Sample records for rhenium trioxide reo3

  1. Reactivity of Hydrogen and Methanol on (001) Surfaces of WO3, ReO3, WO3/ReO3 and ReO3/WO3

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

    Ling, Sanliang; Mei, Donghai; Gutowski, Maciej S.

    2011-05-16

    Bulk tungsten trioxide (WO3) and rhenium trioxide (ReO3) share very similar structures but display different electronic properties. WO3 is a wide bandgap semiconductor while ReO3 is an electronic conductor. With the advanced molecular beam epitaxy techniques, it is possible to make heterostructures comprised of layers of WO3 and ReO3. These heterostructures might display reactivity different than pure WO3 and ReO3. The interactions of two probe molecules (hydrogen and methanol) with the (001) surfaces of WO3, ReO3, and two heterostructures ReO3/WO3 and WO3/ReO3 were investigated at the density functional theory level. Atomic hydrogen prefers to adsorb at the terminal O1C sitesmore » forming a surface hydroxyl on four surfaces. Dissociative adsorption of a hydrogen molecule at the O1C site leads to formation of a water molecule adsorbed at the surface M5C site. This is thermodynamically the most stable state. A thermodynamically less stable dissociative state involves two surface hydroxyl groups O1CH and O2CH. The interaction of molecular hydrogen and methanol with pure ReO3 is stronger than with pure WO3 and the strength of the interaction substantially changes on the WO3/ReO3 and ReO3/WO3 heterostructures. The reaction barriers for decomposition and recombination reactions are sensitive to the nature of heterostructure. The calculated adsorption energy of methanol on WO3(001) of -65.6 kJ/mol is consistent with the previous experimental estimation of -67 kJ/mol. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

  2. Boosting surface charge-transfer doping efficiency and robustness of diamond with WO3 and ReO3

    NASA Astrophysics Data System (ADS)

    Tordjman, Moshe; Weinfeld, Kamira; Kalish, Rafi

    2017-09-01

    An advanced charge-transfer yield is demonstrated by employing single monolayers of transition-metal oxides—tungsten trioxide (WO3) and rhenium trioxide (ReO3)—deposited on the hydrogenated diamond surface, resulting in improved p-type sheet conductivity and thermal stability. Surface conductivities, as determined by Hall effect measurements as a function of temperature for WO3, yield a record sheet hole carrier concentration value of up to 2.52 × 1014 cm-2 at room temperature for only a few monolayers of coverage. Transfer doping with ReO3 exhibits a consistent narrow sheet carrier concentration value of around 3 × 1013 cm-2, exhibiting a thermal stability of up to 450 °C. This enhanced conductivity and temperature robustness exceed those reported for previously exposed surface electron acceptor materials used so far on a diamond surface. X-ray photoelectron spectroscopy measurements of the C1s core level shift as a function of WO3 and ReO3 layer thicknesses are used to determine the respective increase in surface band bending of the accumulation layers, leading to a different sub-surface two-dimensional hole gas formation efficiency in both cases. This substantial difference in charge-exchange efficiency is unexpected since both surface acceptors have very close work functions. Consequently, these results lead us to consider additional factors influencing the transfer doping mechanism. Transfer doping with WO3 reveals the highest yet reported transfer doping efficiency per minimal surface acceptor coverage. This improved surface conductivity performance and thermal stability will promote the realization of 2D diamond-based electronic devices facing process fabrication challenges.

  3. Polymer Photovoltaic Cells with Rhenium Oxide as Anode Interlayer.

    PubMed

    Wei, Jinyu; Bai, Dongdong; Yang, Liying

    2015-01-01

    The effect of a new transition metal oxide, rhenium oxide (ReO3), on the performance of polymer solar cells based on regioregular poly(3-hexylthiophene) (P3HT) and methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM) blend as buffer layer was investigated. The effect of the thickness of ReO3 layer on electrical characteristics of the polymer solar cells was studied. It is found that insertion of ReO3 interfacial layer results in the decreased performance for P3HT: PCBM based solar cells. In order to further explore the mechanism of the decreasing of the open-circuit voltage (Voc), the X-ray photoelectron spectroscopy (XPS) is used to investigate the ReO3 oxidation states. Kelvin Probe method showed that the work function of the ReO3 is estimated to be 5.13eV after thermal evaporation. The results indicated the fact that a portion of ReO3 decomposed during thermal evaporation process, resulting in the formation of a buffer layer with a lower work function. As a consequence, a higher energy barrier was generated between the ITO and the active layer.

  4. Polymer Photovoltaic Cells with Rhenium Oxide as Anode Interlayer

    PubMed Central

    Wei, Jinyu; Bai, Dongdong; Yang, Liying

    2015-01-01

    The effect of a new transition metal oxide, rhenium oxide (ReO3), on the performance of polymer solar cells based on regioregular poly(3-hexylthiophene) (P3HT) and methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM) blend as buffer layer was investigated. The effect of the thickness of ReO3 layer on electrical characteristics of the polymer solar cells was studied. It is found that insertion of ReO3 interfacial layer results in the decreased performance for P3HT: PCBM based solar cells. In order to further explore the mechanism of the decreasing of the open-circuit voltage (Voc), the X-ray photoelectron spectroscopy (XPS) is used to investigate the ReO3 oxidation states. Kelvin Probe method showed that the work function of the ReO3 is estimated to be 5.13eV after thermal evaporation. The results indicated the fact that a portion of ReO3 decomposed during thermal evaporation process, resulting in the formation of a buffer layer with a lower work function. As a consequence, a higher energy barrier was generated between the ITO and the active layer. PMID:26226439

  5. Microwave spectra and quadrupole coupling measurements for methyl rhenium trioxide

    NASA Astrophysics Data System (ADS)

    Sickafoose, S. M.; Wikrent, P.; Drouin, B. J.; Kukolich, S. G.

    1996-12-01

    Microwave rotational transitions for J' ← J = 1 ← 0 and 2 ← 1 were measured in the 6-14 GHz range for methyl rhenium trioxide using a Flygare-Balle type, pulsed-beam spectrometer. The rotational constants for the most abundant isotopomers are B( 187Re) = 3466.964(2) MHz and B( 185Re) = 3467.049(3) MHz. The quadrupole coupling strengths are eQq( 187Re) = 716.55(2) MHz and eQq( 185Re) = 757.19(3) MHz. Transitions were also observed for 13C isotopomers and 18O isotopomers. The value for the ReC bond length obtained from a Kraitchman analysis is R( ReC) = 2.080 Å. The rhenium quadrupole coupling strengths are about 20% smaller than those obtained for HRe(CO) 5.

  6. Laser Desorption Ionization of small molecules assisted by Tungsten oxide and Rhenium oxide particles

    PubMed Central

    Bernier, Matthew; Wysocki, Vicki; Dagan, Shai

    2015-01-01

    Inorganic metal oxides have shown potential as matrices for assisting in laser desorption ionization (LDI) with advantages over the aromatic acids typically used. Rhenium and tungsten oxides are an attractive option due to their high work functions and relative chemical inertness. In this work, it is shown that ReO3 and WO3, in microparticle (μP) powder forms, can efficiently ionize various types of small molecules and provide minimized background contamination at analyte concentrations below 1 ng/μL. This study shows that untreated inorganic WO3 and ReO3 particles are valid matrix options for detection of protonatable, radical, and precharged species under LDI. Qualitatively, the WO3 μP showed an improved detection of apigenin, sodiated glucose, and the precharged analyte choline, while the ReO3 μP allowed detection of protonated cocaine, quinuclidine, ametryn, and radical ions of polyaromatic hydrocarbons at detection levels as low as 50 pg/μL. For thermometer ion survival yield experiments, it was also shown that the ReO3 powder was significantly softer than CCA. Furthermore, it provided higher intensities of cocaine and polyaromatic hydrocarbons, at laser flux values equal to that used with CCA. PMID:26349643

  7. Analysis of the Nuclear Structure of Rhenium-186 Using Neutron-Induced Reactions

    DTIC Science & Technology

    2015-03-26

    5 1.5 Methods ... radioisotope power source for use on the battlefield. 1 Re-Os Cosmochronometer. The isotope 187Re has a half-life in its ground state of 4.35⇥ 1010 years [2...187Os in meteorites permits one to date the nucleosynthesis of rhenium and osmium by high neutron flux events such as supernovae. The Re-Os radioactive

  8. Laser desorption ionization of small molecules assisted by tungsten oxide and rhenium oxide particles.

    PubMed

    Bernier, Matthew C; Wysocki, Vicki H; Dagan, Shai

    2015-07-01

    Inorganic metal oxides have shown potential as matrices for assisting in laser desorption ionization with advantages over the aromatic acids typically used. Rhenium and tungsten oxides are attractive options due to their high work functions and relative chemical inertness. In this work, it is shown that ReO3 and WO3 , in microparticle (μP) powder forms, can efficiently facilitate ionization of various types of small molecules and provide minimized background contamination at analyte concentrations below 1 ng/µL. This study shows that untreated inorganic WO3 and ReO3 particles are valid matrix options for detection of protonatable, radical, and precharged species under laser desorption ionization. Qualitatively, the WO3 μP showed improved detection of apigenin, sodiated glucose, and precharged analyte choline, while the ReO3 μP allowed better detection of protonated cocaine, quinuclidine, ametryn, and radical ions of polyaromatic hydrocarbons at detection levels as low as 50 pg/µL. For thermometer ion survival yield experiments, it was also shown that the ReO3 powder was significantly softer than α-cyano-4-hydroxycinnaminic acid. Furthermore, it provided higher intensities of cocaine and polyaromatic hydrocarbons, at laser flux values equal to those used with α-cyano-4-hydroxycinnaminic acid. Copyright © 2015 John Wiley & Sons, Ltd.

