown...

32 CFR 234.1 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Number 2, the Pentagon heating and sewage treatment plants, and other related facilities are located... Washington County, Maryland, and other related facilities. The Pentagon Reservation shall include all..., by compressed gas, or by spring power; any bow and arrow, crossbow, blowgun, spear gun, hand-thrown...

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.

2016-03-01

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

Uranyl adsorption kinetics within silica gel: dependence on flow velocity and concentration

NASA Astrophysics Data System (ADS)

Dodd, Brandon M.; Tepper, Gary

2017-09-01

Trace quantities of a uranyl dissolved in water were measured using a simple optical method. A dilute solution of uranium nitrate dissolved in water was forced through nanoporous silica gel at fixed and controlled water flow rates. The uranyl ions deposited and accumulated within the silica gel and the uranyl fluorescence within the silica gel was monitored as a function of time using a light emitting diode as the excitation source and a photomultiplier tube detector. It was shown that the response time of the fluorescence output signal at a particular volumetric flow rate or average liquid velocity through the silica gel can be used to quantify the concentration of uranium in water. The response time as a function of concentration decreased with increasing flow velocity.

Photocatalytic CO 2 Reduction by Trigonal-Bipyramidal Cobalt(II) Polypyridyl Complexes: The Nature of Cobalt(I) and Cobalt(0) Complexes upon Their Reactions with CO 2, CO, or Proton

DOE PAGES

Shimoda, Tomoe; Morishima, Takeshi; Kodama, Koichi; ...

2018-04-26

Trigonal-bipyramidal Co(II) complexes are used for photochemical carbon dioxide (CO 2) reduction with Ru(bpy) 3 2+ as a photosensitizer, tri-p-tolylamine (TTA) as a reversible quencher, and triethylamine (TEA) as a sacrificial electron donor to produce carbon monoxide and dihydrogen. Here, the CO 2 reduction is slow because of the large structural changes, spin flipping in the cobalt catalytic intermediates, and an uphill reaction for reduction to catalytically active Co(0) by the photoproduced [Ru(bpy) 3] +.

d +i d chiral superconductivity in a triangular lattice from trigonal bipyramidal complexes

NASA Astrophysics Data System (ADS)

Lu, Chen; Zhang, Li-Da; Wu, Xianxin; Yang, Fan; Hu, Jiangping

2018-04-01

We model the newly predicted high-Tc superconducting candidates constructed by corner-shared trigonal bipyramidal complexes with an effective three-orbital tight-binding Hamiltonian and investigate the pairing symmetry of their superconducting states driven by electron-electron interactions. Our combined weak- and strong-coupling-based calculations consistently identify the chiral d +i d superconductivity as the leading pairing symmetry in a wide doping range with realistic interaction parameters. This pairing state has a nontrivial topological Chern number and can host gapless chiral edge modes, and the vortex cores under magnetic field can carry Majorana zero modes.

Photocatalytic CO 2 Reduction by Trigonal-Bipyramidal Cobalt(II) Polypyridyl Complexes: The Nature of Cobalt(I) and Cobalt(0) Complexes upon Their Reactions with CO 2, CO, or Proton

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shimoda, Tomoe; Morishima, Takeshi; Kodama, Koichi

Trigonal-bipyramidal Co(II) complexes are used for photochemical carbon dioxide (CO 2) reduction with Ru(bpy) 3 2+ as a photosensitizer, tri-p-tolylamine (TTA) as a reversible quencher, and triethylamine (TEA) as a sacrificial electron donor to produce carbon monoxide and dihydrogen. Here, the CO 2 reduction is slow because of the large structural changes, spin flipping in the cobalt catalytic intermediates, and an uphill reaction for reduction to catalytically active Co(0) by the photoproduced [Ru(bpy) 3] +.

Millimeter-wave Interferometric Sensing

DTIC Science & Technology

2011-09-01

THE SECY OF DEFNS ATTN ODDRE (R&AT) THE PENTAGON WASHINGTON DC 20301-3080 1 CD OFC OF THE SECY OF DEFNS ATTN OUSD(A&T) 3080 DEFENSE...PENTAGON WASHINGTON DC 20301-7100 1 UNDER SECY OF DEFNS FOR RSRCH & ENGRG ATTN RSRCH & ADVNCD TECHLGY DEPART OF DEFNS

Pentagon Reservation Maintenance Revolving Fund

DTIC Science & Technology

2001-07-02

financial statements of both the DoD and the Federal Government. The DoD incorporates the Pentagon Reservation Maintenance Revolving Fund into the...Consequently, the DoD must accurately report property, plant, and equipment in order for the Government to achieve a favorable opinion on the consolidated

Tuning TiO2 nanoparticle morphology in graphene-TiO2 hybrids by graphene surface modification

NASA Astrophysics Data System (ADS)

Sordello, Fabrizio; Zeb, Gul; Hu, Kaiwen; Calza, Paola; Minero, Claudio; Szkopek, Thomas; Cerruti, Marta

2014-05-01

We report the hydrothermal synthesis of graphene (GNP)-TiO2 nanoparticle (NP) hybrids using COOH and NH2 functionalized GNP as a shape controller. Anatase was the only TiO2 crystalline phase nucleated on the functionalized GNP, whereas traces of rutile were detected on unfunctionalized GNP. X-Ray Photoelectron spectroscopy (XPS) showed C-Ti bonds on all hybrids, thus confirming heterogeneous nucleation. GNP functionalization induced the nucleation of TiO2 NPs with specific shapes and crystalline facets exposed. COOH functionalization directed the synthesis of anatase truncated bipyramids, bonded to graphene sheets via the {101} facets, while NH2 functionalization induced the formation of belted truncated bipyramids, bonded to graphene via the {100} facets. Belted truncated bipyramids formed on unfunctionalized GNP too, however the NPs were more irregular and rounded. These effects were ascribed to pH variations in the proximity of the functionalized GNP sheets, due to the high density of COOH or NH2 groups. Because of the different reactivity of anatase {100} and {101} crystalline facets, we hypothesize that the hybrid materials will behave differently as photocatalysts, and that the COOH-GNP-TiO2 hybrids will be better photocatalysts for water splitting and H2 production.We report the hydrothermal synthesis of graphene (GNP)-TiO2 nanoparticle (NP) hybrids using COOH and NH2 functionalized GNP as a shape controller. Anatase was the only TiO2 crystalline phase nucleated on the functionalized GNP, whereas traces of rutile were detected on unfunctionalized GNP. X-Ray Photoelectron spectroscopy (XPS) showed C-Ti bonds on all hybrids, thus confirming heterogeneous nucleation. GNP functionalization induced the nucleation of TiO2 NPs with specific shapes and crystalline facets exposed. COOH functionalization directed the synthesis of anatase truncated bipyramids, bonded to graphene sheets via the {101} facets, while NH2 functionalization induced the formation of belted truncated bipyramids, bonded to graphene via the {100} facets. Belted truncated bipyramids formed on unfunctionalized GNP too, however the NPs were more irregular and rounded. These effects were ascribed to pH variations in the proximity of the functionalized GNP sheets, due to the high density of COOH or NH2 groups. Because of the different reactivity of anatase {100} and {101} crystalline facets, we hypothesize that the hybrid materials will behave differently as photocatalysts, and that the COOH-GNP-TiO2 hybrids will be better photocatalysts for water splitting and H2 production. Electronic supplementary information (ESI) available: Statistical analysis of the D : G intensity ratio, additional XPS analysis and TEM micrographs. See DOI: 10.1039/c4nr01322k

Enhancing immunomodulation on innate immunity by shape transition among RNA triangle, square and pentagon nanovehicles

PubMed Central

Khisamutdinov, Emil F.; Li, Hui; Jasinski, Daniel L.; Chen, Jiao; Fu, Jian; Guo, Peixuan

2014-01-01

Modulation of immune response is important in cancer immunotherapy, vaccine adjuvant development and inflammatory or immune disease therapy. Here we report the development of new immunomodulators via control of shape transition among RNA triangle, square and pentagon. Changing one RNA strand in polygons automatically induced the stretching of the interior angle from 60° to 90° or 108°, resulting in self-assembly of elegant RNA triangles, squares and pentagons. When immunological adjuvants were incorporated, their immunomodulation effect for cytokine TNF-α and IL-6 induction was greatly enhanced in vitro and in animals up to 100-fold, while RNA polygon controls induced unnoticeable effect. The RNA nanoparticles were delivered to macrophages specifically. The degree of immunostimulation greatly depended on the size, shape and number of the payload per nanoparticles. Stronger immune response was observed when the number of adjuvants per polygon was increased, demonstrating the advantage of shape transition from triangle to pentagon. PMID:25092921

The pentagon relation and incidence geometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doliwa, Adam, E-mail: doliwa@matman.uwm.edu.pl; Sergeev, Sergey M., E-mail: Sergey.Sergeev@canberra.edu.au

2014-06-01

We define a map S:D²×D²→D²×D², where D is an arbitrary division ring (skew field), associated with the Veblen configuration, and we show that such a map provides solutions to the functional dynamical pentagon equation. We explain that fact in elementary geometric terms using the symmetry of the Veblen and Desargues configurations. We introduce also another map of a geometric origin with the pentagon property. We show equivalence of these maps with recently introduced Desargues maps which provide geometric interpretation to a non-commutative version of Hirota's discrete Kadomtsev–Petviashvili equation. Finally, we demonstrate that in an appropriate gauge the (commutative version ofmore » the) maps preserves a natural Poisson structure—the quasiclassical limit of the Weyl commutation relations. The corresponding quantum reduction is then studied. In particular, we discuss uniqueness of the Weyl relations for the ultra-local reduction of the map. We give then the corresponding solution of the quantum pentagon equation in terms of the non-compact quantum dilogarithm function.« less

PREPARATION OF URANIUM TRIOXIDE

DOEpatents

Buckingham, J.S.

1959-09-01

The production of uranium trioxide from aqueous solutions of uranyl nitrate is discussed. The uranium trioxide is produced by adding sulfur or a sulfur-containing compound, such as thiourea, sulfamic acid, sulfuric acid, and ammonium sulfate, to the uranyl solution in an amount of about 0.5% by weight of the uranyl nitrate hexahydrate, evaporating the solution to dryness, and calcining the dry residue. The trioxide obtained by this method furnished a dioxide with a considerably higher reactivity with hydrogen fluoride than a trioxide prepared without the sulfur additive.

ELECTROLYTIC PRODUCTION OF URANIUM TETRAFLUORIDE

DOEpatents

Lofthouse, E.

1954-08-31

This patent relates to electrolytic methods for the production of uranium tetrafluoride. According to the present invention a process for the production of uranium tetrafluoride comprises submitting to electrolysis an aqueous solution of uranyl fluoride containing free hydrofluoric acid. Advantageously the aqueous solution of uranyl fluoride is obtained by dissolving uranium hexafluoride in water. On electrolysis, the uranyl ions are reduced to uranous tons at the cathode and immediately combine with the fluoride ions in solution to form the insoluble uranium tetrafluoride which is precipitated.

Sorption of uranyl ions from various acido systems by amphoteric epoxy amine ion-exchange resins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rychkov, V.N.; Radionov, B.K.; Molochnikov, L.S.

1995-03-01

Sorption of uranyl ions by epoxy amine ampholytes with N-monomethylenephosphonic acid groups modified with pyridine or quaternary ammonium groups was studied under dynamic conditions. Heterocyclic nitrogen favors sorption of uranyl ion from fluoride, sulfate, and fluoride-sulfate solutions. The ESR studies of mono- and bimetallic forms of nitrogen-containing ampholytes with copper(II) as paramagnetic marker revealed the characteristics of uranium(VI) interaction with cation- and anion-exchange groups and its dependence on the fluoride content in solution.

Modulating Uranium Binding Affinity in Engineered Calmodulin EF-Hand Peptides: Effect of Phosphorylation

PubMed Central

Pardoux, Romain; Sauge-Merle, Sandrine; Lemaire, David; Delangle, Pascale; Guilloreau, Luc; Adriano, Jean-Marc; Berthomieu, Catherine

2012-01-01

To improve our understanding of uranium toxicity, the determinants of uranyl affinity in proteins must be better characterized. In this work, we analyzed the contribution of a phosphoryl group on uranium binding affinity in a protein binding site, using the site 1 EF-hand motif of calmodulin. The recombinant domain 1 of calmodulin from A. thaliana was engineered to impair metal binding at site 2 and was used as a structured template. Threonine at position 9 of the loop was phosphorylated in vitro, using the recombinant catalytic subunit of protein kinase CK2. Hence, the T9TKE12 sequence was substituted by the CK2 recognition sequence TAAE. A tyrosine was introduced at position 7, so that uranyl and calcium binding affinities could be determined by following tyrosine fluorescence. Phosphorylation was characterized by ESI-MS spectrometry, and the phosphorylated peptide was purified to homogeneity using ion-exchange chromatography. The binding constants for uranyl were determined by competition experiments with iminodiacetate. At pH 6, phosphorylation increased the affinity for uranyl by a factor of ∼5, from Kd = 25±6 nM to Kd = 5±1 nM. The phosphorylated peptide exhibited a much larger affinity at pH 7, with a dissociation constant in the subnanomolar range (Kd = 0.25±0.06 nM). FTIR analyses showed that the phosphothreonine side chain is partly protonated at pH 6, while it is fully deprotonated at pH 7. Moreover, formation of the uranyl-peptide complex at pH 7 resulted in significant frequency shifts of the νas(P-O) and νs(P-O) IR modes of phosphothreonine, supporting its direct interaction with uranyl. Accordingly, a bathochromic shift in νas(UO2)2+ vibration (from 923 cm−1 to 908 cm−1) was observed upon uranyl coordination to the phosphorylated peptide. Together, our data demonstrate that the phosphoryl group plays a determining role in uranyl binding affinity to proteins at physiological pH. PMID:22870263

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orona, N.S.; Tasat, D.R., E-mail: deborah.tasat@unsam.edu.ar; School of Dentistry, University of Buenos Aires, M. T. de Alvear 2142

2012-06-15

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

Further evidence that rats rely on local rather than global spatial information to locate a hidden goal: reply to Cheng and Gallistel (2005).

PubMed

McGregor, Anthony; Jones, Peter M; Good, Mark A; Pearce, John M

2006-07-01

Naive male Hooded Lister rats (Rattus norvegicus) were required to find a submerged platform in a right-angled corner between a long and a short wall of a pool in the shape of an irregular pentagon. Tests in a rectangular pool revealed a preference for the corners that corresponded with the correct corner in the pentagon. These findings indicate that rats identified the correct corner in the pentagon by local cues. They contradict the suggestion that rats navigate by moving in a particular direction relative to the principal axis of the shape of their environment.

Defending the Environment at the Department of Defense: Using Environmentally Preferable Purchasing Procedures to Maintain the Pentagon and Other DOD Facilities

EPA Pesticide Factsheets

To demonstrate the ways environmentally preferable purchasing principles are currently being applied, EPA is documenting pilot procurement projects. This case describes efforts by the U.S. DOD to introduce these practices to the Pentagon.

32 CFR Appendix B to Part 516 - Mailing Addresses

Code of Federal Regulations, 2012 CFR

2012-07-01

...-2200 THE AJAG FOR CIVIL LAW & LITIGATION, THE JUDGE ADVOCATE GENERAL, 2200 ARMY PENTAGON, WASHINGTON... National Defense Department of Defense (Continued) DEPARTMENT OF THE ARMY AID OF CIVIL AUTHORITIES AND... STREET, ARLINGTON, VA 22203-1837 CONTRACT LAW DIVISION, THE JUDGE ADVOCATE GENERAL, 2200 ARMY PENTAGON...

32 CFR Appendix B to Part 516 - Mailing Addresses

Code of Federal Regulations, 2011 CFR

2011-07-01

...-2200 THE AJAG FOR CIVIL LAW & LITIGATION, THE JUDGE ADVOCATE GENERAL, 2200 ARMY PENTAGON, WASHINGTON... National Defense Department of Defense (Continued) DEPARTMENT OF THE ARMY AID OF CIVIL AUTHORITIES AND... STREET, ARLINGTON, VA 22203-1837 CONTRACT LAW DIVISION, THE JUDGE ADVOCATE GENERAL, 2200 ARMY PENTAGON...

32 CFR Appendix B to Part 516 - Mailing Addresses

Code of Federal Regulations, 2013 CFR

2013-07-01

...-2200 THE AJAG FOR CIVIL LAW & LITIGATION, THE JUDGE ADVOCATE GENERAL, 2200 ARMY PENTAGON, WASHINGTON... National Defense Department of Defense (Continued) DEPARTMENT OF THE ARMY AID OF CIVIL AUTHORITIES AND... STREET, ARLINGTON, VA 22203-1837 CONTRACT LAW DIVISION, THE JUDGE ADVOCATE GENERAL, 2200 ARMY PENTAGON...

78 FR 59341 - Proposed Collection; Comment Request

Federal Register 2010, 2011, 2012, 2013, 2014

2013-09-26

...; Comment Request AGENCY: Pentagon Force Protection Agency, DoD. ACTION: Notice. SUMMARY: In compliance with Section 3506(c)(2)(A) of the Paperwork Reduction Act of 1995, the Pentagon Force Protection Agency (PFPA... minimize the burden of the information collection on respondents, including through the use of automated...

Inertial shear flow of assemblies of frictionless polygons: Rheology and microstructure.

PubMed

Azéma, Émilien; Radjaï, Farhang; Roux, Jean-Noël

2018-01-05

Motivated by the understanding of shape effects in granular materials, we numerically investigate the macroscopic and microstructural properties of anisotropic dense assemblies of frictionless polydisperse rigid pentagons in shear flow, and compare them with similar systems of disks. Once subjected to large cumulative shear strains their rheology and microstructure are investigated in uniform steady states, depending on inertial number I, which ranges from the quasistatic limit ([Formula: see text]) to 0.2. In the quasistatic limit both systems are devoid of Reynolds dilatancy, i.e., flow at their random close packing density. Both macroscopic friction angle [Formula: see text], an increasing function of I , and solid fraction [Formula: see text], a decreasing function of I, are larger with pentagons than with disks at small I, but the differences decline for larger I and, remarkably, nearly vanish for [Formula: see text]. Under growing I , the depletion of contact networks is considerably slower with pentagons, in which increasingly anisotropic, but still well-connected force-transmitting structures are maintained throughout the studied range. Whereas contact anisotropy and force anisotropy contribute nearly equally to the shear strength in disk assemblies, the latter effect dominates with pentagons at small I, while the former takes over for I of the order of 10 -2 . The size of clusters of grains in side-to-side contact, typically comprising more than 10 pentagons in the quasistatic limit, very gradually decreases for growing I.

A combined photoelectron spectroscopy and ab initio study of the quasi-planar B24(-) cluster.

PubMed

Popov, Ivan A; Piazza, Zachary A; Li, Wei-Li; Wang, Lai-Sheng; Boldyrev, Alexander I

2013-10-14

The structure and chemical bonding of the 24-atom boron cluster are investigated using photoelectron spectroscopy and ab initio calculations. The joint experimental and theoretical investigation shows that B24(-) possesses a quasi-planar structure containing fifteen outer and nine inner atoms with six of the inner atoms forming a filled pentagonal moiety. The central atom of the pentagonal moiety is puckered out of plane by 0.9 Å, reminiscent of the six-atom pentagonal caps of the well-known B12 icosahedral unit. The next closest isomer at the ROCCSD(T) level of theory has a tubular double-ring structure. Comparison of the simulated spectra with the experimental data shows that the global minimum quasi-planar B24(-) isomer is the major contributor to the observed photoelectron spectrum, while the tubular isomer has no contribution to the experiment. Chemical bonding analyses reveal that the periphery of the quasi-planar B24 constitutes 15 classical 2c-2e B-B σ-bonds, whereas delocalized σ- and π-bonds are found in the interior of the cluster with one unique 6c-2e π-bond responsible for bonding in the B-centered pentagon. The current work suggests that the 24-atom boron cluster continues to be quasi-2D, albeit the tendency to form filled pentagonal units, characteristic of 3D cage-like structures of bulk boron, is observed.

Protein scaffolds for selective enrichment of metal ions

DOEpatents

He, Chuan; Zhou, Lu; Bosscher, Michael

2016-02-09

Polypeptides comprising high affinity for the uranyl ion are provided. Methods for binding uranyl using such proteins are likewise provided and can be used, for example, in methods for uranium purification or removal.

Uranyl(VI) nitrate salts: modeling thermodynamic properties using the binding mean spherical approximation theory and determination of "fictive" binary data.

PubMed

Ruas, Alexandre; Bernard, Olivier; Caniffi, Barbara; Simonin, Jean-Pierre; Turq, Pierre; Blum, Lesser; Moisy, Philippe

2006-02-23

This work is aimed at a description of the thermodynamic properties of highly concentrated aqueous solutions of uranyl nitrate at 25 degrees C. A new resolution of the binding mean spherical approximation (BIMSA) theory, taking into account 1-1 and also 1-2 complex formation, is developed and used to reproduce, from a simple procedure, experimental uranyl nitrate osmotic coefficient variation with concentration. For better consistency of the theory, binary uranyl perchlorate and chloride osmotic coefficients are also calculated. Comparison of calculated and experimental values is made. The possibility of regarding the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O as a "simple" solution (in the sense of Zdanovskii, Stokes, and Robinson) is examined from water activity and density measurements. Also, an analysis of existing uranyl nitrate binary data is proposed and compared with our obtained data. On the basis of the concept of "simple" solution, values for density and water activity for the binary system UO(2)(NO(3))(2)/H(2)O are proposed in a concentration range on which uranyl nitrate precipitates from measurements on concentrated solutions of the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O. This new set of binary data is "fictive" in the sense that the real binary system is not stable chemically. Finally, a new, interesting predictive capability of the BIMSA theory is shown.

A procedure for quantitation of total oxidized uranium for bioremediation studies

USGS Publications Warehouse

Elias, Dwayne A.; Senko, John M.; Krumholz, Lee R.

2003-01-01

A procedure was developed for the quantitation of complexed U(VI) during studies on U(VI) bioremediation. These studies typically involve conversion of soluble or complexed U(VI) (oxidized) to U(IV) (the reduced form which is much less soluble). Since U(VI) freely exchanges between material adsorbed to the solid phase and the dissolved phase, uranium bioremediation experiments require a mass balance of U in both its soluble and adsorbed forms as well as in the reduced sediment bound phase. We set out to optimize a procedure for extraction and quantitation of sediment bound U(VI). Various extractant volumes to sediment ratios were tested and it was found that between 1:1 to 8:1 ratios (v/w) there was a steady increase in U(VI) recovered, but no change with further increases in v/w ratio.Various strengths of NaHCO3, Na-EDTA, and Na-citrate were used to evaluate complexed U(VI) recovery, while the efficiency of a single versus repeated extraction steps was compared with synthesized uranyl-phosphate and uranyl-hydroxide. Total recovery with 1 M NaHCO3 was 95.7% and 97.9% from uranyl-phosphate and uranyl-hydroxide, respectively, compared to 80.7% and 89.9% using 450 mM NaHCO3. Performing the procedure once yielded an efficiency of 81.1% and 92.3% for uranyl-phosphate and uranyl-hydroxide, respectively, as compared to three times. All other extractants yielded 7.9–82.0% in both experiments.

Cyber Operations and Cyber Terrorism, Handbook Number 1.02

DTIC Science & Technology

2005-08-15

Quinn, “Teen Hackers Plead Guilty to Stunning Pentagon Attacks,” Reuters, 31 July 1998, 1; available from http://www.geocities.com/ Area51 ...Hackers Plead Guilty to Stunning Pentagon Attacks.” Reuters, 31 July 1998, 1. Available from http://www.geocities.com/ Area51 /Shadowlands/6583

Worldwide Emerging Environmental Issues Affecting the U.S. Military. May 2009

DTIC Science & Technology

2009-05-01

devices can disable the power grid of an entire region; and research on computer-mediated telepathy such as Silent Talk might one day be used to intercept...Pentagon Preps Soldier Telepathy Push http://www.wired.com/dangerroom/2009/05/pentagon-preps-soldier- telepathy -push/ Item 2. New International

77 FR 57560 - Agency Information Collection Activities: Submission for OMB Review; Comment Request

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-18

... (Pentagon Federal) is piloting this fall. The research is designed to result in recommendations for.... The research activities will be conducted by phone surveys of consumers who will have received the... collection titled, ``Pentagon Federal Credit Card Agreement Simplification Survey.'' The proposed collection...

Engineered nano-magnetic iron oxide-urea-activated carbon nanolayer sorbent for potential removal of uranium (VI) from aqueous solution

NASA Astrophysics Data System (ADS)

Mahmoud, Mohamed E.; Khalifa, Mohamed A.; El Wakeel, Yasser M.; Header, Mennatllah S.; Abdel-Fattah, Tarek M.

2017-04-01

A novel magnetic nanosorbent was designed using chemical grafting of nano-magnetite (Nano-Fe3O4) with nanolayer of activated carbon (AC) via urea intermediate for the formation of Nano-Fe3O4-Urea-AC. Characterizing was carried out using FT-IR, SEM, HR-TEM, TGA, point of zero charge (Pzc) and surface area analysis. The designed sorbent maintained its magnetic properties and nanosized structure in the range of 8.7-14.1 nm. The surface area was identified as 389 m2/g based on the BET method. Sorption of uranyl ions from aqueous solutions was studied and evaluated in different experimental conditions. Removal of uranyl ions increased with increasing in pH value and the maximum percentage removal was established at pH 5.0. The removal and sorption processes of uranyl ions by Nano-Fe3O4-Urea-AC sorbent were studied and optimized using the batch technique. The key variables affecting removal of uranyl ions were studied including the effect of the contact time, dosage of Nano-Fe3O4-Urea-AC sorbent, reaction temperature, initial uranyl ions concentration and interfering anions and cations.

Immobilization of selenate by iron in aqueous solution under anoxic conditions and the influence of uranyl

NASA Astrophysics Data System (ADS)

Puranen, Anders; Jonsson, Mats; Dähn, Rainer; Cui, Daqing

2009-08-01

In proposed high level radioactive waste repositories a large part of the spent nuclear fuel (SNF) canisters are commonly composed of iron. Selenium is present in spent nuclear fuel as a long lived fission product. This study investigates the influence of iron on the uptake of dissolved selenium in the form of selenate and the effect of the presence of dissolved uranyl on the above interaction of selenate. The iron oxide, and selenium speciation on the surfaces was investigated by Raman spectroscopy. X-ray Absorption Spectroscopy was used to determine the oxidation state of the selenium and uranium on the surfaces. Under the simulated groundwater conditions (10 mM NaCl, 2 mM NaHCO 3, <0.1 ppm O 2) the immobilized selenate was found to be reduced to oxidation states close to zero or lower and uranyl was found to be largely reduced to U(IV). The near simultaneous reduction of uranyl was found to greatly enhance the rate of selenate reduction. These findings suggest that the presence of uranyl being reduced by an iron surface could substantially enhance the rate of reduction of selenate under anoxic conditions relevant for a repository.

Tris-amidoximate uranyl complexes via η2 binding mode coordinated in aqueous solution shown by X-ray absorption spectroscopy and density functional theory methods.

PubMed

Zhang, Linjuan; Qie, Meiying; Su, Jing; Zhang, Shuo; Zhou, Jing; Li, Jiong; Wang, Yu; Yang, Shitong; Wang, Shuao; Li, Jingye; Wu, Guozhong; Wang, Jian Qiang

2018-03-01

The present study sheds some light on the long-standing debate concerning the coordination properties between uranyl ions and the amidoxime ligand, which is a key ingredient for achieving efficient extraction of uranium. Using X-ray absorption fine structure combined with theoretical simulation methods, the binding mode and bonding nature of a uranyl-amidoxime complex in aqueous solution were determined for the first time. The results show that in a highly concentrated amidoxime solution the preferred binding mode between UO 2 2+ and the amidoxime ligand is η 2 coordination with tris-amidoximate species. In such a uranyl-amidoximate complex with η 2 binding motif, strong covalent interaction and orbital hybridization between U 5f/6d and (N, O) 2p should be responsible for the excellent binding ability of the amidoximate ligand to uranyl. The study was performed directly in aqueous solution to avoid the possible binding mode differences caused by crystallization of a single-crystal sample. This work also is an example of the simultaneous study of local structure and electronic structure in solution systems using combined diagnostic tools.

Coordination characteristics of uranyl BBP complexes: Insights from an electronic structure analysis

DOE PAGES

Pemmaraju, Chaitanya Das; Copping, Roy; Smiles, Danil E.; ...

2017-03-21

Here, organic ligand complexes of lanthanide/actinide ions have been studied extensively for applications in nuclear fuel storage and recycling. Several complexes of 2,6-bis(2-benzimidazyl)pyridine (H2BBP) featuring the uranyl moiety have been reported recently, and the present study investigates the coordination characteristics of these complexes using density functional theory-based electronic structure analysis. In particular, with the aid of several computational models, the nonplanar equatorial coordination about uranyl, observed in some of the compounds, is studied and its origin traced to steric effects.

Many faces of carbon

NASA Astrophysics Data System (ADS)

Wang, Qian; Zhang, Shunhong; Jena, Puru

2016-12-01

Due to the special electronic configuration, small atomic size, light mass, and flexible bonding features, carbon exhibits many different structural configurations with very different physical and chemical properties. Here we focus our discussion on three recent forms of carbon, namely, metallic carbon, magnetic carbon, and all-pentagon-based carbon. The metallic carbon can be used for metallic interconnects in future electronic circuits, nano devices and microprocessors while the magnetic carbon can have applications in spintronics. All-pentagon-based carbon nano-structure, penta-graphene, not only expands the family of carbon materials with a number of new features, but also provides the materials basis for the 2D packing of pentagons pursued by mathematicians for almost a century.

Proteogenomic insights into uranium tolerance of a Chernobyl's Microbacterium bacterial isolate.

PubMed

Gallois, Nicolas; Alpha-Bazin, Béatrice; Ortet, Philippe; Barakat, Mohamed; Piette, Laurie; Long, Justine; Berthomieu, Catherine; Armengaud, Jean; Chapon, Virginie

2018-04-15

Microbacterium oleivorans A9 is a uranium-tolerant actinobacteria isolated from the trench T22 located near the Chernobyl nuclear power plant. This site is contaminated with different radionuclides including uranium. To observe the molecular changes at the proteome level occurring in this strain upon uranyl exposure and understand molecular mechanisms explaining its uranium tolerance, we established its draft genome and used this raw information to perform an in-depth proteogenomics study. High-throughput proteomics were performed on cells exposed or not to 10μM uranyl nitrate sampled at three previously identified phases of uranyl tolerance. We experimentally detected and annotated 1532 proteins and highlighted a total of 591 proteins for which abundances were significantly differing between conditions. Notably, proteins involved in phosphate and iron metabolisms show high dynamics. A large ratio of proteins more abundant upon uranyl stress, are distant from functionally-annotated known proteins, highlighting the lack of fundamental knowledge regarding numerous key molecular players from soil bacteria. Microbacterium oleivorans A9 is an interesting environmental model to understand biological processes engaged in tolerance to radionuclides. Using an innovative proteogenomics approach, we explored its molecular mechanisms involved in uranium tolerance. We sequenced its genome, interpreted high-throughput proteomic data against a six-reading frame ORF database deduced from the draft genome, annotated the identified proteins and compared protein abundances from cells exposed or not to uranyl stress after a cascade search. These data show that a complex cellular response to uranium occurs in Microbacterium oleivorans A9, where one third of the experimental proteome is modified. In particular, the uranyl stress perturbed the phosphate and iron metabolic pathways. Furthermore, several transporters have been identified to be specifically associated to uranyl stress, paving the way to the development of biotechnological tools for uranium decontamination. Copyright © 2017. Published by Elsevier B.V.

Exploring New Assembly Modes of Uranyl Terephthalate: Templated Syntheses and Structural Regulation of a Series of Rare 2D → 3D Polycatenated Frameworks

DOE PAGES

Mei, Lei; Wang, Cong-zhi; Zhu, Liu-zheng; ...

2017-06-23

In this paper, the reaction of uranyl nitrate with terephthalic acid (H 2TP) under hydrothermal conditions in the presence of an organic base, 1,3-(4,4'-bispyridyl)propane (BPP) or 4,4'-bipyridine (BPY), provided four uranyl terephthalate compounds with different entangled structures by a pH-tuning method. [UO 2(TP) 1.5](H 2BPP) 0.5·2H 2O (1) obtained in a relatively acidic solution (final aqueous pH, 4.28) crystallizes in the form of a noninterpenetrated honeycomb-like two-dimensional network structure. An elevation of the solution pH (final pH, 5.21) promotes the formation of a dimeric uranyl-mediated polycatenated framework, [(UO 2) 2(μ-OH) 2(TP) 2] 2(H 2BPP) 2·4.5H 2O (2). Another new polycatenatedmore » framework with a monomeric uranyl unit, [(UO 2) 2(TP) 3](H 2BPP) (3), begins to emerge as a minor accompanying product of 2 when the pH is increased up to 6.61, and turns out to be a significant product at pH 7.00. When more rigid but small-size BPY molecules replace BPP molecules, [UO 2(TP) 1.5](H 2BPP) 0.5 (4) with a polycatenated framework similar to 3 was obtained in a relatively acidic solution (final pH, 4.81). The successful preparation of 2–4 represents the first report of uranyl–organic polycatenated frameworks derived from a simple H 2TP linker. Finally, a direct comparison between these polycatenated frameworks and previously reported uranyl terephthalate compounds suggests that the template and cavity-filling effects of organic bases (such as BPP or BPY), in combination with specific hydrothermal conditions, promote the formation of uranyl terephthalate polycatenated frameworks.« less

A more reactive trigonal-bipyramidal high-spin oxoiron(IV) complex with a cis-labile site.

PubMed

England, Jason; Guo, Yisong; Van Heuvelen, Katherine M; Cranswick, Matthew A; Rohde, Gregory T; Bominaar, Emile L; Münck, Eckard; Que, Lawrence

2011-08-10

The trigonal-bipyramidal high-spin (S = 2) oxoiron(IV) complex [Fe(IV)(O)(TMG(2)dien)(CH(3)CN)](2+) (7) was synthesized and spectroscopically characterized. Substitution of the CH(3)CN ligand by anions, demonstrated here for X = N(3)(-) and Cl(-), yielded additional S = 2 oxoiron(IV) complexes of general formulation [Fe(IV)(O)(TMG(2)dien)(X)](+) (7-X). The reduced steric bulk of 7 relative to the published S = 2 complex [Fe(IV)(O)(TMG(3)tren)](2+) (2) was reflected by enhanced rates of intermolecular substrate oxidation. © 2011 American Chemical Society

Shock-induced deformation features in terrestrial peridot and lunar dunite

NASA Technical Reports Server (NTRS)

Snee, L. W.; Ahrens, T. J.

1975-01-01

Single crystals of terrestrial olivine were experimentally shock-loaded along the 010 line to peak pressures 280, 330, and 440 kbar, and the resulting deformation features were compared to those in olivine from lunar dunite 72415. Recovered fragments were examined to determine the orientation of the planar fractures. With increasing pressure the percentage of pinacoids and prisms decreases, whereas the percentage of bipyramids increases. The complexity of the distribution of bipyramids also increases with increasing pressure. Other shock-induced deformation features, including varying degrees of recrystallization, are found to depend on pressure, as observed by others. Lunar dunite 72415 was examined and found to contain olivine with well-developed shock-deformation features. The relative proportion of pinacoid, prism, and bipyramid planar fractures measured for olivine from 72415 indicates that this rock appears to have undergone shock pressure in the range 330-440 kbar. If this dunite was brought to the surface of the moon as a result of excavation of an Imbrium event-sized impact crater, the shock-pressure range experienced by the sample and the results of cratering calculations suggest that it could have originated no deeper than 50-150 km.

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Non-destructive chemical analyses of these compounds is important for process and environmental monitoring and X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride,more » and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. These compounds have unique spectral signatures that can be used to identify unknown samples.« less

Preliminary experiments on the reduction of the uranyl ion to uraninite by carbonaceous substances

USGS Publications Warehouse

Breger, Irving A.; Moore, Richard T.

1955-01-01

An aqueous solution of uranyl sulfate containing a suspension of subbituminous coal has been heated at 210 C for three days. Examination of the coal at the end of the experiment showed it to contain 31.8 percent uranium recognizable as uraninite by a sharp, strong X-ray diffraction pattern. A similar experiment with degraded spruce wood also led to the formation of uraninite but in lesser quantity and with broader lines in the X-ray diffraction pattern. The ability of coal or wood to reduce the uranyl ion is a critical factor in the correlation of studies of uraniferous coals containing the uranyl ion with studies of uraninite-bearing coalified wood from the Colorado Plateau. Although these results are based an preliminary experiments, they are extremely important geochemically and warrant the development of the series of controlled studies that are proposed.

32 CFR 234.17 - Vehicles and traffic safety.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 32 National Defense 2 2014-07-01 2014-07-01 false Vehicles and traffic safety. 234.17 Section 234...) MISCELLANEOUS CONDUCT ON THE PENTAGON RESERVATION § 234.17 Vehicles and traffic safety. (a) In general. Unless specifically addressed by regulations in this part, traffic and the use of vehicles within the Pentagon...

32 CFR 234.17 - Vehicles and traffic safety.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 32 National Defense 2 2012-07-01 2012-07-01 false Vehicles and traffic safety. 234.17 Section 234...) MISCELLANEOUS CONDUCT ON THE PENTAGON RESERVATION § 234.17 Vehicles and traffic safety. (a) In general. Unless specifically addressed by regulations in this part, traffic and the use of vehicles within the Pentagon...

The Pentagon's Military Analyst Program

ERIC Educational Resources Information Center

Valeri, Andy

2014-01-01

This article provides an investigatory overview of the Pentagon's military analyst program, what it is, how it was implemented, and how it constitutes a form of propaganda. A technical analysis of the program is applied using the theoretical framework of the propaganda model first developed by Noam Chomsky and Edward S. Herman. Definitions…

32 CFR 234.17 - Vehicles and traffic safety.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 32 National Defense 2 2011-07-01 2011-07-01 false Vehicles and traffic safety. 234.17 Section 234...) MISCELLANEOUS CONDUCT ON THE PENTAGON RESERVATION § 234.17 Vehicles and traffic safety. (a) In general. Unless specifically addressed by regulations in this part, traffic and the use of vehicles within the Pentagon...

Effects of catastrophic events on transportation system management and operations : the Pentagon and the national capital region -- September 11, 2001

DOT National Transportation Integrated Search

2002-04-01

The report documents the actions taken by transportation agencies in response to the terrorist attack on the Pentagon in Arlington, Va. on September 11, and is part of a larger effort to examine the impacts of catastrophic events on transportation sy...

Historical Office of the Office of the Secretary of Defense

Science.gov Websites

Contact DOD History Secretaries of Defense Pentagon History Renovations 9/11 Attack Images Pentagon Displays 9/11 Attack Publications Secretaries of Defense Historical Series Acquisition History Cold War Oral History Transcripts National Security Personnel System and British Nuclear History Oral History

32 CFR 234.17 - Vehicles and traffic safety.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 32 National Defense 2 2010-07-01 2010-07-01 false Vehicles and traffic safety. 234.17 Section 234...) MISCELLANEOUS CONDUCT ON THE PENTAGON RESERVATION § 234.17 Vehicles and traffic safety. (a) In general. Unless specifically addressed by regulations in this part, traffic and the use of vehicles within the Pentagon...

75 FR 39921 - Federal Advisory Committee; Defense Business Board (DBB); Correction

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-13

... contact Ms. Debora Duffy, Defense Business Board, 1155 Defense Pentagon, Room 5B-1088A, Washington, DC 20301-1155, [email protected] , (703) 697- 2168. The Board's Designated Federal Officer (DFO) is Ms. Phyllis Ferguson, Defense Business Board, 1155 Defense Pentagon, Room 5B-1088A, Washington, DC 20301-1155...

Old Fears Haunt New Social Science

ERIC Educational Resources Information Center

Glenn, David

2008-01-01

In September 1965, not long after news broke about a Pentagon-sponsored program to study social conflict in South America, the Social Science Research Council played host to a meeting on overseas research. Feelings were raw. Opposition to the Vietnam War was mounting, and many scholars worried that the Pentagon's studies of conflict and…

78 FR 54471 - Proposed Data Collections Submitted for Public Comment and Recommendations

Federal Register 2010, 2011, 2012, 2013, 2014

2013-09-04

... days of this notice. Proposed Project World Trade Center Health Program Enrollment & Appeals--Pentagon... information includes the definition of each population: A Pentagon responder is someone who was a member of a... number, date of birth, and gender. The World Trade Center Health Program (WTCHP) expects to receive...

A Geometric Principle May Guide Self-Assembly of Fullerene Cages from Clathrin Triskelia and from Carbon Atoms☆

PubMed Central

Schein, Stan; Sands-Kidner, Michelle

2008-01-01

Abstract Clathrin triskelia and carbon atoms alike self-assemble into a limited selection of fullerene cages (with n three connected vertices, 3n/2 edges, 12 pentagonal faces, and (n−20)/2 hexagonal faces). We show that a geometric constraint—exclusion of head-to-tail dihedral angle discrepancies (DADs)—explains this limited selection as well as successful assembly into such closed cages in the first place. An edge running from a pentagon to a hexagon has a DAD, since the dihedral angles about the edge broaden from its pentagon (tail) end to its hexagon (head) end. Of the 21 configurations of a central face and surrounding faces, six have such DAD vectors arranged head-to-tail. Of the 5770 mathematically possible fullerene cages for n ≤ 60, excluding those with any of the six configurations leaves just 15 cages plus buckminsterfullerene (n = 60), among them the known clathrin cages. Of the 216,739 mathematically possible cages for 60 < n ≤ 84, just the 50 that obey the isolated-pentagon rule, among them known carbon cages, pass. The absence of likely fullerenes for some n (30,34,46,48,52–58,62–68) explains the abundance of certain cages, including buckminsterfullerene. These principles also suggest a “probable roads” path to self-assembly in place of pentagon-road and fullerene-road hypotheses. PMID:17921209

Surface catalysis of uranium(VI) reduction by iron(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liger, E.; Charlet, L.; Van Cappellen, P.

1999-10-01

Colloidal hematite ({alpha}-Fe{sub 2}O{sub 3}) is used as model solid to investigate the kinetic effect of specific adsorption interactions on the chemical reduction of uranyl (U{sup VI}O{sub 2}{sup 2+}) by ferrous iron. Acid-base titrations and Fe(II) and uranyl adsorption experiments are performed on hematite suspensions, under O{sub 2}- and CO{sub 2}-free conditions. The results are explained in terms of a constant capacitance surface complexation model of the hematite-aqueous solution interface. Two distinct Fe(II) surface complexes are required to reproduce the data: ({equivalent{underscore}to}Fe{sup III}OFe{sup II}){sup +} (or {equivalent{underscore}to}Fe{sup III}OFe{sup II}(OH{sub 2}){sub n}{sup +}) and {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0} (or {equivalent{underscore}to}Fe{sup III}OFe{supmore » II}(OH{sub 2}){sub n{minus}1}OH{sup 0}). The latter complex represents a significant fraction of total adsorbed Fe(II) at pH {gt} 6.5. Uranyl binding to the hematite particles is characterized by a sharp adsorption edge between pH 4 and pH 5.5. Because of the absence of competing aqueous carbonate complexes, uranyl remains completely adsorbed at pH {gt} 7. A single mononuclear surface complex accounts for the adsorption of uranyl over the entire range of experimental conditions. Although thermodynamically feasible, no reaction between uranyl and Fe(II) is observed in homogeneous solution at pH 7.5, for periods of up to three days. In hematite suspensions, however, surface-bound uranyl reacts on a time scale of hours. Based on Fourier Transformed Infrared spectra, chemical reduction of U(VI) is inferred to be the mechanism responsible for the disappearance of uranyl. The kinetics of uranyl reduction are quantified by measuring the decrease with time of the concentration of U(VI) extractable from the hematite particles by NaHCO{sub 3}. In the presence of excess Fe(II), the initial rate of U(VI) reduction exhibits a first-order dependence on the concentration of adsorbed uranyl. The pseudo-first-order rate constant varies with pH (range, 6--7.5) and the total (dissolved + adsorbed) concentration of Fe(II) (range, 2--160 {micro}M). When analyzing the rate data in terms of the calculated surface speciation, the variability of the rate constant can be accounted for entirely by changes in the concentration of the Fe(II) monohydroxo surface complex {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0}. Therefore, the rate law is derived for the hematite-catalyzed reduction of uranyl by Fe(II), where the bimolecular rate constant {kappa} has a value of 399 {+-} 25 M{sup {minus}1} min{sup {minus}1} at 25 C. The hydroxo surface complex is the rate-controlling reductant species, because it provides the most favorable coordination environment in which electrons are removed from Fe(II). Natural particulate matter collected in the hypolimnion of a seasonally stratified lake also causes the rapid reduction of uranyl by Fe(II), Ferrihydrite, identified in the particulate matter by X-ray diffraction, is one possible mineral phase accelerating the reaction between U(VI) and Fe(II). At near-neutral pH and total Fe(II) levels less than 1 mM, the pseudo-first-order rate constants of chemical U(VI) reduction, measured in the presence of the hematite and lake particles, are of the same order of magnitude as the highest corresponding rate coefficients for enzymatic U(VI) reduction in bacterial cultures. Hence, based on the results of this study, surface-catalyzed U(VI) reduction by Fe(II) is expected to be a major pathway of uranium immobilization in a wide range of redox-stratified environments.« less

Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

PubMed

Armstrong, Christopher R; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E; Burns, Peter C; Navrotsky, Alexandra

2012-02-07

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.

M4FT-15OR03100415 - Update on COF-based Adsorbent Survey

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayes, Richard T.; Dai, Sheng

2015-02-01

This letter report provides an update on activities focused on generating nanoporous adsorbents involving covalent organic frameworks (COF) and zeolitic imidazolium frameworks (ZIF). The adsorbents have been generated and screened in a uranyl-spiked brine (6 ppm U) to understand uranyl-binding behavior. Porous organic polymers (POP) also qualify under this title and are similar to the COF PPN-6 that is discussed herein. Seven COF/POP and one 1 ZIF were synthesized and screened for uranyl adsorption. Seawater screening is on-going via batch testing while flow screening systems are being developed at PNNL.

Method for loading resin beds

DOEpatents

Notz, Karl J.; Rainey, Robert H.; Greene, Charles W.; Shockley, William E.

1978-01-01

An improved method of preparing nuclear reactor fuel by carbonizing a uranium loaded cation exchange resin provided by contacting a H.sup.+ loaded resin with a uranyl nitrate solution deficient in nitrate, comprises providing the nitrate deficient solution by a method comprising the steps of reacting in a reaction zone maintained between about 145.degree.-200.degree. C, a first aqueous component comprising a uranyl nitrate solution having a boiling point of at least 145.degree. C with a second aqueous component to provide a gaseous phase containing HNO.sub.3 and a reaction product comprising an aqueous uranyl nitrate solution deficient in nitrate.

Uranyl peroxide enhanced nuclear fuel corrosion in seawater

PubMed Central

Armstrong, Christopher R.; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E.; Burns, Peter C.; Navrotsky, Alexandra

2012-01-01

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances. PMID:22308442

Molecular dynamics simulations of uranyl adsorption and structure on the basal surface of muscovite

DOE PAGES

Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Cygan, Randall T.

2014-02-05

Anthropogenic activities have led to an increased concentration of uranium on the Earth’s surface and potentially in the subsurface with the development of nuclear waste repositories. Uranium is soluble in groundwater, and its mobility is strongly affected by the presence of clay minerals in soils and in subsurface sediments. We use molecular dynamics simulations to probe the adsorption of aqueous uranyl (UO 2 2+) ions onto the basal surface of muscovite, a suitable proxy for typically ultrafine-grained clay phases. Model systems include the competitive adsorption between potassium counterions and aqueous ions (0.1 M and 1.0 M UO 2Cl 2 ,more » 0.1 M NaCl). We find that for systems with potassium and uranyl ions present, potassium ions dominate the adsorption phenomenon. Potassium ions adsorb entirely as inner-sphere complexes associated with the ditrigonal cavity of the basal surface. Uranyl ions adsorb in two configurations when it is the only ion species present, and in a single configuration in the presence of potassium. Finally, the majority of adsorbed uranyl ions are tilted less than 45° relative to the muscovite surface, and are associated with the Si 4Al 2 rings near aluminum substitution sites.« less

U.S.-China Military Contacts: Issues for Congress

DTIC Science & Technology

2013-03-19

and reporting requirements • Obtain and review the Department of Defense (DOD)’ s plan for upcoming mil- to-mil contacts... the Principal Director for Asian and Pacific Affairs at the Office of the Secretary of Defense , testified that the Pentagon started discussions...Medical Center. September 17 At the Pentagon , Deputy Assistant Secretary of Defense for Asian and Pacific

Resources and Constraints Affecting U.S. Army Activities in Latin America

DTIC Science & Technology

1992-09-01

34 Washington Post, 17 January 1992, p. A12. n 7 Reported in Rick Maze, "Pentagon Persists on Reserve Cuts," Army Times, 30 December 1991, p. 6. 8 As...Security Assistance Agency Room 4B730, The Pentagon Washington, DC 20301 Dr. Riordan Roett SAIS Johns Hopkins University 1740 Massachusetts Avenue Washington

The Pentagonal Principle for Self-Oriented Classes.

ERIC Educational Resources Information Center

Ball, Jerald T.

Under the pentagonal principle, a class is divided into groups of five (or six) to complete a discrete learning task, which is divided into five bits. Students take turns presenting the bits; if one fails, the group takes over. In this rotation, each student leads at least once in the session; the group verifies all steps. The instructor acts…

Advancing U.S. Strategic Communication through Greater Civilian-Military Coordination and Integration

DTIC Science & Technology

2012-06-01

UN and other multilateral institutions. 17 16 Lolita Balder, "Pentagon propaganda an effort to "get the truth out," Associated Press, printed in the...middle east/3578183.stm (accessed March 2, 2012). Lolita Baldor, "Pentagon propaganda an effort to "get the truth out," Associated Press, printed in

Edge-functionalization of armchair graphene nanoribbons with pentagonal-hexagonal edge structures.

PubMed

Ryou, Junga; Park, Jinwoo; Kim, Gunn; Hong, Suklyun

2017-06-21

Using density functional theory calculations, we have studied the edge-functionalization of armchair graphene nanoribbons (AGNRs) with pentagonal-hexagonal edge structures. While the AGNRs with pentagonal-hexagonal edge structures (labeled (5,6)-AGNRs) are metallic, the edge-functionalized (5,6)-AGNRs with substitutional atoms opens a band gap. We find that the band structures of edge-functionalized (5,6)-N-AGNRs by substitution resemble those of defect-free (N-1)-AGNR at the Γ point, whereas those at the X point show the original ones of the defect-free N-AGNR. The overall electronic structures of edge-functionalized (5,6)-AGNRs depend on the number of electrons, supplied by substitutional atoms, at the edges of functionalized (5,6)-AGNRs.

Highly Sensitive and Selective Uranium Detection in Natural Water Systems Using a Luminescent Mesoporous Metal-Organic Framework Equipped with Abundant Lewis Basic Sites: A Combined Batch, X-ray Absorption Spectroscopy, and First Principles Simulation Investigation.

PubMed

Liu, Wei; Dai, Xing; Bai, Zhuanling; Wang, Yanlong; Yang, Zaixing; Zhang, Linjuan; Xu, Lin; Chen, Lanhua; Li, Yuxiang; Gui, Daxiang; Diwu, Juan; Wang, Jianqiang; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2017-04-04

Uranium is not only a strategic resource for the nuclear industry but also a global contaminant with high toxicity. Although several strategies have been established for detecting uranyl ions in water, searching for new uranium sensor material with great sensitivity, selectivity, and stability remains a challenge. We introduce here a hydrolytically stable mesoporous terbium(III)-based MOF material compound 1, whose channels are as large as 27 Å × 23 Å and are equipped with abundant exposed Lewis basic sites, the luminescence intensity of which can be efficiently and selectively quenched by uranyl ions. The detection limit in deionized water reaches 0.9 μg/L, far below the maximum contamination standard of 30 μg/L in drinking water defined by the United States Environmental Protection Agency, making compound 1 currently the only MOF material that can achieve this goal. More importantly, this material exhibits great capability in detecting uranyl ions in natural water systems such as lake water and seawater with pH being adjusted to 4, where huge excesses of competing ions are present. The uranyl detection limits in Dushu Lake water and in seawater were calculated to be 14.0 and 3.5 μg/L, respectively. This great detection capability originates from the selective binding of uranyl ions onto the Lewis basic sites of the MOF material, as demonstrated by synchrotron radiation extended X-ray adsorption fine structure, X-ray adsorption near edge structure, and first principles calculations, further leading to an effective energy transfer between the uranyl ions and the MOF skeleton.

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.; Eiden, Gregory C.; Pemmaraju, C. D.; Prendergast, David; Duffin, Andrew M.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Chemical analyses of these compounds are important for process and environmental monitoring. X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride, and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. The effect of hydration state on the sample, a potential complication in interpreting oxygen K-edge spectra, is discussed. These compounds have unique spectral signatures that can be used to identify unknown samples.

XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai

In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η 2 motifs proposed by small molecule andmore » computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ 2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.« less

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alam, Todd M.; Liao, Zuolei; Nyman, May

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

DOE PAGES

Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai; ...

2015-11-12

In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η 2 motifs proposed by small molecule andmore » computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ 2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.« less

Sorption of uranium in uranyl nitrate solutions on strong cationic resins and its elution with ammonium sulfate. II. Effects of EDTA on thorium decontamination; Estudos de sorpcao de uranio contido em solucoes de nitrato de uranilo por resina cationica forte e sua eluicao com sulfato de amonio. Parte II: efeito de EDTA na descontaminacao do torio (in Portuguese)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ribas, Antonio G.S.; Abrao, Alcidio

1970-05-15

This paper describes the studies of decontamination of thorium present as impurity in uranyl nitrate solutions, which was carried out through strong cationic resin where the thorium was partially retained. Then, the final decontamination was performed percolating the uranyl solution on a second cationic resin, after complexation of thorium (and other impurities) with EDTA. The thorium decontamination and the uranium retention were studied as a function of EDTA/U ratio, uranium concentration and acidity of the influent uranyl nitrate. The elution conditions were also studied as a function of eluent flow rate, concentration and acidity. Several tables and graphs showing themore » final results are included. (tr-auth)« less

Synthesis and characterization of new ion-imprinted polymer for separation and preconcentration of uranyl (UO2(2+)) ions.

PubMed

Ahmadi, Seyed Javad; Noori-Kalkhoran, Omid; Shirvani-Arani, Simindokht

2010-03-15

UO(2)(2+) ion-imprinted polymer materials used for solid-phase extraction were prepared by copolymerization of a ternary complex of uranyl ions with styrene and divinyl benzene in the presence of 2,2'-azobisisobutyronitrile. The imprinted particles were leached by HCl 6M. Various parameters in polymerization steps such as DVB/STY ratio, time of polymerization and temperature of polymerization were varied to achieve the most efficient uranyl-imprinted polymer. X-ray diffraction (XRD), infra-red spectroscopy (IR), thermo gravimetric analysis (TGA), UV-vis and nitrogen sorption were used to characterize the polymer particles. The XRD results showed that uranyl ions were completely removed from the polymer after leaching process. IR Analysis indicated that the N,N'-ethylenebis(pyridoxylideneiminato) remained intact in the polymer even after leaching. Some parameters such as pH, weight of the polymer, elution time, eluent volume and aqueous phase volume which affects the efficiency of the polymer were studied. (c) 2009 Elsevier B.V. All rights reserved.

Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory

DOE PAGES

Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.

2015-04-02

The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K 1 values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO 2 2+ complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K 1 values are significantly overestimated. Accurate predictions of the absolute log K 1 values (root mean square deviation from experiment < 1.0 for logmore » K 1 values ranging from 0 to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.« less

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

DOE PAGES

Alam, Todd M.; Liao, Zuolei; Nyman, May; ...

2016-04-27

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

Uranium XAFS analysis of kidney from rats exposed to uranium

PubMed Central

Kitahara, Keisuke; Numako, Chiya; Terada, Yasuko; Nitta, Kiyohumi; Homma-Takeda, Shino

2017-01-01

The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The U L III-edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate. PMID:28244440

Uranium XAFS analysis of kidney from rats exposed to uranium.

PubMed

Kitahara, Keisuke; Numako, Chiya; Terada, Yasuko; Nitta, Kiyohumi; Shimada, Yoshiya; Homma-Takeda, Shino

2017-03-01

The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The U L III -edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate.

Defense.gov - Special Report - Remembering 9/11: We Will Never Forget

Science.gov Websites

Memorial WASHINGTON, Sept. 10, 2009 – On the eve of the eight-year anniversary of 9/11, Pentagon employees who witnessed that tragedy first-hand took time to reflect from inside the memorial built to commemorate that day. Story Families to Launch Docent Program at Pentagon 9/11 Memorial WASHINGTON, Sept. 10

Optimizing Air Force Depot Programming to Maximize Operational Capability

DTIC Science & Technology

2014-03-27

MONITORING AGENCY NAME(S) AND ADDRESS(ES) AF/A4/ 7P Lt Col Dana C. Pelleltier, dana.c.pelletier2.mil@mail.mil, (703) 693-8395 Lt Col Robert L...Charlesworth, robert.charlesworth@pentagon.af.mi Maj Steven N. Lamb, steven.lamb@pentagon.mil, (703) 695-7049 10. SPONSOR/MONITOR’S ACRONYM(S) AF/A4/ 7P 11

Reforming Pentagon Decisionmaking

DTIC Science & Technology

2006-01-01

that people should make decisions as rationally as possible and that deviations from the rational ideal are undesirable. Recently, however...warfighting; therefore, a rational as opposed to an intuitive system makes sense for investment decisions . Third, many Pentagon planning problems... rational planning processes, consensus among experts is that people use both intuitive and rational techniques to make good decisions F E A T U R E

Novel platens to measure the hardness of a pentagonal shaped tablet.

PubMed

Malladi, Jaya; Sidik, Kurex; Wu, Sutan; McCann, Ryan; Dougherty, Jeffrey; Parab, Prakash; Carragher, Thomas

2017-03-01

Tablet hardness, a measure of the breaking force of a tablet, is based on numerous factors. These include the shape of the tablet and the mode of the application of force. For instance, when a pentagonal-shaped tablet was tested with a traditional hardness tester with flat platens, there was a large variation in hardness measurements. This was due to the propensity of vertices of the tablet to crush, referred to as an "improper break". This article describes a novel approach to measure the hardness of pentagonal-shaped tablets using modified platens. The modified platens have more uniform loading than flat platens. This is because they reduce loading on the vertex of the pentagon and apply forces on tablet edges to generate reproducible tablet fracture. The robustness of modified platens was assessed using a series of studies, which included feasibility and Gauge Repeatability & Reproducibility (R&R) studies. A key finding was that improper breaks, generated frequently with a traditional hardness tester using flat platens, were eliminated. The Gauge R&R study revealed that the tablets tested with novel platens generated consistent values in hardness measurements, independent of batch, hardness level, and day of testing, operator and tablet dosage strength.

Unusual Versatility of the Filamentous, Diazotrophic Cyanobacterium Anabaena torulosa Revealed for Its Survival during Prolonged Uranium Exposure

PubMed Central

Chandwadkar, Pallavi; Nayak, Chandrani

2017-01-01

ABSTRACT Reports on interactions between cyanobacteria and uranyl carbonate are rare. Here, we present an interesting succession of the metabolic responses employed by a marine, filamentous, diazotrophic cyanobacterium, Anabaena torulosa for its survival following prolonged exposure to uranyl carbonate extending up to 384 h at pH 7.8 under phosphate-limited conditions. The cells sequestered uranium (U) within polyphosphates on initial exposure to 100 μM uranyl carbonate for 24 to 28 h. Further incubation until 120 h resulted in (i) significant degradation of cellular polyphosphates causing extensive chlorosis and cell lysis, (ii) akinete differentiation followed by (iii) extracellular uranyl precipitation. X-ray diffraction (XRD) analysis, fluorescence spectroscopy, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopy established the identity of the bioprecipitated uranium as a U(VI) autunite-type mineral, which settled at the bottom of the vessel. Surprisingly, A. torulosa cells resurfaced as small green flakes typical of actively growing colonies on top of the test solutions within 192 to 240 h of U exposure. A consolidated investigation using kinetics, microscopy, and physiological and biochemical analyses suggested a role of inducible alkaline phosphatase activity of cell aggregates/akinetes in facilitating the germination of akinetes leading to substantial regeneration of A. torulosa by 384 h of uranyl incubation. The biomineralized uranium appeared to be stable following cell regeneration. Altogether, our results reveal novel insights into the survival mechanism adopted by A. torulosa to resist sustained uranium toxicity under phosphate-limited oxic conditions. IMPORTANCE Long-term effects of uranyl exposure in cyanobacteria under oxic phosphate-limited conditions have been inadequately explored. We conducted a comprehensive examination of the metabolic responses displayed by a marine cyanobacterium, Anabaena torulosa, to cope with prolonged exposure to uranyl carbonate at pH 7.8 under phosphate limitation. Our results highlight distinct adaptive mechanisms harbored by this cyanobacterium that enabled its natural regeneration following extensive cell lysis and uranium biomineralization under sustained uranium exposure. Such complex interactions between environmental microbes such as Anabaena torulosa and uranium over a broader time range advance our understanding on the impact of microbial processes on uranium biogeochemistry. PMID:28258135

Uranyl coordination in ionic liquids: the competition between ionic liquid anions, uranyl counterions, and Cl- anions investigated by extended X-ray absorption fine structure and UV-visible spectroscopies and molecular dynamics simulations.

PubMed

Gaillard, C; Chaumont, A; Billard, I; Hennig, C; Ouadi, A; Wipff, G

2007-06-11

The first coordination sphere of the uranyl cation in room-temperature ionic liquids (ILs) results from the competition between its initially bound counterions, the IL anions, and other anions (e.g., present as impurities or added to the solution). We present a joined spectroscopic (UV-visible and extended X-ray absorption fine structure)-simulation study of the coordination of uranyl initially introduced either as UO2X2 salts (X-=nitrate NO3-, triflate TfO-, perchlorate ClO4-) or as UO2(SO4) in a series of imidazolium-based ILs (C4mimA, A-=PF6-, Tf2N-, BF4- and C4mim=1-methyl-3-butyl-imidazolium) as well as in the Me3NBuTf2N IL. The solubility and dissociation of the uranyl salts are found to depend on the nature of X- and A-. The addition of Cl- anions promotes the solubilization of the nitrate and triflate salts in the C4mimPF6 and the C4mimBF4 ILs via the formation of chloro complexes, also formed with other salts. The first coordination sphere of uranyl is further investigated by molecular dynamics (MD) simulations on associated versus dissociated forms of UO2X2 salts in C4mimA ILs as a function of A- and X- anions. Furthermore, the comparison of UO2Cl(4)2-, 2 X- complexes with dissociated X- anions, to the UO2X2, 4 Cl- complexes with dissociated chlorides, shows that the former is more stable. The case of fluoro complexes is also considered, as a possible result of fluorinated IL anion's degradation, showing that UO2F42- should be most stable in solution. In all cases, uranyl is found to be solvated as formally anionic UO2XnAmClp2-n-m-p complexes, embedded in a cage of stabilizing IL imidazolium or ammonium cations.

A Mixed-Valent Molybdenum Monophosphate with a Layer Structure: KMo 3P 2O 14

NASA Astrophysics Data System (ADS)

Guesdon, A.; Borel, M. M.; Leclaire, A.; Grandin, A.; Raveau, B.

1994-03-01

A new mixed-valent molybdenum monophosphate with a layer structure KMo 3P 2O 14 has been isolated. It crystallizes in the space group P2 1/ m with a = 8.599(2) Å, b = 6.392(2) Å, c = 10.602(1) Å, and β = 111.65(2)°. The layers [Mo 3P 2O 14] ∞ are parallel to (100) and consist of [MoPO 8] ∞ chains running along limitb→ , in which one MoO 6 octahedron alternates with one PO 4 tetrahedron. In fact, four [MoPO 8] ∞ chains share the corners of their polyhedra and the edges of their octahedra, forming [Mo 4P 4O 24] ∞ columns which are linked through MoO 5 bipyramids along limitc→. The K + ions interleaved between these layers are surrounded by eight oxygens, forming bicapped trigonal prisms KO 8. Besides the unusual trigonal bipyramids MoO 5, this structure is also characterized by a tendency to the localization of the electrons, since one octahedral site is occupied by Mo(V), whereas the other octahedral site and the trigonal bipyramid are occupied by Mo(VI). The similarity of this structure with pure octahedral layer structures suggests the possibility of generating various derivatives, and of ion exchange properties.

Highly anisotropic exchange interactions in a trigonal bipyramidal cyanide-bridged Ni(II)3Os(III)2 cluster.

PubMed

Palii, Andrei V; Reu, Oleg S; Ostrovsky, Sergei M; Klokishner, Sophia I; Tsukerblat, Boris S; Hilfiger, Matthew; Shatruk, Michael; Prosvirin, Andrey; Dunbar, Kim R

2009-06-25

This article is a part of our efforts to control the magnetic anisotropy in cyanide-based exchange-coupled systems with the eventual goal to obtain single-molecule magnets with higher blocking temperatures. We give the theoretical interpretation of the magnetic properties of the new pentanuclear complex {[Ni(II)(tmphen)(2)](3)[Os(III)(CN)(6)](2)} x 6 CH(3)CN (Ni(II)(3)Os(III)(2) cluster). Because the system contains the heavy Os(III) ions, spin-orbit coupling considerably exceeds the contributions from the low-symmetry crystal field and exchange coupling. The magnetic properties of the Ni(II)(3)Os(III)(2) cluster are described in the framework of a highly anisotropic pseudo-spin Hamiltonian that corresponds to the limit of strong spin-orbital coupling and takes into account the complex molecular structure. The model provides a good fit to the experimental data and allows the conclusion that the trigonal axis of the bipyramidal Ni(II)(3)Os(III)(2) cluster is a hard axis of magnetization. This explains the fact that in contrast with the isostructural trigonal bipyramidal Mn(III)(2)Mn(II)(3) cluster, the Ni(II)(3)Os(III)(2) system does not exhibit the single-molecule magnetic behavior.

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

Nitrotyrosine adsorption on defective graphene: A density functional theory study

NASA Astrophysics Data System (ADS)

Majidi, R.; Karami, A. R.

2015-06-01

We have applied density functional theory to study adsorption of nitrotyrosine on perfect and defective graphene sheets. The graphene sheets with Stone-Wales (SW) defect, pentagon-nonagon (5-9) single vacancy, and pentagon-octagon-pentagon (5-8-5) double vacancy were considered. The calculations of adsorption energy showed that nitrotyrosine presents a more strong interaction with defective graphene rather than with perfect graphene sheet. The order of interaction strength is: SW>5-9>5-8-5>perfect graphene. It is found that the electronic properties of perfect and defective graphene are sensitive to the presence of nitrotyrosine. Hence, graphene sheets can be considered as a good sensor for detection of nitrotyrosine molecule which is observed in connection with several human disorders, such as Parkinson's and Alzheimer's disease.

Process for the extraction of technetium from uranium

DOEpatents

Gong, Cynthia-May S.; Poineau, Frederic; Czerwinski, Kenneth R.

2010-12-21

A spent fuel reprocessing method contacts an aqueous solution containing Technetium(V) and uranyl with an acidic solution comprising hydroxylamine hydrochloride or acetohydroxamic acid to reduce Tc(V) to Tc(II, and then extracts the uranyl with an organic phase, leaving technetium(II) in aqueous solution.

Negative Stains Containing Trehalose: Application to Tubular and Filamentous Structures

NASA Astrophysics Data System (ADS)

Harris, J. Robin; Gerber, Max; Gebauer, Wolfgang; Wernicke, Wolfgang; Markl, Jürgen

1996-02-01

Several examples are presented that show the successful application of uranyl acetate and ammonium molybdate negative staining in the presence of trehalose for TEM studies of filamentous and tubular structures. The principal benefit to be gained from the inclusion of trehalose stems from the considerably reduced flattening of the large tubular structures and the greater orientational freedom of single molecules due to an increased depth of the negative stain in the presence of trehalose. Trehalose is likely to provide considerable protection to protein molecules and their assemblies during the drying of negatively stained specimens. Some reduction in the excessive density imparted by uranyl acetate around large assemblies is also achieved. Nevertheless, in the presence of 1% (w/v) trehalose, it is desirable to increase the concentration of negative stain to 5% (w/v) for ammonium molybdate and to 4% for uranyl acetate to produce satisfactory image contrast. In general, the ammonium molybdate-trehalose negative stain is more satisfactory than the uranyl acetate-trehalose combination, because of the greater electron beam sensitivity of the uranyl negative stain. Reassembled taxol-stabilized pig brain microtubules, together with collagen fibrils, sperm tails, helical filaments, and reassociated hemocyanin (KLH2), all from the giant keyhole limpet Megathura crenulata, have been studied by negative staining in the presence of trehalose. In all cases satisfactory TEM imaging conditions were readily obtained on the specimens, as long as regions of excessively deep stain were avoided.

Inhibition of poly(ADP-ribose)polymerase-1 and DNA repair by uranium

PubMed Central

Cooper, Karen L.; Dashner, Erica J.; Tsosie, Ranalda; Cho, Young Mi; Lewis, Johnnye

2015-01-01

Uranium has radiological and non-radiological effects within biological systems and there is increasing evidence for genotoxic and carcinogenic properties attributable to uranium through its heavy metal properties. In this study, we report that low concentrations of uranium (as uranyl acetate; <10 μM) is not cytotoxic to human embryonic kidney cells or normal human keratinocytes; however, uranium exacerbates DNA damage and cytotoxicity induced by hydrogen peroxide, suggesting that uranium may inhibit DNA repair processes. Concentrations of uranyl acetate in the low micromolar range inhibited the zinc finger DNA repair protein poly(ADP-ribose) polymerase (PARP)-1 and caused zinc loss from PARP-1 protein. Uranyl acetate exposure also led to zinc loss from the zinc finger DNA repair proteins Xeroderma Pigmentosum, Complementation Group A (XPA) and aprataxin (APTX). In keeping with the observed inhibition of zinc finger function of DNA repair proteins, exposure to uranyl acetate enhanced retention of induced DNA damage. Co-incubation of uranyl acetate with zinc largely overcame the impact of uranium on PARP-1 activity and DNA damage. These findings present evidence that low concentrations of uranium can inhibit DNA repair through disruption of zinc finger domains of specific target DNA repair proteins. This may provide a mechanistic basis to account for the published observations that uranium exposure is associated with DNA repair deficiency in exposed human populations. PMID:26627003

Inhibition of poly(ADP-ribose)polymerase-1 and DNA repair by uranium.

PubMed

Cooper, Karen L; Dashner, Erica J; Tsosie, Ranalda; Cho, Young Mi; Lewis, Johnnye; Hudson, Laurie G

2016-01-15

Uranium has radiological and non-radiological effects within biological systems and there is increasing evidence for genotoxic and carcinogenic properties attributable to uranium through its heavy metal properties. In this study, we report that low concentrations of uranium (as uranyl acetate; <10 μM) is not cytotoxic to human embryonic kidney cells or normal human keratinocytes; however, uranium exacerbates DNA damage and cytotoxicity induced by hydrogen peroxide, suggesting that uranium may inhibit DNA repair processes. Concentrations of uranyl acetate in the low micromolar range inhibited the zinc finger DNA repair protein poly(ADP-ribose) polymerase (PARP)-1 and caused zinc loss from PARP-1 protein. Uranyl acetate exposure also led to zinc loss from the zinc finger DNA repair proteins Xeroderma Pigmentosum, Complementation Group A (XPA) and aprataxin (APTX). In keeping with the observed inhibition of zinc finger function of DNA repair proteins, exposure to uranyl acetate enhanced retention of induced DNA damage. Co-incubation of uranyl acetate with zinc largely overcame the impact of uranium on PARP-1 activity and DNA damage. These findings present evidence that low concentrations of uranium can inhibit DNA repair through disruption of zinc finger domains of specific target DNA repair proteins. This may provide a mechanistic basis to account for the published observations that uranium exposure is associated with DNA repair deficiency in exposed human populations. Copyright © 2015 Elsevier Inc. All rights reserved.

SEPARATION OF URANYL AND RUTHENIUM VALUES BY THE TRIBUTYL PHOSPHATE EXTRACTION PROCESS

DOEpatents

Wilson, A.S.

1961-05-01

A process is given for separating uranyl values from ruthenium values contained in an aqueous 3 to 4 M nitric acid solution. After the addition of hydrogen peroxide to obtain a concentration of 0.3 M, the uranium is selectively extracted with kerosene-diluted tributyl phosphate.

Probing hydrogen and halogen-oxo interactions in uranyl coordination polymers: a combined crystallographic and computational study

DOE PAGES

Carter, Korey P.; Kalaj, Mark; Kerridge, Andrew; ...

2018-01-01

Four uranyl compounds containing either benzoic acid ( 1 ), m -chlorobenzoic acid ( 2 ), m -bromobenzoic acid ( 3 ), or m -iodobenzoic acid ( 4 ) are described, and the latter two compounds are used to probe non-covalent interaction strengths via structural, vibrational, and computational means.

Direct observation of the core/double-shell architecture of intense dual-mode luminescent tetragonal bipyramidal nanophosphors

NASA Astrophysics Data System (ADS)

Kim, Su Yeon; Jeong, Jong Seok; Mkhoyan, K. Andre; Jang, Ho Seong

2016-05-01

Highly efficient downconversion (DC) green-emitting LiYF4:Ce,Tb nanophosphors have been synthesized for bright dual-mode upconversion (UC) and DC green-emitting core/double-shell (C/D-S) nanophosphors--Li(Gd,Y)F4:Yb(18%),Er(2%)/LiYF4:Ce(15%),Tb(15%)/LiYF4--and the C/D-S structure has been proved by extensive scanning transmission electron microscopy (STEM) analysis. Colloidal LiYF4:Ce,Tb nanophosphors with a tetragonal bipyramidal shape are synthesized for the first time and they show intense DC green light via energy transfer from Ce3+ to Tb3+ under illumination with ultraviolet (UV) light. The LiYF4:Ce,Tb nanophosphors show 65 times higher photoluminescence intensity than LiYF4:Tb nanophosphors under illumination with UV light and the LiYF4:Ce,Tb is adapted into a luminescent shell of the tetragonal bipyramidal C/D-S nanophosphors. The formation of the DC shell on the core significantly enhances UC luminescence from the UC core under irradiation of near infrared light and concurrently generates DC luminescence from the core/shell nanophosphors under UV light. Coating with an inert inorganic shell further enhances the UC-DC dual-mode luminescence by suppressing the surface quenching effect. The C/D-S nanophosphors show 3.8% UC quantum efficiency (QE) at 239 W cm-2 and 73.0 +/- 0.1% DC QE. The designed C/D-S architecture in tetragonal bipyramidal nanophosphors is rigorously verified by an energy dispersive X-ray spectroscopy (EDX) analysis, with the assistance of line profile simulation, using an aberration-corrected scanning transmission electron microscope equipped with a high-efficiency EDX. The feasibility of these C/D-S nanophosphors for transparent display devices is also considered.Highly efficient downconversion (DC) green-emitting LiYF4:Ce,Tb nanophosphors have been synthesized for bright dual-mode upconversion (UC) and DC green-emitting core/double-shell (C/D-S) nanophosphors--Li(Gd,Y)F4:Yb(18%),Er(2%)/LiYF4:Ce(15%),Tb(15%)/LiYF4--and the C/D-S structure has been proved by extensive scanning transmission electron microscopy (STEM) analysis. Colloidal LiYF4:Ce,Tb nanophosphors with a tetragonal bipyramidal shape are synthesized for the first time and they show intense DC green light via energy transfer from Ce3+ to Tb3+ under illumination with ultraviolet (UV) light. The LiYF4:Ce,Tb nanophosphors show 65 times higher photoluminescence intensity than LiYF4:Tb nanophosphors under illumination with UV light and the LiYF4:Ce,Tb is adapted into a luminescent shell of the tetragonal bipyramidal C/D-S nanophosphors. The formation of the DC shell on the core significantly enhances UC luminescence from the UC core under irradiation of near infrared light and concurrently generates DC luminescence from the core/shell nanophosphors under UV light. Coating with an inert inorganic shell further enhances the UC-DC dual-mode luminescence by suppressing the surface quenching effect. The C/D-S nanophosphors show 3.8% UC quantum efficiency (QE) at 239 W cm-2 and 73.0 +/- 0.1% DC QE. The designed C/D-S architecture in tetragonal bipyramidal nanophosphors is rigorously verified by an energy dispersive X-ray spectroscopy (EDX) analysis, with the assistance of line profile simulation, using an aberration-corrected scanning transmission electron microscope equipped with a high-efficiency EDX. The feasibility of these C/D-S nanophosphors for transparent display devices is also considered. Electronic supplementary information (ESI) available: XRD patterns, PL and PLE spectra, SEM and HR-TEM images, PL decay times, photographs showing the transparent nanophosphor solutions and their dual-mode luminescence, and additional EDX data. See DOI: 10.1039/c5nr05722a

Pentagon Reservation Maintenance Revolving Fund Financial Statements - FY 1992

DTIC Science & Technology

1993-06-25

3.2 million were reported. The Fund is resourced through direct appropriations and reimbursements from tenants of the Pentagon Reservation. For FY...and liabilities of $3.2 million. The Fund is resourced through direct appropriations and reimbursements from Fund property users. For FY 1992 the...Financial Statements - FY1992 4 Overview e. SizeofthePRMRF: Dollars expended: Building Operations Renovation Projects Tenant Reimbursable Total

Weakly-bridged dimeric diorganotin(IV) compounds derived from pyruvic acid hydrazone Schiff base ligands: Synthesis, characterization and crystal structures

NASA Astrophysics Data System (ADS)

Hong, Min; Yin, Han-Dong; Cui, Ji-Chun

2011-03-01

We report the synthesis of four diorganotin(IV) compounds of Schiff base pyruvic acid hydrazone derivatives formulated as [R 2SnLY] 2, where L 1 is 2-SC 4H 3CON 2C(CH 3)CO 2 with Y = CH 3CH 2CH 2CH 2OH, R = n-Bu ( 1); L 2 is C 6H 5CON 2C(CH 3)CO 2 with Y = CH 3CH 2OH, R = p-F-Bz ( 2); L 3 is 2-HOC 6H 4CON 2C(CH 3)CO 2 with Y dbnd H 2O, R = p-CN -Bz ( 3); and L 4 is 4-NO 2-C 6H 4CON 2C(CH 3)CO 2 with Y dbnd CH 3CH 2OH, R = Bz ( 4). The structures of all compounds have been established by a combination of single-crystal X-ray diffraction analysis, 1H and 119Sn NMR spectroscopy, IR spectroscopy, and elemental analysis. Studies reveal that four ligands present the same coordination mode with tin center, which all present tridentate ONO donor Schiff bases and coordinate to the tin center in an enolic form. In compounds 1- 4, each tin atom is seven-coordinated and exhibits a distorted pentagonal bipyramid with a planar SnO 4N unit and two apical alkyl carbon atoms, thus forming a weakly-bridged dimeric molecule. Additionally, the distance of Sn⋯O bridge in each compound is obviously affected by the choice of different alkyl groups and coordination solvent molecules, which fluctuates in the range of 2.571(5)-2.839(4) Å. Furthermore, the supramolecular structure analysis show that there are two types of supramolecular infrastructures, 1D chain or 2D network, which are formed by intermolecular O-H···N or C-H⋯X (X = O, N or F) hydrogen bonds.

Tuning the Origin of Magnetic Relaxation by Substituting the 3d or Rare-Earth Ions into Three Isostructural Cyano-Bridged 3d-4f Heterodinuclear Compounds.

PubMed

Zhang, Yan; Guo, Zhen; Xie, Shuang; Li, Hui-Li; Zhu, Wen-Hua; Liu, Li; Dong, Xun-Qing; He, Wei-Xun; Ren, Jin-Chao; Liu, Ling-Zhi; Powell, Annie K

2015-11-02

Three isostructural cyano-bridged 3d-4f compounds, [YFe(CN)6(hep)2(H2O)4] (1), [DyFe(CN)6(hep)2(H2O)4] (2), and [DyCo(CN)6(hep)2(H2O)4] (3), were successfully assembled by site-targeted substitution of the 3d or rare-earth ions. All compounds have been structurally characterized to display slightly distorted pentagonal-bipyramidal local coordination geometry around the rare-earth ions. Magnetic analyses revealed negligible magnetic coupling in compound 1, antiferromagnetic intradimer interaction in 2, and weak ferromagnetic coupling through dipolar-dipolar interaction in 3. Under an applied direct-current (dc) field, 1 (Hdc = 2.5 kOe, τ0 = 1.3 × 10(-7) s, and Ueff/kB = 23 K) and 3 (Hdc = 2.0 kOe, τ0 = 7.1 × 10(-11) s, and Ueff/kB = 63 K) respectively indicated magnetic relaxation behavior based on a single [Fe(III)]LS ion and a Dy(III) ion; nevertheless, 2 (Hdc = 2.0 kOe, τ0 = 9.7 × 10(-8) s, and Ueff/kB = 23 K) appeared to be a single-molecule magnet based on a cyano-bridged DyFe dimer. Compound 1, which can be regarded as a single-ion magnet of the [Fe(III)]LS ion linked to a diamagnetic Y(III) ion in a cyano-bridged heterodimer, represents one of the rarely investigated examples based on a single Fe(III) ion explored in magnetic relaxation behavior. It demonstrated that the introduction of intradimer magnetic interaction of 2 through a cyano bridge between Dy(III) and [Fe(III)]LS ions negatively affects the energy barrier and χ″(T) peak temperature compared to 3.

Three-dimensional visualization of coated vesicle formation in fibroblasts

PubMed Central

1980-01-01

Fibroblasts apparently ingest low density lipoproteins (LDL) by a selective mechanism of receptor-mediated endocytosis involving the formation of coated vesicles from the plasma membrane. However, it is not known exactly how coated vesicles collect LDL receptors and pinch off from the plasma membrane. In this report, the quick-freeze, deep- etch, rotary-replication method has been applied to fibroblasts; it displays with unusual clarity the coats that appear under the plasma membrane at the start of receptor-mediated endocytosis. These coats appear to be polygonal networks of 7-nm strands or struts arranged into 30-nm polygons, most of which are hexagons but some of which are 5- and 7-sided rings. The proportion of pentagons in each network increases as the coated area of the plasma membrane puckers up from its planar configuration (where the network is mostly hexagons) to its most sharply curved condition as a pinched-off coated vesicle. Coats around the smallest vesicles (which are icosahedrons of hexagons and pentagons) appear only slightly different from "empty coats" purified from homogenized brain, which are less symmetrical baskets containing more pentagons than hexagons. A search for structural intermediates in this coat transformation allows a test of T. Kanaseki and K. Kadota's (1969. J. Cell Biol. 42:202--220.) original idea that an internal rearrangement in this basketwork from hexagons to pentagons could "power" coated vesicle formation. The most noteworthy variations in the typical hexagonal honeycomb are focal juxtapositions of 5- and 7-sided polygons at points of partial contraction and curvature in the basketwork. These appear to precede complete contraction into individual pentagons completely surrounded by hexagons, which is the pattern that characterizes the final spherical baskets around coated vesicles. PMID:6987244

Surface-enhanced Raman scattering from silver nanostructures with different morphologies

NASA Astrophysics Data System (ADS)

Zhang, W. C.; Wu, X. L.; Kan, C. X.; Pan, F. M.; Chen, H. T.; Zhu, J.; Chu, Paul K.

2010-07-01

Scanning electron microscopy and X-ray diffraction reveal that four different types of crystalline silver nanostructures including nanoparticles, nanowires, nanocubes, and bipyramids are synthesized by a solvothermal method by reducing silver nitrate with ethylene glycol using poly(vinylpyrrolidone) as an adsorption agent and adding different quantities of sodium chloride to the solution. These nanostructures which exhibit different surface plasma resonance properties in the ultraviolet-visible region are shown to be good surface-enhanced Raman scattering (SERS) substrates using rhodamine 6G molecules. Our results demonstrate that the silver nanocubes, bipyramids with sharp corners and edges, and aggregated silver nanoparticles possess better SERS properties than the silver nanowires, indicating that they can serve as high-sensitivity substrates in SERS-based measurements.

Crystal structure of catena-poly[N,N,N′,N′-tetra­methyl­guanidinium [(chlorido­cadmate)-di-μ-chlorido

PubMed Central

Ndiaye, Mamadou; Samb, Abdoulaye; Diop, Libasse; Maris, Thierry

2016-01-01

In the structure of the title salt, {(C5H14N3)[CdCl3]}n, the CdII atom of the complex anion is five-coordinated by one terminal and four bridging Cl atoms. The corresponding coordination polyhedron is a distorted trigonal bipyramid, with Cd—Cl distances in the range 2.4829 (4)–2.6402 (4) Å. The bipyramids are condensed into a polyanionic zigzag chain extending parallel to [101]. The tetra­methyl­guanidinium cations are situated between the polyanionic chains and are linked to them through N—H⋯Cl hydrogen bonds, forming a layered network parallel to (010). PMID:26870572

CONTINUOUS PRECIPITATION METHOD FOR CONVERSION OF URANYL NITRATE TO URANIUM HEXAFLUORIDE

DOEpatents

Reinhart, G.M.; Collopy, T.J.

1962-11-13

A continuous precipitation process is given for converting a uranyl nitrate solution to uranium tetrafluoride. A stream of the uranyl nitrate solution and a stream of an aqueous ammonium hydroxide solution are continuously introduced into an agitated reaction zone maintained at a pH of 5.0 to 6.5. Flow rates are adjusted to provide a mean residence time of the resulting slurry in the reaction zone of at least 30 minutes. After a startup period of two hours the precipitate is recovered from the effluent stream by filtration and is converted to uranium tetrafluoride by reduction to uranium dioxide with hydrogen and reaction of the uranium dioxide with anhydrous hydrogen fluoride. (AEC)

ANALYTICAL METHOD FOR THE DETERMINATION OF BORON IN URANYL NITRATE SOLUTIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1962-01-01

A method was developed for the determination of boron in uranyl nitrate solutions. The boron is separated from uranium and other impurities by distillation of methyl borate. It is determined absorptiometrically by means of curcumin in the presence of orthochlorophenol, perchloric acid, and acetic anhydride. The limit of detection is judged to be not greater than 0.05 mu g, but is dependent on the purity of the reagents used. The coefficient of variation on 210 results at the 0.2 mu g boron level was 26% with a bias of -25%. The method may be applied to depleted uranyl nitrate solutionsmore » and uranium slag recovery liquors. (auth)« less

Biosensing for the Environment and Defence: Aqueous Uranyl Detection Using Bacterial Surface Layer Proteins

PubMed Central

Conroy, David J.R.; Millner, Paul A.; Stewart, Douglas I.; Pollmann, Katrin

2010-01-01

The fabrication of novel uranyl (UO22+) binding protein based sensors is reported. The new biosensor responds to picomolar levels of aqueous uranyl ions within minutes using Lysinibacillus sphaericus JG-A12 S-layer protein tethered to gold electrodes. In comparison to traditional self assembled monolayer based biosensors the porous bioconjugated layer gave greater stability, longer electrode life span and a denser protein layer. Biosensors responded specifically to UO22+ ions and showed minor interference from Ni2+, Cs+, Cd2+ and Co2+. Chemical modification of JG-A12 protein phosphate and carboxyl groups prevented UO22+ binding, showing that both moieties are involved in the recognition to UO22+. PMID:22399904

ELECTROLYTIC PREPARATION OF UF$sub 4$

DOEpatents

Allen, A.L.; Anderson, R.W.; Powell, E.W.