  9. Oxorhenium complexes bearing the water-soluble tris(pyrazol-1-yl)methanesulfonate, 1,3,5-triaza-7-phosphaadamantane, or related ligands, as catalysts for Baeyer-Villiger oxidation of ketones.

    PubMed

    Martins, Luísa M D R S; Alegria, Elisabete C B A; Smoleński, Piotr; Kuznetsov, Maxim L; Pombeiro, Armando J L

    2013-04-15

    New rhenium(VII or III) complexes [ReO3(PTA)2][ReO4] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), [ReO3(mPTA)][ReO4]I (2) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [ReO3(HMT)2][ReO4] (3) (HMT = hexamethylenetetramine), [ReO3(η(2)-Tpm)(PTA)][ReO4] (4) [Tpm = hydrotris(pyrazol-1-yl)methane, HC(pz)3, pz = pyrazolyl], [ReO3(Hpz)(HMT)][ReO4] (5) (Hpz = pyrazole), [ReO(Tpms)(HMT)] (6) [Tpms = tris(pyrazol-1-yl)methanesulfonate, O3SC(pz)3(-)] and [ReCl2{N2C(O)Ph}(PTA)3] (7) have been prepared from the Re(VII) oxide Re2O7 (1-6) or, in the case of 7, by ligand exchange from the benzoyldiazenido complex [ReCl2{N2C(O)Ph}(Hpz)(PPh3)2], and characterized by IR and NMR spectroscopies, elemental analysis and electrochemical properties. Theoretical calculations at the density functional theory (DFT) level of theory indicated that the coordination of PTA to both Re(III) and Re(VII) centers by the P atom is preferable compared to the coordination by the N atom. This is interpreted in terms of the Re-PTA bond energy and hard-soft acid-base theory. The oxo-rhenium complexes 1-6 act as selective catalysts for the Baeyer-Villiger oxidation of cyclic and linear ketones (e.g., 2-methylcyclohexanone, 2-methylcyclopentanone, cyclohexanone, cyclopentanone, cyclobutanone, and 3,3-dimethyl-2-butanone or pinacolone) to the corresponding lactones or esters, in the presence of aqueous H2O2. The effects of a variety of factors are studied toward the optimization of the process.

  10. Towards understanding the mechanism of rhenium and osmium precipitation in tungsten and its implication for tungsten-based alloys

    NASA Astrophysics Data System (ADS)

    Li, Yu-Hao; Zhou, Hong-Bo; Deng, Huiqiu; Lu, Gang; Lu, Guang-Hong

    2018-07-01

    Using a first-principles method in combination with thermodynamic models, we investigate the interaction between rhenium/osmium (Re/Os) and defects to explore the mechanism of radiation-induced Re/Os precipitation in tungsten (W). We demonstrate that radiation-induced defects play a key role in the solute precipitation in W, especially for self-interstitial atoms (SIAs). The presence of SIAs can significantly reduce the total nucleation free energy change of Re/Os, and thus facilitate the nucleation of Re/Os in W. Further, SIA is shown to be easily trapped by Re/Os once overcoming a low energy barrier, forming a W-Re/Os mixed dumbbell. Such W-Re/Os dumbbell forms a high stable Re/Os-Re/Os dumbbell structure with the substitutional Re/Os atoms, which can serve as a trapping centre for subsequent interstitial-Re/Os, leading to the growth of Re/Os-rich clusters. Consequently, an interstitial-mediated migration and aggregation mechanism for Re/Os precipitation in W has been proposed. Our results reveale that the alloying elements-defects interaction has significantly effect on their behaviors under irradiation, which should be considered in the design of W-based alloys for future fusion devices.

  11. Structure of rhenium-containing sodium borosilicate glass

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

    Goel, Ashutosh; McCloy, John S.; Windisch, Charles F.

    2013-03-01

    A series of sodium borosilicate glasses were synthesized with increasing fractions of KReO4 or Re2O7, to 10000 ppm (1 mass%) target Re in glass, to assess the effects of large concentrations of rhenium on glass structure and to estimate the solubility of technetium, a radioactive component in typical low active waste nuclear waste glasses. Magic angle spinning nuclear magnetic resonance (MAS-NMR), Fourier transform infrared (FTIR) spectroscopy, and Raman spectroscopy were performed to characterize the glasses as a function of Re source additions. In general, silicon was found coordinated in a mixture of Q2 and Q3 structural units, while Al wasmore » 4-coordinated and B was largely 3-coordinate and partially 4-coordinated. The rhenium source did not appear to have significant effects on the glass structure. Thus, at the up to the concentrations that remain in dissolved in glass, ~3000 ppm Re by mass maximum. , the Re appeared to be neither a glass-former nor a strong glass modifier., Rhenium likely exists in isolated ReO4- anions in the interstices of the glass network, as evidenced by the polarized Raman spectrum of the Re glass in the absence of sulfate. Analogous to SO42-¬ in similar glasses, ReO4- is likely a network modifier and forms alkali salt phases on the surface and in the bulk glass above solubility.« less

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

    DOE PAGES

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

    2014-12-20

    Perrhenate (ReO 4 -), as a TcO 4 - analogue, was incorporated into mixed-anion sodalites from binary solutions containing ReO 4 - and a competing anion X n- (Cl -, CO 3 2-, SO 4 2-, MnO 4 -, or WO 4 2-). For this study, our objective was to determine the extent of solid solution formation and the dependence of competing ion selectivity on ion size. Using equivalent aqueous concentrations of the anions (ReO 4 -/X n- molar ratio = 1:1), we synthesized mixed-anion sodalites from zeolite and NaOH at 90 °C for 96 h. The resulting solids weremore » characterized by bulk chemical analysis, powder X-ray diffraction, scanning electron microscopy, and X-ray absorption near edge structure (XANES) spectroscopy to determine crystal structure, chemical composition, morphology, and rhenium (Re) oxidation state. Rhenium in the solid phase occurred predominately as Re(VII)O 4 - in the sodalites, which have a primitive cubic pattern in the space group P43n. The refined unit-cell parameters of the mixed sodalites ranged from 8.88 to 9.15 Å and showed a linear dependence on the size and mole fraction of the incorporated anion(s). The ReO 4 - selectivity, represented by its distribution coefficient (K d), increased in the following order: Cl - < NO 3 - < MnO 4 - and CO 3 2- < SO 4 2- < WO 4 2- for the monovalent and divalent anions, respectively. The relationship between the ReO 4 - distribution coefficient and competing anion size was nonlinear. When the difference in ionic radius (DIR) between ReO 4 - and X n - (n = 1 or 2) was greater than ~ 12%, then ReO 4 - incorporation into sodalite was insignificant. The results imply that anion size is the major factor that determines sodalite anion compositions. Given the similarity in chemical behavior and anion size, ReO 4 - serves as a suitable analogue for TcO 4 - under oxidizing conditions where both elements are expected to remain as oxyanions in the + 7 oxidation state.« less

  13. Solid-state (185/187)Re NMR and GIPAW DFT study of perrhenates and Re2(CO)10: chemical shift anisotropy, NMR crystallography, and a metal-metal bond.

    PubMed

    Widdifield, Cory M; Perras, Frédéric A; Bryce, David L

    2015-04-21

    Advances in solid-state nuclear magnetic resonance (SSNMR) methods, such as dynamic nuclear polarization (DNP), intricate pulse sequences, and increased applied magnetic fields, allow for the study of systems which even very recently would be impractical. However, SSNMR methods using certain quadrupolar probe nuclei (i.e., I > 1/2), such as (185/187)Re remain far from fully developed due to the exceedingly strong interaction between the quadrupole moment of these nuclei and local electric field gradients (EFGs). We present a detailed high-field (B0 = 21.1 T) experimental SSNMR study on several perrhenates (KReO4, AgReO4, Ca(ReO4)2·2H2O), as well as ReO3 and Re2(CO)10. We propose solid ReO3 as a new rhenium SSNMR chemical shift standard due to its reproducible and sharp (185/187)Re NMR resonances. We show that for KReO4, previously poorly understood high-order quadrupole-induced effects (HOQIE) on the satellite transitions can be used to measure the EFG tensor asymmetry (i.e., ηQ) to nearly an order-of-magnitude greater precision than competing SSNMR and nuclear quadrupole resonance (NQR) approaches. Samples of AgReO4 and Ca(ReO4)2·2H2O enable us to comment on the effects of counter-ions and hydration upon Re(vii) chemical shifts. Calcium-43 and (185/187)Re NMR tensor parameters allow us to conclude that two proposed crystal structures for Ca(ReO4)2·2H2O, which would be considered as distinct, are in fact the same structure. Study of Re2(CO)10 provides insights into the effects of Re-Re bonding on the rhenium NMR tensor parameters and rhenium oxidation state on the Re chemical shift value. As overtone NQR experiments allowed us to precisely measure the (185/187)Re EFG tensor of Re2(CO)10, we were able to measure rhenium chemical shift anisotropy (CSA) for the first time in a powdered sample. Experimental observations are supported by gauge-including projector augmented-wave (GIPAW) density functional theory (DFT) calculations, with NMR tensor calculations also provided for NH4ReO4, NaReO4 and RbReO4. These calculations are able to reproduce many of the experimental trends in rhenium δiso values and EFG tensor magnitudes. Using KReO4 as a prototypical perrhenate-containing system, we establish a correlation between the tetrahedral shear strain parameter (|ψ|) and the nuclear electric quadrupolar coupling constant (CQ), which enables the refinement of the structure of ND4ReO4. Shortcomings in traditional DFT approaches, even when including relativistic effects via the zeroth-order regular approximation (ZORA), for calculating rhenium NMR tensor parameters are identified for Re2(CO)10.

  14. Osmium isotopes and mantle convection.

    PubMed

    Hauri, Erik H

    2002-11-15

    The decay of (187)Re to (187)Os (with a half-life of 42 billion years) provides a unique isotopic fingerprint for tracing the evolution of crustal materials and mantle residues in the convecting mantle. Ancient subcontinental mantle lithosphere has uniquely low Re/Os and (187)Os/(188)Os ratios due to large-degree melt extraction, recording ancient melt-depletion events as old as 3.2 billion years. Partial melts have Re/Os ratios that are orders of magnitude higher than their sources, and the subduction of oceanic or continental crust introduces into the mantle materials that rapidly accumulate radiogenic (187)Os. Eclogites from the subcontinental lithosphere have extremely high (187)Os/(188)Os ratios, and record ages as old as the oldest peridotites. The data show a near-perfect partitioning of Re/Os and (187)Os/(188)Os ratios between peridotites (low) and eclogites (high). The convecting mantle retains a degree of Os-isotopic heterogeneity similar to the lithospheric mantle, although its amplitude is modulated by convective mixing. Abyssal peridotites from the ocean ridges have low Os isotope ratios, indicating that the upper mantle had undergone episodes of melt depletion prior to the most recent melting events to produce mid-ocean-ridge basalt. The amount of rhenium estimated to be depleted from the upper mantle is 10 times greater than the rhenium budget of the continental crust, requiring a separate reservoir to close the mass balance. A reservoir consisting of 5-10% of the mantle with a rhenium concentration similar to mid-ocean-ridge basalt would balance the rhenium depletion of the upper mantle. This reservoir most likely consists of mafic oceanic crust recycled into the mantle over Earth's history and provides the material that melts at oceanic hotspots to produce ocean-island basalts (OIBs). The ubiquity of high Os isotope ratios in OIB, coupled with other geochemical tracers, indicates that the mantle sources of hotspots contain significant quantities (greater than 10%) of lithologically distinct mafic material which represents ancient oceanic lithosphere cycled through the convecting mantle on a time-scale of 800 million years or more.

  15. Supported rhenium complexes: almost uniform rhenium tricarbonyls synthesized from CH3Re(CO)5 and HY zeolite.

    PubMed

    Lobo-Lapidus, Rodrigo J; Gates, Bruce C

    2010-11-02

    Supported rhenium complexes were prepared from CH(3)Re(CO)(5) and dealuminated HY zeolite or NaY zeolite, each with a Si/Al atomic ratio of 30. The samples were characterized with infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopies. EXAFS data characterizing the sample formed by the reaction of CH(3)Re(CO)(5) with dealuminated HY zeolite show that the rhenium complexes were bonded to the zeolite frame, incorporating, on average, three carbonyl ligands per Re atom (as shown by Re-C and multiple-scattering Re-O EXAFS contributions). The IR spectra, consistent with this result, show that the supported rhenium carbonyls were bonded near aluminum sites of the zeolite, as shown by the decrease in intensity of the IR bands characterizing the acidic silanol groups resulting from the reaction of the rhenium carbonyl with the zeolite. This supported metal complex was characterized by narrow peaks in the ν(CO) region of the IR spectrum, indicating highly uniform species. In contrast, the species formed from CH(3)Re(CO)(5) on NaY zeolite lost fewer carbonyl ligands than those formed on HY zeolite and were significantly less uniform, as indicated by the greater breadth of the ν(CO) bands in the IR spectra. The results show the importance of zeolite H(+) sites for the formation of uniform supported rhenium carbonyls from CH(3)Re(CO)(5); the formation of such uniform complexes did not occur on the NaY zeolite.

  16. Behaviors of transmutation elements Re and Os and their effects on energetics and clustering of vacancy and self-interstitial atoms in W

    NASA Astrophysics Data System (ADS)

    Li, Yu-Hao; Zhou, Hong-Bo; Jin, Shuo; Zhang, Ying; Deng, Huiqiu; Lu, Guang-Hong

    2017-04-01

    We investigate the behaviors of rhenium (Re) and osmium (Os) and their interactions with point defects in tungsten (W) using a first-principles method. We show that Re atoms are energetically favorable to disperse separately in bulk W due to the Re-Re repulsive interaction. Despite the attractive interaction between Os atoms, there is still a large activation energy barrier of 1.10 eV at the critical number of 10 for the formation of Os clusters in bulk W based on the results of the total nucleation free energy change. Interestingly, the presence of vacancy can significantly reduce the total nucleation free energy change of Re/Os clusters, suggesting that vacancy can facilitate the nucleation of Re/Os in W. Re/Os in turn has an effect on the stability of the vacancy clusters (V n ) in W, especially for small vacancy clusters. A single Re/Os atom can raise the total binding energies of V2 and V3 obviously, thus enhancing their formation. Further, we demonstrate that there is a strong attractive interaction between Re/Os and self-interstitial atoms (SIAs). Re/Os could increase the diffusion barrier of SIAs and decrease their rotation barrier, while the interstitial-mediated path may be the optimal diffusion path of Re/Os in W. Consequently, the synergistic effect between Re/Os and point defects plays a key role in Re/Os precipitation and the evolution of defects in irradiated W.

  17. New insights into hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds by rhenium(V)-dioxo complexes.

    PubMed

    Huang, Liangfang; Wang, Wenmin; Wei, Xiaoqin; Wei, Haiyan

    2015-04-23

    The hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds catalyzed by high-valent rhenium(V)-dioxo complex ReO2I(PPh3)2 (1) were studied computationally to determine the underlying mechanism. Our calculations revealed that the ionic outer-sphere pathway in which the organic substrate attacks the Si center in an η(1)-silane rhenium adduct to prompt the heterolytic cleavage of the Si-H bond is the most energetically favorable process for rhenium(V)-dioxo complex 1 catalyzed hydrosilylation of imines. The activation energy of the turnover-limiting step was calculated to be 22.8 kcal/mol with phenylmethanimine. This value is energetically more favorable than the [2 + 2] addition pathway by as much as 10.0 kcal/mol. Moreover, the ionic outer-sphere pathway competes with the [2 + 2] addition mechanism for rhenium(V)-dioxo complex 1 catalyzing the hydrosilylation of carbonyl compounds. Furthermore, the electron-donating group on the organic substrates would induce a better activity favoring the ionic outer-sphere mechanistic pathway. These findings highlight the unique features of high-valent transition-metal complexes as Lewis acids in activating the Si-H bond and catalyzing the reduction reactions.

  18. Supported Rhenium Complexes: Almost Uniform Rhenium Tricarbonyls Synthesized from CH[subscript 3]Re(CO)[subscript 5] and HY Zeolite

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

    Lobo-Lapidus, Rodrigo J.; Gates, Bruce C.