1958-11-01

A method is presented for converting hexavalent aranium to uranium tetrafluoride. The method consists of electrolyzing a solution of uranyl fluoride in hydrofluoric acld at about 90 icient laborato C. The uranyl ions are reduced at the cathode and a hydrated uranium tetrafluoride precipitates. The precipitate is separated and subsequently dehydrated to UF/sub 4/.

Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates

DOE PAGES

Miskowiec, Andrew J.; Kirkegaard, Marie C.; Huq, Ashfia; ...

2015-11-17

We report a novel production method for uranium oxy uoride [(UO 2) 7F 14(H 2O) 7] 4H 2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl uoride, UO 2F 2, through the gas phase at ambient temperatures fol- lowed by desiccation by equilibration with a dry environment. We follow the structure of [(UO 2) 7F 14(H 2O) 7] 4H 2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous struc- ture), and a water molecule binds as an equatorialmore » ligand to the uranyl ion. Quasielas- tic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform re- stricted motion on a length scale commensurate with the O{H bond (r = 0.92 A). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps -1) than their hydrogen-bonded partners (Dr = 28.7 ps -1).« less

Is Julian Assange an International Version of Daniel Ellsberg and WikiLeaks the Modern Equivalent of the Pentagon Papers?

ERIC Educational Resources Information Center

Freivogel, William H.

2011-01-01

History has placed the stamp of approval on the publication of the Pentagon Papers, the top-secret history of the Vietnam War. If WikiLeaks editor-in-chief Julian Assange is another Daniel Ellsberg, then it is possible the website's disclosures will be viewed over time as similarly in the public interest. A classroom discussion on the release of…

The Pentagon Reporters,

DTIC Science & Technology

1983-01-01

Sperling , whose breakfast group of reporters meets with leading people in Washington and has become an institution in itself. Its Washington staff...particularly 61 NEWS SERVICES European and military history: "So I know who von Clausewitz was, know about the German military staff, know some of the...Down the Pentagon Drain," of news leaks, 165 67 Sperling , Godfrey (Christian Science USS Nautilus, 18 Monitor), 31 U2, 40, 90 SSAM (Soldier, Sailor

The Pendulum of War and Politics

DTIC Science & Technology

2013-05-16

Neil Sheehan, Fox Butterfield, Hendrick Smith and E. W. Kenworthy, The Pentagon Papers: The Secret History of the Vietnam War (New York: Quadrangle...65. Lexington: D.C. Heath and Company, 1995. McNamara, Robert S. In Retrospect, The Tragedy and Lessons of Vietnam. New York: Time Books, 1995...University Press of Kansas, 2005. Sheehan, Neil . The Pentagon Papers: As Published by the New York Times . Toronto, New York: Bantam Books , 1971. Sheehan

Reforming Pentagon Strategic Decisionmaking. Strategic Forum. Number 221, July 2006

DTIC Science & Technology

2006-07-01

capability that would improve Pentagon decisionmaking. Blink and Think It is commonly assumed that people can and should make decisions as rationally ... rationality ,” which not only helps them make decisions but also introduces a range of nonrational psychologi- cal factors into their thinking. An otherwise...decisionmaking shortcuts that limit their ability to make rational decisions . Strategic Forum No. 221July 2006 Institute for National Strategic Studies

Department of Everything: Department of Defense Spending That Has Little to Do With National Security

DTIC Science & Technology

2012-11-01

and Mathematics (STEM) programs that duplicate the work of the Department of Education and local school districts ($10.7 billion). The Department of...of science, technology, engineering, and mathematics (STEM).16 The Pentagon recently joined the cooking show craze by partnering with the...of DOD Science, Technology, Engineering, and Mathematics (STEM) Programs,” 2010. 17 The Pentagon Channel, “The Grill Sergeants,” http

Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

PubMed

Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

2017-11-02

Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of triscarbonato uranyl reduction by aqueous ferrous iron: a theoretical study.

PubMed

Wander, Matthew C F; Kerisit, Sebastien; Rosso, Kevin M; Schoonen, Martin A A

2006-08-10

Uranium is a pollutant whose mobility is strongly dependent on its oxidation state. While U(VI) in the form of the uranyl cation is readily reduced by a range of natural reductants, by contrast complexation of uranyl by carbonate greatly reduces its reduction potential and imposes increased electron transfer (ET) distances. Very little is known about the elementary processes involved in uranium reduction from U(VI) to U(V) to U(IV) in general. In this study, we examine the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution. A combination of molecular dynamics (MD) simulations and density functional theory (DFT) electronic structure calculations is employed to compute the parameters that enter into Marcus' ET model, including the thermodynamic driving forces, reorganization energies, and electronic coupling matrix elements. MD simulations predict that two ferrous iron atoms will bind in an inner-sphere fashion to the three-membered carbonate ring of triscarbonato uranyl, forming the charge-neutral ternary Fe(2)UO(2)(CO(3))(3)(H(2)O)(8) complex. Through a sequential proton-coupled electron-transfer mechanism (PCET), the first ET step converting U(VI) to U(V) is predicted by DFT to occur with an electronic barrier that corresponds to a rate on the order of approximately 1 s(-1). The second ET step converting U(V) to U(IV) is predicted to be significantly endergonic. Therefore, U(V) is a stabilized end product in this ET system, in agreement with experiment.

Ultrasensitive detection of uranyl by graphene oxide-based background reduction and RCDzyme-based enzyme strand recycling signal amplification.

PubMed

Li, Ming-Hui; Wang, Yong-Sheng; Cao, Jin-Xiu; Chen, Si-Han; Tang, Xian; Wang, Xiao-Feng; Zhu, Yu-Feng; Huang, Yan-Qin

2015-10-15

We proposed a novel strategy which combines graphene oxide-based background reduction with RCDzyme-based enzyme strand recycling amplification for ultrahigh sensitive detection of uranyl. The RCDzyme is designed to contain a guanine (G)-rich sequence that replaces the partial sequence in an uranyl-specific DNAzyme. This multifunctional probe can act as the target recognition element, DNAzyme and the primer of signal amplification. The presence of UO2(2+) can induce the cleavage of the substrate strands in RCDzyme. Then, each released enzyme strand can hybridize with another substrate strands to trigger many cycles of the cleavage by binding uranyl, leading to the formation of more G-quadruplexes by split guanine-rich oligonucleotide fragments. The resulting G-quadruplexes could bind to N-methyl-mesoporphyrin IX (NMM), causing an amplified detection signal for the target uranyl. Next, graphene oxide-based background reduction strategy was further employed for adsorbing free ssDNA and NMM, thereby providing a proximalis zero-background signal. The combination of RCDzyme signal amplification and proximalis zero-background signal remarkably improves the sensitivity of this method, achieving a dynamic range of two orders of magnitude and giving a detection limit down to 86 pM, which is much lower than those of related literature reports. These achievements might be helpful in the design of highly sensitive analytical platform for wide applications in environmental and biomedical fields. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of maleic acid and uranyl on mercurial diuresis in dogs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nigrovic, V.; Koechel, D.A.; Cafruny, E.J.

1973-01-01

The effects of two nephrotoxic agents were studied in anesthetized dogs undergoing mercurial diuresis. One of the agents, uranyl, accumulates in the kidneys when administered as the acetate salt but does not readily react with sulfhydryl groups. In acute experiments uranyl acetate in doses up to 5 ..mu..mol/kg produced no change in the urinary excretion of sodium or chloride. Uranyl acetate given before the injection of mercury(II) did not reduce the diuretic response to inorganic mercury. The other compound, maleic acid, accumulates in the kidneys and also reacts readily with sulfhydryl groups. The administration of small doses of maleic acidmore » did not change the excretion of sodium but it decreased the excretion of chloride. The administration of maleic acid either before or after the administration of mercury completely abolished the diuretic response. The inhibition occurred without significant changes in urinary pH. Diuretic responses to ethacrynic acid, furosemide, hydrochlorothiazide or acetazolamide were preserved in maleate-treated dogs. Both the lack of any effect of uranyl on mercurial diuresis and the specific inhibition of mercurial diuresis by maleic acid support the presently accepted view that the renal diuretic receptor for mercury(II) has at least one sulfhydryl binding site. Although the inhibition is ascribed to competition between mercury(II) and maleate for binding on the receptor, it is conceivable that the reduction in urinary chloride excretion produced by maleate may be responsible, in part, for refractoriness to mercury(II).« less

Hydrothermal synthesis of uranyl squarates and squarate-oxalates: hydrolysis trends and in situ oxalate formation.

PubMed

Rowland, Clare E; Cahill, Christopher L

2010-07-19

We report the synthesis of two uranyl squarates and two mixed-ligand uranyl squarate-oxalates from aqueous solutions under hydrothermal conditions. These products exhibit a range of uranyl building units from squarates with monomers in (UO(2))(2)(C(4)O(4))(5).6NH(4).4H(2)O (1; a = 16.731(17) A, b = 7.280(8) A, c = 15.872(16) A, beta = 113.294(16) degrees , monoclinic, P2(1)/c) and chains in (UO(2))(2)(OH)(2)(H(2)O)(2)(C(4)O(4)) (2; a = 12.909(5) A, b = 8.400(3) A, c = 10.322(4) A, beta = 100.056(7) degrees , monoclinic, C2/c) to two squarate-oxalate polymorphs with dimers in (UO(2))(2)(OH)(C(4)O(4))(C(2)O(4)).NH(4).H(2)O (3; a = 9.0601(7) A, b = 15.7299(12) A, c = 10.5108(8) A, beta = 106.394(1) degrees , monoclinic, P2(1)/n; and 4; a = 8.4469(6) A, b = 7.7589(5) A, c = 10.5257(7) A, beta = 105.696(1) degrees , monoclinic, P2(1)/m). The dominance at low pH of monomeric species and the increasing occurrence of oligomeric species with increasing pH suggests that uranyl hydrolysis, mUO(2)(2+) + nH(2)O right harpoon over left harpoon [(UO(2))(m)(OH)(n)](2m-n) + nH(+), has a significant role in the identity of the inorganic building unit. Additional factors that influence product assembly include in situ hydrolysis of squaric acid to oxalic acid, dynamic metal to ligand concentration, and additional binding modes resulting from the introduction of oxalate anions. These points and the effects of uranyl hydrolysis with changing pH are discussed in the context of the compounds presented herein.

Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O=U=O]²⁺ Asymmetric Stretch

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibson, John K.; Hu, Hanshi; Van Stipdonk, Michael J.

2015-04-09

The gas-phase complex UO₂(TMOGA)₂²⁺ (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700–1800 cm⁻¹ was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm⁻¹ (<1%) and a maximum deviation of 21 cm⁻¹ (<2%). The only IR peak assigned to the linear uranyl moiety was the asymmetric ν₃ mode, which appeared at 965 cm⁻¹ and was predicted by DFT as 953 cm⁻¹. This ν₃ frequency is red-shifted relative tomore » bare uranyl, UO₂²⁺, by ca. 150 cm⁻¹ due to electron donation from the TMOGA ligands. Based on the degree of red-shifting, it is inferred that two TMOGA oxygen-donor ligands have a greater effective gas basicity than the four monodentate acetone ligands in UO₂(acetone)₄²⁺. The uranyl ν₃ frequency was also computed for uranyl coordinated by two TMGA ligands, in which the central Oether of TMOGA has been replaced by CH₂. The computed ν₃ for UO₂(TMGA)₂²⁺, 950 cm⁻¹, is essentially the same as that for UO₂(TMOGA)₂²⁺, suggesting that electron donation to uranyl from the Oether of TMOGA is minor. The computed ν₃ asymmetric stretching frequencies for the three actinyl complexes, UO₂(TMOGA)₂²⁺, NpO₂(TMOGA)₂²⁺ and PuO₂(TMOGA)₂²⁺, are comparable. This similarity is discussed in the context of the relationship between ν₃ and intrinsic actinide-oxygen bond energies in actinyl complexes.« less

Mixed-Ligand Uranyl Polyrotaxanes Incorporating a Sulfate/Oxalate Coligand: Achieving Structural Diversity via pH-Dependent Competitive Effect.

PubMed

Xie, Zhen-Ni; Mei, Lei; Hu, Kong-Qiu; Xia, Liang-Shu; Chai, Zhi-Fang; Shi, Wei-Qun

2017-03-20

A mixed-ligand system provides an alternative route to tune the structures and properties of metal-organic compounds by introducing functional organic or inorganic coligands. In this work, five new uranyl-based polyrotaxane compounds incorporating a sulfate or oxalate coligand have been hydrothermally synthesized via a mixed-ligand method. Based on C6BPCA@CB6 (C6BPCA = 1,1'-(hexane-1,6-diyl)bis(4-(carbonyl)pyridin-1-ium), CB6 = cucurbit[6]uril) ligand, UPS1 (UO 2 (L) 0.5 (SO 4 )(H 2 O)·2H 2 O, L = C6BPCA@CB6) is formed by the alteration of initial aqueous solution pH to a higher acidity. The resulting 2D uranyl polyrotaxane sheet structure of UPS1 is based on uranyl-sulfate ribbons connected by the C6BPCA@CB6 pseudorotaxane linkers. By using oxalate ligand instead of sulfate, four oxalate-containing uranyl polyrotaxane compounds, UPO1-UPO4, have been acquired by tuning reaction pH and ligand concentration: UPO1 (UO 2 (L) 0.5 (C 2 O 4 ) 0.5 (NO 3 )·3H 2 O) in one-dimensional chain was obtained at a low pH value range (1.47-1.89) and UPO2 (UO 2 (L)(C 2 O 4 )(H 2 O)·7H 2 O)obtained at a higher pH value range (4.31-7.21). By lowering the amount of oxalate, another two uranyl polyrotaxane network UPO3 ((UO 2 ) 2 (L) 0.5 (C 2 O 4 ) 2 (H 2 O)) and UPO4 ((UO 2 ) 2 O(OH)(L) 0.5 (C 2 O 4 ) 0.5 (H 2 O)) could be acquired at a low pH value of 1.98 and a higher pH value over 6, respectively. The UPO1-UPO4 compounds, which display structural diversity via pH-dependent competitive effect of oxalate, represent the first series of mixed-ligand uranyl polyrotaxanes with organic ligand as the coligand. Moreover, the self-assembly process and its internal mechanism concerning pH-dependent competitive effect and other related factors such as concentration of the reagents and coordination behaviors of the coligands were discussed in detail.

Unusual Versatility of the Filamentous, Diazotrophic Cyanobacterium Anabaena torulosa Revealed for Its Survival during Prolonged Uranium Exposure.

PubMed

Acharya, Celin; Chandwadkar, Pallavi; Nayak, Chandrani

2017-05-01

Reports on interactions between cyanobacteria and uranyl carbonate are rare. Here, we present an interesting succession of the metabolic responses employed by a marine, filamentous, diazotrophic cyanobacterium, Anabaena torulosa for its survival following prolonged exposure to uranyl carbonate extending up to 384 h at pH 7.8 under phosphate-limited conditions. The cells sequestered uranium (U) within polyphosphates on initial exposure to 100 μM uranyl carbonate for 24 to 28 h. Further incubation until 120 h resulted in (i) significant degradation of cellular polyphosphates causing extensive chlorosis and cell lysis, (ii) akinete differentiation followed by (iii) extracellular uranyl precipitation. X-ray diffraction (XRD) analysis, fluorescence spectroscopy, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopy established the identity of the bioprecipitated uranium as a U(VI) autunite-type mineral, which settled at the bottom of the vessel. Surprisingly, A. torulosa cells resurfaced as small green flakes typical of actively growing colonies on top of the test solutions within 192 to 240 h of U exposure. A consolidated investigation using kinetics, microscopy, and physiological and biochemical analyses suggested a role of inducible alkaline phosphatase activity of cell aggregates/akinetes in facilitating the germination of akinetes leading to substantial regeneration of A. torulosa by 384 h of uranyl incubation. The biomineralized uranium appeared to be stable following cell regeneration. Altogether, our results reveal novel insights into the survival mechanism adopted by A. torulosa to resist sustained uranium toxicity under phosphate-limited oxic conditions. IMPORTANCE Long-term effects of uranyl exposure in cyanobacteria under oxic phosphate-limited conditions have been inadequately explored. We conducted a comprehensive examination of the metabolic responses displayed by a marine cyanobacterium, Anabaena torulosa , to cope with prolonged exposure to uranyl carbonate at pH 7.8 under phosphate limitation. Our results highlight distinct adaptive mechanisms harbored by this cyanobacterium that enabled its natural regeneration following extensive cell lysis and uranium biomineralization under sustained uranium exposure. Such complex interactions between environmental microbes such as Anabaena torulosa and uranium over a broader time range advance our understanding on the impact of microbial processes on uranium biogeochemistry. Copyright © 2017 American Society for Microbiology.

Alteration, adsorption and nucleation processes on clay-water interfaces: Mechanisms for the retention of uranium by altered clay surfaces on the nanometer scale

NASA Astrophysics Data System (ADS)

Schindler, Michael; Legrand, Christine A.; Hochella, Michael F.

2015-03-01

Nano-scale processes on the solid-water interface of clay minerals control the mobility of metals in the environment. These processes can occur in confined pore spaces of clay buffers and barriers as well as in contaminated sediments and involve a combination of alteration, adsorption and nucleation processes of multiple species and phases. This study characterizes nano-scale processes on the interface between clay minerals and uranyl-bearing solution near neutral pH. Samples of clay minerals with a contact pH of ∼6.7 are collected from a U mill and mine tailings at Key Lake, Saskatchewan, Canada. The tailings material contains Cu-, As-, Co-, Mo-, Ni-, Se-bearing polymetallic phases and has been deposited with a surplus of Ca(OH)2 and Na2CO3 slaked lime. Small volumes of mill-process solutions containing sulfuric acid and U are occasionally discharged onto the surface of the tailings and are neutralized after discharge by reactions with the slaked lime. Transmission electron microscopy (TEM) in combination with the focused ion beam (FIB) technique and other analytical methods (SEM, XRD, XRF and ICP-OES) are used to characterize the chemical and mineralogical composition of phases within confined pore spaces of the clay minerals montmorillonite and kaolinite and in the surrounding tailings material. Alteration zones around the clay minerals are characterized by different generations of secondary silicates containing variable proportions of adsorbed uranyl- and arsenate-species and by the intergrowth of the silicates with the uranyl-minerals cuprosklodowskite, Cu[(UO2)2(SiO3OH)2](H2O)6 and metazeunerite, Cu[(UO2)(AsO4)2](H2O)8. The majority of alteration phases such as illite, illite-smectite, kaolinite and vermiculite have been most likely formed in the sedimentary basin of the U-ore deposit and contain low amounts of Fe (<5 at.%). Iron-enriched Al-silicates or illite-smectites (Fe >10 at.%) formed most likely in the limed tailings at high contact pH (∼10.5) and their structure is characterized by a low degree of long-range order. Adsorption of U and nucleation of metazeunerite and cuprosklodowskite are strongly controlled by the presence of the adsorbed oxy-anion species arsenate and silica on the Fe-enriched silicates. Heterogeneous nucleation of nano-crystals of the uranyl minerals occurs most likely on adsorption sites of binary uranyl-, arsenate- and silica-complexes as well as on ternary uranyl-arsenate or uranyl-silicate complexes. The uranyl minerals occur as aggregates of misoriented nano-size crystals and are the result of supersaturated solutions and a high number of nucleation sites that prevented the formation of larger crystals through Oswald ripening. The results of this study provide an understanding of interfacial nano-scale processes between uranyl species and altered clay buffers in a potential Nuclear Waste repository as similar alteration conditions of clays may occur in a multi-barrier system.

Packing and self-assembly of truncated triangular bipyramids

NASA Astrophysics Data System (ADS)

Haji-Akbari, Amir; Chen, Elizabeth R.; Engel, Michael; Glotzer, Sharon C.

2013-07-01

Motivated by breakthroughs in the synthesis of faceted nano- and colloidal particles, as well as theoretical and computational studies of their packings, we investigate a family of truncated triangular bipyramids. We report dense periodic packings with small unit cells that were obtained via numerical and analytical optimization. The maximal packing fraction ϕmax changes continuously with the truncation parameter t. Eight distinct packings are identified based on discontinuities in the first and second derivatives of ϕmax(t). These packings differ in the number of particles in the fundamental domain (unit cell) and the type of contacts between the particles. In particular, we report two packings with four particles in the unit cell for which both ϕmax(t) and ϕmax'(t) are continuous and the discontinuity occurs in the second derivative only. In the self-assembly simulations that we perform for larger boxes with 2048 particles, only one out of eight packings is found to assemble. In addition, the degenerate quasicrystal reported previously for triangular bipyramids without truncation [Haji-Akbari , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.107.215702 107, 215702 (2011)] assembles for truncations as high as 0.45. The self-assembly propensities for the structures formed in the thermodynamic limit are explained using the isoperimetric quotient of the particles and the coordination number in the disordered fluid and in the assembled structure.

Correlation between ionic radii of metals and thermal decomposition of supramolecular structure of azodye complexes

NASA Astrophysics Data System (ADS)

El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Eldesoky, A. M.; Morgan, Sh. M.

2015-01-01

An interesting azodye heterocyclic ligand of copper(II), cobalt(II), nickel(II) and uranyl(II) complexes have been synthesized by the reaction of metal salts with 5-(2,3-dimethyl-1-phenylpyrazol-5-one azo)-2-thioxo-4-thiazolidinone (HL) yields 1:1 and 1:2 (M:L) complexes depending on the reaction conditions. The elemental analysis, magnetic moments, spectral (UV-Vis, IR, 1H and 13C NMR and ESR) and thermal studies were used to characterize the isolated complexes. The molecular structures of the ligand tautomers are optimized theoretically and the quantum chemical parameters are calculated. The IR spectra showed that the ligand (HL) act as monobasic tridentate/neutral bidentate through the (sbnd Ndbnd N), enolic (Csbnd O)- and/or oxygen keto moiety groups forming a five/six-membered structures. According to intramolecular hydrogen bond leads to increasing of the complexes stability. The molar conductivities show that all the complexes are non-electrolytes. The ESR spectra indicate that the free electron is in dxy orbital. The calculated bonding parameter indicates that in-plane σ-bonding is more covalent than in-plane π-bonding. The coordination geometry is five/six-coordinated trigonal bipyramidal for complex (1) and octahedral for complexes (2-6). The value of covalency factor β12 and orbital reduction factor K accounts for the covalent nature of the complexes. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. The synthesized ligand (HL) and its Cu(II) complexes (1, 2 and 4) are screened for their biological activity against bacterial and fungal species. The ligand (HL) showed antimicrobial activities against Escherichia coli. The ligand (HL) and its Cu(II) complexes (2 and 4) have very high antifungal activity against Penicillium italicum. The inhibitive action of ligand (HL), against the corrosion of C-steel in 2 M HCl solution has been investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS).

The Sky This Week, 2016 February 16 - 23 - Naval Oceanography Portal

Science.gov Websites

very nice pentagon shape. The southernmost star in the pentagon, Al Nath, is "shared" as the are here: Home › USNO › News, Tours & Events › Sky This Week › The Sky This Week, 2016 February 16 - 23 USNO Logo USNO Navigation Tour Information USNO Scientific Colloquia Sky This Week The Sky

Crystallographic interpretation of Galois symmetries for magnetic pentagonal ring

NASA Astrophysics Data System (ADS)

Milewski, J.; Lulek, T.; Łabuz, M.

2017-03-01

Galois symmetry of exact Bethe Ansatz eigenstates for the magnetic pentagonal ring within the XXX model are investigated by a comparison with crystallographic constructions of space groups. It follows that the arithmetic symmetry of Bethe parameters for the interior of the Brillouin zone admits crystallographic interpretation, in terms of the periodic square Z2 ×Z2 , that is the two-dimensional crystal lattice with Born-Karman period two in both directions.

The Integrated Library System Design Concepts for a Complete Serials Control Subsystem.

DTIC Science & Technology

1984-08-20

7AD-fl149 379 THE INTEGRTED LIBRARY SYSTEM DESIGN CONCEPTS FOR A 1/COMPLETE SERIALS CONTROL UBSYSTEM(U) ONLINE COMPUTER SYSTEMS INC GERMANTOWN MD 28...CONTROL SUBSYSTEM Presented to: The Pentagon Library The Pentagon Washington, DC 20310 Prepared by: Online Computer Systems, Inc. 20251 Century Blvd...MDA903-82-C-0535 9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT, PROJECT, TASK AREA & WORK UNIT NUMBERS Online Computer Systems, Inc

A one-dimensional ice structure built from pentagons

NASA Astrophysics Data System (ADS)

Carrasco, Javier; Michaelides, Angelos

2010-03-01

Heterogeneous nucleation of water plays a key role in fields as diverse as atmospheric chemistry, astrophysics, and biology. Ice nucleation on metal surfaces offers an opportunity to watch this process unfold, providing a molecular-scale description at a well-defined, planar interface. We discuss a density-functional theory study on a metal surface specifically designed to understand such phenomena. Together with our colleges at the University of Liverpool, we found that the nanometer wide water-ice chains experimentally observed to nucleate and grow on Cu(110) are built from a face sharing arrangement of water pentagons [1]. The novel one-dimensional pentagon structure maximizes the water-metal bonding whilst simultaneously maintaining a strong hydrogen bonding network. These results reveal an unanticipated structural adaptability of water-ice films, demonstrating that the presence of the substrate can be sufficient to favor non-conventional structural units. [4pt] [1] J. Carrasco et al., Nature Mater. 8, 427 (2009).

A one-dimensional ice structure built from pentagons

NASA Astrophysics Data System (ADS)

Carrasco, Javier; Michaelides, Angelos; Forster, Matthew; Haq, Sam; Raval, Rasmita; Hodgson, Andrew

2009-05-01

Heterogeneous ice nucleation has a key role in fields as diverse as atmospheric chemistry and biology. Ice nucleation on metal surfaces affords an opportunity to watch this process unfold at the molecular scale on a well-defined, planar interface. A common feature of structural models for such films is that they are built from hexagonal arrangements of molecules. Here we show, through a combination of scanning tunnelling microscopy, infrared spectroscopy and density-functional theory, that about 1-nm-wide ice chains that nucleate on Cu(110) are not built from hexagons, but instead are built from a face-sharing arrangement of water pentagons. The pentagon structure is favoured over others because it maximizes the water-metal bonding while maintaining a strong hydrogen-bonding network. It reveals an unanticipated structural adaptability of water-ice films, demonstrating that the presence of the substrate can be sufficient to favour non-hexagonal structural units.

Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arnold, John

The uranyl cation (UO 2 2+) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due tomore » the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.« less

Removal of toxic uranium from synthetic nuclear power reactor effluents using uranyl ion imprinted polymer particles.

PubMed

Preetha, Chandrika Ravindran; Gladis, Joseph Mary; Rao, Talasila Prasada; Venkateswaran, Gopala

2006-05-01

Major quantities of uranium find use as nuclear fuel in nuclear power reactors. In view of the extreme toxicity of uranium and consequent stringent limits fixed by WHO and various national governments, it is essential to remove uranium from nuclear power reactor effluents before discharge into environment. Ion imprinted polymer (IIP) materials have traditionally been used for the recovery of uranium from dilute aqueous solutions prior to detection or from seawater. We now describe the use of IIP materials for selective removal of uranium from a typical synthetic nuclear power reactor effluent. The IIP materials were prepared for uranyl ion (imprint ion) by forming binary salicylaldoxime (SALO) or 4-vinylpyridine (VP) or ternary SALO-VP complexes in 2-methoxyethanol (porogen) and copolymerizing in the presence of styrene (monomer), divinylbenzene (cross-linking monomer), and 2,2'-azobisisobutyronitrile (initiator). The resulting materials were then ground and sieved to obtain unleached polymer particles. Leached IIP particles were obtained by leaching the imprint ions with 6.0 M HCl. Control polymer particles were also prepared analogously without the imprint ion. The IIP particles obtained with ternary complex alone gave quantitative removal of uranyl ion in the pH range 3.5-5.0 with as low as 0.08 g. The retention capacity of uranyl IIP particles was found to be 98.50 mg/g of polymer. The present study successfully demonstrates the feasibility of removing uranyl ions selectively in the range 5 microg - 300 mg present in 500 mL of synthetic nuclear power reactor effluent containing a host of other inorganic species.

Dehydration-driven evolution of topological complexity in ethylamonium uranyl selenates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Krivovichev, Sergey V.; Tananaev, Ivan G.

Single crystals of four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules, (C{sub 2}H{sub 8}N){sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) (I), (C{sub 2}H{sub 8}N){sub 3}[(UO{sub 2})(SeO{sub 4}){sub 2}(HSeO{sub 4})] (II), (C{sub 2}H{sub 8}N)[(UO{sub 2})(SeO{sub 4})(HSeO{sub 3})] (III), and (C{sub 2}H{sub 8}N)(H{sub 3}O)[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (IV) have been prepared by isothermal evaporation from aqueous solutions. Uranyl-containing 1D and 2D units have been investigated using topological approach and information-based complexity measurements that demonstrate the evolution of structural units and the increase of topological complexity with the decrease of H{sub 2}O content. - Graphical abstract: Single crystals ofmore » four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules have been prepared by isothermal evaporation from aqueous solutions. Structural analysis and information-based topological complexity calculations points to the possible sequence of crystalline phases formation, showing both topological and structural branches of evolution. - Highlights: • Single crystals of four novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • Dehydration processes drives the evolution of topological complexity of 1D and 2D structural units.« less

Structure of water clusters on graphene: A classical molecular dynamics approach

NASA Astrophysics Data System (ADS)

Maekawa, Yuki; Sasaoka, Kenji; Yamamoto, Takahiro

2018-03-01

The microscopic structure of surface water adsorbed on graphene is elucidated theoretically by classical molecular dynamics simulation. At a low temperature (100 K), the main polygon consisting of hydrogen bonds in single-layered water on graphene is tetragonal, whereas the dominant polygons in double-layered water are tetragonal, pentagonal, and hexagonal. On the other hand, at room temperature, the tetragonal, pentagonal, and hexagonal water clusters are the main structures in both single- and double-layered water.

International Law and the Changing Character of War. Volume 87

DTIC Science & Technology

2011-01-01

38. Id. 39. See Londono, supra note 25. 40. See, e.g., Rowan Scarborough, Pentagon Notebook: McPeak calls McCain too fat , WASHINGTON TIMES, June 26...jet fight- ers."), available at http://www.washtimes.com/news/2008/jun/26/pentagon-notebook-mcpeak -calls-mccain-too- fat /?page=2. 41. Michael Hoffman...involve "not just reasoning with opponents, but also bringing pressure, arm twisting, encouraging sanctions, and shaming ." 114 The concept of framing

FLAME DENITRATION AND REDUCTION OF URANIUM NITRATE TO URANIUM DIOXIDE

DOEpatents

Hedley, W.H.; Roehrs, R.J.; Henderson, C.M.

1962-06-26

A process is given for converting uranyl nitrate solution to uranium dioxide. The process comprises spraying fine droplets of aqueous uranyl nitrate solution into a hightemperature hydrocarbon flame, said flame being deficient in oxygen approximately 30%, retaining the feed in the flame for a sufficient length of time to reduce the nitrate to the dioxide, and recovering uranium dioxide. (AEC)

SHINE and Mini-SHINE Column Designs for Recovery of Mo from 140 g-U/L Uranyl Sulfate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stepinski, Dominique C.; Vandegrift, George F.

Argonne is assisting SHINE Medical Technologies (SHINE) in their efforts to develop an accelerator-driven process that utilizes a uranyl-sulfate solution for the production of fission Mo-99. In an effort to design a Mo-recovery system for the SHINE project using low-enriched uranium (LEU), we conducted batch, breakthrough, and pulse tests to determine the Mo isotherm, mass-transfer zone (MTZ), and system parameters for a 130 g-U/L uranyl sulfate solution at pH 1 and 80°C, as described previously. The VERSE program was utilized to calculate the MTZ under various loading times and velocities. The results were then used to design Mo separation andmore » recovery columns employing a pure titania sorbent (110-μm particles, S110, and 60 Å pore size). The plant-scale column designs assume Mo will be separated from 271 L of a 141 g-U/L uranyl sulfate solution, pH 1, containing 0.0023 mM Mo. The VERSE-designed recovery systems have been tested and verified in laboratory-scale experiments, and this approach was found to be very successful.« less

Structure, Kinetics, and Thermodynamics of the Aqueous Uranyl(VI) Cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerisit, Sebastien N.; Liu, Chongxuan

2013-08-20

Molecular simulation techniques are employed to gain insights into the structural, kinetic, and thermodynamic properties of the uranyl(VI) cation (UO22+) in aqueous solution. The simulations make use of an atomistic potential model (force field) derived in this work and based on the model of Guilbaud and Wipff (Guilbaud, P.; Wipff, G. J. Mol. Struct. (THEOCHEM) 1996, 366, 55-63). Reactive flux and thermodynamic integration calculations show that the derived potential model yields predictions for the water exchange rate and free energy of hydration, respectively, that are in agreement with experimental data. The water binding energies, hydration shell structure, and self-diffusion coefficientmore » are also calculated and discussed. Finally, a combination of metadynamics and transition path sampling simulations is employed to probe the mechanisms of water exchange reactions in the first hydration shell of the uranyl ion. These atomistic simulations indicate, based on two-dimensional free energy surfaces, that water exchanges follow an associative interchange mechanism. The nature and structure of the water exchange transition states are also determined. The improved potential model is expected to lead to more accurate predictions of uranyl adsorption energies at mineral surfaces using potential-based molecular dynamics simulations.« less

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Periodic density functional theory investigation of the uranyl ion sorption on three mineral surfaces: a comparative study.

PubMed

Roques, Jérôme; Veilly, Edouard; Simoni, Eric

2009-06-04

Canister integrity and radionuclides retention is of prime importance for assessing the long term safety of nuclear waste stored in engineered geologic depositories. A comparative investigation of the interaction of uranyl ion with three different mineral surfaces has thus been undertaken in order to point out the influence of surface composition on the adsorption mechanism(s). Periodic DFT calculations using plane waves basis sets with the GGA formalism were performed on the TiO(2)(110), Al(OH)(3)(001) and Ni(111) surfaces. This study has clearly shown that three parameters play an important role in the uranyl adsorption mechanism: the solvent (H(2)O) distribution at the interface, the nature of the adsorption site and finally, the surface atoms' protonation state.

Periodic Density Functional Theory Investigation of the Uranyl Ion Sorption on Three Mineral Surfaces: A Comparative Study

PubMed Central

Roques, Jérôme; Veilly, Edouard; Simoni, Eric

2009-01-01

Canister integrity and radionuclides retention is of prime importance for assessing the long term safety of nuclear waste stored in engineered geologic depositories. A comparative investigation of the interaction of uranyl ion with three different mineral surfaces has thus been undertaken in order to point out the influence of surface composition on the adsorption mechanism(s). Periodic DFT calculations using plane waves basis sets with the GGA formalism were performed on the TiO2(110), Al(OH)3(001) and Ni(111) surfaces. This study has clearly shown that three parameters play an important role in the uranyl adsorption mechanism: the solvent (H2O) distribution at the interface, the nature of the adsorption site and finally, the surface atoms’ protonation state. PMID:19582222

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

DOE PAGES

Dewji, Shaheen A.; Croft, Stephen; Hertel, Nolan E.

2016-12-16

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systemsmore » in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Furthermore, quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.« less

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dewji, Shaheen A.; Croft, Stephen; Hertel, Nolan E.

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systemsmore » in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Furthermore, quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.« less

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

NASA Astrophysics Data System (ADS)

Dewji, S. A.; Croft, S.; Hertel, N. E.

2017-03-01

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO2(NO3)2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.

Interaction of Uranium with Bacterial Cell Surfaces: Inferences from Phosphatase-Mediated Uranium Precipitation.

PubMed

Kulkarni, Sayali; Misra, Chitra Seetharam; Gupta, Alka; Ballal, Anand; Apte, Shree Kumar

2016-08-15

Deinococcus radiodurans and Escherichia coli expressing either PhoN, a periplasmic acid phosphatase, or PhoK, an extracellular alkaline phosphatase, were evaluated for uranium (U) bioprecipitation under two specific geochemical conditions (GCs): (i) a carbonate-deficient condition at near-neutral pH (GC1), and (ii) a carbonate-abundant condition at alkaline pH (GC2). Transmission electron microscopy revealed that recombinant cells expressing PhoN/PhoK formed cell-associated uranyl phosphate precipitate under GC1, whereas the same cells displayed extracellular precipitation under GC2. These results implied that the cell-bound or extracellular location of the precipitate was governed by the uranyl species prevalent at that particular GC, rather than the location of phosphatase. MINTEQ modeling predicted the formation of predominantly positively charged uranium hydroxide ions under GC1 and negatively charged uranyl carbonate-hydroxide complexes under GC2. Both microbes adsorbed 6- to 10-fold more U under GC1 than under GC2, suggesting that higher biosorption of U to the bacterial cell surface under GC1 may lead to cell-associated U precipitation. In contrast, at alkaline pH and in the presence of excess carbonate under GC2, poor biosorption of negatively charged uranyl carbonate complexes on the cell surface might have resulted in extracellular precipitation. The toxicity of U observed under GC1 being higher than that under GC2 could also be attributed to the preferential adsorption of U on cell surfaces under GC1. This work provides a vivid description of the interaction of U complexes with bacterial cells. The findings have implications for the toxicity of various U species and for developing biological aqueous effluent waste treatment strategies. The present study provides illustrative insights into the interaction of uranium (U) complexes with recombinant bacterial cells overexpressing phosphatases. This work demonstrates the effects of aqueous speciation of U on the biosorption of U and the localization pattern of uranyl phosphate precipitated as a result of phosphatase action. Transmission electron microscopy revealed that location of uranyl phosphate (cell associated or extracellular) was primarily influenced by aqueous uranyl species present under the given geochemical conditions. The data would be useful for understanding the toxicity of U under different geochemical conditions. Since cell-associated precipitation of metal facilitates easy downstream processing by simple gravity-based settling down of metal-loaded cells, compared to cumbersome separation techniques, the results from this study are of considerable relevance to effluent treatment using such cells. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Interaction of Uranium with Bacterial Cell Surfaces: Inferences from Phosphatase-Mediated Uranium Precipitation

PubMed Central

Kulkarni, Sayali; Misra, Chitra Seetharam; Gupta, Alka; Ballal, Anand

2016-01-01

ABSTRACT Deinococcus radiodurans and Escherichia coli expressing either PhoN, a periplasmic acid phosphatase, or PhoK, an extracellular alkaline phosphatase, were evaluated for uranium (U) bioprecipitation under two specific geochemical conditions (GCs): (i) a carbonate-deficient condition at near-neutral pH (GC1), and (ii) a carbonate-abundant condition at alkaline pH (GC2). Transmission electron microscopy revealed that recombinant cells expressing PhoN/PhoK formed cell-associated uranyl phosphate precipitate under GC1, whereas the same cells displayed extracellular precipitation under GC2. These results implied that the cell-bound or extracellular location of the precipitate was governed by the uranyl species prevalent at that particular GC, rather than the location of phosphatase. MINTEQ modeling predicted the formation of predominantly positively charged uranium hydroxide ions under GC1 and negatively charged uranyl carbonate-hydroxide complexes under GC2. Both microbes adsorbed 6- to 10-fold more U under GC1 than under GC2, suggesting that higher biosorption of U to the bacterial cell surface under GC1 may lead to cell-associated U precipitation. In contrast, at alkaline pH and in the presence of excess carbonate under GC2, poor biosorption of negatively charged uranyl carbonate complexes on the cell surface might have resulted in extracellular precipitation. The toxicity of U observed under GC1 being higher than that under GC2 could also be attributed to the preferential adsorption of U on cell surfaces under GC1. This work provides a vivid description of the interaction of U complexes with bacterial cells. The findings have implications for the toxicity of various U species and for developing biological aqueous effluent waste treatment strategies. IMPORTANCE The present study provides illustrative insights into the interaction of uranium (U) complexes with recombinant bacterial cells overexpressing phosphatases. This work demonstrates the effects of aqueous speciation of U on the biosorption of U and the localization pattern of uranyl phosphate precipitated as a result of phosphatase action. Transmission electron microscopy revealed that location of uranyl phosphate (cell associated or extracellular) was primarily influenced by aqueous uranyl species present under the given geochemical conditions. The data would be useful for understanding the toxicity of U under different geochemical conditions. Since cell-associated precipitation of metal facilitates easy downstream processing by simple gravity-based settling down of metal-loaded cells, compared to cumbersome separation techniques, the results from this study are of considerable relevance to effluent treatment using such cells. PMID:27287317

Summer Research Program (1992). High School Apprenticeship Program (HSAP) Reports. Volume 13. Phillips Laboratory

DTIC Science & Technology

1992-12-28

Chief, Cloud Physics Section at the Phillips Laboratory Geophysics Directorate, for his assistance both in my research, and in preparing this paper; Lisa...American soccerball . Due to their hollow closed structure, the buckyballs can be used to "cage" other molecules. This potential has created a great deal of...forming a symmetrical sphere. 12-3 Physically modeling the fullerene on the computer began with the formation of a single pentagon. This pentagon was

Structural and electronic stability of a volleyball-shaped B80 fullerene

NASA Astrophysics Data System (ADS)

Wang, Xiao-Qian

2010-10-01

We have studied the structural and electronic characteristics of a volleyball-shaped B80 cage using first-principles density-functional calculations. In contrast to the popularly ratified “magic” B80 buckyball with 20 hexagonal pyramids and 12 hollow pentagons, the volleyball-shaped B80 constitutes 12 pentagonal pyramids, 8 hexagonal pyramids, and 12 hollow hexagons. The B80 volleyball is markedly more stable than the previously assumed magic B80 buckyball, which is attributed to the improved aromaticity associated with the distinct configuration.

The Military/Media Clash and the New Principle of War: Media Spin

DTIC Science & Technology

1993-06-01

the War (New York: Birch Lane Press, 1991), 23. 124. U.S. News & World Report staff, Triumph Without Victory: The Unreported History of the Persian... Birch Lane Press, 1991. Williams, Pete. "The Persian Gulf, The Pentagon, The Press." Defense 91, May/June 1991, 10-15. ___ "The Press and the Persian Gulf...January 1992, 1. Nathan, Debbie . "Just the Good News Please: The Pentagon Prefers ’Hi-Mom’ Coverage." The Progressive, February 1991, 25-28. "No

United States Intervention in Panama: The Battle Continues

DTIC Science & Technology

1991-02-11

U. S. presencc in Panama in accbrda~nce with Panama Canal Tra atiuzs, arid; support the Pentagon’s proposed post -cold war concept of retucing the...the Pentagon’s proposed post -cold war concept of reducing the number of unified commands. IDT10TA4 , ADi sr I o L: r 91-01546 9 6 7 064 11111 H11Il01l...success of Operation Just Cause, there were no post -invasion plans for rebuilding :;q - 5 Panama. According to General Frederick Woerner, former

The FBI is Leading the Way by Making the Private Sector an Integral Part of the Counterterrorism Homeland Security Enterprise

DTIC Science & Technology

2012-09-01

Pentagon, U.S. National Parks and Monuments and Reagan National Airport. Amidst the PCC sits Pentagon City Mall, home to more than 170 stores, a movie...integrated into the homeland security apparatus. As the threat our nation and her allies face continues to evolve, so must our responses. Integrating the...Advisor Dan Moran, PhD Chair, Department of National Security Affairs iv THIS PAGE INTENTIONALLY LEFT BLANK v ABSTRACT This thesis

PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION

DOEpatents

Warf, J.C.