    2010-12-07

    Supported rhenium complexes were prepared from CH{sub 3}Re(CO){sub 5} and dealuminated HY zeolite or NaY zeolite, each with a Si/Al atomic ratio of 30. The samples were characterized with infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopies. EXAFS data characterizing the sample formed by the reaction of CH{sub 3}Re(CO){sub 5} with dealuminated HY zeolite show that the rhenium complexes were bonded to the zeolite frame, incorporating, on average, three carbonyl ligands per Re atom (as shown by Re-C and multiple-scattering Re-O EXAFS contributions). The IR spectra, consistent with this result, show that the supported rhenium carbonyls were bondedmore » near aluminum sites of the zeolite, as shown by the decrease in intensity of the IR bands characterizing the acidic silanol groups resulting from the reaction of the rhenium carbonyl with the zeolite. This supported metal complex was characterized by narrow peaks in the {nu}{sub CO} region of the IR spectrum, indicating highly uniform species. In contrast, the species formed from CH{sub 3}Re(CO){sub 5} on NaY zeolite lost fewer carbonyl ligands than those formed on HY zeolite and were significantly less uniform, as indicated by the greater breadth of the {nu}{sub CO} bands in the IR spectra. The results show the importance of zeolite H{sup +} sites for the formation of uniform supported rhenium carbonyls from CH{sub 3}Re(CO){sub 5}; the formation of such uniform complexes did not occur on the NaY zeolite.« less

  19. The Electrodeposition of Rhenium and Its Alloys

    DTIC Science & Technology

    2015-09-18

    of the coating . In order to improve the stability of such layers, thermal treatment is required. The observation of the H0.57ReO3 phase is...the range of 10–100 nm on conductive and non- conductive substrates, either as a stand-alone coating or as a seed DISTRIBUTION A: Distribution approved... coatings on carbons, carbon-carbon composites, semiconducting and non- conducting surfaces. Pure Re cannot be deposited from electroless plating

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

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

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

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

  1. Negative thermal ion mass spectrometry of osmium, rhenium, and iridium

    NASA Technical Reports Server (NTRS)

    Creaser, R. A.; Papanastassiou, D. A.; Wasserburg, G. J.

    1991-01-01

    This paper describes a technique for obtaining, in a conventional surface ionization mass spectrometer, intense ion beams of negatively charged oxides of Os, Re, and Ir by thermal ionization. It is shown that the principal ion species of these ions are OsO3(-), ReO4(-), and IrO2(-), respectively. For Re-187/Os-187 studies, this technique offers the advantage of isotopic analyses without prior chemical separation of Re from Os.

  2. Exploring the thermal expansion of fluorides and oxyfluorides with rhenium trioxide-type structures: From negative to positive thermal expansion

    NASA Astrophysics Data System (ADS)

    Greve, Benjamin K.

    This thesis explores the thermal expansion and high pressure behavior of some materials with the ReO3 structure type. This structure is simple and has, in principle, all of the features necessary for negative thermal expansion (NTE) arising from the transverse thermal motion of the bridging anions and the coupled rotation of rigid units; however, ReO 3 itself only exhibits mild NTE across a narrow temperature range at low temperatures. ReO3 is metallic because of a delocalized d-electron, and this may contribute to the lack of NTE in this material. The materials examined in this thesis are all based on d 0 metal ions so that the observed thermal expansion behavior should arise from vibrational, rather than electronic, effects. In Chapter 2, the thermal expansion of scandium fluoride, ScF3 , is examined using a combination of in situ synchrotron X-ray and neutron variable temperature diffraction. ScF3 retains the cubic ReO3 structure across the entire temperature range examined (10 - 1600 K) and exhibits pronounced negative thermal expansion at low temperatures. The magnitude of NTE in this material is comparable to that of cubic ZrW2O8, which is perhaps the most widely studied NTE material, at room temperature and below. This is the first report of NTE in an ReO3 type structure across a wide temperature range. Chapter 3 presents a comparison between titanium oxyfluoride, TiOF 2, and a vacancy-containing titanium hydroxyoxyfluoride, Ti x(O/OH/F)3. TiOF2 was originally reported to adopt the cubic ReO3 structure type under ambient conditions, therefore the initial goal for this study was to examine the thermal expansion of this material and determine if it displayed interesting behavior such as NTE. During the course of the study, it was discovered that the original synthetic method resulted in Tix(O/OH/F)3, which does adopt the cubic ReO3 structure type. The chemical composition of the hydroxyoxyfluoride is highly dependent upon synthesis conditions and subsequent heat treatments. This material readily pyrohydrolyizes at low temperatures (≈350 K). It was also observed that TiOF does not adopt the cubic ReO 3 structure; at room temperature it adopts a rhombohedrally distorted variant of the ReO3 structure. Positive thermal expansion was observed for TiOF2 from 120 K through decomposition into TiO2. At ≈400 K, TiOF2 undergoes a structural phase transition from rhombohedral to cubic symmetry. High pressure diffraction studies revealed a cubic to rhombohedral phase transition for Tix(O/OH/F) 3 between 0.5-1 GPa. No phase transitions were observed for TiOF 2 on compression. In Chapter 4, an in situ variable pressure-temperature diffraction experiment examining the effects of pressure on the coefficients of thermal expansion (CTE) for ScF3 and TaO2F is presented. In the manufacture and use of composites, which is a possible application for low and NTE materials, stresses may be experienced. Pressure was observed to have a negligible effect on cubic ScF3's CTE; however, for TaO 2F the application of modest pressures, such as those that might be experienced in the manufacture or use of composites, has a major effect on its CTE. This effect is associated with a pressure-induced phase transition from cubic to rhombohedral symmetry upon compression. TaO2F was prepared from the direct reaction of Ta2O5 with TaF 5 and from the digestion of Ta2O5 in hot hydrofluoric acid. The effects of pressure on the two samples of TaO2F were qualitatively similar. The slightly different properties for the samples are likely due to differences in their thermal history leading to differing arrangements of oxide and fluoride in these disordered materials. In Chapter 5, the local structures of TiOF2 and TaO2 F are examined using pair distribution functions (PDFs) obtained from X-ray total scattering experiments. In these materials, the anions (O/F) are disordered over the available anion positions. While traditional X-ray diffraction provides detailed information about the average structures of these materials, it is not sufficient to fully understand their thermal expansion. Fits of simple structural models to the low r portions of PDFs for these materials indicate the presence of geometrically distinct M -X-M (M = Ti, Ta; X = O, F) linkages, and a simple analysis of the TaO2F variable temperature PDFs indicates that these distinct links respond differently to temperature.

  3. Competitive Incorporation of Perrhenate and Nitrate into Sodalite

    DOE PAGES

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

    2014-10-03

    Nuclear waste storage tanks at the Hanford site in southeastern Washington have released highly alkaline solutions, containing radioactive and other contaminants, into subsurface sediments. When this waste reacts with subsurface sediments, feldspathoid minerals (sodalite, cancrinite) can form, sequestering pertechnetate ( 99TcO 4 –) and other ions. This study investigates the potential for incorporation of perrhenate (ReO 4 –), a chemical surrogate for 99TcO 4 –, into mixed perrhenate/nitrate (ReO 4 –/NO 3 –) sodalite. Mixed-anion sodalites were hydrothermally synthesized in the laboratory from zeolite A in sodium hydroxide, nitrate, and perrhenate solutions at 90 °C for 24 h. The resultingmore » solids were characterized by bulk chemical analysis, X-ray diffraction, scanning electron microscopy, and X-ray absorption near edge structure spectroscopy (XANES) to determine the products’ chemical composition, structure, morphology, and Re oxidation state. The XANES data indicated that nearly all rhenium (Re) was incorporated as Re(VII)O 4 –. The nonlinear increase of the unit cell parameter with ReO 4 –/NO 3 – ratios suggests formation of two separate sodalite phases in lieu of a mixed-anion sodalite. The results reveal that the sodalite cage is highly selective toward NO 3 – over ReO 4 –. Calculated enthalpy and Gibbs free energy of formation at 298 K for NO 3 - and ReO 4 -sodalite suggest that NO 3 – incorporation into the cage is favored over the incorporation of the larger ReO 4 –, due to the smaller ionic radius of NO 3 –. In conclusion, based on these results, it is expected that NO 3 –, which is present at significantly higher concentrations in alkaline waste solutions than 99TcO 4 –, will be strongly preferred for incorporation into the sodalite cage.« less

  4. Rhenium-188: Availability from the W-188/Re-188 Generator and Status of Current Applications

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

    Pillai, M R A; Dash, A; Knapp Jr, Russ F

    Rhenium-188 is one of the most readily available generator derived and useful radionuclides for therapy emitting - particles (2.12 MeV, 71.1% and 1.965 MeV, 25.6%) and imageable gammas (155 KeV, 15.1%). The 188W/188Re generator is an ideal source for the long term (4-6 months) continuous availability of no carrier added (nca) 188Re suitable for the preparation of radiopharmaceuticals for radionuclide therapy. The challenges associated with the double neutron capture route of production of the parent 188W radionuclide have been a major impediment in the progress of application of 188Re. Tungsten-188 of adequate specific activity can be prepared only in 2-3more » of the high flux reactors operating in the World. Several useful technologies have been developed for the preparation of clinical grade 188W/188Re generator. Since the specific activity of 188W used in the generator is relatively low (<5 Ci/g), the eluted 188ReO4- can have low radioactive concentration often insufficient for radiopharmaceutical preparation. However, several efficient post elution concentration techniques have been developed that yield clinically useful 188ReO4-. Rhenium-188 has been used for the preparation of therapeutic radiopharmaceuticals for the management of diseases such as bone metastasis, rheumatoid arthritis and primary cancers. Several early phase clinical studies using radiopharmaceuticals based on 188Re-labeled phosphonates, antibodies, peptides, lipiodol and particulates have been reported. This article reviews the availability, and use of188Re including a discussion of why broader use of 188Re has not progressed as ecpected as a popular radionuclide for therapy.« less