1958-08-19

A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.

PROCESS FOR EXTRACTING NEPTUNIUM AND PLUTONIUM FROM NITRIC ACID SOLUTIONS OF SAME CONTAINING URANYL NITRATE WITH A TERTIARY AMINE

DOEpatents

Sheppard, J.C.

1962-07-31

A process of selectively extracting plutonium nitrate and neptunium nitrate with an organic solution of a tertiary amine, away from uranyl nitrate present in an aqueous solution in a maximum concentration of 1M is described. The nitric acid concentration is adjusted to about 4M and nitrous acid is added prior to extraction. (AEC)

[La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})] the first lanthanum uranyl-vanadate with structure built from two types of sheets based upon the uranophane anion-topology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mer, A.; Obbade, S.; Rivenet, M.

2012-01-15

The new lanthanum uranyl vanadate divanadate, [La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})] was obtained by reaction at 800 Degree-Sign C between lanthanum chloride, uranium oxide (U{sub 3}O{sub 8}) and vanadium oxide (V{sub 2}O{sub 5}) and the structure was determined from single-crystal X-ray diffraction data. This compound crystallizes in the orthorhombic system with space group P2{sub 1}2{sub 1}2{sub 1} and unit-cell parameters a=6.9470(2) A, b=7.0934(2) A, c=25.7464(6) A, V=1268.73(5) A{sup 3}, Z=4. A full matrix least-squares refinement yielded R{sub 1}=0.0219 for 5493 independent reflections. The crystal structure is characterized by the stacking of uranophane-type sheets {sup 2}{sub {infinity}}[(UO{sub 2})(VO{sub 4})]{sup -}more » and double layers {sup 2}{sub {infinity}}[La(UO{sub 2})(V{sub 2}O{sub 7})]{sup +} connected through La-O bonds involving the uranyl oxygen of the uranyl-vanadate sheets. The double layers result from the connection of two {sup 2}{sub {infinity}}[La(UO{sub 2})(VO{sub 4}){sub 2}]{sup -} sheets derived from the uranophane anion-topology by replacing half of the uranyl ions by lanthanum atoms and connected through the formation of divanadate entities. - Graphical abstract: A view of the three-dimensional structure of [La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})]. Highlights: Black-Right-Pointing-Pointer New lanthanum uranyl vanadate divanadate has been synthesized. Black-Right-Pointing-Pointer Structure was determined from single-crystal X-ray diffraction data. Black-Right-Pointing-Pointer Structure is characterized by uranophane-type sheets and double layers {sup 2}{sub {infinity}}[La(UO{sub 2})(V{sub 2}O{sub 7})]{sup +}.« less

3D morphology of Au and Au@Ag nanobipyramids

NASA Astrophysics Data System (ADS)

Burgin, Julien; Florea, Ileana; Majimel, Jérôme; Dobri, Adam; Ersen, Ovidiu; Tréguer-Delapierre, Mona

2012-02-01

The morphologies of Au and Au@Ag nanobipyramids were investigated using electron tomography. The 3D reconstruction reveals that the Au bipyramids have an irregular six-fold twinning structure with highly stepped dominant {151} facets. These short steps/edges stabilized via surface adsorbed CTAB favor the growth of silver on the lateral facets leading to strong blue shifts in longitudinal plasmon surface resonance.The morphologies of Au and Au@Ag nanobipyramids were investigated using electron tomography. The 3D reconstruction reveals that the Au bipyramids have an irregular six-fold twinning structure with highly stepped dominant {151} facets. These short steps/edges stabilized via surface adsorbed CTAB favor the growth of silver on the lateral facets leading to strong blue shifts in longitudinal plasmon surface resonance. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr11454b

Inhibition of poly(ADP-ribose)polymerase-1 and DNA repair by uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooper, Karen L.; Dashner, Erica J.; Tsosie, Ranalda

Uranium has radiological and non-radiological effects within biological systems and there is increasing evidence for genotoxic and carcinogenic properties attributable to uranium through its heavy metal properties. In this study, we report that low concentrations of uranium (as uranyl acetate; < 10 μM) is not cytotoxic to human embryonic kidney cells or normal human keratinocytes; however, uranium exacerbates DNA damage and cytotoxicity induced by hydrogen peroxide, suggesting that uranium may inhibit DNA repair processes. Concentrations of uranyl acetate in the low micromolar range inhibited the zinc finger DNA repair protein poly(ADP-ribose) polymerase (PARP)-1 and caused zinc loss from PARP-1 protein.more » Uranyl acetate exposure also led to zinc loss from the zinc finger DNA repair proteins Xeroderma Pigmentosum, Complementation Group A (XPA) and aprataxin (APTX). In keeping with the observed inhibition of zinc finger function of DNA repair proteins, exposure to uranyl acetate enhanced retention of induced DNA damage. Co-incubation of uranyl acetate with zinc largely overcame the impact of uranium on PARP-1 activity and DNA damage. These findings present evidence that low concentrations of uranium can inhibit DNA repair through disruption of zinc finger domains of specific target DNA repair proteins. This may provide a mechanistic basis to account for the published observations that uranium exposure is associated with DNA repair deficiency in exposed human populations. - Highlights: • Low micromolar concentration of uranium inhibits polymerase-1 (PARP-1) activity. • Uranium causes zinc loss from multiple DNA repair proteins. • Uranium enhances retention of DNA damage caused by ultraviolet radiation. • Zinc reverses the effects of uranium on PARP activity and DNA damage repair.« less

Cyanex based uranyl sensitive polymeric membrane electrodes.

PubMed

Badr, Ibrahim H A; Zidan, W I; Akl, Z F

2014-01-01

Novel uranyl selective polymeric membrane electrodes were prepared using three different low-cost and commercially available Cyanex extractants namely, bis(2,4,4-trimethylpentyl) phosphinic acid [L1], bis(2,4,4-trimethylpentyl) monothiophosphinic acid [L2] and bis(2,4,4-trimethylpentyl) dithiophosphinic acid [L3]. Optimization and performance characteristics of the developed Cyanex based polymer membrane electrodes were determined. The influence of membrane composition (e.g., amount and type of ionic sites, as well as type of plasticizer) on potentiometric responses of the prepared membrane electrodes was studied. Optimized Cyanex-based membrane electrodes exhibited Nernstian responses for UO₂(2+) ion over wide concentration ranges with fast response times. The optimized membrane electrodes based on L1, L2 and L3 exhibited Nernstian responses towards uranyl ion with slopes of 29.4, 28.0 and 29.3 mV decade(-1), respectively. The optimized membrane electrodes based on L1-L3 showed detection limits of 8.3 × 10(-5), 3.0 × 10(-5) and 3.3 × 10(-6) mol L(-1), respectively. The selectivity studies showed that the optimized membrane electrodes exhibited high selectivity towards UO₂(2+) ion over large number of other cations. Membrane electrodes based on L3 exhibited superior potentiometric response characteristics compared to those based on L1 and L2 (e.g., widest linear range and lowest detection limit). The analytical utility of uranyl membrane electrodes formulated with Cyanex extractant L3 was demonstrated by the analysis of uranyl ion in different real samples for nuclear safeguards verification purposes. The results obtained using direct potentiometry and flow-injection methods were compared with those measured using the standard UV-visible and inductively coupled plasma spectroscopic methods. © 2013 Published by Elsevier B.V.

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

The first stable lower fullerene: C{sub 36}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piskoti, C.; Zettl, A.

1998-08-01

A new pure carbon material, presumably composed of thirty six carbon atom molecules, has been synthesized and isolated in milligram quantities. It appears as though these molecules have a closed cage structure making them the smallest member of a new class of molecules known as fullerenes, most notably of which is the soccer ball shaped C{sub 60}. However, unlike other known fullerenes, any closed, fullerene-like C{sub 36} cage will necessarily contain fused pentagon rings. Therefore, this molecule apparently violates the isolated pentagon rule, a criterion which requires isolated pentagons for stability in fullerene molecules. Striking parallels between this problem andmore » the synthesis of other fused five member fused ring systems will be discussed. Also, it will be shown that certain biological structures known as clathrin behave in a manner which gives excellent predictions about fullerenes and nanotubes. These predictions help to explain the presence of abundant quantities of C{sub 36} in arced graphite soot. {copyright} {ital 1998 American Institute of Physics.}« less

Incorporation of Np(V) and U(VI) in Carbonate and Sulfate Minerals Crystallized from Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balboni, Enrica; Morrison, Jessica M.; Wang, Zheming

2015-02-15

The neptunyl Np(V)O2 + and uranyl U(VI)O2 2+ ions are soluble in groundwater, although their interaction with minerals in the subsurface may impact their mobility. One mechanism for the immobilization of actinyl ions in the subsurface is coprecipitation in low-temperature minerals that form naturally, or that are induced to form as part of a remediation strategy. Important differences in the crystal-chemical behavior of the Np(V) neptunyl and U(VI) uranyl ions suggest their behavior towards incorporation into growing crystals may differ significantly. Using a selection of low temperature minerals synthesized in aqueous systems under ambient conditions, this study examines the factorsmore » that impact the structural incorporation of the Np(V) neptunyl and U(VI) uranyl ions in carbonate and sulfate minerals.« less

PROCESSES OF RECOVERING URANIUM FROM A CALUTRON

DOEpatents

Baird, D.O.; Zumwalt, L.R.

1958-07-15

An improved process is described for recovering the residue of a uranium compound which has been subjected to treatment in a calutron, from the parts of the calutron disposed in the source region upon which the residue is deposited. The process may be utilized when the uranium compound adheres to a surface containing metals of the group consisting of copper, iron, chromium, and nickel. The steps comprise washing the surface with an aqueous acidic oxidizing solvent for the uranium whereby there is obtained an acidic aqueous Solution containing uranium as uranyl ions and metals of said group as impurities, treating the acidic solution with sodium acetate in the presenee of added sodium nitrate to precipitate the uranium as sodium uranyl acetate away from the impurities in the solution, and separating the sodium uranyl acetate from the solution.

Structure of force networks in tapped particulate systems of disks and pentagons. I. Clusters and loops.

PubMed

Pugnaloni, Luis A; Carlevaro, C Manuel; Kramár, M; Mischaikow, K; Kondic, L

2016-06-01

The force network of a granular assembly, defined by the contact network and the corresponding contact forces, carries valuable information about the state of the packing. Simple analysis of these networks based on the distribution of force strengths is rather insensitive to the changes in preparation protocols or to the types of particles. In this and the companion paper [Kondic et al., Phys. Rev. E 93, 062903 (2016)10.1103/PhysRevE.93.062903], we consider two-dimensional simulations of tapped systems built from frictional disks and pentagons, and study the structure of the force networks of granular packings by considering network's topology as force thresholds are varied. We show that the number of clusters and loops observed in the force networks as a function of the force threshold are markedly different for disks and pentagons if the tangential contact forces are considered, whereas they are surprisingly similar for the network defined by the normal forces. In particular, the results indicate that, overall, the force network is more heterogeneous for disks than for pentagons. Such differences in network properties are expected to lead to different macroscale response of the considered systems, despite the fact that averaged measures (such as force probability density function) do not show any obvious differences. Additionally, we show that the states obtained by tapping with different intensities that display similar packing fraction are difficult to distinguish based on simple topological invariants.

In Situ Bioremediation of Perchlorate in Vadose Zone Soil Using Gaseous Electron Donors

DTIC Science & Technology

2009-11-01

National Aeronautics and Space Administration ND Non-detect NDMA N-Nitrosodimethylamine No. Number NO3- Nitrate OD Outside diameter O&M...Nitrite xv • Selenate • Arsenate • Chromate and dichromate (i.e., hexavalent chromium) • Uranylate • Pertechnetate • N-Nitrosodimethylamine ( NDMA ...Arsenate • Chromate and dichromate (i.e., hexavalent chromium) • Uranylate • Pertechnetate • N-Nitrosodimethylamine ( NDMA ) • Trichloroethene (TCE

Recuperation of uranyl ions from effluents by means of microbiological collectors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cecal, A.; Palamaru, I.; Humelnicu, D.

1997-12-31

This paper deals with the study of bioaccumulation of uranyl ions (UO{sub 2}{sup 2+}) from industrial effluents, using microbiological collectors: Nostoc linkia sp., Tolipotrix sp., Spirulina sp., Porphyridium cruentum and also the glucide extract of P. cruentum. The values of retaining degree of UO{sub 2}{sup 2+} on the biomass, for several experimental conditions, were established between 14.22 and 91.99%.

Patch testing with uranyl acetate in veterans exposed to depleted uranium during the 1991 Gulf war and the Iraqi conflict.

PubMed

Shvartsbeyn, Marianna; Tuchinda, Papapit; Gaitens, Joanna; Squibb, Katherine S; McDiarmid, Melissa A; Gaspari, Anthony A

2011-01-01

The Depleted Uranium Follow-Up Program is a clinical surveillance program run by the Baltimore Veterans Affairs Medical Center since 1993 for veterans of the Gulf and Iraqi wars who were exposed to depleted uranium (DU) as a result of "friendly-fire" incidents. In 2009, 40 veterans from this cohort were screened for skin reactivity to metals by patch-testing with extended metal series and uranyl acetate (0.25%, 2.5%, and 25%). A control arm comprised 46 patients without any known occupational exposures to DU who were seen at the University of Maryland Dermatology Clinic for evaluation of allergic contact dermatitis. Excluding irritant reactions, no patch-test reactions to uranyl acetate were observed in the participants. Irritant reactions to DU were more common in the clinic cohort, likely reflective of the demographic differences between the two arms of the study. Biologic monitoring of urine uranium concentrations in the DU program participants with 24-hour urine samples showed evidence of percutaneous uranium absorption from the skin patches. We conclude that dermatitis observed in a subset of the veterans was unrelated to their military DU exposure. Our data suggest that future studies of skin testing with uranyl acetate should utilize 0.25%, the least irritating concentration.

KINETICS OF THE DISSOLUTION OF URANIUM DIOXIDE IN CARBONATE-BICARBONATE SOLUTIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schortmann, W.E.; DeSesa, M.A.

The kinetics of the dissolution of uranium dioxide in sodium carbonate- sodium bicarbonate solutions were determined. The study was undertaken in order to obtain fundamental information about the commercial carbonate process for leaching uranium from its ores. A rate equation incorporating the effects of surface area oxygen partial pressure, temperature, and reagent concentrations was empirically developed. A mechanism consisting essentially of two consecutive reactions at steady state is proposed. These reactions are the oxidation of U/ sup 4+/ to U/sup 6+/ and the subsequent formation of the uranyl dicarbonate complexion. Depending on the conditions, either or both of these reactionsmore » can determine the over-all rate. The conversion of uranyl dicarbonate to the uranyl tricarbonate complexion is postulated to be very rapid. In the suggested mechanism, the rate-determining phase of the oxidation is the dissociation of adsorbed molecular oxygen. and both the carbonate and bicarbonate ions play equivalent roles in the formation of the uranyl dicarbonate. As indicated by their high activation energies of about 13 and 14 kcal per mole uranium, both reactions are chemical rather than diffusional processes. A mathematical examination of the proposed mechanism produced a rate equation consistent with the experimental information. The credibility of the mechanism was thereby strengthened. (auth)« less

Cellular distribution of uranium after acute exposure of renal epithelial cells: SEM, TEM and nuclear microscopy analysis

NASA Astrophysics Data System (ADS)

Carrière, Marie; Gouget, Barbara; Gallien, Jean-Paul; Avoscan, Laure; Gobin, Renée; Verbavatz, Jean-Marc; Khodja, Hicham

2005-04-01

The major health effect of uranium exposure has been reported to be chemical kidney toxicity, functional and histological damages being mainly observed in proximal tubule cells. Uranium enters the proximal tubule as uranyl-bicarbonate or uranyl-citrate complexes. The aim of our research is to investigate the mechanisms of uranium toxicity, intracellular accumulation and repartition after acute intoxication of rat renal proximal tubule epithelial cells, as a function of its chemical form. Microscopic observations of renal epithelial cells after acute exposure to uranyl-bicarbonate showing the presence of intracellular precipitates as thin needles of uranyl-phosphate localized in cell lysosomes have been published. However the initial site of precipitates formation has not been identified yet: they could either be formed outside the cells before internalization, or directly inside the cells. Uranium solubility as a function and initial concentration was specified by ICP-MS analysis of culture media. In parallel, uranium uptake and distribution in cell monolayers exposed to U-bicarbonate was investigated by nuclear microprobe analyses. Finally, the presence of uranium precipitates was tested out by scanning electron microscopic observations (SEM), while extracellular and/or intracellular precipitates were observed on thin sections of cells by transmission electron microscopy (TEM).

Uranium: A Dentist's perspective

PubMed Central

Toor, R. S. S.; Brar, G. S.

2012-01-01

Uranium is a naturally occurring radionuclide found in granite and other mineral deposits. In its natural state, it consists of three isotopes (U-234, U-235 and U-238). On an average, 1% – 2% of ingested uranium is absorbed in the gastrointestinal tract in adults. The absorbed uranium rapidly enters the bloodstream and forms a diffusible ionic uranyl hydrogen carbonate complex (UO2HCO3+) which is in equilibrium with a nondiffusible uranyl albumin complex. In the skeleton, the uranyl ion replaces calcium in the hydroxyapatite complex of the bone crystal. Although in North India, there is a risk of radiological toxicity from orally ingested natural uranium, the principal health effects are chemical toxicity. The skeleton and kidney are the primary sites of uranium accumulation. Acute high dose of uranyl nitrate delays tooth eruption, and mandibular growth and development, probably due to its effect on target cells. Based on all previous research and recommendations, the role of a dentist is to educate the masses about the adverse effects of uranium on the overall as well as the dental health. The authors recommended that apart from the discontinuation of the addition of uranium to porcelain, the Public community water supplies must also comply with the Environmental Protection Agency (EPA) standards of uranium levels being not more than 30 ppb (parts per billion). PMID:24478959

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments.

PubMed

Stewart, Brandy D; Mayes, Melanie A; Fendorf, Scott

2010-02-01

Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a range of aqueous uranyl species. U(VI) adsorption is directly linked to UO(2)(2+) speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K(d) values decrease from 48 to 17 L kg(-1) for goethite, from 64 to 29 L kg (-1) for Hanford sediments, and from 95 to 51 L kg(-1) for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ( approximately 5) and limited dissolved calcium are optimal for uranium adsorption.

Validation of gamma-ray detection techniques for safeguards monitoring at natural uranium conversion facilities

NASA Astrophysics Data System (ADS)

Dewji, S. A.; Lee, D. L.; Croft, S.; Hertel, N. E.; Chapman, J. A.; McElroy, R. D.; Cleveland, S.

2016-07-01

Recent IAEA circulars and policy papers have sought to implement safeguards when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under the revised policy, IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed to develop and validate concepts of nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO2(NO3)2) solution exiting solvent extraction was identified as a key measurement point (KMP), where gamma-ray spectroscopy was selected as the process monitoring tool. The Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory was employed to simulate the full-scale operating conditions of a purified uranium-bearing aqueous stream exiting the solvent extraction process in an NUCP. Nondestructive assay techniques using gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely way. This work investigated gamma-ray signatures of uranyl nitrate circulating in the UNCLE facility and evaluated various gamma-ray detector sensitivities to uranyl nitrate. These detector validation activities include assessing detector responses to the uranyl nitrate gamma-ray signatures for spectrometers based on sodium iodide, lanthanum bromide, and high-purity germanium detectors. The results of measurements under static and dynamic operating conditions at concentrations ranging from 10-90 g U/L of natural uranyl nitrate are presented. A range of gamma-ray lines is examined, including attenuation for transmission measurement of density and concentration. It was determined that transmission-corrected gamma-ray spectra provide a reliable way to monitor the 235U concentration of uranyl nitrate solution in transfer pipes in NUCPs. Furthermore, existing predictive and analysis methods are adequate to design and realize practical designs. The 137Cs transmission source employed in this work is viable but not optimal for 235U densitometry determination. Validated simulations assessed the viability of 133Ba and 57Co as alternative densitometry sources. All three gamma-ray detectors are viable for monitoring natural uranium feed; although high-purity germanium is easiest to interpret, it is, however, the least attractive as an installation instrument. Overall, for monitoring throughput in a facility such as UNCLE, emulating the uranium concentration and pump speeds of the Springfields conversion facility in the United Kingdom, an uncertainty of less than 0.17% is required in order to detect the diversion of 1 SQ of uranyl nitrate through changes in uranium concentration over an accountancy period of one year with a detection probability of 50%. Although calibrated gamma-ray detection systems are capable of determining the concentration of uranium content in NUCPs, it is only in combination with verifiable operator declarations and supporting data, such as flow rate and enrichment, that safeguards conclusions can be drawn.

Passively Q-switched Tm-doped fiber laser based on concave gold bipyramids assembled quasi-2D saturable absorber

NASA Astrophysics Data System (ADS)

Song, Jiaxin; Wu, Hanshuo; Wu, Jian; Xu, Jiangming; Xiao, Hu; Leng, Jinyong; Zhou, Pu; Liu, Zejin

2018-07-01

We demonstrated a concave gold bipyramids (CAuBPs) quasi-2D saturable absorbers (SAs) based ~2 μm band fiber laser for the first time. CAuBPs were synthesized by using modified aqueous wet-chemical synthesis method. Through controlling the size and morphology of CAuBPs, the longitudinal surface plasmon resonance peak of CAuBPs based quasi-2D SA is tuned to be ~2 μm. Passively Q-switched lasing of thulium-doped fiber laser is achieved successfully with a maximum average output power of 9.72 mW and ~9% slope efficiency. The minimum pulse width is 4.56 µs at the repetition rate of 20 kHz. Experimental results reveals that CAuBPs could be used as SAs in the 2 µm region, which verifies the saturable absorption properties of CAuBPs.

Interfacing the Defense Standard Ammunition Computer System and the Air Force Combat Ammunition System: A Search for an Alternate Method.

DTIC Science & Technology

1985-09-01

S. Barnes, for all the guidance received throughout this effort, and to my reader, Capt Rich Mabe , for his suggestions which helped me organize the...Pentagon AV225-0568 Washington DC 4. Capt Thomas James AFLMC/LGY AV446-4524 Gunter AFS AL 5. Herman Stein JDSSC/C321 Pentagon AV227-5762 Washington DC...Division, McLean VA, undated. 37. Itze, Capt Joe, ESD/ALSE. Telephone interview. Hanscom AFB MA, 30 May 1985. 38. James , Capt Thomas G., Computer

Fullerene-like CS x: A first-principles study of synthetic growth

NASA Astrophysics Data System (ADS)

Goyenola, C.; Gueorguiev, G. K.; Stafström, S.; Hultman, L.

2011-04-01

Fullerene-Like (FL) Sulpho-Carbide (CSx) compounds have been addressed by first principles calculations. Geometry optimization and cohesive energy results are presented for the relative stability of precursor species such as C2S, CS2, and C2S2 in isolated form. The energy cost for structural defects, arising from the substitution of C by S is also reported. Similar to previously synthesized FL-CNx and FL-CPx compounds, the pentagon, the double pentagon defects as well as the Stone-Wales defects are confirmed as energetically feasible in CSx compounds.

Polyoxotungstates now also with pentagonal units: supramolecular chemistry and tuning of magnetic exchange in {(M)M5}12V30 Keplerates (M = Mo, W).

PubMed

Todea, Ana Maria; Merca, Alice; Bögge, Hartmut; Glaser, Thorsten; Engelhardt, Larry; Prozorov, Ruslan; Luban, Marshall; Müller, Achim

2009-06-21

The deliberate synthesis of the Keplerate [K(20) subset{(W)W(5)O(21)(SO(4))}(12)(VO)(30)(SO(4))(H(2)O)(63)](18-) with 20 pores all closed by K(+) in a supramolecular fashion proves that it is possible to follow new routes in polyoxotungstate chemistry based on pentagonal {(W)W(5)}-type units and to tune magnetic exchange couplings in {(M)M(5)}(12)M'(30) type Keplerates.

Defense Department Cyber Efforts: More Detailed Guidance Needed to Ensure Military Services Develop Appropriate Cyberspace Capabilities

DTIC Science & Technology

2011-05-01

communications and on computer networks—its Global Information Grid—which are potentially jeopardized by the millions of denial-of-service attacks, hacking ...Director,a National Security Agency Chief of Staff Joint Operations Center Defense Information Systems Agency Command Center J1 J2 J3 J4 J5 J6 J7 J8...DC Joint Staff • J39, Operations, Pentagon, Washington, DC • J5 , Strategic Plans and Policy, Pentagon, Washington, DC U.S. Strategic Command • J882

Method for photochemical reduction of uranyl nitrate by tri-N-butyl phosphate and application of this method to nuclear fuel reprocessing

DOEpatents

De Poorter, Gerald L.; Rofer-De Poorter, Cheryl K.

1978-01-01

Uranyl ion in solution in tri-n-butyl phosphate is readily photochemically reduced to U(IV). The product U(IV) may effectively be used in the Purex process for treating spent nuclear fuels to reduce Pu(IV) to Pu(III). The Pu(III) is readily separated from uranium in solution in the tri-n-butyl phosphate by an aqueous strip.

Uranyl mediated photofootprinting reveals strong E. coli RNA polymerase--DNA backbone contacts in the +10 region of the DeoP1 promoter open complex.

PubMed Central

Jeppesen, C; Nielsen, P E

1989-01-01

Employing a newly developed uranyl photofootprinting technique (Nielsen et al. (1988) FEBS Lett. 235, 122), we have analyzed the structure of the E. coli RNA polymerase deoP1 promoter open complex. The results show strong polymerase DNA backbone contacts in the -40, -10, and most notably in the +10 region. These results suggest that unwinding of the -12 to +3 region of the promoter in the open complex is mediated through polymerase DNA backbone contacts on both sides of this region. The pattern of bases that are hyperreactive towards KMnO4 or uranyl within the -12 to +3 region furthermore argues against a model in which this region is simply unwound and/or single stranded. The results indicate specific protein contacts and/or a fixed DNA conformation within the -12 to +3 region. Images PMID:2503811

Synthesis of microspheres of triuranium octaoxide by simultaneous water and nitrate extraction from ascorbate-uranyl sols.

PubMed

Brykala, M; Deptula, A; Rogowski, M; Lada, W; Olczak, T; Wawszczak, D; Smolinski, T; Wojtowicz, P; Modolo, G

A new method for synthesis of uranium oxide microspheres (diameter <100 μm) has been developed. It is a variant of our patented Complex Sol-Gel Process, which has been used to synthesize high-quality powders of a wide variety of complex oxides. Starting uranyl-nitrate-ascorbate sols were prepared by addition of ascorbic acid to uranyl nitrate hexahydrate solution and alkalizing by aqueous ammonium hydroxide and then emulsified in 2-ethylhexanol-1 containing 1v/o SPAN-80. Drops of emulsion were firstly gelled by extraction of water by the solvent. Destruction of the microspheres during thermal treatment, owing to highly reactive components in the gels, requires modification of the gelation step by Double Extraction Process-simultaneously extraction of water and nitrates using Primene JMT, which completely eliminates these problem. Final step was calcination in air of obtained microspheres of gels to triuranium octaoxide.

Study of Pulsed Columns with the System. Uranyl Nitrate-Nitric Acid-Water- Tributylphosphate; ETUDE DES COLONNES A PULSATIONS A L'AIDE DU SYSTEME NITRATE D'URANYLE-ACIDE NITRIQUEEAU-TRIBUTYLPHOSPHATE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durandet, J.; Defives, D.; Choffe, B.

1959-10-31

The performsnce of a pulsed column with perforated plates was studied with the aid of a uranyl nitrate-nitric acid --water --tributyl phosphate system. The extraction of uranium from an aqueous acidic solution by an organic solvent and the extraction of uranium from organic solutions by water were the two cases investigated. The variation of the efficiency and the capacity of the pulsed column was determined as a function of the pulse amplitude and frequency, of the total flow rate, of the diameter of the holes, and of the choice of dispersed phase. The results showed that for a given amplitudemore » and total flow rate the efficiency has a maximum with an increase in frequency. (J.S.R.)« less

Thermal stability of uranyl complexes with neutral oxygen-containing organic bases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kobets, L.V.

1987-03-01

The thermal stability of uranyl chloride, nitrate, and oxalate with a series of neutral oxygen-containing organic ligands is discussed. It was found that the temperatures of removal of chlorine are higher than the stripping of the first molecule of the base in complexes UO/sub 2/Cl/sub 2/ x 2L. This is an indication of greater strength of the bonds of the Cl/sup -/ ions to the uranyl group in comparison with the investigated bases. It was shown that the temperatures of removal of a mole of neutral ligands depend little on the nature of the anions and exhibit a correlation withmore » the donor capacity of the bases: Ac < TBP < DMFA similarly ordered DMSO < TBPO similarly ordered PyO. The chemistry of the decomposition of the complexes and the strength of the binding of the acido- and neutral ligands in them are discussed.« less

Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite–selenates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Kovrugin, Vadim M.; Tyumentseva, Olga S.

2015-09-15

Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (I), [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O)] (II), [C{sub 4}H{sub 15}N{sub 3}][H{sub 3}O]{sub 0.5}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 2.93}(SeO{sub 3}){sub 0.07}(H{sub 2}O)](NO{sub 3}){sub 0.5} (III), [C{sub 2}H{sub 8}N]{sub 3}[H{sub 5}O{sub 2}][(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub 2}(H{sub 2}O){sub 5} (IV), [C{sub 2}H{sub 8}N]{sub 2}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 4}(HSeO{sub 3})(H{sub 2}O)](H{sub 2}SeO{sub 3}){sub 0.2} (V), [C{sub 4}H{sub 12}N]{sub 3}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 5}(H{sub 2}O)] (VI), and [C{sub 2}H{sub 8}N]{sub 3}(C{sub 2}H{sub 7}N)[(UO{sub 2}){sub 3}(SeO{sub 4}){submore » 4}(HSeO{sub 3})(H{sub 2}O)] (VII) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite–selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U–O{sub br}–Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers. - Graphical abstract: Crystal structures of the seven novel Se-contaning uranyl oxysalts that contain protonated organic molecules as interlayer species have been investigated from the viewpoints of topology of interpolyhedral linkages, isomeric variations and flexibility of structural units. - Highlights: • Single crystals of seven novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • The method of orientation matrices was applied to distinguish geometrical isomers. • The flexibility of structural complexes specifies the undulation of layered structural units.« less

Neptunium incorporation into select uranyl phases and thermal analysis of select uranyl phases

NASA Astrophysics Data System (ADS)

Klingensmith, Amanda Leigh

Alteration of spent nuclear fuel in a geological repository under oxidizing conditions is likely to result in abundant uranyl compounds. The proposed repository at Yucca Mountain, Nevada is intended to store about 70,000 metric tons of spent nuclear fuel in the unsaturated zone of a welded tuff sequence. Following failure of canisters that encapsulate the waste, contents may be exposed both to air and water and undergo repetitive wetting and drying events. Incorporation of radionuclides into the uranyl alteration phases may significantly reduce their mobility, thereby impacting repository performance. Of particular interest is 237Np owing to its long half-life (2.14 x 106 years) and potential mobility in groundwater. Powders of the synthetic uranyl phase soddyite, (UO2) 2(SiO4)(H2O)2, a framework type structure, and uranophane, Ca[(UO2)(SiO3OH)]2(H 2O)5, kasolite, Pb[(UO2)(SiO4)]H 2O, Na compreignacite, Na2[(UO2)3O 2(OH)3]2(H2O)7, and becquerelite, Ca[(UO2)3O2(OH)3]2(H 2O)8, all of which are sheet type structures, were synthesized in the presence of Np5+ under varying temperature and pH conditions. Uranophane, kasolite, boltwoodite K[(UO2)(SiO3OH)](H 2O)1.5, and Na boltwoodite K,Na[(UO2)(SiO 3OH)](H2O)1.5 were synthesized in the presence of Np as well as P, Ca and/or Mg. Single crystals of Na metaschoepite, Na[(UO 2)4O2(OH)5]˙5H2O were synthesized in the presence of Np5+ and laser ablation verified that Np can be incorporated within the structure of a uranyl phase. Incorporation of Np5+ into soddyite increased steadily with synthesis temperature. Np incorporation into uranophane, becquerelite, and kasolite was not dependent on synthesis temperature. Np uptake in uranophane and kasolite was found to be dependent on synthesis pH, with an increase in Np uptake with higher pH. Uranophane, boltwoodite and Na boltwoodite showed an increase in Np incorporation in the presence of P. Boltwoodite showed an even higher Np uptake when Mg and P were both present in the synthesis. Thermal analysis was completed for the uranyl phases soddyite, becquerelite, Na compreignacite, uranophane, and kasolite. TGA curves for becquerelite, Na compreignacite and uranophane showed loss of interlayer water groups by 100°C. Soddyite and kasolite showed more gradual TGA curves and retention of water groups up to 400°C for soddyite and 550°C for kasolite, with agreement shown by high temperature powder XRD data.

Nitrogen-doped graphene anchored with mixed growth patterns of CuPt alloy nanoparticles as a highly efficient and durable electrocatalyst for the oxygen reduction reaction in an alkaline medium.

PubMed

Illathvalappil, Rajith; Dhavale, Vishal M; Bhange, Siddheshwar N; Kurungot, Sreekumar

2017-07-06

A highly active and durable CuPt alloy catalyst with trigonal bipyramidal and truncated cube-type mixed morphologies, anchored on the nitrogen-doped graphene (NGr) surface (CuPt-TBTC/NGr), was prepared by a simple and fast method. The obtained CuPt alloy showed improved oxygen reduction reaction (ORR) activity, with a 30 mV positive shift in the half-wave potential value, as compared to the state-of-the-art Pt/C catalyst in a 0.1 M KOH solution. The CuPt alloy with the trigonal bipyramidal morphology possesses porous type inter-connected sides, which help to achieve improved mass transport of oxygen during the ORR. The exposure of the (111) plane of the CuPt alloy further improved the catalytic activity towards the dioxygen reduction in alkaline media. The ORR activity of the NGr-supported CuPt alloy was found to be dependent on the reaction time, and improved activity was obtained on the material derived at a reaction time of 90 min (CuPt-TBTC/NGr-90). The material synthesized at a lower or higher reaction time than 90 min resulted in a partially formed trigonal bipyramidal morphology with more truncated cubes or agglomerated trigonal bipyramidal and truncated cubes with closed type structures, respectively. Along with the high intrinsic ORR activity, CuPt-TBTC/NGr-90 displayed excellent electrochemical stability. Even after repeated 1000 potential cycling in a window ranging from 0.10 to 1.0 V (vs. RHE), the system clearly outperformed the state-of-the-art Pt/C catalyst with 15 and 60 mV positive shifts in the onset and half-wave potentials, respectively. CuPt-TBTC/NGr-90 also exhibited 2.1 times higher mass activity and 2.2 times higher specific activity, compared to Pt/C at 0.90 V (vs. RHE). Finally, a zinc-air battery fabricated with the alloy catalyst as the air electrode displayed a peak power density of 300 mW cm -2 , which is much higher than the peak power density of 253 mW cm -2 obtained for the state-of-the-art Pt/C catalyst as the air electrode.

Response to the comment “Uranyl-chloride speciation and uranium transport in hydrothermal brines: Comment on Migdisov et al. (2018)” by Dargent et al.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Migdisov, A. A.; Runde, W.; Williams-Jones, A. E.

We welcome the comments provided by Dargent et al. (2018) and appreciate the effort they have made to evaluate our recently reported data on the stability of uranyl(VI) chloride complexes as function of temperature (Migdisov et al., 2018). We also appreciate the opportunity provided by the editor to clarify issues in our paper that were not clearly articulated or in error.

A roadmap to uranium ionic liquids: anti-crystal engineering.

PubMed

Yaprak, Damla; Spielberg, Eike T; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja-Verena

2014-05-19

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C4mim) cation. As dithiocarbamate ligands binding to the UO2(2+) unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure-property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. These materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of vibration frequencies of uranyl ion in complexes with neutral bases (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kobets, L.V.; Umreiko, D.S.

1986-12-01

It has been shown that any estimate of the changes in vibration frequencies of UO/sub 2//sup 2 +/ applies only to the series of isostructural compounds with similar stoichiometry. Either the same values of stretching vibration frequencies of uranyl correspond to complexes with ligands that have different donor abilities, or changes in these frequencies are not great and do not reflect the real increase in the donor ability of the bases with respect to proton-containing acceptors. When the acido ligands are replaced or the stoichiometry of the complexes is changed, no correlations can be carried out, since, besides the basicitiesmore » of donors, other parameters such as the dentateness of the ligand, and hence the symmetry and the structure of the compound, are also varied. In this paper, the authors evaluate the contributions of the ligands to the shift of the vibration frequencies of uranyl that have been made and do not take into account the characteristic features of the compounds which therefore led to very different values of the contributions for one and the same ligand in different compounds. To evaluate the shifts produced by the ligands, the value of 1065 cm/sup -1/ was taken as the vibration frequency of a hypothetical fee uranyl ion, not perturbed by bonds with equatorial ligands. The authors also evaluate the contributions of ions able to form polymer structures.« less

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stewart, B.D.; Mayes, Melanie; Fendorf, Scott

2010-01-01

Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a rangemore » of aqueous uranyl species. U(VI) adsorption is directly linked to UO{sub 2}{sup 2+} speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K{sub d} values decrease from 48 to 17 L kg{sup -1} for goethite, from 64 to 29 L kg{sup -1} for Hanford sediments, and from 95 to 51 L kg{sup -1} for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ({approx}5) and limited dissolved calcium are optimal for uranium adsorption.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Veelen, Arjen; Bargar, John R.; Law, Gareth T. W.

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO 3] and brucite [Mg(OH) 2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (P CO2 = 10 –3.5) or reduced partial pressures of carbon dioxide (P CO2 = 10 –4.5). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented withmore » its O axial = U(VI) = O axial linkage at high angles (60–80°) to both magnesite (101¯4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the “effective” number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ~ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. Lastly, these results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.« less

Uranium immobilization and nanofilm formation on magnesium-rich minerals

DOE PAGES

van Veelen, Arjen; Bargar, John R.; Law, Gareth T. W.; ...

2016-03-18

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO 3] and brucite [Mg(OH) 2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (P CO2 = 10 –3.5) or reduced partial pressures of carbon dioxide (P CO2 = 10 –4.5). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented withmore » its O axial = U(VI) = O axial linkage at high angles (60–80°) to both magnesite (101¯4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the “effective” number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ~ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. Lastly, these results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.« less

Uranium Immobilization and Nanofilm Formation on Magnesium-Rich Minerals.

PubMed

van Veelen, Arjen; Bargar, John R; Law, Gareth T W; Brown, Gordon E; Wogelius, Roy A

2016-04-05

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO3] and brucite [Mg(OH)2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (PCO2 = 10(-3.5)) or reduced partial pressures of carbon dioxide (PCO2 = 10(-4.5)). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented with its Oaxial═U(VI)═Oaxial linkage at high angles (60-80°) to both magnesite (101̅4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the "effective" number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ∼ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. These results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.

A roadmap to uranium ionic liquids: Anti-crystal engineering

DOE PAGES

Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias; ...

2014-04-15

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C 4mim) cation. As dithiocarbamate ligands binding to the UO 2 2+ unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand withmore » the aim to establish structure–property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. As a result, these materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery.« less

PdSe2: Pentagonal Two-Dimensional Layers with High Air Stability for Electronics.

PubMed

Oyedele, Akinola D; Yang, Shize; Liang, Liangbo; Puretzky, Alexander A; Wang, Kai; Zhang, Jingjie; Yu, Peng; Pudasaini, Pushpa R; Ghosh, Avik W; Liu, Zheng; Rouleau, Christopher M; Sumpter, Bobby G; Chisholm, Matthew F; Zhou, Wu; Rack, Philip D; Geohegan, David B; Xiao, Kai

2017-10-11

Most studied two-dimensional (2D) materials exhibit isotropic behavior due to high lattice symmetry; however, lower-symmetry 2D materials such as phosphorene and other elemental 2D materials exhibit very interesting anisotropic properties. In this work, we report the atomic structure, electronic properties, and vibrational modes of few-layered PdSe 2 exfoliated from bulk crystals, a pentagonal 2D layered noble transition metal dichalcogenide with a puckered morphology that is air-stable. Micro-absorption optical spectroscopy and first-principles calculations reveal a wide band gap variation in this material from 0 (bulk) to 1.3 eV (monolayer). The Raman-active vibrational modes of PdSe 2 were identified using polarized Raman spectroscopy, and a strong interlayer interaction was revealed from large, thickness-dependent Raman peak shifts, agreeing with first-principles Raman simulations. Field-effect transistors made from the few-layer PdSe 2 display tunable ambipolar charge carrier conduction with a high electron field-effect mobility of ∼158 cm 2 V -1 s -1 , indicating the promise of this anisotropic, air-stable, pentagonal 2D material for 2D electronics.

Penta-graphene: A new carbon allotrope

DOE PAGES

Zhang, Shunhong; Zhou, Jian; Wang, Qian; ...

2015-02-02

A 2D metastable carbon allotrope, penta-graphene, composed entirely of carbon pentagons and resembling the Cairo pentagonal tiling, is proposed in this paper. State-of-the-art theoretical calculations confirm that the new carbon polymorph is not only dynamically and mechanically stable, but also can withstand temperatures as high as 1000 K. Due to its unique atomic configuration, penta-graphene has an unusual negative Poisson’s ratio and ultrahigh ideal strength that can even outperform graphene. Furthermore, unlike graphene that needs to be functionalized for opening a band gap, penta-graphene possesses an intrinsic quasi-direct band gap as large as 3.25 eV, close to that of ZnOmore » and GaN. Equally important, penta-graphene can be exfoliated from T12-carbon. When rolled up, it can form pentagon-based nanotubes which are semiconducting, regardless of their chirality. When stacked in different patterns, stable 3D twin structures of T12-carbon are generated with band gaps even larger than that of T12-carbon. Finally, the versatility of penta-graphene and its derivatives are expected to have broad applications in nanoelectronics and nanomechanics.« less

Lanthanide Organophosphate Spiro Polymers: Synthesis, Structure, and Magnetocaloric Effect in the Gadolinium Polymer.

PubMed

Gupta, Sandeep K; Bhat, Gulzar A; Murugavel, Ramaswamy

2017-08-07

Spirocyclic lanthanide organophosphate polymers, {[Ln(dipp)(dippH)(CH 3 OH)(H 2 O) 2 ](CH 3 OH) 2 } n [Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11)], have been prepared from the reaction of Ln(NO 3 ) 3 ·xH 2 O with sterically hindered 2,6-diisopropylphenyl phosphate (dippH 2 ) using aqueous NaOH as the base. The one-dimensional chainlike lanthanide (III) organophosphate coordination polymers have been characterized with the aid of analytical and spectroscopic methods. The single crystal structure determination of polymers (2-5 and 7-11) reveals that in these compounds the hydrophobic organic groups of the phosphate provide a protective coating for the inorganic lanthanide phosphate polymeric chain. The encapsulation of inorganic lanthanide phosphate core, which has very low solubility product, within the organic groups assists in the facile crystallization of the polymers. The di- and monoanionic organophosphate ligands dipp 2- and dippH - display [2.111] and [2.110] binding modes, respectively, in 2-5 and 7. However, they exhibit only [2.110] binding mode in the case of 8-11. This results in the formation of two different types of polymers. While the lighter rare-earth metal ions in 2-5 and 7 display eight coordinate biaugmented trigonal prismatic geometry, the heavier rare-earth metal ions in 9-11 exhibit a seven coordinate capped trigonal prismatic environment. The Tb(III) ion in 8 displays distorted pentagonal bipyramidal geometry. Magnetic studies reveal the presence of weak antiferromagnetic interactions between the Ln(III) ions through the organophosphate ligand. The isotropic Gd(III) polymer 7 exhibits a maximum entropy change of 17.83 J kg -1 K -1 for a field change of 7.0 T at 2.5 K, which is significant considering the high molecular weight of the organophosphate ligand. These polymers represent the first family of any structurally characterized rare-earth organophosphate polymers derived from monoesters of phosphoric acid.

Flux-mediated syntheses, structural characterization and low-temperature polymorphism of the p-type semiconductor Cu2Ta4O11

NASA Astrophysics Data System (ADS)

King, Nacole; Sullivan, Ian; Watkins-Curry, Pilanda; Chan, Julia Y.; Maggard, Paul A.

2016-04-01

A new low-temperature polymorph of the copper(I)-tantalate, α-Cu2Ta4O11, has been synthesized in a molten CuCl-flux reaction at 665 °C for 1 h and characterized by powder X-ray diffraction Rietveld refinements (space group Cc (#9), a=10.734(1) Å, b = 6.2506(3) Å, c=12.887(1) Å, β = 106.070(4)°). The α-Cu2Ta4O11 phase is a lower-symmetry monoclinic polymorph of the rhombohedral Cu2Ta4O11 structure (i.e., β-Cu2Ta4O11 space group R 3 ̅ c (#167), a = 6.2190(2) Å, c=37.107(1) Å), and related crystallographically by ahex=amono/√3, bhex=bmono, and chex=3cmonosinβmono. Its structure is similar to the rhombohedral β-Cu2Ta4O11 and is composed of single layers of highly-distorted and edge-shared TaO7 and TaO6 polyhedra alternating with layers of nearly linearly-coordinated Cu(I) cations and isolated TaO6 octahedra. Temperature dependent powder X-ray diffraction data show the α-Cu2Ta4O11 phase is relatively stable under vacuum at 223 K and 298 K, but reversibly transforms to β-Cu2Ta4O11 by at least 523 K and higher temperatures. The symmetry-lowering distortions from β-Cu2Ta4O11 to α-Cu2Ta4O11 arise from the out-of-center displacements of the Ta 5d0 cations in the TaO7 pentagonal bipyramids. The UV-vis diffuse reflectance spectrum of the monoclinic α-Cu2Ta4O11 shows an indirect bandgap transition of ∼2.6 eV, with the higher-energy direct transitions starting at ∼2.7 eV. Photoelectrochemical measurements on polycrystalline films of α-Cu2Ta4O11 show strong cathodic photocurrents of ∼1.5 mA/cm2 under AM 1.5 G solar irradiation.

Metal-organic frameworks in cadmium(II) complexes with 5-methoxyindole-2-carboxylic acid: structure, vibrational spectra and DFT calculations

NASA Astrophysics Data System (ADS)

Morzyk-Ociepa, Barbara; Szmigiel, Ksenia; Dysz, Karolina; Turowska-Tyrk, Ilona; Michalska, Danuta

2016-11-01

Two new complexes of Cd(II) with an O-deprotonated anion of 5-methoxyindole-2-carboxylic acid (5-MeOI2CA), of the formulas [Cd(5-MeOI2CA)2(H2O)2]n (1) and [Cd3(5-MeOI2CA)6(H2O)4(DMSO)4]ṡ2DMSO (2) were synthesized. In the polymeric complex 1, the 5-MeOI2CA anion acts as a bidentate bridging ligand and the coordination environment around the Cd(II) ion can be described as a distorted octahedron. Single crystal X-ray diffraction analysis of 2 has revealed that this complex is a trimer and it crystallizes in the monoclinic system (space group P21/c with a = 20.3403(4), b = 14.3079(2), c = 15.0603(3) Å, β = 92.4341(17)°, V = 4379.00(14) Å3 and Z = 2). In 2, the 5-MeOI2CA anions act as bidentate bridging and bidentate chelating ligands. The asymmetric unit of 2 contains two crystallographically independent Cd(II) cations. One of the cations is coordinated to six oxygen atoms and shows an octahedral geometry with a rhombic deformation. The other Cd(II) cation adopts a distorted seven-coordinate pentagonal-bipyramidal geometry involving seven oxygen atoms. In 2, the DMSO solvent molecules play a key role in the formation of metal-organic frameworks by filling voids, which are created by the bridging and chelating 5-MeOI2CA anions, the cadmium cations and the other DMSO molecules coordinated to cadmium. Comprehensive theoretical calculations (including the optimized structural parameters, harmonic frequencies and vibrational intensities) were performed for 2 using the B3LYP method with the 6-311++G(d,p)/LanL2DZ basis sets. The infrared and Ramana spectra were measured and a detailed assignment of the experimental spectra of 2 was performed. All cadmium-oxygen stretching vibrations occur in the range below 400 cm-1.

Validation of gamma-ray detection techniques for safeguards monitoring at natural uranium conversion facilities

DOE PAGES

Dewji, Shaheen A.; Lee, Denise L.; Croft, Stephen; ...

2016-03-28

Recent IAEA circulars and policy papers have sought to implement safeguards when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under the revised policy, IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed to develop and validate concepts of nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP).more » In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP), where gamma-ray spectroscopy was selected as the process monitoring tool. The Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory was employed to simulate the full-scale operating conditions of a purified uranium-bearing aqueous stream exiting the solvent extraction process in an NUCP. Nondestructive assay techniques using gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely way. This work investigated gamma-ray signatures of uranyl nitrate circulating in the UNCLE facility and evaluated various gamma-ray detector sensitivities to uranyl nitrate. These detector validation activities include assessing detector responses to the uranyl nitrate gamma-ray signatures for spectrometers based on sodium iodide, lanthanum bromide, and high-purity germanium detectors. The results of measurements under static and dynamic operating conditions at concentrations ranging from 10–90 g U/L of natural uranyl nitrate are presented. A range of gamma-ray lines is examined, including attenuation for transmission measurement of density and concentration. It was determined that transmission-corrected gamma-ray spectra provide a reliable way to monitor the 235U concentration of uranyl nitrate solution in transfer pipes in NUCPs. Furthermore, existing predictive and analysis methods are adequate to design and realize practical designs. The 137Cs transmission source employed in this work is viable but not optimal for 235U densitometry determination. Validated simulations assessed the viability of 133Ba and 57Co as alternative densitometry sources. All three gamma-ray detectors are viable for monitoring natural uranium feed; although high-purity germanium is easiest to interpret, it is, however, the least attractive as an installation instrument. Overall, for monitoring throughput in a facility such as UNCLE, emulating the uranium concentration and pump speeds of the Springfields conversion facility in the United Kingdom, an uncertainty of less than 0.17% is required in order to detect the diversion of 1 SQ of uranyl nitrate through changes in uranium concentration over an accountancy period of one year with a detection probability of 50%. As a result, calibrated gamma-ray detection systems are capable of determining the concentration of uranium content in NUCPs, it is only in combination with verifiable operator declarations and supporting data, such as flow rate and enrichment, that safeguards conclusions can be drawn.« less

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.

2003-01-01

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

Metallic carbon materials

DOEpatents

Cohen, Marvin Lou; Crespi, Vincent Henry; Louie, Steven Gwon Sheng; Zettl, Alexander Karlwalter

1999-01-01

Novel metallic forms of planar carbon are described, as well as methods of designing and making them. Nonhexagonal arrangements of carbon are introduced into a graphite carbon network essentially without destroying the planar structure. Specifically a form of carbon comprising primarily pentagons and heptagons, and having a large density of states at the Fermi level is described. Other arrangements of pentagons and heptagons that include some hexagons, and structures incorporating squares and octagons are additionally disclosed. Reducing the bond angle symmetry associated with a hexagonal arrangement of carbons increases the likelihood that the carbon material will have a metallic electron structure.

Effects of nitrogenous substituent groups on the benzene dication

NASA Astrophysics Data System (ADS)

Forgy, C. C.; Schlimgen, A. W.; Mazziotti, D. A.

2018-05-01

The benzene dication possesses a pentagonal-pyramidal structure with a hexacoordinated carbon. In contrast, halogenated benzene dications retain a similar structure to their parent molecules. In this work, we report on theoretical studies of the structures of the dications of benzene with nitrogenous substituents. We find that the nitrobenzene dication favours a near ideal pentagonal-pyramidal structure, while the aniline dication favours a flat, hexagonal structure. Reduced-density-matrices methods give predictions in agreement with available ab initio calculations and experiment. These results are also compared with those from the Hartree-Fock method and density functional theory.

GRAPHITE PRODUCTION UTILIZING URANYL NITRATE HEXAHYDRATE CATALYST

DOEpatents

Sheinberg, H.; Armstrong, J.R.; Schell, D.H.

1964-03-10

ABS>The graphitizing of a mixture composed of furfuryl alcohol binder and uranyl nitrate hexahydrate hardener and the subsequent curing, baking, and graphitizing with pressure being initially applied prior to curing are described. The pressure step may be carried out by extrusion, methyl cellulose being added to the mixture before the completion of extrusion. Uranium oxide may be added to the graphitizable mixture prior to the heating and pressure steps. The graphitizable mixture may consist of discrete layers of different compositions. (AEC)

Method of precipitating uranium from an aqueous solution and/or sediment

DOEpatents

Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

2013-08-20

A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

Criticality experiments and analysis of molybdenum reflected cylindrical uranyl fluoride water solution reactors

NASA Technical Reports Server (NTRS)

Fieno, D.; Fox, T.; Mueller, R.

1972-01-01

Clean criticality data were obtained from molybdenum-reflected cylindrical uranyl-fluoride-water solution reactors. Using ENDF/B molybdenum cross sections, a nine energy group two-dimensional transport calculation of a reflected reactor configuration predicted criticality to within 7 cents of the experimental value. For these reactors, it was necessary to compute the reflector resonance integral by a detailed transport calculation at the core-reflector interface volume in the energy region of the two dominant resonances of natural molybdenum.

Carbonate-H2O2 Leaching for Sequestering Uranium from Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Horng-Bin; Weisheng, Liao; Wai, Chien

Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with little loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

Carbonate-H₂O₂ leaching for sequestering uranium from seawater.

PubMed

Pan, Horng-Bin; Liao, Weisheng; Wai, Chien M; Oyola, Yatsandra; Janke, Christopher J; Tian, Guoxin; Rao, Linfeng

2014-07-28

Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1 M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to the formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with minimal loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

SEPARATION OF BARIUM VALUES FROM URANYL NITRATE SOLUTIONS

DOEpatents

Tompkins, E.R.

1959-02-24

The separation of radioactive barium values from a uranyl nitrate solution of neutron-irradiated uranium is described. The 10 to 20% uranyl nitrate solution is passed through a flrst column of a cation exchange resin under conditions favoring the adsorption of barium and certain other cations. The loaded resin is first washed with dilute sulfuric acid to remove a portion of the other cations, and then wash with a citric acid solution at pH of 5 to 7 to recover the barium along with a lesser amount of the other cations. The PH of the resulting eluate is adjusted to about 2.3 to 3.5 and diluted prior to passing through a smaller second column of exchange resin. The loaded resin is first washed with a citric acid solution at a pH of 3 to elute undesired cations and then with citric acid solution at a pH of 6 to eluts the barium, which is substantially free of undesired cations.

URANIUM RECOVERY PROCESS

DOEpatents

Hyman, H.H.; Dreher, J.L.

1959-07-01

The recovery of uranium from the acidic aqueous metal waste solutions resulting from the bismuth phosphate carrier precipitation of plutonium from solutions of neutron irradiated uranium is described. The waste solutions consist of phosphoric acid, sulfuric acid, and uranium as a uranyl salt, together with salts of the fission products normally associated with neutron irradiated uranium. Generally, the process of the invention involves the partial neutralization of the waste solution with sodium hydroxide, followed by conversion of the solution to a pH 11 by mixing therewith sufficient sodium carbonate. The resultant carbonate-complexed waste is contacted with a titanated silica gel and the adsorbent separated from the aqueous medium. The aqueous solution is then mixed with sufficient acetic acid to bring the pH of the aqueous medium to between 4 and 5, whereby sodium uranyl acetate is precipitated. The precipitate is dissolved in nitric acid and the resulting solution preferably provided with salting out agents. Uranyl nitrate is recovered from the solution by extraction with an ether such as diethyl ether.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abrao, Alcidio.; Araujo, Jose Adroaldo de; Franca Junior, J.M.

This paper describes a technique for the production of nuclear grade ammonium diuranate (ADU) using uranyl sulfate solutions obtained as eluate from the ion exchange (strong cationic resin) purification of uranium, by precipitation with NH{sub 3} gas. The precipitation of ADU by direct introduction of NH{sub 3} gas into acid uranyl sulfate solution has as consequence a high coprecipitation of sulfate ion, reaching ratios as high as 10 to 14% SO{sub 4}/ADU. To overcome this serious inconvenience, the reverse order of addition of reagents was studied, the ADU precipitation being done in such a way that the pH of themore » mixture was kept higher than 6 during the whole precipitation. This modification, in conjunction with the adjustment of other precipitation parameters, like temperature, precipitation time, aging time, concentration of uranium in uranyl sulfate and pH, allowed a sucessful precipitation of ADU with low sulfate content. The technique was applied at pilot plant scale, using batch and continuous precipitation, in both cases the obtained ADU was low in sulfate.« less

A novel stable 3D luminescent uranyl complex for highly efficient and sensitive recognition of Ru3+ and biomolecules

NASA Astrophysics Data System (ADS)

Tian, Hong-Hong; Chen, Liang-Ting; Zhang, Rong-Lan; Zhao, Jian-She; Liu, Chi-Yang; Weng, Ng Seik

2018-02-01

A novel highly stable 3D luminescent uranyl coordination polymer, namely {[UO2(L)]·DMA}n (1), was assembled with uranyl salt and a glycine-derivative ligand [6-(carboxymethyl-amino)-4-oxo-4,5-dihydro-[1,3,5]triazin-2-ylamino]-acetic acid (H2L) under solvothermal reaction. Besides, It was found that complex 1 possesses excellent luminescent properties, particularly the efficient selectivity and sensitivity in the recognition of Ru3+, biomacromolecule bovine serum albumin (BSA), biological small molecules dopamine (DA), ascorbic acid (AA) and uric acid (UA) in the water solution based on a "turn-off" mechanism. Accordingly, the luminescent explorations also demonstrated that complex 1 could be acted as an efficient luminescent probe with high quenching efficiency and low detection limit for selectively detecting Ru3+ and biomolecules (DA, AA, UA and BSA). It was noted that the framework structure of complex 1 still remains highly stable after quenching, which was verified by powder X-ray diffraction (PXRD).

Recovery of uranium from an irradiated solid target after removal of molybdenum-99 produced from the irradiated target

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reilly, Sean Douglas; May, Iain; Copping, Roy

A process for minimizing waste and maximizing utilization of uranium involves recovering uranium from an irradiated solid target after separating the medical isotope product, molybdenum-99, produced from the irradiated target. The process includes irradiating a solid target comprising uranium to produce fission products comprising molybdenum-99, and thereafter dissolving the target and conditioning the solution to prepare an aqueous nitric acid solution containing irradiated uranium. The acidic solution is then contacted with a solid sorbent whereby molybdenum-99 remains adsorbed to the sorbent for subsequent recovery. The uranium passes through the sorbent. The concentrations of acid and uranium are then adjusted tomore » concentrations suitable for crystallization of uranyl nitrate hydrates. After inducing the crystallization, the uranyl nitrate hydrates are separated from a supernatant. The process results in the purification of uranyl nitrate hydrates from fission products and other contaminants. The uranium is therefore available for reuse, storage, or disposal.« less

Polymorphism in alkali metal uranyl nitrates: Synthesis and crystal structure of gamma-K(UO2)(NO3)3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J.; Krivovichev, Sergey V.; Burns, Peter C.

2011-07-20

Single crystals of γ-K(UO₂)(NO₃)₃ were prepared from aqueous solutions by evaporation. The crystal structure [orthorhombic, Pbca (61), a = 9.2559(3) Å, b = 12.1753(3) Å, c = 15.8076(5) Å, V = 1781.41(9) ų, Z = 8] was determined by direct methods and refined to R₁ = 0.0267 on the basis of 3657 unique observed reflections. The structure is composed of isolated anionic uranyl trinitrate units, [(UO₂)(NO₃)₃] –, that are linked through eleven-coordinated K + cations. Both known polymorphs of K(UO₂)(NO₃)₃ (α- and γ-phases) can be considered as based upon sheets of isolated complex [(UO₂)(NO₃)₃] – ions separated by K +more » cations. The existence of polymorphism in the two K[UO₂(NO₃)₃] polymorphs is due to the different packing modes of uranyl trinitrate clusters that adopt the same two-dimensional but different three-dimensional arrangements.« less

ELECTRON STAINS

PubMed Central

Zobel, C. Richard; Beer, Michael

1961-01-01

Chemical studies have been carried out on the interaction of DNA with uranyl salts. The effect of variations in pH, salt concentration, and structural integrity of the DNA on the stoichiometry of the salt-substrate complex have been investigated. At pH 3.5 DNA interacts with uranyl ions in low concentration yielding a substrate metal ion complex with a UO2++/P mole ratio of about ½ and having a large association constant. At low pH's (about 2.3) the mole ratio decreases to about ⅓. Destruction of the structural integrity of the DNA by heating in HCHO solutions leads to a similar drop in the amount of metal ion bound. Raising the pH above 3.5 leads to an apparent increase in binding as does increasing the concentration of the salt solution. This additional binding has a lower association constant. Under similar conditions DNA binds about seven times more uranyl ion than bovine serum albumin, indicating useful selectivity in staining for electron microscopy. PMID:13788706

Efficient tetracycline adsorption and photocatalytic degradation of rhodamine B by uranyl coordination polymer

NASA Astrophysics Data System (ADS)

Ren, Ya-Nan; Xu, Wei; Zhou, Lin-Xia; Zheng, Yue-Qing

2017-07-01

Two mixed uranyl-cadmium malonate coordination polymers [(UO2)2Cd(H-bipy)2(mal)4(H2O)2]·4H2O 1 and [(UO2)Cd(bipy)(mal)2]·H2O 2 (H2mal = malonic acid, bipy =4,4‧-bipyridine) have been synthesized in room temperature. Compound 1 represents a one-dimensional (1D) chain assembly of Cd(II) ions, uranyl centers and malonate ligands. Compound 2 exhibits a two-dimensional (2D) 2D +2D → 3D polycatenated framework based on inclined interlocked 2D 44 sql grids. The two compounds have been characterized by elemental analysis, IR and UV-vis spectroscopy, thermal analysis, powder X-ray diffraction and photoluminescence spectroscopy. And the ferroelectric property of 2 also has been studied. Moreover, compound 2 exhibits good photocatalytic activity for dye degradation under UV light and is excellent adsorbent for removing tetracycline antibiotics in the aqueous solution.

Evaluating transition state structures of vanadium-phosphatase protein complexes using shape analysis.

PubMed

Sánchez-Lombardo, Irma; Alvarez, Santiago; McLauchlan, Craig C; Crans, Debbie C

2015-06-01

Shape analysis of coordination complexes is well-suited to evaluate the subtle distortions in the trigonal bipyramidal (TBPY-5) geometry of vanadium coordinated in the active site of phosphatases and characterized by X-ray crystallography. Recent studies using the tau (τ) analysis support the assertion that vanadium is best described as a trigonal bipyramid, because this geometry is the ideal transition state geometry of the phosphate ester substrate hydrolysis (C.C. McLauchlan, B.J. Peters, G.R. Willsky, D.C. Crans, Coord. Chem. Rev. http://dx.doi.org/10.1016/j.ccr.2014.12.012 ; D.C. Crans, M.L. Tarlton, C.C. McLauchlan, Eur. J. Inorg. Chem. 2014, 4450-4468). Here we use continuous shape measures (CShM) analysis to investigate the structural space of the five-coordinate vanadium-phosphatase complexes associated with mechanistic transformations between the tetrahedral geometry and the five-coordinate high energy TBPY-5 geometry was discussed focusing on the protein tyrosine phosphatase 1B (PTP1B) enzyme. No evidence for square pyramidal geometries was observed in any vanadium-protein complexes. The shape analysis positioned the metal ion and the ligands in the active site reflecting the mechanism of the cleavage of the organic phosphate in a phosphatase. We identified the umbrella distortions to be directly on the reaction path between tetrahedral phosphate and the TBPY-5-types of high-energy species. The umbrella distortions of the trigonal bipyramid are therefore identified as being the most relevant types of transition state structures for the phosphoryl group transfer reactions for phosphatases and this may be related to the possibility that vanadium is an inhibitor for enzymes that support both exploded and five-coordinate transition states. Copyright © 2015 Elsevier Inc. All rights reserved.

High-level ab initio calculations for the four low-lying families of minima of (H2O)(20): 1. Estimates of MP2/CBS binding energies and comparison with empirical potentials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fanourgakis, Georgios S.; Apra, Edoardo; Xantheas, Sotiris S.

2004-08-08

We report estimates of complete basis set (CBS) limits at the second-order Møller-Plesset perturbation level of theory (MP2) for the binding energies of the lowest lying isomers within each of the four major families of minima of (H2O)20. These were obtained by performing MP2 calculations with the family of correlation-consistent basis sets up to quadruple zeta quality, augmented with additional diffuse functions (aug-cc-pVnZ, n=D, T, Q). The MP2/CBS estimates are: -200.1 kcal/mol (dodecahedron, 30 hydrogen bonds), -212.6 kcal/mol (fused cubes, 36 hydrogen bonds), -215.0 (face-sharing pentagonal prisms, 35 hydrogen bonds) and –217.9 kcal/mol (edge-sharing pentagonal prisms, 34 hydrogen bonds). Themore » energetic ordering of the various (H2O)20 isomers does not follow monotonically the number of hydrogen bonds as in the case of smaller clusters such as the different isomers of the water hexamer. The dodecahedron lies ca. 18 kcal/mol higher in energy than the most stable edge-sharing pentagonal prism isomer. The TIP4P, ASP-W4, TTM2-R, AMOEBA and TTM2-F empirical potentials also predict the energetic stabilization of the edge-sharing pentagonal prisms with respect to the dodecahedron, albeit they universally underestimate the cluster binding energies with respect to the MP2/CBS result. Among them, the TTM2-F potential was found to predict the absolute cluster binding energies to within < 1% from the corresponding MP2/CBS values, whereas the error for the rest of the potentials considered in this study ranges from 3-5%.« less

Soft tissue distraction using pentagonal frame for long-standing traumatic flexion deformity of interphalangeal joints.

PubMed

Nazerani, Shaharm; Keramati, Mohammad Reza; Vahedian, Jalal; Fereshtehnejad, Seyed-Mohammad

2012-01-01

Interphalangeal joint contracture is a challenging complication of hand trauma, which reduces the functional capacity of the entire hand. In this study we evaluated the results of soft tissue distraction with no collateral ligament transection or volar plate removal in comparison with traditional operation of contracture release and partial ligament transection and volar plate removal. In this prospective study, a total of 40 patients in two equal groups (A and B) were studied. Patients suffering from chronic flexion contracture of abrasive traumatic nature were included. Group A were treated by soft tissue distraction using pentagonal frame technique and in Group B the contracture release was followed by finger splinting. Analyzed data revealed a significant difference between the two groups for range of motion in the proximal interphalangeal joints (P less than 0.05), while it was not meaningful in the distal interphalangeal joints (P larger than 0.05). There was not a significant difference in the degrees of flexion contracture between groups (P larger than 0.05). Regression analysis showed that using pentagonal frame technique significantly increased the mean improvement in range of motion of proximal interphalangeal joints (P less than 0.001), while the higher the preoperative flexion contracture was observed in proximal interphalangeal joints, the lower improvement was achieved in range of motion of proximal interphalangeal joints after intervention (P less than 0.001). Soft tissue distraction using pentagonal frame technique with gradual and continuous collateral ligament and surrounding joint tissues distraction combined with skin Z-plasty significantly improves the range of motion in patients with chronic traumatic flexion deformity of proximal and/or distal interphalangeal joints.

A Family of Uranyl Coordination Polymers Containing O-Donor Dicarboxylates and Trispyridyltriazine Guests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thangavelu, Sonia G.; Cahill, Christopher L.

Four uranyl coordination polymers [UO2(C6H8O4)(H2O)2](C18H12N6)2 (1), [UO2(C8H4O4)(H2O)2](C18H12N6)2 (2), Na[(UO2)(C12H6O4)2](C18H13N6)·H2O (3), and Na[(UO2)(C16H8O4)(C6H3NO2)](C18H12N6)·H2O (4) containing aliphatic (adipic acid) or aromatic linkers (1,4-benzene dicarboxylic acid (BDC), 1,4-napthalene dicarboxylic acid (NDC), anthracene 9,10-dicarboxylic acid (ADC)) were synthesized and characterized using single crystal X-ray diffraction, powder X-ray diffraction, and luminescence spectroscopy. The π-stacking distances or the number of π–π interactions present between trispyridyltriazine (TPTZ) guests or the host framework in 1–4 may be affected by the size of the O-donor linker (adipic acid < BDC < NDC < ADC). Luminescence studies show that substitution between adipic acid and BDC influences the emission of 1more » and 2, in which the emission of 1 shows a red shift relative to that of 2. Uranyl emission was not observed in 3 and 4, and may be attributed to the position of the NDC and ADC triplet state relative to the emissive uranyl species.« less

A Family of Uranyl Coordination Polymers Containing O-Donor Dicarboxylates and Trispyridyltriazine Guests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thangavelu, Sonia G.; Cahill, Christopher L.

2016-01-06

Four uranyl coordination polymers [UO2(C6H8O4)(H2O)2](C18H12N6)2 (1), [UO2(C8H4O4)(H2O)2](C18H12N6)2 (2), Na[(UO2)(C12H6O4)2](C18H13N6)·H2O (3), and Na[(UO2)(C16H8O4)(C6H3NO2)](C18H12N6)·H2O (4) containing aliphatic (adipic acid) or aromatic linkers (1,4-benzene dicarboxylic acid (BDC), 1,4-napthalene dicarboxylic acid (NDC), anthracene 9,10-dicarboxylic acid (ADC)) were synthesized and characterized using single crystal X-ray diffraction, powder X-ray diffraction, and luminescence spectroscopy. The π-stacking distances or the number of π–π interactions present between trispyridyltriazine (TPTZ) guests or the host framework in 1–4 may be affected by the size of the O-donor linker (adipic acid < BDC < NDC < ADC). Luminescence studies show that substitution between adipic acid and BDC influences the emission of 1more » and 2, in which the emission of 1 shows a red shift relative to that of 2. Uranyl emission was not observed in 3 and 4, and may be attributed to the position of the NDC and ADC triplet state relative to the emissive uranyl species.« less

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

USGS Publications Warehouse

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

2006-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

2012-08-08

Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirschner, Matthew S.; Ding, Wendu; Li, Yuxiu

In this study, we demonstrate that coherent acoustic phonons derived from plasmonic nanoparticles can modulate electronic interactions with proximal excitonic molecular species. A series of gold bipyramids with systematically varied aspect ratios and corresponding localized surface plasmon resonance energies, functionalized with a J-aggregated thiacarbocyanine dye molecule, produce two hybridized states that exhibit clear anti-crossing behavior with a Rabi splitting energy of 120 meV. In metal nanoparticles, photoexcitation generates coherent acoustic phonons that cause oscillations in the plasmon resonance energy. In the coupled system, these photo-generated oscillations alter the metal nanoparticle’s energetic contribution to the hybridized system and, as a result,more » change the coupling between the plasmon and exciton. We demonstrate that such modulations in the hybridization is consistent across a wide range of bipyramid ensembles. We also use Finite-Difference Time Domain calculations to develop a simple model describing this behavior. Lastly, such oscillatory plasmonic-excitonic nanomaterials (OPENs) offer a route to manipulate and dynamically-tune the interactions of plasmonic/excitonic systems and unlock a range of potential applications.« less

Structure of alkali tellurite glasses from neutron diffraction and molecular orbital calculations

NASA Astrophysics Data System (ADS)

Niida, Haruki; Uchino, Takashi; Jin, Jisun; Kim, Sae-Hoon; Fukunaga, Toshiharu; Yoko, Toshinobu

2001-01-01

The structure of pure TeO2 and alkali tellurite glasses has been examined by neutron diffraction and ab initio molecular orbital methods. The experimental radial distribution functions along with the calculated results have demonstrated that the basic structural units in tellurite glasses change from highly strained TeO4 trigonal bipyramids to more regular TeO3 trigonal pyramids with increasing alkali content. It has also been shown that the TeO3 trigonal pyramids do not exist in the form of isolated units in the glass network but interact with each other to form intertrigonal Te⋯O linkages. The present results suggest that nonbridging oxygen (NBO) atoms in tellurite glasses do not exist in their "pure" form; that is, all the NBO atoms in TeO3 trigonal bipyramids will interact with the first- and/or second-neighbor Te atoms, resulting in the three-dimensional continuous random network even in tellurite glasses with over 30 mol % of alkali oxides.

Then Came the Fire: Personal Accounts From the Pentagon, 11 September 2001

DTIC Science & Technology

2011-01-01

office to let folks there know what had happened. Maj. Lorie A. Brown was the Chief Nurse of the DiLorenzo Clinic at the Pentagon. She was... nurse , three medics—grab vests, grab radios, grab this. “Go, you’re going to three and four. Call me when you get there and let me know what you...volunteers coming in—”I’m a doc,” “I’m a nurse ,” “I’m here to help. What can I do?” “Okay, here’s a vest, here’s a bag. You’re going to”—you know

Bond topography and nanostructure of hydrogenated fullerene-like carbon films: A comparative study

NASA Astrophysics Data System (ADS)

Wang, Yongfu; Gao, Kaixiong; Shi, Jing; Zhang, Junyan

2016-09-01

Fullerene-like nanostructural hydrogenated amorphous carbon (FL-C:H) films were prepared by dc- and pulse- plasma enhanced chemical vapor deposition technique (PECVD). Both the films exhibit relatively stresses (0.63 GPa) in spite of their FL features and nanostructural bonding configurations, especially the pentagonal carbon rings. The creation of pentagonal rings is not fully driven by thermodynamics, but is closely related to compressive stress determined by the ion bombardment at the discharged state of the pulse- and dc- discharged plasmas methods. The dc method leads to FL's basal planes which contain less cross-linkages, and causes amorphous strongly hydrogenated structures.

Posttraumatic stress disorder, alcohol use, and perceived safety after the terrorist attack on the pentagon.

PubMed

Grieger, Thomas A; Fullerton, Carol S; Ursano, Robert J

2003-10-01

The authors examined posttraumatic stress disorder (PTSD), alcohol use, and perceptions of safety in a sample of survivors of the September 11, 2001, terrorist attack on the Pentagon. Analyses were conducted to examine the effect of past traumatic experience, trauma exposure, initial emotional response, and peritraumatic dissociation on probable PTSD, substance use, and perceived safety among 77 survivors seven months after the attack. Eleven respondents (14 percent) had PTSD. Those with PTSD reported higher levels of initial emotional response and peritraumatic dissociation. Ten respondents (13 percent) reported increased use of alcohol. Women were more than five times as likely as men to have PTSD and almost seven times as likely to report increased use of alcohol. Persons with higher peritraumatic dissociation were more likely to develop PTSD and report increased alcohol use. Those with lower perceived safety at seven months had higher initial emotional response and greater peritraumatic dissociation and were more likely to have PTSD, to have increased alcohol use, and to be female. The association of perceived safety with gender, the presence of PTSD, and increased alcohol use among survivors of the terrorist attack on the Pentagon warrants further study.

PdSe 2: Pentagonal Two-Dimensional Layers with High Air Stability for Electronics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oyedele, Akinola D.; Yang, Shize; Liang, Liangbo

Most studied two-dimensional (2D) materials exhibit isotropic behavior due to high lattice symmetry; however, lower-symmetry 2D materials such as phosphorene and other elemental 2D materials exhibit very interesting anisotropic properties. In this work, we report the atomic structure, electronic properties, and vibrational modes of few-layered PdSe 2, exfoliated from bulk crystals, a pentagonal 2D layered noble transition metal dichalcogenide with a puckered morphology that is air-stable. Micro-absorption optical spectroscopy and first-principles calculations reveal a wide band gap variation in this material from ~0 (bulk) to ~1.3 eV (monolayer). The Raman active vibrational modes of PdSe 2 were identified using polarizedmore » Raman spectroscopy, and the strong interlayer interaction was revealed from the large thickness-dependent Raman peak shifts, agreeing with first-principles Raman simulations. Field-effect transistors made from the few-layer PdSe 2 display tunable ambipolar charge carrier conduction with a high electron apparent field-effect mobility of ~158 cm 2V -1s -1, indicating the promise of this anisotropic, air-stable, pentagonal 2D material for 2D electronics.« less

PdSe 2: Pentagonal Two-Dimensional Layers with High Air Stability for Electronics

DOE PAGES

Oyedele, Akinola D.; Yang, Shize; Liang, Liangbo; ...

2017-09-05

Most studied two-dimensional (2D) materials exhibit isotropic behavior due to high lattice symmetry; however, lower-symmetry 2D materials such as phosphorene and other elemental 2D materials exhibit very interesting anisotropic properties. In this work, we report the atomic structure, electronic properties, and vibrational modes of few-layered PdSe 2, exfoliated from bulk crystals, a pentagonal 2D layered noble transition metal dichalcogenide with a puckered morphology that is air-stable. Micro-absorption optical spectroscopy and first-principles calculations reveal a wide band gap variation in this material from ~0 (bulk) to ~1.3 eV (monolayer). The Raman active vibrational modes of PdSe 2 were identified using polarizedmore » Raman spectroscopy, and the strong interlayer interaction was revealed from the large thickness-dependent Raman peak shifts, agreeing with first-principles Raman simulations. Field-effect transistors made from the few-layer PdSe 2 display tunable ambipolar charge carrier conduction with a high electron apparent field-effect mobility of ~158 cm 2V -1s -1, indicating the promise of this anisotropic, air-stable, pentagonal 2D material for 2D electronics.« less

Structure of force networks in tapped particulate systems of disks and pentagons. II. Persistence analysis.

PubMed

Kondic, L; Kramár, M; Pugnaloni, Luis A; Carlevaro, C Manuel; Mischaikow, K

2016-06-01

In the companion paper [Pugnaloni et al., Phys. Rev. E 93, 062902 (2016)10.1103/PhysRevE.93.062902], we use classical measures based on force probability density functions (PDFs), as well as Betti numbers (quantifying the number of components, related to force chains, and loops), to describe the force networks in tapped systems of disks and pentagons. In the present work, we focus on the use of persistence analysis, which allows us to describe these networks in much more detail. This approach allows us not only to describe but also to quantify the differences between the force networks in different realizations of a system, in different parts of the considered domain, or in different systems. We show that persistence analysis clearly distinguishes the systems that are very difficult or impossible to differentiate using other means. One important finding is that the differences in force networks between disks and pentagons are most apparent when loops are considered: the quantities describing properties of the loops may differ significantly even if other measures (properties of components, Betti numbers, force PDFs, or the stress tensor) do not distinguish clearly or at all the investigated systems.

Experiments on Anion Exchange with Amberlite Ir-120 Resin; ENSAYOS DE INTERCAMBIO ANIONICO CON RESINA AMBERLITA Ir-120

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cellini, R.F.; Palomino, J.V.

1956-01-01

The ion exchange of the uranyl ion on Amberlite Ir-120 resin was studied with different uranyl ion concentrations. Elution with sulfuric acid was investlgated and the elution curve for the experimental conditions was determined. From the concentrations of the ions of Cu/sup 2+/, Ni/sup 2+/, Fe/sup 3+/, Cd/sup 2+/, Mn/sup 2+/, and Cr/sup 3+/ the maximum exchange capacity was tested and elation curves with 4 N sulfuric acid were obtained. (tr-auth)

Reductive stripping process for the recovery of uranium from wet-process phosphoric acid

DOEpatents

Hurst, Fred J.; Crouse, David J.

1984-01-01

A reductive stripping flow sheet for recovery of uranium from wet-process phosphoric acid is described. Uranium is stripped from a uranium-loaded organic phase by a redox reaction converting the uranyl to uranous ion. The uranous ion is reoxidized to the uranyl oxidation state to form an aqueous feed solution highly concentrated in uranium. Processing of this feed through a second solvent extraction cycle requires far less stripping reagent as compared to a flow sheet which does not include the reductive stripping reaction.

Amine templating effect absent in uranyl sulfates synthesized with 1,4-n-butyldiamine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J., E-mail: ljouffret@nd.edu; Wylie, Ernest M.; Burns, Peter C.

2013-01-15

Two new uranyl sulfates, (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2}){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS2) and (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2})(SO{sub 4}){sub 2}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS3), were synthesized and their crystal structures determined. NDUS2 was obtained in highly acidic media heat-treated at 373 K and subsequently maintained at 278 K until crystals formed after two months. NDUS3 results from the degradation of NDUS2 over the course of a few days. NDUS2 and NDUS3 crystallize in the monoclinic space group P2{sub 1}/n, a=10.9075(4) A, b=10.4513(4) A, c=17.7881(7) A, {beta}=97.908(2) Degree-Sign , V=2008.52(13) A{sup 3}, Z=4, at 140 K and a=8.8570(4) A,more » b=7.3299(3) A, c=20.4260(9) A, {beta}=95.140(2) Degree-Sign , V=1320.74(10) A{sup 3}, Z=4, at 140 K, respectively. The compounds contain interlayer 1,4-n-butyldiammonium cations that charge-balance the anionic structural units. - Graphical abstract: Amine templating effect absent in uranyl sulfates synthesized with 1,4-diaminobutane, as shown by the synthesis of two new uranyl sulfates, (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2}){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS2) and (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2})(SO{sub 4}){sub 2}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS3). Highlights: Black-Right-Pointing-Pointer Two layered uranyl sulfates were synthesized. Black-Right-Pointing-Pointer Amine molecules are located in the interlayers of the compounds. Black-Right-Pointing-Pointer No templating effect of the amine was observed. Black-Right-Pointing-Pointer Amine molecules are only charge balancing cations in the structures.« less

Use of spectroscopic techniques for uranium(VI)/montmorillonite interaction modeling.

PubMed

Kowal-Fouchard, A; Drot, R; Simoni, E; Ehrhardt, J J

2004-03-01

To experimentally identify both clay sorption sites and sorption equilibria and to understand the retention mechanisms at a molecular level, we have characterized the structure of hexavalent uranium surface complexes resulting from the interaction between the uranyl ions and the surface retention groups of a montmorillonite clay. We have performed laser-induced fluorescence spectroscopy (LIFS) and X-ray photoelectron spectroscopy (XPS) on uranyl ion loaded montmorillonite. These structural results were then compared to those obtained from the study of uranyl ions sorbed onto an alumina and also from U(VI) sorbed on an amorphous silica. This experimental approach allowed for a clear determination of the reactive surface sites of montmorillonite for U(VI) sorption. The lifetime values and the U4f XPS spectra of uranium(VI) sorbed on montmorillonite have shown that this ion is sorbed on both exchange and edge sites. The comparison of U(VI)/clay and U(VI)/oxide systems has determined that the interaction between uranyl ions and montmorillonite edge sites occurs via both [triple bond]AlOH and [triple bond]SiOH surface groups and involves three distinct surface complexes. The surface complexation modeling of the U(VI)/montmorillonite sorption edges was determined using the constant capacitance model and the above experimental constraints. The following equilibria were found to account for the uranyl sorption mechanisms onto montmorillonite for metal concentrations ranged from 10(-6) to 10(-3) M and two ionic strengths (0.1 and 0.5 M): 2[triple bond]XNa + UO2(2+) <==> ([triple bond]X)2UO2 + 2Na+, log K0(exch) = 3.0; [triple bond]Al(OH)2 + UO2(2+) <==> [triple bond]Al(OH)2UO2(2+), log K0(Al) = 14.9; [triple bond]Si(OH)2 + UO2(2+) <==> [triple bond]SiO2UO2 + 2H+, log K0(Si1) = -3.8; and [triple bond]Si(OH)2 + 3UO2(2+) + 5H2O <==> [triple bond]SiO2(UO2)3(OH)5- + 7H+, log K0(Si2) = -20.0.

Interfacial Interaction of Titania Nanoparticles and Ligated Uranyl Species: A Relativistic DFT Investigation.

PubMed

Zhao, Hong-Bo; Zheng, Ming; Schreckenbach, Georg; Pan, Qing-Jiang

2017-03-06

To understand interfacial behavior of actinides adsorbed onto mineral surfaces and unravel their structure-property relationship, the structures, electronic properties, and energetics of various ligated uranyl species adsorbed onto TiO 2 surface nanoparticle clusters (SNCs) were examined using relativistic density functional theory. Rutile (110) and anatase (101) titania surfaces, experimentally known to be stable, were fully optimized. For the former, models studied include clean and water-free Ti 27 O 64 H 20 (dry), partially hydrated (Ti 27 O 64 H 20 )(H 2 O) 8 (sol) and proton-saturated [(Ti 27 O 64 H 20 )(H 2 O) 8 (H) 2 ] 2+ (sat), while defect-free and defected anatase SNCs involving more than 38 TiO 2 units were considered. The aquouranyl sorption onto rutile SNCs is energetically preferred, with interaction energies of -8.54, -10.36, and -2.39 eV, respectively. Energy decomposition demonstrates that the sorption is dominated by orbital attractive interactions and modified by steric effects. Greater hydrogen-bonding involvement leads to increased orbital interactions (i.e., more negative energy) from dry to sol/sat complexes, while much larger steric interaction in the sat complex significantly reduces the sorption interaction (i.e., more positive energy). For dry SNC, adsorbates were varied from aquo to aquo-carbonato, to carbonato, to hydroxo uranyl species. Longer U-O surf /U-Ti distances and more positive sorption energies were calculated upon introducing carbonato and hydroxo ligands, indicative of weaker uranyl sorption onto the substrate. This is consistent with experimental observations that the uranyl sorption rate decreases upon raising solution pH value or adding carbon dioxide. Anatase SNCs adsorbing aquouranyl are even more exothermic, because more bonds are formed than in the case of rutile. Moreover, the anatase sorption can be tuned by surface defects as well as its Ti and O stoichiometry. All the aquouranyl-SNC complexes show similar character of molecular orbitals and energetic order although differing in highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps and orbital energy levels, but changes can be accomplished by adding carbonato and hydroxo ligands.

Vibrational Properties of Anhydrous and Partially Hydrated Uranyl Fluoride

DOE PAGES

Anderson, Brian B.; Kirkegaard, Marie C.; Miskowiec, Andrew J.; ...

2017-01-01

Uranyl fluoride (UO 2F 2) is a hygroscopic powder with two main structural phases: an anhydrous crystal and a partially hydrated crystal of the same R¯3m symmetry. The formally closed-shell electron structure of anhydrous UO 2F 2 is amenable to density functional theory calculations. We use density functional perturbation theory (DFPT) to calculate the vibrational frequencies of the anhydrous crystal structure and employ complementary inelastic neutron scattering and temperature-dependent Raman scattering to validate those frequencies. As a model closed-shell actinide, we investigated the effect of LDA, GGA, and non-local vdW functionals as well as the spherically-averaged Hubbard +U correction onmore » vibrational frequencies, electronic structure, and geometry of anhydrous UO 2F 2. A particular choice of U eff = 5.5 eV yields the correct U Oyl bond distance and vibrational frequencies for the characteristic Eg and A1g modes that are within the resolution of experiment. Inelastic neutron scattering and Raman scattering suggest a degree of water coupling to the lattice vibrations in the more experimentally accessible partially hydrated UO 2F 2 system, with the symmetric O-U-O stretching vibration shifted approximately 47 cm -1 lower in energy compared to the anhydrous structure. Evidence of water interaction with the uranyl ion is present from a two-peak decomposition of the uranyl stretching vibration in the Raman spectra and anion hydrogen stretching vibrations in the inelastic neutron scattering spectra. A first-order dehydration phase transition temperature is definitively identified to be 125 °C using temperature-dependent Raman scattering.« less

Structural characterization of environmentally relevant ternary uranyl citrate complexes present in aqueous solutions and solid state materials.