  5. Rhenium-188: availability from the (188)W/(188)Re generator and status of current applications.

    PubMed

    Pillai, M R A; Dash, Ashutosh; Knapp, F F

    2012-07-01

    Rhenium-188 is one of the most readily available generator derived and useful radionuclides for therapy emitting β(-) particles (2.12 MeV, 71.1% and 1.965 MeV, 25.6%) and imageable gammas (155 keV, 15.1%). The (188)W/(188)Re generator is an ideal source for the long term (4-6 months) continuous availability of no carrier added (nca) (188)Re suitable for the preparation of radiopharmaceuticals for radionuclide therapy. The challenges associated with the double neutron capture route of production of the parent (188)W radionuclide have been a major impediment in the progress of application of (188)Re. Tungsten-188 of adequate specific activity can be prepared only in 2-3 of the high flux reactors operating in the World. Several useful technologies have been developed for the preparation of clinical grade (188)W/(188)Re generators. Since the specific activity of (188)W used in the generator is relatively low 185 GBq( < 5 Ci)/g], the eluted (188)ReO(4)(-) can have low radioactive concentration often insufficient for radiopharmaceutical preparation. However, several efficient post elution concentration techniques have been developed that yield clinically useful (188)ReO(4)(-) solutions. Rhenium-188 has been used for the preparation of therapeutic radiopharmaceuticals for the management of diseases such as bone metastasis, rheumatoid arthritis and primary cancers. Several early phase clinical studies using radiopharmaceuticals based on (188)Re-labeled phosphonates, antibodies, peptides, lipiodol and particulates have been reported. This article reviews the availability and use of (188)Re including a discussion of why broader use of (188)Re has not progressed as expected as a popular radionuclide for therapy.

  6. Dissecting the Re-Os molybdenite geochronometer.

    PubMed

    Barra, Fernando; Deditius, Artur; Reich, Martin; Kilburn, Matt R; Guagliardo, Paul; Roberts, Malcolm P

    2017-11-22

    Rhenium and osmium isotopes have been used for decades to date the formation of molybdenite (MoS 2 ), a common mineral in ore deposits and the world's main source of molybdenum and rhenium. Understanding the distribution of parent 187 Re and radiogenic daughter 187 Os isotopes in molybdenite is critical in interpreting isotopic measurements because it can compromise the accurate determination and interpretation of mineralization ages. In order to resolve the controls on the distribution of these elements, chemical and isotope mapping of MoS 2 grains from representative porphyry copper-molybdenum deposits were performed using electron microprobe and nano-scale secondary ion mass spectrometry. Our results show a heterogeneous distribution of 185,187 Re and 192 Os isotopes in MoS 2 , and that both 187 Re and 187 Os isotopes are not decoupled as previously thought. We conclude that Re and Os are structurally bound or present as nanoparticles in or next to molybdenite grains, recording a complex formation history and hindering the use of microbeam techniques for Re-Os molybdenite dating. Our study opens new avenues to explore the effects of isotope nuggeting in geochronometers.

  7. Rhenium-osmium isotope systematics of Group 2A and Group 4A iron meteorites

    NASA Technical Reports Server (NTRS)

    Creaser, R. A.; Papanastassiou, D. A.; Wasserburg, G. J.

    1993-01-01

    We are investigating the Re-Os isotope systematics of two groups of magmatic iron meteorites (2A, 4A) in an attempt to establish precise 'total rock' isochrons by the Re-Os system. The Re-187/Os-187 isotope system is recognized as a method by which the ages of iron meteorites can be directly determined and that can provide information on the timing of FeNi segregation and core formation in planetesimals. The Re-Os isotope system permits the direct absolute dating of the metal phase in iron meteorites. Indirect dating of iron meteorites has been achieved in the past through the Rb-Sr, K-Ar, and most recently, Sm-Nd for silicate inclusions, where present. Relative dating has been obtained directly by extensive studies of the short-lived system Pd-107/Ag-107 for the metal and sulfide phases and indirectly using I-129/Xe-129 in silicate and sulfide inclusions.

  8. Re-Os isotopic systematics in chromitites from the Stillwater Complex, Montana, USA

    NASA Astrophysics Data System (ADS)

    Marcantonio, Franco; Zindler, Alan; Reisberg, Laurie; Mathez, E. A.

    1993-08-01

    New Re-Os isotopic data on chromitites of the Stillwater Complex demonstrate isotopic equilibrium between cumulate chromite and whole rock. Initial osmium isotopic ratios for the chromitites, chosen for their freshness, are consistent with derivation from a mantle-derived magma that suffered little or no interaction with the continental crust prior to crystallization. Molybdenite, separated from a sample of the G-chromitite, yields a Re-Os age of 2740 Ma, indistinguishable from the age of the intrusion. The presence of molybdenite documents rhenium, and probably osmium, mobilization by hydrothermal fluids that permeated the intrusion shortly after crystallization. Initial osmium isotopic variability observed in chromitites and other rocks from the Stillwater Complex could result from interaction with these fluids. In this context, there is no compelling reason to call on assimilation of crust by mantle-derived magma to explain the osmium or neodymium isotopic variability. Although osmium isotopic systematics have been affected by hydrothermal processes, Re-Os results demonstrate that more than 95 percent of the osmium, and by inference other PGEs in the Stillwater Complex, derive from the mantle.

  9. Determination of rhenium content in molybdenite by ICP-MS after separation of the major matrix by solvent extraction with N-benzoyl-N-phenylhydroxalamine.

    PubMed

    Li, Jie; Zhong, Li-feng; Tu, Xiang-lin; Liang, Xi-rong; Xu, Ji-feng

    2010-05-15

    A simple and rapid analytical method for determining the concentration of rhenium in molybdenite for Re-Os dating was developed. The method used isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS) after the removal of major matrix elements (e.g., Mo, Fe, and W) from Re by solvent extraction with N-benzoyl-N-phenylhydroxylamine (BPHA) in chloroform solution. The effect on extraction efficiency of parameters such as pH (HCl concentration), BPHA concentration, and extraction time were also assessed. Under the optimal experimental conditions, the validity of the separation method was accessed by measuring (187)Re/(185)Re values for a molybdenite reference material (JDC). The obtained values were in good agreement with previously measured values of the Re standard. The proposed method was applied to replicate Re-Os dating of JDC and seven samples of molybdenite from the Yuanzhuding large Cu-Mo porphyry deposit. The results demonstrate good precision and accuracy for the proposed method. The advantages of the method (i.e., simplicity, efficiency, short analysis time, and low cost) make it suitable for routine analysis.

  10. Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield, Anhui, China

    USGS Publications Warehouse

    Liu, Gaisheng; Chou, C.-L.; Peng, Z.; Yang, G.

    2008-01-01

    Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re-Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The ??Osvalues of the two pyrite samples are +17 and +18, respectively. Such high ??Osvalues are reported for the first time for recycles crustal materials from a sedimentary basin. ?? Springer-Verlag 2007.

  11. Late Carboniferous porphyry copper mineralization at La Voluntad, Neuquén, Argentina: Constraints from Re-Os molybdenite dating

    NASA Astrophysics Data System (ADS)

    Garrido, Mirta; Barra, Fernando; Domínguez, Eduardo; Ruiz, Joaquin; Valencia, Victor A.

    2008-07-01

    The La Voluntad porphyry Cu-Mo deposit in Neuquén, Argentina, is one of several poorly known porphyry-type deposits of Paleozoic to Early Jurassic age in the central and southern Andes. Mineralization at La Voluntad is related to a tonalite porphyry from the Chachil Plutonic Complex that intruded metasedimentary units of the Piedra Santa Complex. Five new Re-Os molybdenite ages from four samples representing three different vein types (i.e., quartz-molybdenite, quartz-sericite-molybdenite and quartz-sericite-molybdenite ± chalcopyrite-pyrite) are identical within error and were formed between ~312 to ~316 Ma. Rhenium and Os concentrations range between 34 to 183 ppm and 112 to 599 ppb, respectively. The new Re-Os ages indicate that the main mineralization event at La Voluntad, associated to sericitic alteration, was emplaced during a time span of 1.7 ± 3.2 Ma and that the deposit is Carboniferous in age, not Permian as previously thought. La Voluntad is the oldest porphyry copper deposit so far recognized in the Andes and indicates the presence of an active magmatic arc, with associated porphyry style mineralization, at the proto-Pacific margin of Gondwana during the Early Pennsylvanian.