PubMed

Basile, Madeline; Unruh, Daniel K; Flores, Erin; Johns, Adam; Forbes, Tori Z

2015-02-14

Organic acids are important metal chelators in environmental systems and tend to form soluble complexes in aqueous solutions, ultimately influencing the transport and bioavailability of contaminants in surface and subsurface waters. This is particularly true for the formation of uranyl citrate complexes, which have been utilized in advanced photo- and bioremediation strategies for soils contaminated with nuclear materials. Given the complexity of environmental systems, the formation of ternary or heterometallic uranyl species in aqueous solutions are also expected, particularly with Al(iii) and Fe(iii) cations. These ternary forms are reported to be more stable in aqueous solutions, potentially enhancing contaminant mobility and uptake by organisms, but the exact coordination geometries of these soluble molecular complexes have not been elucidated. To provide insight into the nature of these species, we have developed a series of geochemical model compounds ([(UO(2))(2)Al(2)(C(6)H(4)O(7))(4)](6-) (U(2)Al(2)), [(UO(2))(2)Fe(2)(C(6)H(4)O(7))(4)](6-) (U(2)Fe(2)-1) and [(UO(2))(2)Fe(2)(C(6)H(4)O(7))(4)(H(2)O)(2)](6-) (U(2)Fe(2)-2) and [(UO(2))(2)Fe(4)(OH)(4)(C(6)H(4)O(7))(4)](8-) (U(2)Fe(4))) that were characterized by single-crystal X-ray diffraction and vibrational spectroscopy. Mass spectroscopy was then employed to compare the model compounds to species present in aqueous solutions to provide an enhanced understanding of the ternary uranyl citrate complexes that could be relevant in natural systems.

Dehydration of the Uranyl Peroxide Studtite, [UO 2(η 2-O 2)(H 2O) 2]·2H 2O, Affords a Drastic Change in the Electronic Structure: A Combined X-ray Spectroscopic and Theoretical Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vitova, Tonya; Pidchenko, Ivan; Biswas, Saptarshi

The dehydration of studtite, [UO 2(2-O 2)(H 2O)2]·2H 2O, to metastudtite, [UO 2(2-O 2)(H 2O) 2], uranyl peroxide minerals that are major oxidative alteration phases of UO2 under conditions of geological storage, has been studied using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy. XPS of the U 4f region shows small but significant differences between studtite and metastudtite, with the 4f binding energy of studtite the highest reported for a uranyl mineral studied by this technique. Further information on the changes in the electronic structure was elucidated using U M4-edge High Energy Resolution XANES (HR-XANES) spectroscopy, which directly probesmore » f-orbital states. The transition from the 3d to the 5f* orbital is sensitive to variations of the U=Oaxial bond length and to changes in the bond covalency. We report evidences that the covalence in the uranyl fragment decreases upon dehydration. Photoluminescence spectroscopy at near liquid helium temperatures reveals significant spectral differences between the two materials, correlating with the X-ray spectroscopy results. A theoretical investigation has been conducted on the structures of both studtite and metastudtite and benchmarked to the HR-XANES spectra. These illustrate the sensitivity of the 3d to the 5f * transition towards U=Oaxial bond variation.« less

Bis(N-ethyl-N-methyl-dithio-carbamato-κS,S')diphenyl-tin(IV).

PubMed

Muthalib, Amirah Faizah; Baba, Ibrahim; Ng, Seik Weng

2010-03-03

The dithio-carbamate anions in the title compound, [Sn(C(6)H(5))(2)(C(4)H(8)NS(2))(2)], chelate to the Sn(IV) atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol-ecule lies across a twofold rotation axis.

Bis(N-isopropyl-N-methyl-dithio-carbamato-κS,S')diphenyl-tin(IV).

PubMed

Muthalib, Amirah Faizah; Baba, Ibrahim; Farina, Yang; Ng, Seik Weng

2010-03-03

The dithio-carbamate anions in the title compound, [Sn(C(6)H(5))(2)(C(5)H(10)NS(2))(2)], chelate to the Sn(IV) atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol-ecule lies across a twofold rotation axis.

Impact of pore size on the sorption of uranyl under seawater conditions

DOE PAGES

Mayes, Richard T.; Gorka, Joanna; Dai, Sheng

2016-04-05

The extraction of uranium from seawater has received significant interest recently, because of the possibility of a near-limitless supply of uranium to fuel the nuclear power industry. While sorbent development has focused primarily on polymeric sorbents, nanomaterials represent a new area that has the potential to surpass the current polymeric sorbents, because of the high surface areas that are possible. Mesoporous carbon materials are a stable, high-surface-area material capable of extracting various chemical species from a variety of environments. Herein, we report the use of a dual templating process to understand the effect of pore size on the adsorption ofmore » uranyl ions from a uranyl brine consisting of seawater-relevant sodium, chloride, and bicarbonate ions. It was found that pore size played a more significant role in the effective use of the grafted polymer, leading to higher uranium capacities than the surface area. Furthermore, the pore size must be tailored to meet the demands of the extraction medium and analyte metal to achieve efficacy as an adsorbent.« less

Polymorphism in Alkali Metal Uranyl Nitrates: Synthesis and Crystal Structure of γ-K(UO2)(NO3)3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J.; Krivovichev, Sergey V.; Burns, Peter C.

2011-07-20

Single crystals of γ-K(UO2)(NO3)3 were prepared from aqueous solutions by evaporation. The crystal structure [orthorhombic, Pbca (61), a = 9.2559(3) Å, b = 12.1753(3) Å, c = 15.8076(5) Å, V = 1781.41(9) Å3, Z = 8] was determined by direct methods and refined to R1 = 0.0267 on the basis of 3657 unique observed reflections. The structure is composed of isolated anionic uranyl trinitrate units, [(UO2)(NO3)3]–, that are linked through eleven-coordinated K+ cations. Both known polymorphs of K(UO2)(NO3)3 (α- and γ-phases) can be considered as based upon sheets of isolated complex [(UO2)(NO3)3]– ions separated by K+ cations. The existence ofmore » polymorphism in the two K[UO2(NO3)3] polymorphs is due to the different packing modes of uranyl trinitrate clusters that adopt the same two-dimensional but different three-dimensional arrangements.« less

Probing the oxygen environment in UO(2)(2+) by solid-state 17O nuclear magnetic resonance spectroscopy and relativistic density functional calculations.

PubMed

Cho, Herman; de Jong, Wibe A; Soderquist, Chuck Z

2010-02-28

A combined theoretical and solid-state (17)O nuclear magnetic resonance (NMR) study of the electronic structure of the uranyl ion UO(2)(2+) in (NH(4))(4)UO(2)(CO(3))(3) and rutherfordine (UO(2)CO(3)) is presented, the former representing a system with a hydrogen-bonding environment around the uranyl oxygens and the latter exemplifying a uranyl environment without hydrogens. Relativistic density functional calculations reveal unique features of the U-O covalent bond, including the finding of (17)O chemical shift anisotropies that are among the largest for oxygen ever reported (>1200 ppm). Computational results for the oxygen electric field gradient tensor are found to be consistently larger in magnitude than experimental solid-state (17)O NMR measurements in a 7.05 T magnetic field indicate. A modified version of the Solomon theory of the two-spin echo amplitude for a spin-5/2 nucleus is developed and applied to the analysis of the (17)O echo signal of U (17)O(2)(2+).

MRAPs, Irregular Warfare, and Pentagon Reform

DTIC Science & Technology

2009-01-01

76 JFQ / issue 55, 4 th quarter 2009 ndupress .ndu.edu MRAPs, Irregular Warfare, and Pentagon Reform By C h r i s t o p h e r J . l a m b , m...a t t h e w J . s C h m i D t , and b e r i t g . F i t z s i m m o n s Mine resistant ambush protected (MRAP) vehicles offer an excellent...issue 55, 4 th quarter 2009 / JFQ 77 LAMB, SCHMIDT, and FITZSIMMONS By C h r i s t o p h e r J . l a m b , m a t t h e w J . s C h m i D t

"The only feasible means." The Pentagon's ambivalent relationship with the Nuremberg Code.

PubMed

Moreno, J D

1996-01-01

Convinced that armed conflict with the Soviet Union was all but inevitable, that such conflict would involve unconventional atomic, biological, and chemical warfare, and that research with human subjects was essential to respond to the threat, in the early 1950s the U.S. Department of Defense promulgated a policy governing human experimentation based on the Nuremberg Code. Yet the policymaking process focused on the abstract issue of whether human experiments should go forward at all, ignoring the reality of humans subjects research already under way and leaving unanswered ethical questions about how to conduct such research. Documents newly released to the Advisory Committee on Human Radiation Experiments tell the story of the Pentagon policy.

SEPARATION OF URANYL NITRATE BY EXTRACTION

DOEpatents

Stoughton, R.W.; Steahly, F.L.

1958-08-26

A process is presented for obtaining U/sup 233/ from solutions containing Pa/sup 233/. A carrier precipitate, such as MnO/sub 2/, is formed in such solutions and carries with it the Pa/sup 233/ present. This precipitate is then dissolved in nitric acid and the solution is aged to allow decay of the Pa/ sup 233/ into U/sup 233/. After a sufficient length of time the U/sup 233/ bearing solution is made 2.5 to 4.5 Molar in manganese nitrate by addition thereof, and the solution is then treated with ether to obtain uranyl nitrate by solvent extraction techniques.

ADSORPTION METHOD FOR SEPARATING THORIUM VALUES FROM URANIUM VALUES

DOEpatents

Boyd, G.E.; Russell, E.R.; Schubert, J.

1959-08-01

An improved ion exchange method is described for recovery of uranium and thorium values as separate functions from an aqueous acidic solution containing less than 10/sup -3/ M thorium ions and between 0.1 and 1 M uranyl ions. The solution is passed through a bed of cation exchange resin in the acid form to adsorb all the thorium ions and a portion of the uranyl ions. The uranium is eluted by means of aqueous 0.1 to 0.4 M sulfuric acid. The thorium may then be stripped from the resin by elution with aqueous 0.5 M oxalic acid.

ADSORPTION METHOD FOR SEPARATING THORIUM VALUES FROM URANIUM VALUES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boyd, G.E.; Russell, E.R.; Schubert, J.

An improved ion exchange method is described for recovery of uranium and thorium values as separate functions from an aqueous acidic solution containing less than 10/sup -3/ M thorium ions and between 0.1 and 1 M uranyl ions. The solution is passed through a bed of cation exchange resin in the acid form to adsorb all the thorium ions and a portion of the uranyl ions. The uranium is eluted by means of aqueous 0.1 to 0.4 M sulfuric acid. The thorium may then be stripped from the resin by elution with aqueous 0.5 M oxalic acid.

A route to oligosaccharide-appended salicylaldehydes: useful building blocks for the synthesis of metal-salophen complexes.

PubMed

Bedini, Emiliano; Forte, Gianpiero; De Castro, Cristina; Parrilli, Michelangelo; Dalla Cort, Antonella

2013-08-16

A simple and general synthetic protocol to obtain oligosaccharide-appended salicylaldehydes, key intermediates for the synthesis of water-soluble metal-salophen complexes, is here reported. Six new aldehydes have been prepared and fully characterized as well as the corresponding zinc- and uranyl-salophen complexes. These new derivatives show very good solubility in water. Preliminary studies on the association of compound 19-U, that is, the uranyl maltotetraose derivative, with hydrogen phosphate and fluoride provide very encouraging results and open up the possibility of using such compounds for the efficient recognition of anions in pure water.

A pseudo-tetragonal tungsten bronze superstructure: a combined solution of the crystal structure of K6.4(Nb,Ta)(36.3)O94 with advanced transmission electron microscopy and neutron diffraction.

PubMed

Paria Sena, Robert; Babaryk, Artem A; Khainakov, Sergiy; Garcia-Granda, Santiago; Slobodyanik, Nikolay S; Van Tendeloo, Gustaaf; Abakumov, Artem M; Hadermann, Joke

2016-01-21

The crystal structure of the K6.4Nb28.2Ta8.1O94 pseudo-tetragonal tungsten bronze-type oxide was determined using a combination of X-ray powder diffraction, neutron diffraction and transmission electron microscopy techniques, including electron diffraction, high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), annular bright field STEM (ABF-STEM) and energy-dispersive X-ray compositional mapping (STEM-EDX). The compound crystallizes in the space group Pbam with unit cell parameters a = 37.468(9) Å, b = 12.493(3) Å, c = 3.95333(15) Å. The structure consists of corner sharing (Nb,Ta)O6 octahedra forming trigonal, tetragonal and pentagonal tunnels. All tetragonal tunnels are occupied by K(+) ions, while 1/3 of the pentagonal tunnels are preferentially occupied by Nb(5+)/Ta(5+) and 2/3 are occupied by K(+) in a regular pattern. A fractional substitution of K(+) in the pentagonal tunnels by Nb(5+)/Ta(5+) is suggested by the analysis of the HAADF-STEM images. In contrast to similar structures, such as K2Nb8O21, also parts of the trigonal tunnels are fractionally occupied by K(+) cations.

The Physical Basis for the Head-to-Tail Rule that Excludes Most Fullerene Cages from Self-Assembly☆

PubMed Central

Schein, Stan; Sands-Kidner, Michelle; Friedrich, Tara

2008-01-01

Abstract In the companion article, we proposed that fullerene cages with head-to-tail dihedral angle discrepancies do not self-assemble. Here we show why. If an edge abuts a pentagon at one end and a hexagon at the other, the dihedral angle about the edge increases, producing a dihedral angle discrepancy (DAD) vector. The DADs about all five/six edges of a central pentagonal/hexagonal face are determined by the identities—pentagon or hexagon—of its five/six surrounding faces. Each “Ring”—central face plus specific surrounding faces—may have zero, two, or four edges with DAD. In most Rings, the nonplanarity induced by DADs is shared among surrounding faces. However, in a Ring that has DADs arranged head of one to tail of another, the nonplanarity cannot be shared, so some surrounding faces would be especially nonplanar. Because the head-to-tail exclusion rule is an implicit geometric constraint, the rule may operate either by imposing a kinetic barrier that prevents assembly of certain Rings or by imposing an energy cost that makes those Rings unlikely to last in an equilibrium circumstance. Since Rings with head-to-tail DADs would be unlikely to self-assemble or last, fullerene cages with those Rings would be unlikely to self-assemble. PMID:17921208

Synthesis and sensing properties of D5h pentagonal silver star nanoparticles.

PubMed

Cathcart, Nicole; Coombs, Neil; Gourevich, Ilya; Kitaev, Vladimir

2016-11-03

In this work, we use silver decahedral nanoparticle (AgDeNP) seeds to synthesize pentagonal silver stars (AgStDeNPs) and study the sensing properties of these nanoparticles. The regrowth process of AgStDeNPs is kinetically-controlled, so the purity of the seed NPs is critical to avoid secondary deposition in the highly non-equilibrium reduction. To control the regrowth process, surface blocking with sodium polyacrylate (PANa) was implemented. PANa moderates rough silver nanostructures typically obtained by reduction with ascorbic acid. To modulate polymer binding to the surface and thus to tune surface blocking, pH served as a key synthetic parameter. Under optimal regrowth conditions, new sliver was deposited on the highest energy sites of the decahedra - the vertices of the rims - to yield pentagonal stars. The universality of this regrowth process was established with several different seed particles. The sharpness and size of the stellated tips are tunable by the amount of added silver. Gold deposition onto AgStDeNPs enables the preparation of diverse structures with enhanced stability. Ease of transformation, e.g. rounding, of star branches opens a promising venue for enhanced SPR sensing. Also, AgStDeNPs enable femtomolar detection of 5,5-dithiobis(2-nitrobenzoic acid) in SERS.

Continuum study on the oscillatory characteristics of carbon nanocones inside single-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Ansari, R.; Sadeghi, F.; Darvizeh, M.

2016-02-01

This article aims to present a comprehensive study on the oscillatory behavior of concentric carbon nanocones (CNCs) inside carbon nanotubes (CNTs) using a continuum approach. To this end, the optimum radius of nanotube for which the nanocone lies on the tube axis is determined based on the distribution of suction energy. Using the Runge-Kutta numerical integration scheme, the equation of motion is solved numerically to attain the time history of displacement and velocity of nanocone. It is observed that the oscillation of nanocone occurs with respect to its axial equilibrium distance which moves further away from the middle axis of nanotube as the number of pentagons increases. A novel semi-analytical expression as a function of geometrical parameters, initial conditions and cone vertex direction is also proposed for the precise evaluation of oscillation frequency. With respect to the proposed frequency expression, a detailed parametric study is conducted to get an insight into the effects of number of pentagons, cone vertex direction and initial conditions on the oscillatory behavior of CNC-CNT oscillators. It is found that nanocones with more pentagons generate greater maximum frequencies inside nanotubes. Furthermore, it is shown that higher maximum frequencies can be achieved if the nanocone enters the nanotube from base.

Architecture of clathrin fullerene cages reflects a geometric constraint--the head-to-tail exclusion rule--and a preference for asymmetry.

PubMed

Schein, Stan

2009-03-27

Fullerene cages have n trivalent vertices, 12 pentagonal faces, and (n-20)/2 hexagonal faces. The smallest cage in which all of the pentagons are surrounded by hexagons and thus isolated from each other has 60 vertices and is shaped like a soccer ball. The protein clathrin self-assembles into fullerene cages of a variety of sizes and shapes, including smaller ones with adjacent pentagons as well as larger ones, but the variety is limited. To explain the range of clathrin architecture and how these fullerene cages self-assemble, we proposed a hypothesis, the "head-to-tail exclusion rule" (the "Rule"). Of the 5769 small clathrin cage isomers with n< or =60 vertices and adjacent pentagons, the Rule permits just 15, three identified in 1976 and 12 others. A "weak version" of the Rule permits another 99. Based on cryo-electron tomography, Cheng et al. reported six raw clathrin fullerene cages. One was among the three identified in 1976. Here, (1) we identify the remaining five. (2) Four are new and are among the 12 others permitted by the Rule. (3) One, also new, is among the 99 weak version cages. (4) Of particular note, none of the remaining 5565 excluded cages has been identified. These findings provide powerful experimental confirmation of the Rule and the principle on which it is based. (5) Surprisingly, the newly identified clathrin cages are among the least symmetric of those permitted. (6) By devising a method for counting assembly paths, (7) we show that asymmetric cages can be assembled by larger numbers of paths, thus providing a kinetic explanation for the prevalence of asymmetric cages. (8) Finally, we show that operation during cage growth of the Rule greatly increases the likelihood of producing a closed fullerene cage, specifically one of those permitted, but efficient assembly still appears to require internal remodeling.

Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

NASA Astrophysics Data System (ADS)

Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

2008-09-01

The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate ( I), bromo-(2-formylpyridinethiosemicarbazono)copper ( II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate ( III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I III at a concentration of 10-5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

Shape-dependence of the thermal and photochemical reactions of methanol on nanocrystalline anatase TiO2

NASA Astrophysics Data System (ADS)

Bennett, David A.; Cargnello, Matteo; Diroll, Benjamin T.; Murray, Christopher B.; Vohs, John M.

2016-12-01

Structure-activity relationships and the influence of particle size and shape on the partial- and photo-oxidation of methanol on nanocrystalline anatase TiO2 were investigated using temperature-programmed desorption. The study employed two distinct nanoparticle morphologies: truncated bipyramids exposing primarily {101} facets, and flatter platelets exposing primarily {001} surfaces, whose nominal sizes ranged from 10 to 25 nm. The platelets were found to be more active for thermally-driven reactions, such as coupling of methoxide groups to produce dimethyl ether, and deoxygenation to produce methane. A dependence of the reactivity of {001} facets for the coupling of methoxide groups to produce dimethyl ether on facet size was also observed. In contrast to the thermally-driven reactions, the bipyramidal nanoparticles were observed to be more active for a range of photochemical reactions, including oxidation and coupling to produce methyl formate, and photo-decomposition of surface methoxide species. This study also shows how well-defined nanocrystals can be used to help bridge the materials gap between studies of single crystal model catalysts and their high surface area industrial analogs.

Effects of structural distortion induced by Sc substitution in LuFe2O4

NASA Astrophysics Data System (ADS)

Jeong, Jinwon; Noh, Han-Jin; Kim, Sung Baek

2014-06-01

We have studied the correlation between the structural distortion and the electronic/magnetic properties in single-crystalline (Lu,Sc)Fe2O4 (Sc = 0.05 and 0.3) by using X-ray diffraction (XRD), magnetic susceptibility, and X-ray absorption spectroscopy (XAS)/X-ray magnetic circular dichroism (XMCD) measurements. The Rietveld structure analysis of the XRD patterns revealed that the Sc substitution induced an elongation of the FeO5 bipyramidal cages in LuFe2O4 and increased the Fe2O4 bilayer thickness. A non-negligible decrease in the ferrimagnetic transition temperature T C is observed in the magnetic susceptibility curve of the Sc = 0.3 sample, but the XAS/XMCD spectra do not show any difference except for a small reduction of dichroism signals at the Fe3+absorption edge. We interpret this suppression of TC to be the result of a decreased spin-orbit coupling effect in the Fe2+ e 1 g doublet under D 3 h symmetry, which is induced by the weakened structural asymmetry of the FeO5 bipyramids.

Phonon-Driven Oscillatory Plasmonic Excitonic Nanomaterials

DOE PAGES

Kirschner, Matthew S.; Ding, Wendu; Li, Yuxiu; ...

2017-12-01

In this study, we demonstrate that coherent acoustic phonons derived from plasmonic nanoparticles can modulate electronic interactions with proximal excitonic molecular species. A series of gold bipyramids with systematically varied aspect ratios and corresponding localized surface plasmon resonance energies, functionalized with a J-aggregated thiacarbocyanine dye molecule, produce two hybridized states that exhibit clear anti-crossing behavior with a Rabi splitting energy of 120 meV. In metal nanoparticles, photoexcitation generates coherent acoustic phonons that cause oscillations in the plasmon resonance energy. In the coupled system, these photo-generated oscillations alter the metal nanoparticle’s energetic contribution to the hybridized system and, as a result,more » change the coupling between the plasmon and exciton. We demonstrate that such modulations in the hybridization is consistent across a wide range of bipyramid ensembles. We also use Finite-Difference Time Domain calculations to develop a simple model describing this behavior. Lastly, such oscillatory plasmonic-excitonic nanomaterials (OPENs) offer a route to manipulate and dynamically-tune the interactions of plasmonic/excitonic systems and unlock a range of potential applications.« less

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

PubMed

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

2008-01-01

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

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes.

PubMed

Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

2016-12-01

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (U VI O 2 2+ ) coordinated by formate or acetate ligands. Anionic complexes containing U VI O 2 2+ and formate ligands fragment by decarboxylation and elimination of CH 2 =O, ultimately to produce an oxo-hydride species [U VI O 2 (O)(H)] - . Cationic species ultimately dissociate to make [U VI O 2 (OH)] + . Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH 3 CO 2 •, with associated reduction of uranyl to U V O 2 + . Subsequent CID steps cause elimination of CO 2 and CH 4 , ultimately to produce [U V O 2 (O)] - . Loss of CH 4 occurs by an intra-complex H + transfer process that leaves U V O 2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH 2 =C=O to leave [U V O 2 (O)] - . Elimination of CH 4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H 2 O. The reactions of other anionic species with gas-phase H 2 O create hydroxyl products, presumably through the elimination of H 2 . Graphical Abstract ᅟ.

Uranyl extraction by N,N-dialkylamide ligands studied using static and dynamic DFT simulations.

PubMed

Sieffert, Nicolas; Wipff, Georges

2015-02-14

We report DFT static and dynamic studies on uranyl complexes [UO(2)(NO(3))x(H(2)O)(y)L(z)](2-x) involved in the uranyl extraction from water to an "oil" phase (hexane) by an amide ligand L (N,N-dimethylacetamide). Static DFT results "in solution" (continuum SMD models for water and hexane) predict that the stepwise formation of [UO(2)(NO(3))(2)L(2)] from the UO(2)(H(2)O)(5)(2+) species is energetically favourable, and allow us to compare cis/trans isomers of penta- and hexa-coordinated complexes and key intermediates in the two solvents. DFT-MD simulations of [UO(2)(NO(3))(2)L(2)], [UO(2)(NO(3))(2)(H(2)O)L(2)], and [UO(2)(NO(3))(H(2)O)L(2)](+) species in explicit solvent environments (water, hexane, or the water/hexane interface) represented at the MM or full-DFT level reveal a versatile solvent dependent binding mode of nitrates, also evidenced by metadynamics simulations. In water and at the interface, the latter exchange from bi- to monodentate, via in plane rotational motions in some cases. Remarkably, structures of complexes at the interface are more "water-like" than gas phase- or hexane-like. Thus, the order of U-O(NO(3))/U-O(L) bond distances observed in the gas phase (U-O(nit) < U-OL) is inverted at the interface and in water. Overall, the results are consistent with the experimental observation of uranyl extraction from nitric acid solutions by amide analogues (bearing "fatty" substituents), and allow us to propose possible extraction mechanisms, involving complexation of L "right at the interface". They also point to the importance of the solvent environment and the dynamics on the structure and stability of the complexes.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

2015-05-22

the hexahydrate [UO 2(NO 3) 2(H 2O) 6] (UNH) and the trihydrate [UO 2(NO 3) 2(H 2O) 3] (UNT) forms. Their stabilities depend on both relative humidity and temperature. Both phases have previously been studied by infrared transmission spectroscopy, but the data were limited by both instrumental resolution and the ability to prepare the samples as pellets without desiccating them. We report time-resolved infrared (IR) measurements using an integrating sphere that allow us to observe the transformation from the hexahydrate to the trihydrate simply by flowing dry nitrogen gas over the sample. Hexahydrate samples were prepared and confirmed via knownmore » XRD patterns, then measured in reflectance mode. The hexahydrate has a distinct uranyl asymmetric stretch band at 949.0 cm -1 that shifts to shorter wavelengths and broadens as the sample dehydrates and recrystallizes to the trihydrate, first as a blue edge shoulder but ultimately resulting in a doublet band with reflectance peaks at 966 and 957 cm -1. The data are consistent with transformation from UNH to UNT since UNT has two non-equivalent UO 2 2+ sites. The dehydration of UO 2(NO 3) 2(H 2O) 6 to UO 2(NO 3) 2(H 2O) 3 is both a morphological and structural change that has the lustrous lime green crystals changing to the dull greenish yellow of the trihydrate. Crystal structures and phase transformation were confirmed theoretically using DFT calculations and experimentally via microscopy methods. Both methods showed a transformation with two distinct sites for the uranyl cation in the trihydrate, as opposed to a single crystallographic site in the hexahydrate.« less

Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Medvedkov, Ya. A.; Serezhkina, L. B., E-mail: Lserezh@samsu.ru; Grigor’ev, M. S.

2016-05-15

Two new malonate-containing uranyl complexes with carbamide of the formulas [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}] (I) and [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 3}] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO{sub 2}(C{sub 2}O{sub 4})(Urea){sub 3}] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}]{sub ∞} belonging to the crystal-chemical group AT{sup 11}M{sub 2}{sup 1} (A = UO{sub 2}{sup 2+}, T{sup 11} = C{sub 3}H{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea) of uranyl complexes.more » Crystals II and III are composed of the molecular complexes [UO{sub 2}(L)(Urea){sub 3}], where L = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, belonging to the crystal-chemical group AB{sup 01}M{sub 3}{sup 1} (A = UO{sub 2}{sup 2+}, B{sup 01} = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.« less

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

NASA Astrophysics Data System (ADS)

Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

2016-12-01

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

UO₂²⁺ uptake by proteins: understanding the binding features of the super uranyl binding protein and design of a protein with higher affinity.

PubMed

Odoh, Samuel O; Bondarevsky, Gary D; Karpus, Jason; Cui, Qiang; He, Chuan; Spezia, Riccardo; Gagliardi, Laura

2014-12-17

The capture of uranyl, UO2(2+), by a recently engineered protein (Zhou et al. Nat. Chem. 2014, 6, 236) with high selectivity and femtomolar sensitivity has been examined by a combination of density functional theory, molecular dynamics, and free-energy simulations. It was found that UO2(2+) is coordinated to five carboxylate oxygen atoms from four amino acid residues of the super uranyl binding protein (SUP). A network of hydrogen bonds between the amino acid residues coordinated to UO2(2+) and residues in its second coordination sphere also affects the protein's uranyl binding affinity. Free-energy simulations show how UO2(2+) capture is governed by the nature of the amino acid residues in the binding site, the integrity and strength of the second-sphere hydrogen bond network, and the number of water molecules in the first coordination sphere. Alteration of any of these three factors through mutations generally results in a reduction of the binding free energy of UO2(2+) to the aqueous protein as well as of the difference between the binding free energies of UO2(2+) and other ions (Ca(2+), Cu(2+), Mg(2+), and Zn(2+)), a proxy for the protein's selectivity over these ions. The results of our free-energy simulations confirmed the previously reported experimental results and allowed us to discover a mutant of SUP, specifically the GLU64ASP mutant, that not only binds UO2(2+) more strongly than SUP but that is also more selective for UO2(2+) over other ions. The predictions from the computations were confirmed experimentally.

Theoretical Insights into Monometallofullerene Th@C76: Strong Covalent Interaction between Thorium and the Carbon Cage.

PubMed

Zhao, Pei; Zhao, Xiang; Ehara, Masahiro

2018-03-19

Th@C 76 has been studied by density functional theory combined with statistical mechanics calculations. The results reveal that Th@ T d (19151)-C 76 satisfying the isolated pentagon rule possesses the lowest energy. Nevertheless, considering the enthalpy-entropy interplay, Th@ C 1 (17418)-C 76 with one pair of adjacent pentagons is thermodynamically favorable at elevated temperatures, which is reported for the first time. The bonding critical points in both isomers were analyzed to disclose covalent interactions between the inner Th and cages. In addition, the Wiberg bond orders of M-C bonding in different endohedral metallofullerenes (EMFs) were investigated to prove stronger covalent interactions of Th-C in Th-based EMFs.

Protein Hydrogel Microbeads for Selective Uranium Mining from Seawater.

PubMed

Kou, Songzi; Yang, Zhongguang; Sun, Fei

2017-01-25

Practical methods for oceanic uranium extraction have yet to be developed in order to tap into the vast uranium reserve in the ocean as an alternative energy. Here we present a protein hydrogel system containing a network of recently engineered super uranyl binding proteins (SUPs) that is assembled through thiol-maleimide click chemistry under mild conditions. Monodisperse SUP hydrogel microbeads fabricated by a microfluidic device further enable uranyl (UO 2 2+ ) enrichment from natural seawater with great efficiency (enrichment index, K = 2.5 × 10 3 ) and selectivity. Our results demonstrate the feasibility of using protein hydrogels to extract uranium from the ocean.

Chemical controls on uranyl citrate speciation and the self-assembly of nanoscale macrocycles and sandwich complexes in aqueous solutions.

PubMed

Basile, M; Unruh, D K; Gojdas, K; Flores, E; Streicher, L; Forbes, T Z

2015-03-28

Uranyl citrate forms trimeric species at pH > 5.5, but exact structural characteristics of these important oligomers have not previously been reported. Crystallization and structural characterization of the trimers suggests the self-assembly of the 3 : 3 and 3 : 2 U : Cit complexes into larger sandwich and macrocyclic molecules. Raman spectroscopy and ESI-MS have been utilized to investigate the relative abundance of these species in solution under varying pH and citrate concentrations. Additional dynamic light scattering experiments indicate that self-assembly of the larger molecules does occur in aqueous solution.

2,6-Diiminopiperidin-1-ol: an overlooked motif relevant to uranyl and transition metal binding on poly(amidoxime) adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, Zachary C.; Cardenas, Allan Jay P.; Corbey, Jordan F.

2016-01-01

Glutardiamidoxime, a structural motif on sorbents used in uranium extraction from seawater, was discovered to cyclize in situ at room temperature to 2,6-diimino-piperidin-1-ol in the presence of uranyl nitrate. The new diimino motif was also generated when exposed to competing transition metals Cu(II) and Ni(II). Multinuclear μ-O bridged U(VI), Cu(II), and Ni(II) complexes featuring bound diimino ligands were isolated. A Cu(II) complex with the historically relevant cyclic imide dioxime motif is also reported for structural comparison to the reported diimino complexes.

METHOD FOR DISSOLVING ZIRCONIUM-URANIUM COMPOSITIONS

DOEpatents

Gens, T.A.

1961-07-18

A method is descrioed for treating a zirconium-- uranium composition to form a stable solution from which uranium and other values may be extracted by contacting the composition with at least a 4 molar aqueous solution of ammonium fluoride at a temperature of about 100 deg C, adding a peroxide, in incremental amounts, to the heated solution throughout the period of dissolution until all of the uranium is converted to soluble uranyl salt, adding nitric acid to the resultant solution to form a solvent extraction feed solution to convert the uranyl salt to a solvent extractable state, and thereafter recovering the uranium and other desired values from the feed solution by solvent extraction.

Observation of a brine layer on an ice surface with an environmental scanning electron microscope at higher pressures and temperatures.

PubMed

Krausko, Ján; Runštuk, Jiří; Neděla, Vilém; Klán, Petr; Heger, Dominik

2014-05-20

Observation of a uranyl-salt brine layer on an ice surface using backscattered electron detection and ice surface morphology using secondary-electron detection under equilibrium conditions was facilitated using an environmental scanning electron microscope (ESEM) at temperatures above 250 K and pressures of hundreds of Pa. The micrographs of a brine layer over ice grains prepared by either slow or shock freezing provided a complementary picture of the contaminated ice grain boundaries. Fluorescence spectroscopy of the uranyl ions in the brine layer confirmed that the species exists predominately in the solvated state under experimental conditions of ESEM.

A ω-mercaptoundecylphosphonic acid chemically modified gold electrode for uranium determination in waters in presence of organic matter.

PubMed

Merli, Daniele; Protti, Stefano; Labò, Matteo; Pesavento, Maria; Profumo, Antonella

2016-05-01

A chemically modified electrode (CME) on a gold surface assembled with a ω-phosphonic acid terminated thiol was investigated for its capability to complex uranyl ions. The electrode, characterized by electrochemical techniques, demonstrated to be effective for the determination of uranyl at sub-μgL(-1) level by differential pulse adsorptive stripping voltammetry (DPAdSV) in environmental waters, also in presence of humic matter and other potential chelating agents. The accuracy of the measurements was investigated employing as model probes ligands of different complexing capability (humic acids and EDTA). Copyright © 2016 Elsevier B.V. All rights reserved.

Simultaneous reduction of arsenic(V) and uranium(VI) by mackinawite: role of uranyl arsenate precipitate formation.

PubMed

Troyer, Lyndsay D; Tang, Yuanzhi; Borch, Thomas

2014-12-16

Uranium (U) and arsenic (As) often occur together naturally and, as a result, can be co-contaminants at sites of uranium mining and processing, yet few studies have examined the simultaneous redox dynamics of U and As. This study examines the influence of arsenate (As(V)) on the reduction of uranyl (U(VI)) by the redox-active mineral mackinawite (FeS). As(V) was added to systems containing 47 or 470 μM U(VI) at concentrations ranging from 0 to 640 μM. In the absence of As(V), U was completely removed from solution and fully reduced to nano-uraninite (nano-UO2). While the addition of As(V) did not reduce U uptake, at As(V) concentrations above 320 μM, the reduction of U(VI) was limited due to the formation of a trögerite-like uranyl arsenate precipitate. The presence of U also significantly inhibited As(V) reduction. While less U(VI) reduction to nano-UO2 may take place in systems with high As(V) concentrations, formation of trögerite-like mineral phases may be an acceptable reclamation end point due to their high stability under oxic conditions.

Spectroscopy and DFT studies of uranyl carbonate, rutherfordine, UO2CO3: a model for uranium transport, carbon dioxide sequestration, and seawater species

NASA Astrophysics Data System (ADS)

Kalashnyk, N.; Perry, D. L.; Massuyeau, F.; Faulques, E.

2017-12-01

Several optical microprobe experiments of the anhydrous uranium carbonate—rutherfordine—are presented in this work and compared to periodic density functional theory results. Rutherfordine is the simplest uranyl carbonate and constitutes an ideal model system for the study of the rich uranium carbonate family relevant for environmental sustainability. Micro-Raman, micro-reflectance, and micro-photoluminescence (PL) spectroscopy studies have been carried out in situ on native, micrometer-sized crystals. The sensitivity of these techniques is sufficient to analyze minute amounts of samples in natural environments without using x-ray analysis. In addition, very intense micro-PL and micro-reflectance spectra that were not reported before add new results on the ground and excited states of this mineral. The optical gap value determined experimentally is found at about 2.6-2.8 eV. Optimized geometry, band structure, and phonon spectra have been calculated. The main vibrational lines are identified and predicted by this theoretical study. This work is pertinent for optical spectroscopy, for identification of uranyl species in various environmental settings, and for nuclear forensic analysis.

Effects of a low-radiotoxicity uranium salt (uranyl acetate) on biochemical and hematological parameters of the catfish, Clarias gariepinus

NASA Astrophysics Data System (ADS)

Al-Ghanim, Khalid A.; Ahmad, Zubair; Al-Kahem Al-Balawi, Hmoud F.; Al-Misned, Fahad; Maboob, Shahid; Suliman, El-Amin M.

2016-01-01

Specimens of Clarias gariepinus were treated with lethal (70, 75, 80, 85, 90, and 95 mg/L) and sub-lethal concentrations (8, 12 and 16 mg/L) of uranyl acetate, a low-radiotoxicity uranium salt. The LC 50 value was registered as 81.45 mg/L. The protein and glycogen concentrations in liver and muscles were decreased in the fish exposed to sub-lethal concentrations. The red blood cell (RBC) and white blood cell (WBC) counts, haemoglobin (Hb) concentration and haematocrit (Hct) values were decreased. Different blood indices like mean corpuscular volume (MCV), mean corpuscular haemoglobin (MCH) and mean corpuscular haemoglobin concentration (MCHC) were negatively affected. Level of plasma glucose was elevated whereas protein was decreased. The level of calcium concentration (Ca) was declined in the blood of exposed fish whereas magnesium (Mg) remains unchanged. The activity level of glutamic-oxaloacetic transaminase (GOT) and glutamic-pyruvic transaminase (GPT) was elevated in exposed fish. These effects were more pronounced in the last period of exposure and in higher concentrations. Results of the present study indicate that uranyl acetate has adverse effects on Clarias gariepinus and causes changes in the biochemical and hematological parameters of the fish.

Site-specific incorporation of uranyl carbonate species at the calcite surface

NASA Astrophysics Data System (ADS)

Reeder, Richard J.; Elzinga, Evert J.; Tait, C. Drew; Rector, K. D.; Donohoe, Robert J.; Morris, David E.

2004-12-01

Spatially resolved luminescence spectra from U(VI) co-precipitated at the (101¯4) growth surface of synthetic calcite single crystals confirm heterogeneous incorporation corresponding to the distribution of structurally non-equivalent steps composing the vicinal surfaces of spiral growth hillocks. Spectral structure from U(VI) luminescence at the "-" vicinal regions and featureless, weak luminescence at the "+" vicinal regions are consistent with previously reported observations of enrichment at the former sites during calcite growth. Luminescence spectra differ between the non-equivalent regions of the crystal, with the spectral features from the "-" vicinal region corresponding to those observed in bulk calcite samples. Subtle spectral shifts are observed from U(VI) co-precipitated with microcrystalline calcite synthesized by a different method, and all of the U(VI)-calcite sample spectra differ significantly from that of U(VI) co-precipitated with aragonite. The step-selective incorporation of U(VI) can be explained by a proposed model in which the allowed orientation for adsorption of the dominant calcium uranyl triscarbonate species is controlled by the atomic arrangement at step edges. Differences in the tilt angles of carbonate groups between non-equivalent growth steps favor adsorption of the calcium uranyl triscarbonate species at "-" steps, as observed in experiments.

Nuclear forensics investigation of morphological signatures in the thermal decomposition of uranyl peroxide.

PubMed

Schwerdt, Ian J; Olsen, Adam; Lusk, Robert; Heffernan, Sean; Klosterman, Michael; Collins, Bryce; Martinson, Sean; Kirkham, Trenton; McDonald, Luther W

2018-01-01

The analytical techniques typically utilized in a nuclear forensic investigation often provide limited information regarding the process history and production conditions of interdicted nuclear material. In this study, scanning electron microscopy (SEM) analysis of the surface morphology of amorphous-UO 3 samples calcined at 250, 300, 350, 400, and 450°C from uranyl peroxide was performed to determine if the morphology was indicative of the synthesis route and thermal history for the samples. Thermogravimetic analysis-mass spectrometry (TGA-MS) and differential scanning calorimetry (DSC) were used to correlate transitions in the calcined material to morphological transformations. The high-resolution SEM images were processed using the Morphological Analysis for Material Attribution (MAMA) software. Morphological attributes, particle area and circularity, indicated significant trends as a result of calcination temperature. The quantitative morphological analysis was able to track the process of particle fragmentation and subsequent sintering as calcination temperature was increased. At the 90% confidence interval, with 1000 segmented particles, the use of Kolmogorov-Smirnov statistical comparisons allowed discernment between all calcination temperatures for the uranyl peroxide route. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Oxo-exchange of gas-phase uranyl, neptunyl, and plutonyl with water and methanol.

PubMed

Lucena, Ana F; Odoh, Samuel O; Zhao, Jing; Marçalo, Joaquim; Schreckenbach, Georg; Gibson, John K

2014-02-17

A challenge in actinide chemistry is activation of the strong bonds in the actinyl ions, AnO2(+) and AnO2(2+), where An = U, Np, or Pu. Actinyl activation in oxo-exchange with water in solution is well established, but the exchange mechanisms are unknown. Gas-phase actinyl oxo-exchange is a means to probe these processes in detail for simple systems, which are amenable to computational modeling. Gas-phase exchange reactions of UO2(+), NpO2(+), PuO2(+), and UO2(2+) with water and methanol were studied by experiment and density functional theory (DFT); reported for the first time are experimental results for UO2(2+) and for methanol exchange, as well as exchange rate constants. Key findings are faster exchange of UO2(2+) versus UO2(+) and faster exchange with methanol versus water; faster exchange of UO2(+) versus PuO2(+) was quantified. Computed potential energy profiles (PEPs) are in accord with the observed kinetics, validating the utility of DFT to model these exchange processes. The seemingly enigmatic result of faster exchange for uranyl, which has the strongest oxo-bonds, may reflect reduced covalency in uranyl as compared with plutonyl.

New insight into the ternary complexes of uranyl carbonate in seawater.

PubMed

Beccia, M R; Matara-Aho, M; Reeves, B; Roques, J; Solari, P L; Monfort, M; Moulin, C; Den Auwer, C

2017-11-01

Uranium is naturally present in seawater at trace levels and may in some cases be present at higher concentrations, due to anthropogenic nuclear activities. Understanding uranium speciation in seawater is thus essential for predicting and controlling its behavior in this specific environmental compartment and consequently, its possible impact on living organisms. The carbonato calcic complex Ca 2 UO 2 (CO 3 ) 3 was previously identified as the main uranium species in natural seawater, together with CaUO 2 (CO 3 ) 3 2- . In this work, we further investigate the role of the alkaline earth cation in the structure of the ternary uranyl-carbonate complexes. For this purpose, artificial seawater, free of Mg 2+ and Ca 2+ , using Sr 2+ as a spectroscopic probe was prepared. Combining TRLIF and EXAFS spectroscopy, together with DFT and theoretical thermodynamic calculations, evidence for the presence of Sr alkaline earth counter ion in the complex structure can be asserted. Furthermore, data suggest that when Ca 2+ is replaced by Sr 2+ , SrUO 2 (CO 3 ) 3 2- is the main complex in solution and it occurs with the presence of at least one monodentate carbonate in the uranyl coordination sphere. Copyright © 2017 Elsevier Ltd. All rights reserved.

75 FR 25215 - Privacy Act of 1974; Systems of Records

Federal Register 2010, 2011, 2012, 2013, 2014

2010-05-07

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Science Scope.

ERIC Educational Resources Information Center

Stone, Richard, Ed.

1995-01-01

Discusses an education project launched by the National Academy of Sciences and the Pentagon to turn laid-off aerospace engineers into science teachers at Los Angeles middle schools and high schools. (MKR)

Bis(N-ethyl-N-methyl­dithio­carbamato-κ2 S,S′)diphenyl­tin(IV)

PubMed Central

Muthalib, Amirah Faizah; Baba, Ibrahim; Ng, Seik Weng

2010-01-01

The dithio­carbamate anions in the title compound, [Sn(C6H5)2(C4H8NS2)2], chelate to the SnIV atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol­ecule lies across a twofold rotation axis. PMID:21580470

Bis(N-isopropyl-N-methyl­dithio­carbamato-κ2 S,S′)diphenyl­tin(IV)

PubMed Central

Muthalib, Amirah Faizah; Baba, Ibrahim; Farina, Yang; Ng, Seik Weng

2010-01-01

The dithio­carbamate anions in the title compound, [Sn(C6H5)2(C5H10NS2)2], chelate to the SnIV atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol­ecule lies across a twofold rotation axis. PMID:21580469

Structural, spectroscopic and redox properties of uranyl complexes with a maleonitrile containing ligand.

PubMed

Hardwick, Helen C; Royal, Drew S; Helliwell, Madeleine; Pope, Simon J A; Ashton, Lorna; Goodacre, Roy; Sharrad, Clint A

2011-06-14

The reaction of uranyl nitrate hexahydrate with the maleonitrile containing Schiff base 2,3-bis[(4-diethylamino-2-hydroxybenzylidene)amino]but-2-enedinitrile (salmnt((Et(2)N)(2))H(2)) in methanol produces [UO(2)(salmnt((Et2N)2))(H(2)O)] (1) where the uranyl equatorial coordination plane is completed by the N(2)O(2) tetradentate cavity of the (salmnt((Et(2)N)(2)))(2-) ligand and a water molecule. The coordinated water molecule readily undergoes exchange with pyridine (py), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF) and triphenylphosphine oxide (TPPO) to give a series of [UO(2)(salmnt((Et(2)N)(2)))(L)] complexes (L = py, DMSO, DMF, TPPO; 2-5, respectively). X-Ray crystallography of 1-5 show that the (salmnt((Et(2)N)(2)))(2-) ligand is distorted when coordinated to the uranyl moiety, in contrast to the planar structure observed for the free protonated ligand (salmnt((Et(2)N)(2))H(2)). The Raman spectra of 1-5 only display extremely weak bands (819-828 cm(-1)) that can be assigned to the typically symmetric O=U=O stretch. This stretching mode is also observed in the infrared spectra for all complexes 1-5 (818-826 cm(-1)) predominantly caused by the distortion of the tetradentate (salmnt((Et(2)N)(2)))(2-) ligand about the uranyl equatorial plane resulting in a change in dipole for this bond stretch. The solution behaviour of 2-5 was studied using NMR, electronic absorption and emission spectroscopy, and cyclic voltammetry. Complexes 2-5 exhibit intense absorptions in the visible region of the spectrum due to intramolecular charge transfer (ICT) transitions and the luminescence lifetimes (< 5 ns) indicate the emission arises from ligand-centred excited states. Reversible redox processes assigned to the {UO(2)}(2+)/{UO(2)}(+) couple are observed for complexes 2-5 (2: E(1/2) = -1.80 V; 3,5: E(1/2) = -1.78 V; 4: E(1/2) = -1.81 V : vs. ferrocenium/ferrocene {Fc(+)/Fc}, 0.1 M Bu(4)NPF(6)) in dichloromethane (DCM). These are some of the most negative half potentials for the {UO(2)}(2+)/{UO(2)}(+) couple observed to date and indicate the strong electron donating nature of the (salmnt((Et(2)N)(2)))(2-) ligand. Multiple uranyl redox processes are clearly seen for [UO(2)(salmnt((Et(2)N)(2)))(L)] in L (L = py, DMSO, DMF; 2-4: 0.1 M Bu(4)NPF(6)) indicating the relative instability of these complexes when competing ligands are present, but the reversible {UO(2)}(2+)/{UO(2)}(+) couple for the intact complexes can still be assigned and shows the position of this couple can be modulated by the solvation environment. Several redox processes were also observed between +0.2 and +1.2 V (vs. Fc(+)/Fc) that prove the redox active nature of the maleonitrile-containing ligand.

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

NASA Astrophysics Data System (ADS)

Kerisit, S.; Liu, C.

2010-12-01

Uranium is a major groundwater contaminant at uranium processing and mining sites as a result of intentional and accidental discharges of uranium-containing waste products into subsurface environments. Recent characterization has shown that uranium preferentially associates with intragrain and intra-aggregate domains in some of the uranium-contaminated sediments collected from the US Department of Energy Hanford Site [1, 2]. In these sediments, uranium existed as precipitated and/or adsorbed phases in grain micropores with nano- to microscale sizes. Desorption and diffusion characterization studies and continuum-scale modeling indicated that ion diffusion in the microfractures is a major mechanism that led to preferential uranium concentration in the microfracture regions and will control the future mobility of uranium in the subsurface sediments [1, 3-4]. However, the diffusion properties of uranyl species in the intragrain regions, especially at the solid-liquid interface, are still poorly understood. Therefore, a general aim of this work is to provide atomic-level insights into the contribution of microscopic surface effects to the slow diffusion process of uranyl species in porous media with nano- to microsized fractures. In this presentation, we will first present molecular dynamics (MD) simulations of feldspar-water interfaces to investigate their interfacial structure and dynamics and establish a theoretical framework for subsequent simulations of water and ion diffusion at these interfaces [5]. We will then report on MD simulations carried out to probe the effects of confinement and of the presence of the mineral surface on the diffusion of water and electrolyte ions in nanosized feldspar fractures [6]. Several properties of the mineral-water interface were varied, such as the fracture width, the ionic strength of the contacting solution, and the surface charge. Our calculations reveal a 2.0-2.5 nm interfacial region within which the diffusion properties of water and that of the electrolyte ions differ significantly from those in bulk aqueous solutions. We will then present MD simulations of the diffusion of a series of alkaline-earth uranyl carbonate species in aqueous solutions [7]. The MD simulations show that the alkaline-earth uranyl carbonate complexes have distinct water exchange dynamics, which could lead to different reactivities. Finally, we will present recent results on the diffusion and adsorption of uranyl carbonate species in intragrain micropores, modeled with the feldspar-water interfaces mentioned in the above, to help interpret the diffusion behavior of uranium in contaminated sediments. [1] Liu C. et al. Geochim. Cosmochim. Acta 68 4519 (2004) [2] McKinley J. P. et al. Geochim. Cosmochim. Acta 70 1873 (2006) [3] Liu C. et al. Water Resour. Res. 42 W12420 (2006) [4] Ilton E. S. et al. Environ. Sci. Technol. 42 1565 (2009) [5] Kerisit S. et al. Geochim. Cosmochim. Acta 72 1481 (2008) [6] Kerisit S. and Liu C. Environ. Sci. Technol. 43 777 (2009) [7] Kerisit S. and Liu C. Geochim. Cosmochim. Acta 74 4937 (2010)

Density functional study of structural and electronic properties of bimetallic silver-gold clusters: Comparison with pure gold and silver clusters

NASA Astrophysics Data System (ADS)

Bonacic-Koutecky, Vlasta; Burda, Jaroslav; Mitric, Roland; Ge, Maofa; Zampella, Giuseppe; Fantucci, Piercarlo

2002-08-01

Bimetallic silver-gold clusters offer an excellent opportunity to study changes in metallic versus "ionic" properties involving charge transfer as a function of the size and the composition, particularly when compared to pure silver and gold clusters. We have determined structures, ionization potentials, and vertical detachment energies for neutral and charged bimetallic AgmAun 3[less-than-or-equal](m+n)[less-than-or-equal]5 clusters. Calculated VDE values compare well with available experimental data. In the stable structures of these clusters Au atoms assume positions which favor the charge transfer from Ag atoms. Heteronuclear bonding is usually preferred to homonuclear bonding in clusters with equal numbers of hetero atoms. In fact, stable structures of neutral Ag2Au2, Ag3Au3, and Ag4Au4 clusters are characterized by the maximum number of hetero bonds and peripheral positions of Au atoms. Bimetallic tetramer as well as hexamer are planar and have common structural properties with corresponding one-component systems, while Ag4Au4 and Ag8 have 3D forms in contrast to Au8 which assumes planar structure. At the density functional level of theory we have shown that this is due to participation of d electrons in bonding of pure Aun clusters while s electrons dominate bonding in pure Agm as well as in bimetallic clusters. In fact, Aun clusters remain planar for larger sizes than Agm and AgnAun clusters. Segregation between two components in bimetallic systems is not favorable, as shown in the example of Ag5Au5 cluster. We have found that the structures of bimetallic clusters with 20 atoms Ag10Au10 and Ag12Au8 are characterized by negatively charged Au subunits embedded in Ag environment. In the latter case, the shape of Au8 is related to a pentagonal bipyramid capped by one atom and contains three exposed negatively charged Au atoms. They might be suitable for activating reactions relevant to catalysis. According to our findings the charge transfer in bimetallic clusters is responsible for formation of negatively charged gold subunits which are expected to be reactive, a situation similar to that of gold clusters supported on metal oxides.

Tessellating the Sphere with Regular Polygons

ERIC Educational Resources Information Center

Soto-Johnson, Hortensia; Bechthold, Dawn

2004-01-01

Tessellations in the Euclidean plane and regular polygons that tessellate the sphere are reviewed. The regular polygons that can possibly tesellate the sphere are spherical triangles, squares and pentagons.

DoD No FEAR Act

Science.gov Websites

Secretary of Defense Principal Deputy Under Secretary Military Deputy Chief of Staff Health Affairs Manpower Research Projects Agency, Defense Legal Services Agency, Defense Security Cooperation Agency, Pentagon

HIV in military.

PubMed

1996-05-31

The House of Representatives approved a defense authorization bill that requires the Pentagon to discharge service members who test positive for HIV antibodies. This is the second measure of its kind. Last year, Rep. Robert K. Dornan (R-CA) pushed through Congress a similar measure that was repealed after encountering public opposition. President Clinton said he will veto the defense bill in its current form. The bill provides $13 billion in spending beyond the amount the Pentagon requested, resurrects plans for the Star Wars missile defense system, and rescinds Clinton's don't ask, don't tell policy toward gay men and lesbians in the military. Rep. Peter Torkildsen (R-MA) is confident that the HIV provision can be stricken when the bill goes to a House-Senate conference committee in a few weeks.

Simple Method for Constructing RNA Triangle, Square, Pentagon by Tuning Interior RNA 3WJ Angle from 60° to 90° or 108°.

PubMed

Khisamutdinov, Emil F; Bui, My Nguyen Hoan; Jasinski, Daniel; Zhao, Zhengyi; Cui, Zheng; Guo, Peixuan

2015-01-01

Precise shape control of architectures at the nanometer scale is an intriguing but extremely challenging facet. RNA has recently emerged as a unique material and thermostable building block for use in nanoparticle construction. Here, we describe a simple method from design to synthesis of RNA triangle, square, and pentagon by stretching RNA 3WJ native angle from 60° to 90° and 108°, using the three-way junction (3WJ) of the pRNA from bacteriophage phi29 dsDNA packaging motor. These methods for the construction of elegant polygons can be applied to other RNA building blocks including the utilization and application of RNA 4-way, 5-way, and other multi-way junctions.

Recovery of Uranium from Seawater: Preparation and Development of Polymer-Supported Extractants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spiro, Alexandratos

2013-12-01

A new series of polymer-supported extractants is proposed for the removal and recovery of uranium from seawater. The objective is to produce polymers with improved stability, loading capacity, and sorption kinetics compared to what is found with amidoximes. The target ligands are diphosphonates and aminomethyldiphosphonates. Small molecule analogues, especially of aminomethyldiphos-phonates, have exceptionally high stability constants for the uranyl ion. The polymeric diphosphonates will have high affinities due to their ability to form six-membered rings with the uranyl ion while the aminomethyldiphosphonates may have yet higher affinities due to possible tridentate coordination and their greater acidity. A representative set ofmore » the polymers to be prepared are indicated.« less

PROCESS FOR SEPARATION OF HEAVY METALS

DOEpatents

Duffield, R.B.

1958-04-29

A method is described for separating plutonium from aqueous acidic solutions of neutron-irradiated uranium and the impurities associated therewith. The separation is effected by adding, to the solution containing hexavalent uranium and plutonium, acetate ions and the ions of an alkali metal and those of a divalent metal and thus forming a complex plutonium acetate salt which is carried by the corresponding complex of uranium, such as sodium magnesium uranyl acetate. The plutonium may be separated from the precipitated salt by taking the same back into solution, reducing the plutonium to a lower valent state on reprecipitating the sodium magnesium uranyl salt, removing the latter, and then carrying the plutonium from ihe solution by means of lanthanum fluoride.

PROCESS OF PREPARING URANIUM-IMPREGNATED GRAPHITE BODY

DOEpatents

Kanter, M.A.

1958-05-20

A method for the fabrication of graphite bodies containing uniformly distributed uranium is described. It consists of impregnating a body of graphite having uniform porosity and low density with an aqueous solution of uranyl nitrate hexahydrate preferably by a vacuum technique, thereafter removing excess aqueous solution from the surface of the graphite, then removing the solvent water from the body under substantially normal atmospheric conditions of temperature and pressure in the presence of a stream of dry inert gas, and finally heating the dry impregnated graphite body in the presence of inert gas at a temperature between 800 and 1400 d C to convert the uranyl nitrate hexahydrate to an oxide of uranium.

Molecular characterization of Bacillus thuringiensis isolated from diverse habitats of India.

PubMed

Patel, Ketan D; Chudasama, Chaitanyasinh J; Ingle, Sanjay S

2012-08-01

Bacillus thuringiensis (Bt) strains were isolated from 94 samples from different geographical regions. Novel types of crystalline inclusion bodies were observed from some of the isolates. Crystalline inclusions of bipyramidal, spherical and cuboidal morphology were found produced by most of the isolates. Isolate GS12 showed crystal on one side of spore while isolate GM108 formed crystals on both termini of spore. Isolate GN31 produced large sized bipyramidal crystals. SDS-PAGE analysis of the spore crystal suspension showed major protein bands in the range of 29 and 140 kDa. Two new serovars of Bt viz. GS4 and GN24 having H3abce and H3ab serotype respectively were isolated. Toxicity comparable to the reference strain Bacillus thuringiensis subs. kurstaki (Btk) HD-1 was observed for the isolates GM20, GM17 and MP3 against larvae of Helicoverpa armigera. Some of the isolates harboring cry genes like cry1Ac and cry2 did not show any toxicity towards H. armigera while most of the isolates were harboring cry1, cry1Ac and cry2 gene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Purification, crystallization and preliminary X-ray analysis of a thermostable glycoside hydrolase family 43 β-xylosidase from Geobacillus thermoleovorans IT-08

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rohman, Ali; Oosterwijk, Niels van; Kralj, Slavko

2007-11-01

The β-xylosidase was crystallized using PEG 6000 as precipitant. 5% PEG 6000 yielded bipyramid-shaped tetragonal crystals diffracting to 1.55 Å resolution, and 13% PEG 6000 gave rectangular monoclinic crystals diffracting to 1.80 Å resolution. The main enzymes involved in xylan-backbone hydrolysis are endo-1,4-β-xylanase and β-xylosidase. β-Xylosidase converts the xylo-oligosaccharides produced by endo-1,4-β-xylanase into xylose monomers. The β-xylosidase from the thermophilic Geobacillus thermoleovorans IT-08, a member of glycoside hydrolase family 43, was crystallized at room temperature using the hanging-drop vapour-diffusion method. Two crystal forms were observed. Bipyramid-shaped crystals belonging to space group P4{sub 3}2{sub 1}2, with unit-cell parameters a = bmore » = 62.53, c = 277.4 Å diffracted to 1.55 Å resolution. The rectangular crystals belonged to space group P2{sub 1}, with unit-cell parameters a = 57.94, b = 142.1, c = 153.9 Å, β = 90.5°, and diffracted to 1.80 Å resolution.« less

Structural characterization of tellurite glasses doped with transition metal oxides using Raman spectra and ab initio calculations.

PubMed

Mohamed, Tarek A; Shaltout, I; Al Yahyaei, K M

2006-05-01

Systems of iron tellurite glasses were prepared by melt quenching with compositions of [85%TeO2+5%Fe2O3+10%TMO], where transition metal oxides (TMO) are TiO2, V2O5, MnO, CoO, NiO and CuO. Furthermore, the main structural units of these samples have been characterized by means of Raman spectra (150-1200 cm(-1)) as well as wavenumber predictions by means of Gaussian 98 ab initio calculations for the proposed site symmetries of TeO4(4-) triagonal bipyramid (C2v) and Te2O7(6-) bridged tetrahedra (Cs and C1). Aided by normal coordinate analysis, calculated vibrational frequencies, Raman scattering activities, force constants in internal coordinates and potential energy distributions (PEDs), revised vibrational assignments for the fundamental modes have been proposed. The main structural features are correlated to the dominant units of triagonal bipyramid (tbp) or bridged tetrahedral (TeO3+1 binds to TeO3 through TeOTe bridge; corner sharing). Moreover, the Raman spectra of the investigated tellurites reflect a structural change from tbp (coordination number is four) to triagonal pyramidal (coordination number is three).

Large scale atomistic simulation of single-layer graphene growth on Ni(111) surface: molecular dynamics simulation based on a new generation of carbon-metal potential

NASA Astrophysics Data System (ADS)

Xu, Ziwei; Yan, Tianying; Liu, Guiwu; Qiao, Guanjun; Ding, Feng

2015-12-01

To explore the mechanism of graphene chemical vapor deposition (CVD) growth on a catalyst surface, a molecular dynamics (MD) simulation of carbon atom self-assembly on a Ni(111) surface based on a well-designed empirical reactive bond order potential was performed. We simulated single layer graphene with recorded size (up to 300 atoms per super-cell) and reasonably good quality by MD trajectories up to 15 ns. Detailed processes of graphene CVD growth, such as carbon atom dissolution and precipitation, formation of carbon chains of various lengths, polygons and small graphene domains were observed during the initial process of the MD simulation. The atomistic processes of typical defect healing, such as the transformation from a pentagon into a hexagon and from a pentagon-heptagon pair (5|7) to two adjacent hexagons (6|6), were revealed as well. The study also showed that higher temperature and longer annealing time are essential to form high quality graphene layers, which is in agreement with experimental reports and previous theoretical results.To explore the mechanism of graphene chemical vapor deposition (CVD) growth on a catalyst surface, a molecular dynamics (MD) simulation of carbon atom self-assembly on a Ni(111) surface based on a well-designed empirical reactive bond order potential was performed. We simulated single layer graphene with recorded size (up to 300 atoms per super-cell) and reasonably good quality by MD trajectories up to 15 ns. Detailed processes of graphene CVD growth, such as carbon atom dissolution and precipitation, formation of carbon chains of various lengths, polygons and small graphene domains were observed during the initial process of the MD simulation. The atomistic processes of typical defect healing, such as the transformation from a pentagon into a hexagon and from a pentagon-heptagon pair (5|7) to two adjacent hexagons (6|6), were revealed as well. The study also showed that higher temperature and longer annealing time are essential to form high quality graphene layers, which is in agreement with experimental reports and previous theoretical results. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06016h

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions.

PubMed

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan R

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions.

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions

PubMed Central

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan. R.

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions. PMID:26132209

Probing the Oxygen Environment in UO22+ by Solid-State O-17 Nuclear Magnetic Resonance Spectroscopy and Relativistic Density Functional Calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cho, Herman M.; De Jong, Wibe A.; Soderquist, Chuck Z.

A combined theoretical and solid-state O-17 NMR study of the electronic structure of the uranyl ion UO22+ in (NH4)4UO2(CO3)3 and rutherfordine UO2CO3 is presented, the former representing a system with a hydrogen-bonding environment around the uranyl oxygens, and the latter exemplifying a uranyl environment without hydrogens. A fully relativistic ab initio treatment reveals unique features of the U-O covalent bond, including the finding of O-17 chemical shift anisotropies that are among the largest ever reported (>1200 ppm). Computational results for the oxygen electric field gradient tensor are found to be consistently larger in magnitude than experimental solid-state O-17 NMR measurementsmore » in a 7.05 T magnetic field indicate. A modified version of the Solomon theory of the two-spin echo amplitude for a spin-5/2 nucleus is developed and applied to the analysis of the O-17 echo signal of UO22+. The William R. Wiley environmental Molecular Sciences Laboratory is a US Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington. PNNL is operated by Battelle for the US Department of Energy.« less

Time-dependent water dynamics in hydrated uranyl fluoride

DOE PAGES

Miskowiec, Andrew J.; Anderson, Brian B.; Herwig, Kenneth W.; ...

2015-09-15

In this study, uranyl fluoride is a three-layer, hexagonal structure with significant stacking disorder in the c-direction. It supports a range of unsolved ‘thermodynamic’ hydrates with 0–2.5 water molecules per uranium atom, and perhaps more. However, the relationship between water, hydrate crystal structures, and thermodynamic results, collectively representing the chemical pathway through these hydrate structures, has not been sufficiently elucidated. We used high-resolution quasielastic neutron scattering to study the dynamics of water in partially hydrated uranyl fluoride powder over the course of 4 weeks under closed conditions. The spectra are composed of two quasielastic components: one is associated with translationalmore » diffusive motion of water that is approximately five to six times slower than bulk water, and the other is a slow (on the order of 2–300 ps), spatially bounded water motion. The translational component represents water diffusing between the weakly bonded layers in the crystal, while the bounded component may represent water trapped in subnanometre ‘pockets’ formed by the space between uranium-centred polymerisation units. Complementary neutron diffraction measurements do not show any significant structural changes, suggesting that a chemical conversion of the material does not occur in the thermodynamically isolated system on this timescale.« less

Synthesis and structure determination of uranyl peroxide nanospheres in the presence of organic structure directing agents

NASA Astrophysics Data System (ADS)

Forbes, T. Z.; Burns, P. C.

2007-12-01

Recently, actinyl peroxide nanoclusters containing 20, 24, 28, or 32 actinyl polyhedra have been synthesized and their structures identified with single crystal X-ray diffraction [1]. Most nanomaterials are composed of main group elements or transition metals, therefore, these actinyl nanospheres may display vastly different chemical and physical properties due to the presence of filled f-orbitals. A major goal of our research group is to create novel actinyl materials, focusing on nano- and mesoporous materials. The original nanosphere syntheses were limited to inorganic crystallization agents, such as monovalent cations. Over the last decade, the use of organic compounds and surfactants have received increased attention as structure-directing agents for the generation of novel inorganic materials. Using structure-directing organic amines we have successfully synthesized and determined the structures of uranyl nanospheres containing 40 and 50 uranyl polyhedra. The topology of the skeletal U-50 nanosphere is identical to the C50Cl10 fullerene [2]. The topographical relationship between the actinyl nanospheres and fullerene or fullerene-like material may provide additional insight into stable configurations for lower fullerenes. [1] Burns et al., Actinyl peroxide nanospheres. Angewandte Chemie, International Edition, 2005. 44(14): p. 2135. [2] Xie et al., Capturing the Labile Fullerene[50] as C50Cl10. Science, (2004) 305(5671): p. 699.

Establishing the traceability of a uranyl nitrate solution to a standard reference material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jackson, C.H.; Clark, J.P.

1978-01-01

A uranyl nitrate solution for use as a Working Calibration and Test Material (WCTM) was characterized, using a statistically designed procedure to document traceability to National Bureau of Standards Reference Material (SPM-960). A Reference Calibration and Test Material (PCTM) was prepared from SRM-960 uranium metal to approximate the acid and uranium concentration of the WCTM. This solution was used in the characterization procedure. Details of preparing, handling, and packaging these solutions are covered. Two outside laboratories, each having measurement expertise using a different analytical method, were selected to measure both solutions according to the procedure for characterizing the WCTM. Twomore » different methods were also used for the in-house characterization work. All analytical results were tested for statistical agreement before the WCTM concentration and limit of error values were calculated. A concentration value was determined with a relative limit of error (RLE) of approximately 0.03% which was better than the target RLE of 0.08%. The use of this working material eliminates the expense of using SRMs to fulfill traceability requirements for uranium measurements on this type material. Several years' supply of uranyl nitrate solution with NBS traceability was produced. The cost of this material was less than 10% of an equal quantity of SRM-960 uranium metal.« less

Thiocyanate complexes of uranium in multiple oxidation states: a combined structural, magnetic, spectroscopic, spectroelectrochemical, and theoretical study.

PubMed

Hashem, Emtithal; Platts, James A; Hartl, František; Lorusso, Giulia; Evangelisti, Marco; Schulzke, Carola; Baker, Robert J

2014-08-18

A comprehensive study of the complexes A4[U(NCS)8] (A = Cs, Et4N, (n)Bu4N) and A3[UO2(NCS)5] (A = Cs, Et4N) is described, with the crystal structures of [(n)Bu4N]4[U(NCS)8]·2MeCN and Cs3[UO2(NCS)5]·O0.5 reported. The magnetic properties of square antiprismatic Cs4[U(NCS)8] and cubic [Et4N]4[U(NCS)8] have been probed by SQUID magnetometry. The geometry has an important impact on the low-temperature magnetic moments: at 2 K, μeff = 1.21 μB and 0.53 μB, respectively. Electronic absorption and photoluminescence spectra of the uranium(IV) compounds have been measured. The redox chemistry of [Et4N]4[U(NCS)8] has been explored using IR and UV-vis spectroelectrochemical methods. Reversible 1-electron oxidation of one of the coordinated thiocyanate ligands occurs at +0.22 V vs Fc/Fc(+), followed by an irreversible oxidation to form dithiocyanogen (NCS)2 which upon back reduction regenerates thiocyanate anions coordinating to UO2(2+). NBO calculations agree with the experimental spectra, suggesting that the initial electron loss of [U(NCS)8](4-) is delocalized over all NCS(-) ligands. Reduction of the uranyl(VI) complex [Et4N]3[UO2(NCS)5] to uranyl(V) is accompanied by immediate disproportionation and has only been studied by DFT methods. The bonding in [An(NCS)8](4-) (An = Th, U) and [UO2(NCS)5](3-) has been explored by a combination of DFT and QTAIM analysis, and the U-N bonds are predominantly ionic, with the uranyl(V) species more ionic that the uranyl(VI) ion. Additionally, the U(IV)-NCS ion is more ionic than what was found for U(IV)-Cl complexes.

Perrhenate complexation by uranyl in traditional solvents and in ionic liquids: a joint molecular dynamics/spectroscopic study.

PubMed

Chaumont, Alain; Klimchuk, Olga; Gaillard, Clotilde; Billard, Isabelle; Ouadi, Ali; Hennig, Christoph; Wipff, Georges

2012-03-15

The complexation of perrhenate (ReO(4)(-)) anions by the uranyl (UO(2)(2+)) cation has been investigated by joint molecular dynamics simulations and spectroscopic (UV-vis, TRLFS, and EXAFS) studies in aqueous solution, acetonitrile, and three ionic liquids (ILs), namely, [Bmi][Tf(2)N], [Me(3)BuN][Tf(2)N], and [Bu(3)MeN][Tf(2)N] that are based on the same Tf(2)N(-) anion (bis(trifluoromethylsulfonyl)imide) and either Bmi(+) (1-butyl,3-methylimidazolium), Me(3)BuN(+), or Bu(3)MeN(+) cations. They show that ReO(4)(-) behaves as a weak ligand in aqueous solution and as a strong ligand in acetonitrile and in the ILs. According to MD simulations in aqueous solution, the UO(2)(ReO(4))(2) complex quickly dissociates to form UO(2)(H(2)O)(5)(2+), while in acetonitrile, a stable UO(2)(ReO(4))(5)(3-) species forms from dissociated ions. In the ILs, the UO(2)(ReO(4))(n)(2-n) complexes (n = 1 to 5) remained stable along the dynamics, and to assess their relative stabilities, we computed the free energy profiles for stepwise ReO(4)(-) complexation to uranyl. In the two studied ILs, complexation is favored, leading to the UO(2)(ReO(4))(5)(3-) species in [Bmi][Tf(2)N] and to UO(2)(ReO(4))(4)(2-) in [Bu(3)MeN][Tf(2)N]. Furthermore, in both acetonitrile and [Bmi][Tf(2)N] solutions, MD and PMF simulations support the formation of dimeric uranyl complexes [UO(2)(ReO(4))(4)](2)(4-) with two bridging ReO(4)(-) ligands. The simulation results are qualitatively consistent with spectroscopic observations in the different solvents, without firmly concluding, however, on the precise composition and structure of the complexes in the solutions. © 2012 American Chemical Society

Nuclear proliferomics: A new field of study to identify signatures of nuclear materials as demonstrated on alpha-UO3.

PubMed

Schwerdt, Ian J; Brenkmann, Alexandria; Martinson, Sean; Albrecht, Brent D; Heffernan, Sean; Klosterman, Michael R; Kirkham, Trenton; Tasdizen, Tolga; McDonald Iv, Luther W

2018-08-15

The use of a limited set of signatures in nuclear forensics and nuclear safeguards may reduce the discriminating power for identifying unknown nuclear materials, or for verifying processing at existing facilities. Nuclear proliferomics is a proposed new field of study that advocates for the acquisition of large databases of nuclear material properties from a variety of analytical techniques. As demonstrated on a common uranium trioxide polymorph, α-UO 3 , in this paper, nuclear proliferomics increases the ability to improve confidence in identifying the processing history of nuclear materials. Specifically, α-UO 3 was investigated from the calcination of unwashed uranyl peroxide at 350, 400, 450, 500, and 550 °C in air. Scanning electron microscopy (SEM) images were acquired of the surface morphology, and distinct qualitative differences are presented between unwashed and washed uranyl peroxide, as well as the calcination products from the unwashed uranyl peroxide at the investigated temperatures. Differential scanning calorimetry (DSC), UV-Vis spectrophotometry, powder X-ray diffraction (p-XRD), and thermogravimetric analysis-mass spectrometry (TGA-MS) were used to understand the source of these morphological differences as a function of calcination temperature. Additionally, the SEM images were manually segmented using Morphological Analysis for MAterials (MAMA) software to identify quantifiable differences in morphology for three different surface features present on the unwashed uranyl peroxide calcination products. No single quantifiable signature was sufficient to discern all calcination temperatures with a high degree of confidence; therefore, advanced statistical analysis was performed to allow the combination of a number of quantitative signatures, with their associated uncertainties, to allow for complete discernment by calcination history. Furthermore, machine learning was applied to the acquired SEM images to demonstrate automated discernment with at least 89% accuracy. Copyright © 2018 Elsevier B.V. All rights reserved.

Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with Fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry.

PubMed

Pasilis, Sofie; Somogyi, Arpád; Herrmann, Kristin; Pemberton, Jeanne E

2006-02-01

Electrospray ionization (ESI) of uranyl nitrate solutions generates a wide variety of positively and negatively charged ions, including complex adducts of uranyl ions with methoxy, hydroxy, and nitrate ligands. In the positive ion mode, ions detected by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry are sensitive to instrumental tuning parameters such as quadrupole operating frequency and trapping time. Positive ions correspond to oligomeric uranyl nitrate species that can be characterized as having a general formula of [(UO(2))(n)(A)(m)(CH(3)OH)(s)](+) or [(UO(2))(n)(O)(A)(m)(CH(3)OH)(s)](+) with n = 1-4, m = 1-7, s = 0 or 1, and A = OH, NO(3), CH(3)O or a combination of these, although the formation of NO(3)-containing species is preferred. In the negative ion mode, complexes of the form [(UO(2))(NO(3))(m)](-) (m = 1-3) are detected, although the formation of the oxo-containing ions [(UO(2))(O)(n)(NO(3))(m)](-) (n = 1-2, m = 1-2) and the hydroxy-containing ions [(UO(2))(OH)(n)(NO(3))(m)](-) (n = 1-2, m = 0-1) are also observed. The extent of coordinative unsaturation of both positive and negative ions can be determined by ligand association/exchange and H/D exchange experiments using D(2)O and CD(3)OD as neutral reaction partners in the gas-phase. Positive ions are of varying stability and reactivity and may fragment extensively upon collision with D(2)O, CD(3)OD and N(2) in sustained off-resonance irradiation/collision-induced dissociation (SORI-CID) experiments. Electron-transfer reactions, presumably occurring during electrospray ionization but also in SORI-CID, can result in reduction of U(VI) to U(V) and perhaps even U(IV).

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

DOE PAGES

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; ...

2017-10-24

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

Incorporation mechanisms of actinide elements into the structures of U 6+ phases formed during the oxidation of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Burns, Peter C.; Ewing, Rodney C.; Miller, Mark L.

1997-05-01

Uranyl oxide hydrate and uranyl silicate phases will form due to the corrosion and alteration of spent nuclear fuel under oxidizing conditions in silica-bearing solution. The actinide elements in the spent fuel may be incorporated into the structures of these secondary U6+ phases during the long-term corrosion of the UO 2 in spent fuel. The incorporation of actinide elements into the crystal structures of the alteration products may decrease actinide mobility. The crystal chemistry of the various oxidation states of the actinide elements of environmental concern is examined to identify possible incorporation mechanisms. The substitutions Pu 6+U 6+ and (Pu 5+, Np 5+)U 6+ should readily occur in many U 6+ structures, although structural modification may be required to satisfy local bond-valence requirements. Crystal-chemical characteristics of the U 6+ phases indicate that An 4+ (An: actinide)U 6+ substitution is likely to occur in the sheets of uranyl polyhedra that occur in the structures of the minerals schoepite, [(UO 2) 8O 2(OH) 12](H 2O) 12, ianthinite, [U 24+ (UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5, becquerelite, Ca[(UO 2) 3O 2(OH) 3] 2(H 2O) 8, compreignacite, K 2[(UO 2) 3O 2(OH) 3] 2(H 2O) 8, α-uranophane, Ca[(UO 2)(SiO 3OH)] 2(H 2O) 5, and boltwoodite, K(H 2O)[(UO 2)(SiO 4)], all of which are likely to form due to the oxidation and alteration of the UO 2 in spent fuel. The incorporation of An 3+ into the sheets of the structures of α-uranophane and boltwoodite, as well as interlayer sites of various uranyl phases, may occur.

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

NASA Astrophysics Data System (ADS)

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; Runde, W.; Roback, R.; Williams-Jones, A. E.

2018-02-01

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO22+, UO2Cl+, and UO2Cl2°. UO2Cl3- is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species show fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO2Cl42- and UO2Cl53- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T > 150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO2Cl2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO22+ + Cl- = UO2Cl+ are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO22+ + 2Cl- = UO2Cl2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.

Oil Market Assessment

EIA Publications

2001-01-01

Based on Energy Information Administration (EIA) contacts and trade press reports, overall U.S. and global oil supplies appear to have been minimally impacted by yesterday's terrorist attacks on the World Trade Center and the Pentagon.

United States Department of Defense (defense.gov)

Science.gov Websites

is Important for Army's Future Odierno Thanks Press During Briefing at Pentagon Purple Heart Trail Heart Trail Inspires Reflection Army General Honored in Memorial Ceremony Stratcom Commander Discusses

Rational Ligand Design for U(VI) and Pu(IV)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szigethy, Geza

2009-08-12

Nuclear power is an attractive alternative to hydrocarbon-based energy production at a time when moving away from carbon-producing processes is widely accepted as a significant developmental need. Hence, the radioactive actinide power sources for this industry are necessarily becoming more widespread, which is accompanied by the increased risk of exposure to both biological and environmental systems. This, in turn, requires the development of technology designed to remove such radioactive threats efficiently and selectively from contaminated material, whether that be contained nuclear waste streams or the human body. Raymond and coworkers (University of California, Berkeley) have for decades investigated the interactionmore » of biologically-inspired, hard Lewis-base ligands with high-valent, early-actinide cations. It has been established that such ligands bind strongly to the hard Lewis-acidic early actinides, and many poly-bidentate ligands have been developed and shown to be effective chelators of actinide contaminants in vivo. Work reported herein explores the effect of ligand geometry on the linear U(IV) dioxo dication (uranyl, UO 2 2+). The goal is to utilize rational ligand design to develop ligands that exhibit shape selectivity towards linear dioxo cations and provides thermodynamically favorable binding interactions. The uranyl complexes with a series of tetradentate 3-hydroxy-pyridin-2-one (3,2-HOPO) ligands were studied in both the crystalline state as well as in solution. Despite significant geometric differences, the uranyl affinities of these ligands vary only slightly but are better than DTPA, the only FDA-approved chelation therapy for actinide contamination. The terepthalamide (TAM) moiety was combined into tris-beidentate ligands with 1,2- and 3,2-HOPO moieties were combined into hexadentate ligands whose structural preferences and solution thermodynamics were measured with the uranyl cation. In addition to achieving coordinative saturation, these ligands exhibited increased uranyl affinity compared to bis-Me-3,2-HOPO ligands. This result is due in part to their increased denticity, but is primarily the result of the presence of the TAM moiety. In an effort to explore the relatively unexplored coordination chemistry of Pu(IV) with bidentate moieties, a series of Pu(IV) complexes were also crystallized using bidentate hydroxypyridinone and hydroxypyrone ligands. The geometries of these complexes are compared to that of the analogous Ce(IV) complexes. While in some cases these showed the expected structural similarities, some ligand systems led to significant coordination changes. A series of crystal structure analyses with Ce(IV) indicated that these differences are most likely the result of crystallization condition differences and solvent inclusion effects.« less

Puzzles Pastimes Problems.

ERIC Educational Resources Information Center

Eperson, D. B.

1991-01-01

This section includes eight problems to which the journal invites readers to respond. Problem topics include angles in alternate segments, pentominoes, a new triangle of numbers, cricket scores, symmetrical pentagons, inequalities, a pythagorean dissection, and magic squares. (MDH)

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Internal friction and absence of dilatancy of packings of frictionless polygons.

PubMed

Azéma, Émilien; Radjaï, Farhang; Roux, Jean-Noël

2015-01-01

By means of numerical simulations, we show that assemblies of frictionless rigid pentagons in slow shear flow possess an internal friction coefficient (equal to 0.183±0.008 with our choice of moderately polydisperse grains) but no macroscopic dilatancy. In other words, despite side-side contacts tending to hinder relative particle rotations, the solid fraction under quasistatic shear coincides with that of isotropic random close packings of pentagonal particles. Properties of polygonal grains are thus similar to those of disks in that respect. We argue that continuous reshuffling of the force-bearing network leads to frequent collapsing events at the microscale, thereby causing the macroscopic dilatancy to vanish. Despite such rearrangements, the shear flow favors an anisotropic structure that is at the origin of the ability of the system to sustain shear stress.

A structural analysis of small vapor-deposited 'multiply twinned' gold particles

NASA Technical Reports Server (NTRS)

Yang, C. Y.; Heinemann, K.; Yacaman, M. J.; Poppa, H.

1979-01-01

High resolution selected zone dark field, Bragg reflection imaging and weak beam dark field techniques of transmission electron microscopy were used to determine the structure of small gold particles vapor deposited on NaCl substrates. Attention was focused on the analysis of those particles in the 50-150 A range that have pentagonal or hexagonal bright field profiles. These particles have been previously described as multiply twinned crystallites composed of face-centered cubic tetrahedra. The experimental evidence of the present studies can be interpreted on the assumption that the particle structure is a regular icosahedron or decahedron for the hexagonal or the pentagonal particles respectively. The icosahedron is a multiply twinned rhombohedral crystal and the decahedron is a multiply twinned body-centered orthorhombic crystal, each of which constitutes a slight distortion from the face-centered cubic structure.

A jellium model of a catalyst particle in carbon nanotube growth

NASA Astrophysics Data System (ADS)

Artyukhov, Vasilii I.; Liu, Mingjie; Penev, Evgeni S.; Yakobson, Boris I.

2017-06-01

We show how a jellium model can represent a catalyst particle within the density-functional theory based approaches to the growth mechanism of carbon nanotubes (CNTs). The advantage of jellium is an abridged, less computationally taxing description of the multi-atom metal particle, while at the same time in avoiding the uncertainty of selecting a particular atomic geometry of either a solid or ever-changing liquid catalyst particle. A careful choice of jellium sphere size and its electron density as a descriptive parameter allows one to calculate the CNT-metal interface energies close to explicit full atomistic models. Further, we show that using jellium permits computing and comparing the formation of topological defects (sole pentagons or heptagons, the culprits of growth termination) as well as pentagon-heptagon pairs 5|7 (known as chirality-switching dislocation).

Synthesis and isolation of [Fe@Ge(10)](3-): a pentagonal prismatic Zintl ion cage encapsulating an interstitial iron atom.

PubMed

Zhou, Binbin; Denning, Mark S; Kays, Deborah L; Goicoechea, Jose M

2009-03-04

Reaction of an ethylenediamine (en) solution of the Zintl phase precursor K(4)Ge(9) with FeAr(2) (Ar = 2,6-Mes(2)C(6)H(3)) in the presence of 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) yielded the endohedral Zintl ion [Fe@Ge(10)](3-) (1) which was crystallographically characterized as a [K(2,2,2-crypt)](+) salt in [K(2,2,2-crypt)](3)[Fe@Ge(10)]*2en. This unprecedented Zintl ion exhibits a pentagonal prismatic 10-atom germanium cage with an interstitial iron atom in the central cavity. Confirmation of the existence of the cluster anion in solution was corroborated by positive and negative ion mode electrospray mass spectrometry.

Digitized Speech Characteristics in Patients with Maxillectomy Defects.

PubMed

Elbashti, Mahmoud E; Sumita, Yuka I; Hattori, Mariko; Aswehlee, Amel M; Taniguchi, Hisashi

2017-12-06

Accurate evaluation of speech characteristics through formant frequency measurement is important for proper speech rehabilitation in patients after maxillectomy. This study aimed to evaluate the utility of digital acoustic analysis and vowel pentagon space for the prediction of speech ability after maxillectomy, by comparing the acoustic characteristics of vowel articulation in three classes of maxillectomy defects. Aramany's classifications I, II, and IV were used to group 27 male patients after maxillectomy. Digital acoustic analysis of five Japanese vowels-/a/, /e/, /i/, /o/, and /u/-was performed using a speech analysis system. First formant (F1) and second formant (F2) frequencies were calculated using an autocorrelation method. Data were plotted on an F1-F2 plane for each patient, and the F1 and F2 ranges were calculated. The vowel pentagon spaces were also determined. One-way ANOVA was applied to compare all results between the three groups. Class II maxillectomy patients had a significantly higher F2 range than did Class I and Class IV patients (p = 0.002). In contrast, there was no significant difference in the F1 range between the three classes. The vowel pentagon spaces were significantly larger in class II maxillectomy patients than in Class I and Class IV patients (p = 0.014). The results of this study indicate that the acoustic characteristics of maxillectomy patients are affected by the defect area. This finding may provide information for obturator design based on vowel articulation and defect class. © 2017 by the American College of Prosthodontists.

Method for monitoring stack gases for uranium activity

DOEpatents

Beverly, C.R.; Ernstberger, E.G.

1985-07-03

A method for monitoring the stack gases of a purge cascade of gaseous diffusion plant for uranium activity. A sample stream is taken from the stack gases and contacted with a volume of moisture-laden air for converting trace levels of uranium hexafluoride, if any, in the stack gases into particulate uranyl fluoride. A continuous strip of filter paper from a supply roll is passed through this sampling stream to intercept and gather any uranyl fluoride in the sampling stream. This filter paper is then passed by an alpha scintillation counting device where any radioactivity on the filter paper is sensed so as to provide a continuous monitoring of the gas stream for activity indicative of the uranium content in the stack gases. 1 fig.