  12. XPS investigations of tribolayers formed on TiN and (Ti,Re)N coatings

    NASA Astrophysics Data System (ADS)

    Oktay, Serkan; Kahraman, Zafer; Urgen, Mustafa; Kazmanli, Kursat

    2015-02-01

    TiN and (Ti,Re)N coatings were deposited on high-speed-steel substrates by a hybrid coating system composed of cathodic arc PVD and magnetron sputtering techniques. In order to keep rhenium content low (8 ± 1.9 at.%) in the coating, magnetron sputtering technique was utilized to evaporate rhenium. The (Ti,Re)N coating consisted of TiN and ReNx (x > 1.33) phases. The hardness of TiN and (Ti,Re)N were 31 GPa and 29 GPa (± 2 GPa), respectively. Tribological behaviors of the samples were tested against Al2O3 balls at 21 °C (RT) and 150 °C (HT) by reciprocating wear technique. The tribolayers were analyzed by XPS technique. Friction coefficients of TiN were 0.56, 0.35 for 21 °C and 150 °C tests, respectively. Rhenium addition to TiN drastically dropped the friction coefficients to 0.22 and 0.17 for RT and HT samples. Rhenium addition also improved the wear resistance of the coating at both test temperatures. For TiN, main oxide component of the tribolayers was Ti2O3 for RT tests and TiO2 for HT tests. The oxide layer formed on (Ti,Re)N were the mixture of TiO2, Tisbnd Osbnd N, ReO2 and Re2O7 for both test temperatures. Re2O7 provided very low friction coefficient to (Ti,Re)N. The findings are consistent with the crystal chemistry approach.

  13. Experimental determination of the hydrothermal solubility of ReS2 and the Re–ReO2 buffer assemblage and transport of rhenium under supercritical conditions

    PubMed Central

    Xiong, Yongliang; Wood, Scott A

    2002-01-01

    To understand the aqueous species important for transport of rhenium under supercritical conditions, we conducted a series of solubility experiments on the Re–ReO2 buffer assemblage and ReS2. In these experiments, pH was buffered by the K–feldspar–muscovite–quartz assemblage; in sulfur-free systems was buffered by the Re–ReO2 assemblage; and and in sulfur-containing systems were buffered by the magnetite–pyrite–pyrrhotite assemblage. Our experimental studies indicate that the species ReCl40 is dominant at 400°C in slightly acidic to near-neutral, and chloride-rich (total chloride concentrations ranging from 0.5 to 1.0 M) environments, and ReCl3+ may predominate at 500°C in a solution with total chloride concentrations ranging from 0.5 to 1.5 M. The results also demonstrate that the solubility of ReS2 is about two orders of magnitude less than that of ReO2. This finding not only suggests that ReS2 (or a ReS2 component in molybdenite) is the solubility-controlling phase in sulfur-containing, reducing environments but also implies that a mixing process involving an oxidized, rhenium-containing solution and a solution with reduced sulfur is one of the most effective mechanisms for deposition of rhenium. In analogy with Re, TcS2 may be the stable Tc-bearing phase in deep geological repositories of radioactive wastes.

  14. Rhenium-osmium isotope systematics of carbonaceous chondrites

    USGS Publications Warehouse

    Walker, R.J.; Morgan, J.W.

    1989-01-01

    Rhenium and osmium concentrations and Os isotopic compositions of eight carbonaceous chondrites, one LL3 ordinary chondrite, and two iron meteorites were determined by resonance ionization mass spectrometry. Iron meteorite 187Re/186Os and 187OS/186Os ratios plot on the previously determined iron meteorite isochron, but most chondrite data plot 1 to 2 percent above this meteorite isochron. This suggests either that irons have significantly younger Re-Os closure ages than chondrites or that chondrites were formed from precursor materials with different chemical histories from the precursors of irons. Some samples of Semarkona (LL3) and Murray (C2M) meteorites plot 4 to 6 percent above the iron meteorite isochron, well above the field delineated by other chondrites. Murray may have lost Re by aqueous leaching during its preterrestrial history. Semarkona could have experienced a similar loss of Re, but only slight aqueous alteration is evident in the meteorite. Therefore, the isotopic composition of Semarkona could reflect assembly of isotopically heterogeneous components subsequent to 4.55 billion years ago or Os isotopic heterogeneities in the primordial solar nebula.

  15. Catalytic Hydrodeoxygenation of High Carbon Furylmethanes to Renewable Jet-fuel Ranged Alkanes over a Rhenium-Modified Iridium Catalyst.

    PubMed

    Liu, Sibao; Dutta, Saikat; Zheng, Weiqing; Gould, Nicholas S; Cheng, Ziwei; Xu, Bingjun; Saha, Basudeb; Vlachos, Dionisios G

    2017-08-24

    Renewable jet-fuel-range alkanes are synthesized by hydrodeoxygenation of lignocellulose-derived high-carbon furylmethanes over ReO x -modified Ir/SiO 2 catalysts under mild reaction conditions. Ir-ReO x /SiO 2 with a Re/Ir molar ratio of 2:1 exhibits the best performance, achieving a combined alkanes yield of 82-99 % from C 12 -C 15 furylmethanes. The catalyst can be regenerated in three consecutive cycles with only about 12 % loss in the combined alkanes yield. Mechanistically, the furan moieties of furylmethanes undergo simultaneous ring saturation and ring opening to form a mixture of complex oxygenates consisting of saturated furan rings, mono-keto groups, and mono-hydroxy groups. Then, these oxygenates undergo a cascade of hydrogenolysis reactions to alkanes. The high activity of Ir-ReO x /SiO 2 arises from a synergy between Ir and ReO x , whereby the acidic sites of partially reduced ReO x activate the C-O bonds of the saturated furans and alcoholic groups while the Ir sites are responsible for hydrogenation with H 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Monooxorhenium(V) complexes with 222-N2S2 MAMA ligands for bifunctional chelator agents: Syntheses and preliminary in vivo evaluation

    PubMed Central

    Demoin, Dustin Wayne; Dame, Ashley N.; Minard, William D.; Gallazzi, Fabio; Seickman, Gary L.; Rold, Tammy L.; Bernskoetter, Nicole; Fassbender, Michael E.; Hoffman, Timothy J.; Deakyne, Carol A.; Jurisson, Silvia S.

    2016-01-01

    Introduction Targeted radiotherapy using the bifunctional chelate approach with 186/188Re(V) is challenging because of the susceptibility of monooxorhenium(V)-based complexes to oxidize in vivo at high dilution. A monoamine-monoamide dithiol (MAMA)-based bifunctional chelating agent was evaluated with both rhenium and technetium to determine its utility for in vivo applications. Methods A 222-MAMA chelator, 222-MAMA(N-6-Ahx-OEt) bifunctional chelator, and 222- MAMA(N-6-Ahx-BBN(7-14)NH2) were synthesized, complexed with rhenium, radiolabeled with 99mTc and 186Re (carrier added and no carrier added), and evaluated in initial biological distribution studies. Results An IC50 value of 2.0 ± 0.7 nM for natReO-222-MAMA(N-6-Ahx-BBN(7-14)NH2) compared to [125I]-Tyr4-BBN(NH2) was determined through competitive cell binding assays with PC-3 tumor cells. In vivo evaluation of the no-carrier added 99mTc-222-N2S2(N-6-Ahx-BBN(7-14)NH2) complex showed little gastric uptake and blockable pancreatic uptake in normal mice. Conclusions The 186ReO-222-N2S2(N-6-Ahx-BBN(7-14)NH2) complex showed stability in biological media, which indicates that the 222-N2S2 chelator is appropriate for chelating 186/188Re in radiopharmaceuticals involving peptides. Additionally, the in vitro cell studies showed that the ReO-222-N2S2(N-6-Ahx-BBN(7-14)NH2) complex (macroscopically) bound to PC3-tumor cell surface receptors with high affinity. The 99mTc analog was stable in vivo and exhibited pancreatic uptake in mice that was blockable, indicating BB2r targeting. PMID:27694058

  17. Marine and Lacustrine Organic-rich Sedimentary Unit Time Markers: Implications from Rhenium-Osmium Geochronology

    NASA Astrophysics Data System (ADS)

    Selby, D.