Method for monitoring stack gases for uranium activity

DOEpatents

Beverly, Claude R.; Ernstberger, Harold G.

1988-01-01

A method for monitoring the stack gases of a purge cascade of a gaseous diffusion plant for uranium activity. A sample stream is taken from the stack gases and contacted with a volume of moisture-laden air for converting trace levels of uranium hexafluoride, if any, in the stack gases into particulate uranyl fluoride. A continuous strip of filter paper from a supply roll is passed through this sampling stream to intercept and gather any uranyl fluoride in the sampling stream. This filter paper is then passed by an alpha scintillation counting device where any radioactivity on the filter paper is sensed so as to provide a continuous monitoring of the gas stream for activity indicative of the uranium content in the stack gases.

SEPARATION OF URANIUM FROM THORIUM AND PROTACTINIUM

DOEpatents

Musgrave, W.K.R.

1959-06-30

This patent relates to the separation of uranium from thorium and protactinium; such mixtures of elements usually being obtained by neutron irradiation of thorium. The method of separating the constituents has been first to dissolve the mixture of elements in concertrated nitric acid and then to remove the protactinium by absorption on manganese dioxide and the uranium by solvent extraction with ether. Prior to now, comparatively large amounts of thorium were extracted with the uranium. According to the invention this is completely prevented by adding sodium diethyldithiocarbamate to the mixture of soluble nitrate salts. The organic salt has the effect of reacting only with the uranyl nitrate to form the corresponding uranyl salt which can then be selectively extracted from the mixture with amyl acetate.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schoendorff, George E.; De Jong, Wibe A.; Gordon, Mark S.

The formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands, [UO2(H2O)n(RCN)m]2+, has been studied using density functional theory (DFT) with a relativistic effective core potential (RECP) to account for scalar relativistic effects on uranium. It is shown that nitrile addition is favored over the addition of water ligands. Decomposition of these complexes to [UO2OH(H2O)n(RCN)m]+ by the loss of either H3O+ or (RCN+H)+ is also examined. It is found that this reaction occurs when the coordination sphere of uranyl is unsaturated. Additionally, this reaction is influenced by the size of the nitrile ligand with reactions involvingmore » acetonitrile being the most prevalent.« less

Performance of a hydrogen uranyl phosphate-carbon double-layer solid capacitor

NASA Astrophysics Data System (ADS)

Pham-Thi, M.; Adet, Ph.; Velasco, G.; Colomban, Ph.

1986-05-01

A mixture of commercially available carbon black (C) powders and hydrogen uranyl phosphate (HUP) precipitate can be used as the electrode material for miniaturized double-layer capacitors. A solid cell of C-HUP/HUP/C-HUP has a capacitance of 1 F which, given the device area and thickness of 0.8 sq cm and 0.2 cm respectively, corresponds to an energy density of more than 5 J/cu cm. The charge x voltage factor is higher than 5 x 10 to the -6th s and the working voltage is over 1.6 V. The leakage current is lower than 3 microamps at room temperature. The electrolyte can be operated up to about 120 C if the device is hermetically sealed.

Laser removal of loose uranium compound contamination from metal surfaces

NASA Astrophysics Data System (ADS)

Roberts, D. E.; Modise, T. S.

2007-04-01

Pulsed laser removal of surface contamination of uranyl nitrate and uranium dioxide from stainless steel has been studied. Most of the loosely bound contamination has been removed at fluence levels below 0.5 J cm -2, leaving about 5% fixed contamination for uranyl nitrate and 15% for uranium dioxide. Both alpha and beta activities are then sufficiently low that contaminated objects can be taken out of a restricted radiation area for re-use. The ratio of beta to alpha activity is found to be a function of particle size and changes during laser removal. In a separate experiment using technetium-99m, the collection of removed radioactivity in the filter was studied and an inventory made of removed and collected contamination.

Syntheses, structures, and properties of imidazolate-bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) dinuclear complexes of a single macrocyclic ligand with two hydroxyethyl pendants.

PubMed

Li, Dongfeng; Li, Shuan; Yang, Dexi; Yu, Jiuhong; Huang, Jin; Li, Yizhi; Tang, Wenxia

2003-09-22

The imidazolate-bridged homodinuclear Cu(II)-Cu(II) complex, [(CuimCu)L]ClO(4).0.5H(2)O (1), and heterodinuclear Cu(II)-Zn(II) complex, [(CuimZnL(-)(2H))(CuimZnL(-)(H))](ClO(4))(3) (2), of a single macrocyclic ligand with two hydroxyethyl pendants, L (L = 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)tricyclo[22,2,2,2(11,14)]triaconta-1,11,13,24,27,29-hexaene), have been synthesized as possible models for copper-zinc superoxide dismutase (Cu(2),Zn(2)-SOD). Their crystal structures analyzed by X-ray diffraction methods have shown that the structures of the two complexes are markedly different. Complex 1 crystallizes in the orthorhombic system, containing an imidazolate-bridged dicopper(II) [Cu-im-Cu](3+) core, in which the two copper(II) ions are pentacoordinated by virtue of an N4O environment with a Cu.Cu distance of 5.999(2) A, adopting the geometry of distorted trigonal bipyramid and tetragonal pyramid, respectively. Complex 2 crystallizes in the triclinic system, containing two similar Cu-im-Zn cores in the asymmetric unit, in which both the Cu(II) and Zn(II) ions are pentacoordinated in a distorted trigonal bipyramid geometry, with the Cu.Zn distance of 5.950(1)/5.939(1) A, respectively. Interestingly, the macrocyclic ligand with two arms possesses a chairlike (anti) conformation in complex 1, but a boatlike (syn) conformation in complex 2. Magnetic measurements and ESR spectroscopy of complex 1 have revealed the presence of an antiferromagnetic exchange interaction between the two Cu(II) ions. The ESR spectrum of the Cu(II)-Zn(II) heterodinuclear complex 2 displayed a typical signal for mononuclear trigonal bipyramidal Cu(II) complexes. From pH-dependent ESR and electronic spectroscopic studies, the imidazolate bridges in the two complexes have been found to be stable over broad pH ranges. The cyclic voltammograms of the two complexes have been investigated. Both of the two complexes can catalyze the dismutation of superoxide and show rather high activity.

76 FR 18197 - Privacy Act of 1974; System of Records

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American hospitals react to terrorist attacks with determination.

PubMed

Rees, T

2001-01-01

In this timely special section, editor Tom Rees recounts some of the swift, supportive actions health care providers took in response to the Sept. 11 terrorist attacks on the World Trade Center and the Pentagon.

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Retirement Equity for Pentagon Police Heroes Act of 2011

THOMAS, 112th Congress

Sen. Akaka, Daniel K. [D-HI

2011-09-12

Senate - 09/12/2011 Read twice and referred to the Committee on Homeland Security and Governmental Affairs. (All Actions) Tracker: This bill has the status IntroducedHere are the steps for Status of Legislation:

Oxidation and Hydration of U 3O 8 Materials Following Controlled Exposure to Temperature and Humidity

DOE PAGES

Tamasi, Alison L.; Boland, Kevin S.; Czerwinski, Kenneth; ...

2015-03-18

Chemical signatures correlated with uranium oxide processing are of interest to forensic science for inferring sample provenance. Identification of temporal changes in chemical structures of process uranium materials as a function of controlled temperatures and relative humidities may provide additional information regarding sample history. In our study, a high-purity α-U 3O 8 sample and three other uranium oxide samples synthesized from reaction routes used in nuclear conversion processes were stored under controlled conditions over 2–3.5 years, and powder X-ray diffraction analysis and X-ray absorption spectroscopy were employed to characterize chemical speciation. We measured signatures from the α-U 3O 8 samplemore » indicated that the material oxidized and hydrated after storage under high humidity conditions over time. Impurities, such as uranyl fluoride or schoepites, were initially detectable in the other uranium oxide samples. After storage under controlled conditions, the analyses of the samples revealed oxidation over time, although the signature of the uranyl fluoride impurity diminished. The presence of schoepite phases in older uranium oxide material is likely indicative of storage under high humidity and should be taken into account for assessing sample history. Finally, the absence of a signature from a chemical impurity, such as uranyl fluoride hydrate, in an older material may not preclude its presence at the initial time of production.« less

Inducing fluorescence of uranyl acetate as a dual-purpose contrast agent for correlative light-electron microscopy with nanometre precision.

PubMed

Tuijtel, Maarten W; Mulder, Aat A; Posthuma, Clara C; van der Hoeven, Barbara; Koster, Abraham J; Bárcena, Montserrat; Faas, Frank G A; Sharp, Thomas H

2017-09-05

Correlative light-electron microscopy (CLEM) combines the high spatial resolution of transmission electron microscopy (TEM) with the capability of fluorescence light microscopy (FLM) to locate rare or transient cellular events within a large field of view. CLEM is therefore a powerful technique to study cellular processes. Aligning images derived from both imaging modalities is a prerequisite to correlate the two microscopy data sets, and poor alignment can limit interpretability of the data. Here, we describe how uranyl acetate, a commonly-used contrast agent for TEM, can be induced to fluoresce brightly at cryogenic temperatures (-195 °C) and imaged by cryoFLM using standard filter sets. This dual-purpose contrast agent can be used as a general tool for CLEM, whereby the equivalent staining allows direct correlation between fluorescence and TEM images. We demonstrate the potential of this approach by performing multi-colour CLEM of cells containing equine arteritis virus proteins tagged with either green- or red-fluorescent protein, and achieve high-precision localization of virus-induced intracellular membrane modifications. Using uranyl acetate as a dual-purpose contrast agent, we achieve an image alignment precision of ~30 nm, twice as accurate as when using fiducial beads, which will be essential for combining TEM with the evolving field of super-resolution light microscopy.

Distribution of ciprofloxacin into the central nervous system in rats with acute renal or hepatic failure.

PubMed

Naora, K; Ichikawa, N; Hirano, H; Iwamoto, K

1999-05-01

Pharmacokinetic changes of various drugs have been reported in renal or hepatic failure. The present study employed ciprofloxacin, a quinolone antibiotic having neurotoxic side effects, to assess the influence of these diseases on distribution of ciprofloxacin into the central nervous system (CNS). After intravenous dosing of ciprofloxacin (10-30 mg kg(-1)), ciprofloxacin levels in plasma and brain were measured in normal rats (Wistar, male, 10-week-old) and those with acute renal and hepatic injuries which were induced by uranyl nitrate and carbon tetrachloride (CCl4), respectively. In the uranyl nitrate-treated rats, the plasma elimination half-life of ciprofloxacin was prolonged and the total body clearance was reduced when compared with those in the normal rats. Similar but smaller changes were observed in the CCl4-treated group. Brain levels of ciprofloxacin were significantly increased by both uranyl nitrate and CCl4 treatments. A proportional correlation between serum unbound levels and brain levels of ciprofloxacin was observed in the normal group. However, brain-to-serum unbound concentration ratios of ciprofloxacin were reduced in the rats with renal or hepatic failure. These results suggest that renal failure as well as hepatic failure retards elimination of ciprofloxacin from the blood, leading to elevation of the CNS level, and also that ciprofloxacin distribution in the brain is reduced in these disease states.

Oxidation and Hydration of U 3 O 8 Materials Following Controlled Exposure to Temperature and Humidity

DOE PAGES

Tamasi, Alison L.; Boland, Kevin S.; Czerwinski, Kenneth; ...

2015-03-18

Chemical signatures correlated with uranium oxide processing are of interest to forensic science for inferring sample provenance. Identification of temporal changes in chemical structures of process uranium materials as a function of controlled temperatures and relative humidities may provide additional information regarding sample history. In our study, a high-purity α-U 3O 8 sample and three other uranium oxide samples synthesized from reaction routes used in nuclear conversion processes were stored under controlled conditions over 2–3.5 years, and powder X-ray diffraction analysis and X-ray absorption spectroscopy were employed to characterize chemical speciation. We measured signatures from the α-U 3O 8 samplemore » indicated that the material oxidized and hydrated after storage under high humidity conditions over time. Impurities, such as uranyl fluoride or schoepites, were initially detectable in the other uranium oxide samples. After storage under controlled conditions, the analyses of the samples revealed oxidation over time, although the signature of the uranyl fluoride impurity diminished. The presence of schoepite phases in older uranium oxide material is likely indicative of storage under high humidity and should be taken into account for assessing sample history. Finally, the absence of a signature from a chemical impurity, such as uranyl fluoride hydrate, in an older material may not preclude its presence at the initial time of production. LA-UR-15-21495.« less

Coordination trends in alkali metal crown ether uranyl halide complexes: the series [A(crown)]2[UO(2)X(4)] where A=Li, Na, K and X=Cl, Br.

PubMed

Danis, J A; Lin, M R; Scott, B L; Eichhorn, B W; Runde, W H

2001-07-02

UO(2)(C(2)H(3)O(2))(2).2H(2)O reacts with AX or A(C(2)H(3)O(2) or ClO(4)) (where A = Li, Na, K; X = Cl, Br) and crown ethers in HCl or HBr aqueous solutions to give the sandwich-type compounds [K(18-crown-6)](2)[UO(2)Cl(4)] (1), [K(18-crown-6)](2)[UO(2)Br(4)] (2), [Na(15-crown-5)](2)[UO(2)Cl(4)] (3), [Na(15-crown-5)](2)[UO(2)Br(4)] (4), [Li(12-crown-4)](2)[UO(2)Cl(4)] (5), and [Li(12-crown-4)](2)[UO(2)Br(4)] (6). The compounds have been characterized by single-crystal X-ray diffraction, powder diffraction, elemental analysis, IR, and Raman spectroscopy. The [UO(2)X(4)](2-) ions coordinate to two [A(crown)](+) cations through the four halides only (2), through two halides only (3), through the two uranyl oxygens and two halides (3, 4), or through the two uranyl oxygen atoms only (5, 6). Raman spectra reveal nu(U-O) values that correlate with expected trends. The structural trends are discussed within the context of classical principles of hard-soft acid-base theory.

48 CFR 216.504 - Indefinite-quantity contracts.

Code of Federal Regulations, 2011 CFR

2011-10-01

... Deputy Director, Defense Procurement and Acquisition Policy (Contract Policy and International... Policy and International Contracting), OUSD (AT&L) DPAP (CPIC), 3060 Defense Pentagon, Washington, DC... contracts. 216.504 Section 216.504 Federal Acquisition Regulations System DEFENSE ACQUISITION REGULATIONS...

48 CFR 217.7402 - Exceptions.

Code of Federal Regulations, 2011 CFR

2011-10-01

... Acquisition Policy (Contract Policy and International Contracting), 3060 Defense Pentagon, Washington, DC... OF DEFENSE CONTRACTING METHODS AND CONTRACT TYPES SPECIAL CONTRACTING METHODS Undefinitized Contract Actions 217.7402 Exceptions. (a) The following undefinitized contract actions (UCAs) are not subject to...

The Impact of "Instant Analysis"

ERIC Educational Resources Information Center

Robinson, Michael Jay

1977-01-01

Assesses the impact of critical extemporaneous commentary following the major television presentation of "The Selling of the Pentagon" and concludes that immediate analysis tends to diminish program effectiveness and reflect negatively on the person responsible for the analysis. (MH)

Evidence of van Hove singularities in ordered grain boundaries of graphene.

PubMed

Ma, Chuanxu; Sun, Haifeng; Zhao, Yeliang; Li, Bin; Li, Qunxiang; Zhao, Aidi; Wang, Xiaoping; Luo, Yi; Yang, Jinlong; Wang, Bing; Hou, J G

2014-06-06

It has long been under debate whether the electron transport performance of graphene could be enhanced by the possible occurrence of van Hove singularities in grain boundaries. Here, we provide direct experimental evidence to confirm the existence of van Hove singularity states close to the Fermi energy in certain ordered grain boundaries using scanning tunneling microscopy. The intrinsic atomic and electronic structures of two ordered grain boundaries, one with alternative pentagon and heptagon rings and the other with alternative pentagon pair and octagon rings, are determined. It is firmly verified that the carrier concentration and, thus, the conductance around ordered grain boundaries can be significantly enhanced by the van Hove singularity states. This finding strongly suggests that a graphene nanoribbon with a properly embedded ordered grain boundary can be a promising structure to improve the performance of graphene-based electronic devices.

Performance and Maqasid al-Shari'ah's Pentagon-Shaped Ethical Measurement.

PubMed

Bedoui, Houssem Eddine; Mansour, Walid

2015-06-01

Business performance is traditionally viewed from the one-dimensional financial angle. This paper develops a new approach that links performance to the ethical vision of Islam based on maqasid al-shari'ah (i.e., the objectives of Islamic law). The approach involves a Pentagon-shaped performance scheme structure via five pillars, namely wealth, posterity, intellect, faith, and human self. Such a scheme ensures that any firm or organization can ethically contribute to the promotion of human welfare, prevent corruption, and enhance social and economic stability and not merely maximize its own performance in terms of its financial return. A quantitative measure of ethical performance is developed. It surprisingly shows that a firm or organization following only the financial aspect at the expense of the others performs poorly. This paper discusses further the practical instances of the quantitative measurement of the ethical aspects of the system taken at an aggregate level.

Ru(II) complexes containing chelating phosphine ligands. Synthesis, characterizatin, and x-ray crystal structures of dichlorobis (1,2-bis(diphenylphosphino)ethane)Ru(II) and the coordinatetively unsaturated trigonal-bipyramidal cation, chlorobis(1,2-bis(diphenylphosphino)ethane)Ru(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polam, J.R.; Porter, L.C.

1993-01-01

The reaction of trans-RuCl[sub 2](dppe)[sub 2] (1), with AgBF[sub 4] in tetrahydrofuran leads to abstraction of one of the halide ligands to produce the trigonal-bipyrimidal complex. [RuCl(dppe)[sub 2

Composition for detecting uranyl

DOEpatents

Baylor, L.C.; Stephens, S.M.

1994-01-01

The present invention relates to an indicator composition for use in spectrophotometric detection of a substance in a solution, and a method for making the composition. Useful indicators are sensitive to the particular substance being measured, but are unaffected by the fluid and other chemical species that may be present in the fluid. Optical indicators are used to measure the uranium concentration of process solutions in facilities for extracting uranium from ores, production of nuclear fuels, and reprocessing of irradiated fuels. The composition comprises an organohalide covalently bonded to an indicator for the substance, in such a manner that the product is itself an indicator that provides increased spectral resolution for detecting the substance. The indicator is preferably arsenazo III and the organohalide is preferably cyanuric chloride. These form a composition that is ideally suited for detecting uranyl.

Controlled coordination in vanadium(V) dimethylhydrazido compounds.

PubMed

Sakuramoto, Takashi; Moriuchi, Toshiyuki; Hirao, Toshikazu

2016-11-01

The vanadium(V) dimethylhydrazido compounds were structurally characterized to elucidate the effect of the alkoxide ligands in the coordination environment of vanadium(V) hydrazido center. The single-crystal X-ray structure determination of the vanadium(V) dimethylhydrazido compound with isopropoxide ligands revealed a dimeric structure with the V(1)-N(1) distance of 1.680(5)Å, in which each vanadium atom is coordinated in a distorted trigonal-bipyramidal geometry (τ 5 =0.81) with the hydrazido and bridging isopropoxide ligands in the apical positions. On the contrary, nearly tetrahedral arrangement around the vanadium metal center (τ 4 =0.06) with the V(1)-N(1) distance of 1.660(2)Å was observed in the vanadium(V) dimethylhydrazido compound with tert-butoxide ligands. The introduction of the 2,2',2″-nitrilotriethoxide ligand led to a pseudo-trigonal-bipyramidal geometry (τ 5 =0.92) at the vanadium center with the V(1)-N(1) distance of 1.691(5)Å, wherein vanadium atom is pulled out of the plane formed by the nitrilotriethoxide oxygen atoms in the direction of the hydrazido nitrogen. The coordination from the apical ligand in the vanadium(V) dimethylhydrazido compound was found to result in the longer V(1)-N(1) distance. Copyright © 2016 Elsevier Inc. All rights reserved.

An insight to conserved water molecular dynamics of catalytic and structural Zn(+2) ions in matrix metalloproteinase 13 of human.

PubMed

Chakrabarti, Bornali; Bairagya, Hridoy R; Mallik, Payel; Mukhopadhyay, Bishnu P; Bera, Asim K

2011-02-01

Matrix Metalloproteinase (MMP)--13 or Collagenase--3 plays a significant role in the formation and remodeling of bone, tumor invasion and causes osteoarthritis. Water molecular dynamic studies of the five (1XUC, 1XUD, 1XUR, 456C, 830C) PDB and solvated structures of MMP-13 in human have been carried out upto 5 ns on assigning the differential charges (+2, +1, +0.5 e) to both the Zinc ions. The MM and MD-studies have revealed the coordination of three water molecules (W(H), W(I) and W(S)) to Zn(c) and one water to Zn(s). The transition of geometry around the Znc from tetrahedral to octahedral via trigonal bipyramidal, and for Zn(s) from tetrahedral to trigonal bipyramidal are seem interesting. Recognition of two zinc ions through water molecular bridging (Zn(c) - W(H) (W(1))...W(2)....W(3)....H(187) Zn(s)) and the stabilization of variable coordination geometries around metal ions may indicate the possible involvement of Zn(c) ...Zn(s) coupled mechanism in the catalytic process. So the hydrophilic topology and stereochemistry of water mediated coupling between Zn-ions may provide some plausible hope towards the design of some bidentate/polydentate bridging ligands or inhibitors for MMP-13.

Microstructural Characterization of Metal Foams: An Examination of the Applicability of the Theoretical Models for Modeling Foams. Revision 1

NASA Technical Reports Server (NTRS)

Raj, S. V.

2011-01-01

Establishing the geometry of foam cells is useful in developing microstructure-based acoustic and structural models. Since experimental data on the geometry of the foam cells are limited, most modeling efforts use an idealized three-dimensional, space-filling Kelvin tetrakaidecahedron. The validity of this assumption is investigated in the present paper. Several FeCrAlY foams with relative densities varying between 3 and 15 percent and cells per mm (c.p.mm.) varying between 0.2 and 3.9 c.p.mm. were microstructurally evaluated. The number of edges per face for each foam specimen was counted by approximating the cell faces by regular polygons, where the number of cell faces measured varied between 207 and 745. The present observations revealed that 50 to 57 percent of the cell faces were pentagonal while 24 to 28 percent were quadrilateral and 15 to 22 percent were hexagonal. The present measurements are shown to be in excellent agreement with literature data. It is demonstrated that the Kelvin model, as well as other proposed theoretical models, cannot accurately describe the FeCrAlY foam cell structure. Instead, it is suggested that the ideal foam cell geometry consists of 11 faces with three quadrilateral, six pentagonal faces and two hexagonal faces consistent with the 3-6-2 Matzke cell. A compilation of 90 years of experimental data reveals that the average number of cell faces decreases linearly with the increasing ratio of quadrilateral to pentagonal faces. It is concluded that the Kelvin model is not supported by these experimental data.

78 FR 18564 - Reserve Forces Policy Board (RFPB); Notice of Cancellation and Rescheduling of Federal Advisory...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-27

....m. in the Pentagon. Due to weather conditions and a federal government shutdown, the scheduled March... weather conditions and a federal government shutdown, the scheduled March 6, 2013 Board meeting is...

Terrorist Attacks Put Academic Freedom to the Test.

ERIC Educational Resources Information Center

Wilson, Robin; Cox, Ana Marie

2001-01-01

Explores how, in the aftermath of the airplane hijackings and deaths at New York's World Trade Center and the Pentagon, academic freedom may be under threat. Provides examples of student or administrative action against professors offering different viewpoints. (EV)

Time-Resolved Infrared Reflectance Studies of the Dehydration-Induced Transformation of Uranyl Nitrate Hexahydrate to the Trihydrate Form

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO2(NO3)2(H2O)6] often called UNH), the trihydrate [UO2(NO3)2(H2O)3 or UNT], and in very dry environments the dihydrate form [UO2(NO3)2(H2O)2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s the different phases were studied by infrared transmission spectroscopy, but were limited both by instrumental resolution and by the ability to prepare the samples for transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparationmore » and allows dynamic analysis while the sample is exposed to a flow of N2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO2(NO3)2(H2O)6 has a distinct uranyl asymmetric stretch band at 949.0 cm-1 that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm-1. The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO22+ sites. The dehydration of UO2(NO3)2(H2O)6 to UO2(NO3)2(H2O)3 is both a structural and morphological change that has the lustrous lime green UO2(NO3)2(H2O)6 crystals changing to the matte greenish yellow of the trihydrate solid. The phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with but one in the hexahydrate.« less

Uranyl Coordination Polymers Incorporating η5-Cyclopentadienyliron-Functionalized η6-Phthalate Metalloligands: Syntheses, Structures and Photophysical Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerr, Andrew T.; Kumalah, Sayon A.; Holman, K. T.

2013-10-06

The reaction of two η5-cyclopentadienyliron(II)-functionalized terephthalate and phthalate metalloligands, namely [(η5-C5H5)FeII(η6-1,4-HO2CC6H4CO2H)][(η5-C5H5)FeII(η6-1,4-HO2CC6H4CO2)][PF6] and [(η5-C5H5)FeII(η6-1,2-HO2CC6H4CO2H)][(η5-C5H5)FeII(η6-1,2-HO2CC6H4CO2)][PF6]—hereafter [H2 CpFeTP][HCpFeTP][PF6] and [H2 CpFeP][HCpFeP][PF6], respectively—with [UO2(NO3)2]·6H2O under hydrothermal conditions yielded four new coordination polymers; (1) [(UO2)F(HCpFeTP)(PO4H2)]·2H2O, (2) [(UO2)2(CpFeTP)4]·5H2O, (3) [(UO2)2F3(H2O)(CpFeP)], and (4) [H2 CpFeP][UO2F3]. The use of metalloligands has proven to be a viable route towards the incorporation of a secondary metal center into uranyl bearing materials. Depending upon the protonation state, the iron sandwich metalloligands may vary from zwitterionic neutral or monoanionic coordinating species as observed in compounds 1–3, or a positively charged species that hydrogen bonds with anionic [UO2F3]- chains as observed in 4.more » Further, the hydrolysis of the charge balancing PF6 - anion increases the diversity of UO2 2+ coordinating species by contributing both F- and PO4 3- anions (1, 3, 4). The luminescent properties of 1–4 were also studied and revealed the absence of uranyl emission, suggestive of a possible energy transfer from the uranyl cation to the iron(II) metal center.« less

Time-resolved infrared reflectance studies of the dehydration-induced transformation of uranyl nitrate hexahydrate to the trihydrate form

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

2015-09-08

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO 2(NO 3) 2(H 2O) 6] often called UNH), the trihydrate [UO 2(NO 3) 2(H 2O) 3 or UNT], and in very dry environments the dihydrate form [UO 2(NO 3) 2(H 2O) 2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s, the different phases were studied by infrared transmission spectroscopy but were limited both by instrumental resolution and by the ability to prepare the samples formore » transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparation and allows dynamic analysis while the sample is exposed to a flow of N 2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO 2(NO 3) 2(H 2O) 6 has a distinct uranyl asymmetric stretch band at 949.0 cm –1 that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm –1. The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO 2 2+ sites. The dehydration of UO 2(NO 3) 2(H 2O) 6 to UO 2(NO 3) 2(H 2O) 3 is both a structural and morphological change that has the lustrous lime green UO 2(NO 3) 2(H 2O) 6 crystals changing to the matte greenish yellow of the trihydrate solid. As a result, the phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with only one in the hexahydrate.« less

Electrospray ionization of uranyl-citrate complexes

NASA Astrophysics Data System (ADS)

Somogyi, Árpád; Pasilis, Sofie P.; Pemberton, Jeanne E.

2007-09-01

Results presented here demonstrate the usefulness of electrospray ionization and gas-phase ion-molecule reactions to predict structural and electronic differences in complex inorganic ions. Electrospray ionization of uranyl citrate solutions generates positively and negatively charged ions that participate in further ion-molecule reactions in 3D ion trap and FT-ICR mass analyzers. Most ions observed are derived from the major solution uranyl-citrate complexes and involve species of {(UO2)2Cit2}2-, (UO2)3Cit2, and {(UO2)3Cit3}3-, where Cit indicates the citrate trianion, C6H5O73-. In a 3D ion trap operated at relatively high pressure, complex adducts containing solvent molecules, alkali and ammonium cations, and nitrate or chloride anions are dominant, and proton/alkali cation (Na+, K+) exchange is observed for up to six exchangeable protons in an excess of alkali cations. Adduct formation in a FT-ICR cell that is operated at lower pressures is less dominant, and direct detection of positive and negative ions of the major solution complexes is possible. Multiply charged ions are also detected, suggesting the presence of uranium in different oxidation states. Changes in uranium oxidation state are detected by He-CID and SORI-CID fragmentation, and certain fragments undergo association reactions in trapping analyzers, forming "exotic" species such as [(UO2)4O3]-, [(UO2)4O4]-, and [(UO2)4O5]-. Ion-molecule reactions with D2O in the FT-ICR cell indicate substantial differences in H/D exchange rate and D2O accommodation for different ion structures and charge states. Most notably, the positively charged ions [H2(UO2)2Cit2(H)]+ and [(UO2)2(Cit)]+ accommodate two and three D2O molecules, respectively, which reflects well the structural differences, i.e., tighter uranyl-citrate coordination in the former ion than in the latter. The corresponding negatively charged ions accommodate zero or two D2O molecules, which can be rationalized using suggested solution phase structures and charge state distributions.

75 FR 67693 - Proposed Collection; Comment Request

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-03

... forms is essential to reduce preparation and processing time, increase productivity, and maximize... instructions for submitting comments. Mail: Federal Docket Management System Office, 1160 Defense Pentagon... increased because the Department of Defense must make additional written and telephonic inquiries with the...

Polygon patterns on Europa

NASA Technical Reports Server (NTRS)

Smalley, I. J.

1981-01-01

The formation of polygon patterns in the development of crack networks in cooling basalt flows and similar contracting systems, and under natural conditions in an essentially unbounded basalt flow, are analyzed, and the characteristics of hexagonal and pentagonal patterns in isotropic stress fields are discussed.

Financial Reporting at the Washington Headquarters Services

DTIC Science & Technology

2001-03-15

This report is the third, and last, in this series addressing the underlying financial reporting processes that cause abnormal balances on the trial...Forces, the Pentagon Reservation Maintenance Revolving Fund, and the Building Maintenance Fund. Preceding reports addressed financial reporting by the

Through Enemy Eyes: A Soviet View of U.S. Intelligence

DTIC Science & Technology

1980-06-01

Pentagon, and frequently its intelligence departments, while possessing the newest technical means of espionage, artificial earth satellites included...government as proof of official membership in the intellignece community. The characterization of the Hoover Institute of Stanford University is typical

78 FR 56125 - National Days of Prayer and Remembrance, 2013

Federal Register 2010, 2011, 2012, 2013, 2014

2013-09-11

... its core. Where two towers once cast a shadow, men and women gather in the early light to pay their... etched in white marble. At the Pentagon, where a single stone still bears the scars of fire, a Nation...

Photophysical Properties on Functional Pi-Electronic Molecular Systems

DTIC Science & Technology

2012-08-01

the aromaticity; i) it is possible to control the number of conjugated π-electrons by changing the number of connected pyrrole rings, ii) by...flexibilities, and facile capture and release of two pyrrolic protons upon two-electron oxidation and reduction, respectively. Scheme 2. (a...nitrogen atoms of pyrrole A, B, C and D, and the ortho-carbon atom of meso-pentafluorophenyl group in a trigonal bipyramidal manner. The 1 H NMR spectrum

PROCESS FOR THE SEPARATION OF HEAVY METALS

DOEpatents

Gofman, J.W.; Connick, R.E.; Wahl, A.C.

1959-01-27

A method is presented for thc separation of plutonium from uranium and the fission products with which it is associated. The method is based on the fact that hexavalent plutonium forms an insoluble complex precipitate with sodium acetate, as does the uranyl ion, while reduced plutonium is not precipitated by sodium acetate. Several embodiments are shown, e.g., a solution containing plutonium and uranium in the hexavalent state may be contacted with sodium acetate causing the formation of a sodium uranyl acetate precipitate which carries the plutonium values while the fission products remain in solution. If the original solution is treated with a reducing agent, so that the plutonium is reduced while the uranium remains in the hexavalent state, and sodium and acetate ions are added, the uranium will precipitutc while the plutonium remains in solution effecting separation of the Pu from urarium.

Uranyl peroxide nanoclusters at high-pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turner, Katlyn M.; Szymanowski, Jennifer E. S.; Zhang, Fuxiang

Here, U 60 ([UO 2(O 2)(OH)] 60 60– in water) is a uranyl peroxide nanocluster with a fullerene topology and O h symmetry. U 60 clusters can exist in crystalline solids or in liquids; however, little is known of their behavior at high pressures. We compressed the U 60-bearing material: Li 68K 12(OH) 20[UO 2(O 2)(OH)] 60(H 2O) 310 ( Fm3¯; a = 37.884 Å) in a diamond anvil cell to determine its response to increasing pressure. Three length scales and corresponding structural features contribute to the compression response: uranyl peroxide bonds (<0.5 nm), isolated single nanoclusters (2.5 nm), andmore » the long-range periodicity of nanoclusters within the solid (>3.7 nm). Li 68K 12(OH) 20[UO 2(O 2)(OH)] 60(H 2O) 310 transformed to a tetragonal structure below 2 GPa and irreversibly amorphized between 9.6 and 13 GPa. The bulk modulus of the tetragonal U 60-bearing material was 25 ± 2 GPa. The pressure-induced amorphous phase contained intact U 60 clusters, which were preserved beyond the loss of long-range periodicity. The persistence of U 60 clusters at high pressure may have been enhanced by the interaction between U 60 nanoclusters and the alcohol pressure medium. Once formed, U 60 nanoclusters persist regardless of their associated long-range ordering—in crystals, amorphous solids, or solutions.« less

Rapid Dissolution of Soluble Uranyl Phases in Arid, Mine-Impacted Catchments Near Church Rock, NM

DOE Office of Scientific and Technical Information (OSTI.GOV)

deLemos, J.L.; Bostick, B.C.; Quicksall, A.N.

2009-05-14

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

Rapid Dissolution of Soluble Uranyl Phases in Arid, Mine-Impacted Catchments near Church Rock, NM

PubMed Central

DELEMOS, JAMIE L.; BOSTICK, BENJAMIN C.; QUICKSALL, ANDREW N.; LANDIS, JOSHUA D.; GEORGE, CHRISTINE C.; SLAGOWSKI, NAOMI L.; ROCK, TOMMY; BRUGGE, DOUG; LEWIS, JOHNNYE; DURANT, JOHN L.

2008-01-01

We tested the hypothesis that runoff of uranium-bearing particles from mining waste disposal areas was a significant mechanism for redistribution of uranium in the northeastern part of the Upper Puerco River watershed (New Mexico). However, our results were not consistent with this hypothesis. Analysis of >100 sediment and suspended sediment samples collected adjacent to and downstream from uranium source areas indicated that uranium levels in the majority of the samples were not elevated above background. Samples collected within 50 m of a known waste disposal site were subjected to detailed geochemical characterization. Uranium in these samples was found to be highly soluble; treatment with synthetic pore water for 24 h caused dissolution of 10–50% of total uranium in the samples. Equilibrium uranium concentrations in pore water were >4.0 mg/L and were sustained in repeated wetting events, effectively depleting soluble uranium from the solid phase. The dissolution rate of uranium appeared to be controlled by solid-phase diffusion of uranium from within uranium-bearing mineral particles. X-ray adsorption spectroscopy indicated the presence of a soluble uranyl silicate, and possibly a uranyl phosphate. These phases were exhausted in transported sediment suggesting that uranium was readily mobilized from sediments in the Upper Puerco watershed and transported in the dissolved load. These results could have significance for uranium risk assessment as well as mining waste management and cleanup efforts. PMID:18589950

Uranium(VI) Scavenging by Amorphous Iron Phosphate Encrusting Sphaerotilus natans Filaments.

PubMed

Seder-Colomina, Marina; Morin, Guillaume; Brest, Jessica; Ona-Nguema, Georges; Gordien, Nilka; Pernelle, Jean-Jacques; Banerjee, Dipanjan; Mathon, Olivier; Esposito, Giovanni; van Hullebusch, Eric D

2015-12-15

U(VI) sorption to iron oxyhydroxides, precipitation of phosphate minerals, as well as biosorption on bacterial biomass are among the most reported processes able to scavenge U(VI) under oxidizing conditions. Although phosphates significantly influence bacterially mediated as well as iron oxyhydroxide mediated scavenging of uranium, the sorption or coprecipitation of U(VI) with poorly crystalline nanosized iron phosphates has been scarcely documented, especially in the presence of microorganisms. Here we show that dissolved U(VI) can be bound to amorphous iron phosphate during their deposition on Sphaerotilus natans filamentous bacteria. Uranium LIII-edge EXAFS analysis reveals that the adsorbed uranyl ions share an equatorial oxygen atom with a phosphate tetrahedron of the amorphous iron phosphate, with a characteristic U-P distance of 3.6 Å. In addition, the uranyl ions are connected to FeO6 octahedra with U-Fe distances at ~3.4 Å and at ~4.0 Å. The shortest U-Fe distance corresponds to a bidentate edge-sharing complex often reported for uranyl adsorption onto iron oxyhydroxides, whereas the longest U-Fe and U-P distances can be interpreted as a bidentate corner-sharing complex, in which two adjacent equatorial oxygen atoms are shared with the vertices of a FeO6 octahedron and of a phosphate tetrahedron. Furthermore, based on these sorption reactions, we demonstrate the ability of an attached S. natans biofilm to remove uranium from solution without any filtration step.

Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite {(UO2)O2(OH)3}4n and hexanuclear {Th6O4(OH)4} motifs

NASA Astrophysics Data System (ADS)

Liang, Lingling; Zhang, Ronglan; Zhao, Jianshe; Liu, Chiyang; Weng, Ng Seik

2016-11-01

Two new actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) under hydrothermal condition. The combination of H3tci and uranyl nitrate hexahydrate in aqueous solution leads to the isolation of [(UO2)2(H2O)4]0.5(tci)2(UO2)4(OH)4·18H2O (1), which contains two distinct UO22+ coordination environments. Four uranyl cations, linked through μ3-OH respectively, result in the edge-sharing ribbons. Then, the layer structure is constructed by U-O clusters linked through other eight-coordinated uranyl unions, giving rise to a porous structure in the space. Topological analysis reveals that complex 1 belongs to a (4, 8)-connected net with a schläfli symbol of (34.26.3)2(34.46.56.68.73.8). Th3(tci)2O2(OH)2(H2O)3·12H2O (2) generated by the reaction of H3tci and thorium nitrate tetrahydrate, possesses nine-fold coodinated Th(IV) centers with a monocapped square antiprismatic geometry. The hexamers "Th6O4(OH)4" motifs are connected together by the carboxylate groups, showing a three-dimensional structures. Complex 2 takes on an 8-connected architecture and the point symbol is (424.64).

Uranyl peroxide nanoclusters at high-pressure

DOE PAGES

Turner, Katlyn M.; Szymanowski, Jennifer E. S.; Zhang, Fuxiang; ...

2017-08-14

Here, U 60 ([UO 2(O 2)(OH)] 60 60– in water) is a uranyl peroxide nanocluster with a fullerene topology and O h symmetry. U 60 clusters can exist in crystalline solids or in liquids; however, little is known of their behavior at high pressures. We compressed the U 60-bearing material: Li 68K 12(OH) 20[UO 2(O 2)(OH)] 60(H 2O) 310 ( Fm3¯; a = 37.884 Å) in a diamond anvil cell to determine its response to increasing pressure. Three length scales and corresponding structural features contribute to the compression response: uranyl peroxide bonds (<0.5 nm), isolated single nanoclusters (2.5 nm), andmore » the long-range periodicity of nanoclusters within the solid (>3.7 nm). Li 68K 12(OH) 20[UO 2(O 2)(OH)] 60(H 2O) 310 transformed to a tetragonal structure below 2 GPa and irreversibly amorphized between 9.6 and 13 GPa. The bulk modulus of the tetragonal U 60-bearing material was 25 ± 2 GPa. The pressure-induced amorphous phase contained intact U 60 clusters, which were preserved beyond the loss of long-range periodicity. The persistence of U 60 clusters at high pressure may have been enhanced by the interaction between U 60 nanoclusters and the alcohol pressure medium. Once formed, U 60 nanoclusters persist regardless of their associated long-range ordering—in crystals, amorphous solids, or solutions.« less

Silver nanoparticle decorated reduced graphene oxide (rGO) nanosheet: a platform for SERS based low-level detection of uranyl ion.

PubMed

Dutta, Soumen; Ray, Chaiti; Sarkar, Sougata; Pradhan, Mukul; Negishi, Yuichi; Pal, Tarasankar

2013-09-11

Herein, a simple wet-chemical pathway has been demonstrated for the synthesis of silver nanoparticle conjugated reduced graphene oxide nanosheets where dimethylformamide (DMF) is judiciously employed as an efficient reducing agent. Altogether, DMF reduces both silver nitrate (AgNO3) and graphene oxide (GO) in the reaction mixture. Additionally, the presence of polyvinylpyrolidone (PVP) assists the nanophasic growth and homogeneous distribution of the plasmonic nanoparticle Ag(0). Reduction of graphene oxide and the presence of aggregated Ag NPs on reduced graphene oxide (rGO) nanosheets are confirmed from various spectroscopic techniques. Finally, the composite material has been exploited as an intriguing platform for surface enhanced Raman scattering (SERS) based selective detection of uranyl (UO2(2+)) ion. The limit of detection has been achieved to be as low as 10 nM. Here the normal Raman spectral (NRS) band of uranyl acetate (UAc) at 838 cm(-1) shifts to 714 and 730 cm(-1) as SERS bands for pH 5.0 and 12.0, respectively. This distinguished Raman shift of the symmetric stretching mode for UO2(2+) ion is indicative of pronounced charge transfer (CT) effect. This CT effect even supports the higher sensitivity of the protocol toward UO2(2+) over other tested oxo-ions. It is anticipated that rGO nanosheets furnish a convenient compartment to favor the interaction between Ag NPs and UO2(2+) ion through proximity induced adsorption even at low concentration.

Additional studies on mixed uranyl oxide-hydroxide hydrate alteration products of uraninite from the palermo and ruggles granitic pegmatites, grafton county, New Hampshire

USGS Publications Warehouse

Foord, E.E.; Korzeb, S.L.; Lichte, F.E.; Fitzpatrick, J.J.

1997-01-01

Additional studies on an incompletely characterized secondary uranium "mineral" from the Ruggles and Palermo granitic pegmatites, New Hampshire, referred to as mineral "A" by Frondel (1956), reveal a mixture of schoepite-group minerals and related uranyl oxide-hydroxide hydrated compounds. A composite chemical analysis yielded (in wt.%): PbO 4.85 (EMP), UO3 83.5 (EMP), BaO 0.675 (av. of EMP and ICP), CaO 0.167 (av. of EMP and ICP), K2O 2.455 (av. of EMP and ICP), SrO 0.21 (ICP), ThO2 0.85 (ICP), H2O 6.9, ??99.61. Powder-diffraction X-ray studies indicate a close resemblance in patterns between mineral "A" and several uranyl oxide-hydroxide hydrated minerals, including the schoepite family of minerals and UO2(OH)2. The powder-diffraction data for mineral "A" are most similar to those for synthetic UO2.86??1.5H2O and UO2(OH)2, but other phases are likely present as well. TGA analysis of both mineral "A" and metaschoepite show similar weight-loss and first derivative curves. The dominant losses are at 100??C, with secondary events at 400?? and 600??C. IR spectra show the presence of (OH) and H2O. Uraninite from both pegmatites, analyzed by LAM-ICP-MS, shows the presence of Th, Pb, K and Ca.