    2011-12-01

    Geochronology is fundamental to understand the age, rates and durations of Earth processes. This concerned Arthur Holmes who, for much of his career, attempted to define a geological time scale. This is a topic still important to Earth Scientists today, specifically the chronostratigraphy of sedimentary rocks. Here I explore the Re-Os geochronology of marine and lacustrine sedimentary rocks and its application to yield absolute time constraints for stratigraphy. The past decade has seen the pioneering research of Re-Os organic-rich sedimentary rock geochronology blossom into a tool that can now to be used to accurately and precisely determine depositional ages of organic-rich rock units that have experienced up to low grade greenschist metamorphism. This direct dating of sedimentary rocks is critical where volcanic horizons are absent. As a result, this tool has been applied to timescale calibration, basin correlation, formation duration and the timing of key Earth events (e.g., Neoproterozoic glaciations). The application of Re-Os chronometer to the Devonian-Mississippian boundary contained within the Exshaw Formation, Canada, determined an age of 361.3 ± 2.4 Ma. This age is in accord with U-Pb dates of interbedded tuff horizons and also U-Pb zircon date for the type Devonian-Mississippian Hasselbachtal section, Germany. The agreement of the biostratigraphic and U-Pb constraints of the Exshaw Formation with the Re-Os date illustrated the potential of the Re-Os chronometer to yield age determinations for sedimentary packages, especially in the absence of interbedd tuff horizons and biozones. A Re-Os date for the proposed type section of the Oxfordian-Kimmeridgian boundary, Staffin Bay, Isle of Skye, U.K., gave an age of 154.1 ± 2.2 Ma. This Re-Os age presents a 45 % (1.8 Ma) improvement in precision for the basal Kimmeridgian. It also demonstrated that the duration of the Kimmeridgian is nominally 3.3 Ma and thus is 1.6 Ma shorter than previously indicated. In addition to these examples, several studies have presented precise dates for Phanerozoic marine organic-rich units that are in excellent agreement with biostratigraphic determinations. A recent Re-Os study of the Woodford Shale (that was deposited throughout the Frasnian and Famennian) has provided important time markers as well as suggesting that the sedimentation rate of the Formation was relatively constant for ~20 Ma. To date only marine organic-rich sedimentary rocks have been utilized for Re-Os geochronology. However, lacustrine sedimentary rocks provide an invaluable archive of continental geological processes responding to tectonic, climatic and magmatic influences. Correlating these rocks to global geological phenomena requires accurate geochronological frameworks. The organic-rich lacustrine sedimentary units of the Eocene Green River Formation are enriched is Re and Os comparable to that of marine units. The Re-Os dates for the Green River Formation from the Uinta basin are 48.5 ± 0.6 Ma and 49.2 ± 1.0 Ma. These dates are in excellent agreement with Ar/Ar and U/Pb dates of interbedded tuffs in the GRF, therefore demonstrating that lacustrine units can be used for Re-Os geochronology in addition to marine organic-rich units.

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

    DOE PAGES

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

    2016-12-05

    Here we report that treatment and immobilization of technetium-99 ( 99Tc) contained in reprocessed nuclear waste and present in contaminated subsurface systems represents a major environmental challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and meso-porous crystalline solids, specifically sodalite. We synthesized and characterized the structure of perrhenate sodalite, Na 8[AlSiO 4]6(ReO 4) 2, and the structure of a mixed guest perrhenate/pertechnetate sodalite, Na 8[AlSiO 4] 6(ReO 4) 2-x(TcO 4) x. Perrhenate was used as a chemical analogue for pertechnetate. Bulk analyses of each solid confirm a cubic sodalite-type structure (Pmore » $$\\overline{43}$$n, No. 218 space group) with rhenium and technetium in the 7+ oxidation state. High-resolution nanometer scale characterization measurements provide first-of-a-kind evidence that the ReO 4 – anions are distributed in a periodic array in the sample, nanoscale clustering is not observed, and the ReO 4 – anion occupies the center of the sodalite β-cage in Na8[AlSiO4]6(ReO4)2. We also demonstrate, for the first time, that the TcO4– anion can be incorporated into the sodalite structure. Lastly, thermochemistry measurements for the perrhenate sodalite were used to estimate the thermochemistry of pertechnetate sodalite based on a relationship between ionic potential and the enthalpy and Gibbs free energy of formation for previously measured oxyanion-bearing feldspathoid phases. The results collected in this study suggest that micro- and mesoporous crystalline solids maybe viable candidates for the treatment and immobilization of 99Tc present in reprocessed nuclear waste streams and contaminated subsurface environments.« less

  19. Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou provinces, China

    USGS Publications Warehouse

    Horan, M.F.; Morgan, J.W.; Grauch, R.I.; Coveney, R.M.; Murowchick, J.B.; Hulbert, L.J.

    1994-01-01

    Rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of Devonian black shale and an associated Ni-enriched sulfide layer from the Yukon Territory, Canada. The same composition information was also obtained for samples of early Cambrian Ni-Mo-rich sulfide layers hosted in black shale in Guizhou and Hunan provinces, China. This study was undertaken to constrain the origin of the PGE enrichment in the sulfide layers. Samples of the Ni sulfide layer from the Yukon Territory are highly enriched in Re, Os, and other PGE, with distinctly higher Re/192Os but similar Pt/Re, compared to the black shale host. Re-Os isotopic data of the black shale and the sulfide layer are approximately isochronous, and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales. Samples of the Chinese sulfide layers are also highly enriched in Re, Os, and the other PGE. Re/192Os are lower than in the Yukon sulfide layer. Re-Os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 Ma, similar to the depositional age of the black shale host. The osmium isotopic data suggest that Re and PGE enrichment of the brecciated sulfide layers in both the Yukon Territory and in southern China may have occurred near the time of sediment deposition or during early diagenesis, during the middle to late Devonian and early Cambrian, respectively. ?? 1994.

  20. Comment on "Behavior of Re and Os during contact between an aqueous solution and oil: Consequences for the application of the Re-Os geochronometer to petroleum" [Geochim. Cosmochim. Acta 158 (2015) 1-21

    NASA Astrophysics Data System (ADS)

    Wu, Jia; Li, Zhen; Wang, Xuan-ce

    2016-08-01

    In a recent study, Mahdaoui et al. (2015) simulated the contact of oil with Re/Os-bearing aqueous fluids in petroleum reservoirs and concluded that both metals could be rapidly and substantially enriched in the oil fraction. These findings could have significant geological ramifications for the use of rhenium-osmium (Re-Os) geochronology in the age-dating of oil deposits. However, the lack of data reproducibility between parallel experiments and misused parameter of "recovery rate" has cast doubt on the main conclusions of the paper. Re-analyses of the raw data provided sufficient evidence to suggest that in petroleum basins with very low abundances of Re and Os, the extraction of these metals to oil is unlikely to be a geologically instantaneous process as the authors implied in their study. In addition, the possibility of reactor leakage in the contacting experiments cannot be completely ruled out.

  1. Residency of rhenium and osmium in a heavy crude oil

    NASA Astrophysics Data System (ADS)

    DiMarzio, Jenna M.; Georgiev, Svetoslav V.; Stein, Holly J.; Hannah, Judith L.

    2018-01-01

    Rhenium-osmium (Re-Os) isotope geochemistry is an emerging tool for the study of oil formation and migration processes, and a new technology for petroleum exploration. Little is known, however, about the residency of Re and Os within asphaltene and maltene sub-fractions of crude oil. This information is crucial for understanding the 187Re-187Os radiometric clock held in petroleum systems and for interpreting geochronology for key processes such as oil formation, migration, and biodegradation. In this study, a heavy crude oil was separated into soluble (maltene, MALT) and insoluble (asphaltene, ASPH) fractions using n-heptane as the asphaltene-precipitating agent. The asphaltenes were separated sequentially into sub-fractions using two different solvent pairs (heptane-dichloromethane and acetone-toluene), and the bulk maltenes were separated into saturate, aromatic, and resin (SAR) fractions using open column chromatography. Each asphaltene and maltene sub-fraction was analyzed for Re and Os. The asphaltene sub-fractions and the bulk ASPH, MALT, and crude oil were analyzed for a suite of trace metals by ICP-MS. Our results show that Re and Os concentrations co-vary between the asphaltene sub-fractions, and that both elements are found mostly in the more polar and aromatic sub-fractions. Significant Re and Os are also present in the aromatic and resin fractions of the maltenes. However, each asphaltene and maltene sub-fraction has a distinct isotopic composition, and sub-fractions are not isochronous. This suggests that asphaltene sub-fractionation separates Re-Os complexes to the point where the isotopic integrity of the geochronometer is compromised. The mobility of individual Re and Os isotopes and the decoupling possibilities between radiogenic 187Os produced from 187Re remain elusive, but their recognition in this study is a critical first step. Re and Os correlate strongly with Mo and Cd in the asphaltene sub-fractions, suggesting that these metals occupy similar sites. Re-Os and Ni-V budgets also show some similarities, indicating that at least some Re (and possibly Os) could be present in metalloporphyrin form. We conclude that progressive asphaltene precipitation during migration and mixing of oils can change the isotopic ratios of the resultant oil. A sense of process is key to interpretation of Re-Os data for tar mats and live oils, whether isochronous or scattered datasets result. Optimally, by combining data from source rocks, oils, and asphaltenes generated along the migration pathway, we can construct temporal histories for whole petroleum systems.

  2. Rhenium complexes of bidentate, bis-bidentate and tridentate N-heterocyclic carbene ligands.

    PubMed

    Chan, Chung Ying; Barnard, Peter J

    2015-11-28

    A series of eight Rhenium(I)-N-heterocyclic carbene (NHC) complexes of the general form [ReCl(CO)3(C^C)] (where C^C is a bis(NHC) bidentate ligand), [ReCl(CO)3(C^C)]2 (where C^C is a bis-bidentate tetra-NHC ligand) and [Re(CO)3(C^N^C)](+)[X](-) (where C^N^C is a bis(NHC)-amine ligand and the counter ion X is either the ReO4(-) or PF6(-)) have been synthesised using a Ag2O transmetallation protocol. The novel precursor imidazolium salts and Re(I) complexes were characterized by elemental analysis, (1)H and (13)C NMR spectroscopy and the molecular structures for two imidazolium salt and six Re(I) complexes were determined by single crystal X-ray diffraction. These NHC ligand systems are of interest for possible applications in the development of Tc-99m or Re-186/188 radiopharmaceuticals and as such the stability of two complexes of the form [ReCl(CO)3(C^C)] and [Re(CO)3(C^N^C)][ReO4] were evaluated in ligand challenge experiments using the metal binding amino acids L-histidine or L-cysteine. These studies showed that the former was unstable, with the chloride ligand being replaced by either cysteine or histidine, while no evidence for transchelation was observed for the latter suggesting that bis(NHC)-amine ligands of this type may be suitable for biological applications.

  3. Re-Os geochronology and Os isotope fingerprinting of petroleum sourced from a Type I lacustrine kerogen: Insights from the natural Green River petroleum system in the Uinta Basin and hydrous pyrolysis experiments

    NASA Astrophysics Data System (ADS)

    Cumming, Vivien M.; Selby, David; Lillis, Paul G.; Lewan, Michael D.

    2014-08-01

    Rhenium-osmium (Re-Os) geochronology of marine petroleum systems has allowed the determination of the depositional age of source rocks as well as the timing of petroleum generation. In addition, Os isotopes have been applied as a fingerprinting tool to correlate oil to its source unit. To date, only classic marine petroleum systems have been studied. Here we present Re-Os geochronology and Os isotope fingerprinting of different petroleum phases (oils, tar sands and gilsonite) derived from the lacustrine Green River petroleum system in the Uinta Basin, USA. In addition we use an experimental approach, hydrous pyrolysis experiments, to compare to the Re-Os data of naturally generated petroleum in order to further understand the mechanisms of Re and Os transfer to petroleum. The Re-Os geochronology of petroleum from the lacustrine Green River petroleum system (19 ± 14 Ma - all petroleum phases) broadly agrees with previous petroleum generation basin models (∼25 Ma) suggesting that Re-Os geochronology of variable petroleum phases derived from lacustrine Type I kerogen has similar systematics to Type II kerogen (e.g., Selby and Creaser, 2005a,b; Finlay et al., 2010). However, the large uncertainties (over 100% in some cases) produced for the petroleum Re-Os geochronology are a result of multiple generation events occurring through a ∼3000-m thick source unit that creates a mixture of initial Os isotope compositions in the produced petroleum phases. The 187Os/188Os values for the petroleum and source rocks at the time of oil generation vary from 1.4 to 1.9, with the mode at ∼1.6. Oil-to-source correlation using Os isotopes is consistent with previous correlation studies in the Green River petroleum system, and illustrates the potential utility of Os isotopes to characterize the spatial variations within a petroleum system. Hydrous pyrolysis experiments on the Green River Formation source rocks show that Re and Os transfer are mimicking the natural system. This transfer from source to bitumen to oil does not affect source rock Re-Os systematics or Os isotopic compositions. This confirms that Os isotope compositions are transferred intact from source to petroleum during petroleum generation and can be used as a powerful correlation tool. These experiments further confirm that Re-Os systematics in source rocks are not adversely affected by petroleum maturation. Overall this study illustrates that the Re-Os petroleum geochronometer and Os isotope fingerprinting tools can be used on a wide range of petroleum types sourced from variable kerogen types.

  4. Aqueous catalysis: Methylrhenium trioxide (MTO) as a homogeneous catalyst for the Diels-Alder reaction

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

    Zhu, Z.; Espenson, J.H.

    1997-04-16

    The title compound proves to be an effective and efficient catalyst for the Diels-Alder reaction when the dienophile is an {alpha},{beta}-unsaturated ketone or aldehyde. It is especially effective in water. Equal amounts of any such dienophile and any of six representative dienes (isoprene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, cyclopentadiene, 1,2,3,4,5,-pentamethylcyclopentadiene, and 1,3-cyclohexadiene) were used, along with 1% MTO. The reactions gave usually > 90% isolated yield of the cycloaddition product except for the larger dienophiles. Nearly exclusively, there was formed one product isomer, the same one that usually predominates. The reactions were often run in chloroform (mostly) and in other organic solvents. Amore » select number were carried out in water, where the reactions gave a greater product yield in a considerably shorter time. Water, itself, is known to enhance the rates of Diels-Alder reactions, but MTO exerts an additional accelerating effect. Kinetics studies were carried out to show that the rate is proportional to the catalyst concentration. The products do not inhibit the reaction. The desirability of MTO as a Diels-Alder catalyst stems from a combination of favorable properties: the inertness to air/oxygen, the tolerance for many substrates, the use of an aqueous medium, and the absence of product inhibition. The initial step appears to be the (weak) coordination of the carbonyl oxygen to the electropositive rhenium center. Steric crowding around rhenium inhibits reactions of the larger dienophiles. 26 refs., 3 figs., 4 tabs.« less

  5. Rhenium Complex with Noninnocent Dioxolene Ligand: Combined Experimental and ab Initio Study of [(3,5-di-tert-Bu2C6H2O2)ReCl3(OPPh3)].

    PubMed

    Abramov, Pavel A; Gritsan, Nina P; Suturina, Elizaveta A; Bogomyakov, Artem S; Sokolov, Maxim N

    2015-07-20

    Reaction of [ReOCl3(PPh3)2] with 3,5-di-tert-butyl-1,2-benzoquinone (3,5-DTBQ) in hot toluene produces a new complex [(3,5-di-tert-Bu2C6H2O2)Re(OPPh3)Cl3] (1), which was isolated and characterized by elemental analysis, IR, UV-vis spectroscopy, and cyclic voltammetry. In order to clarify the charge state of rhenium and the coordinated dioxolene ligand, X-ray experiments at 150 and 290 K were carried out. The C-O, C-C, and Re-O bond distances at both 150 and 290 K fall between those for semiquinolate (3,5-DTBSQ) and catecholate (3,5-DTBCat) forms; an empirical "metrical oxidation state" of the dioxolene ligand was estimated to be -1.5. High-level ab initio calculations (SOC-CASSCF/NEVPT2) revealed a mixed valence nature of the triplet ground state of complex 1 corresponding to a superposition of the Re(IV)-SQ and Re(V)-cat forms. In agreement with the high-level ab initio and DFT calculations, the temperature dependence of the magnetic susceptibility (5-300 K) is well described in the assumption of the triplet ground state, with the anomalously large zero-field splitting (ZFS) arising from the spin-orbit coupling. According to the ab initio calculations, all absorption bands in the visible region of the electronic absorptions spectrum are assigned to the LMCT bands, with significant contribution of the intraligand transition in the most intense band at 555 nm.

  6. Deceased Slabs Drive Oil

    NASA Astrophysics Data System (ADS)

    Stein, H. J.; Hannah, J. L.

    2017-12-01

    The application of Re-Os isotope geochemistry to dating single oils is a nascent field [1,2]. Challenges include dissection of oils into asphaltene-maltene (ASPH-MALT) components in a way that preserves meaningful chronologic and source information. Significantly, oil-water mixing rapidly transfers Os to the oil, while Re exchange is sluggish [3]. The Os initial ratio of the oil is shifted in the direction of Os carried in the aqueous fluid, whereas the Re-Os isotopic age is preserved. We show that this phenomenon is operative in natural systems. Further, we show that deserpentinization of old oceanic slabs [4], may be linked to expulsion of Os-enriched waters into overlying sedimentary sections - a process that may be of fundamental importance for oil generation. This conclusion does not diminish the role of traditional organic-rich shales as source rocks for the hydrocarbon, but shows that external fluids are essential to petroleum generation. Moreover, the external fluids may be an important driver for expulsion and migration of oils. We have taken apart several petroleum systems from source rock, to residual oil, to tar mat development, to in situ live oil, through to produced oil. In many cases, a fluid with low 187Os/188Os - unlike that of normal basinal brines - provides a critical component to the oil-water mixture. Funding - CHRONOS project supported by Norwegian petroleum industry (Eni-Norge, Lundin, Aker BP) Acknowledgement - Christine Fichler [4], who first queried us on old slabs and oil, and stimulated ideas. [1] Georgiev, S.V., Stein, H.J., Hannah, J.L., Galimberti, R., Nali, M., Yang, G., and Zimmerman, A. (2016) Re-Os dating of maltenes and asphaltenes within single samples of crude oil: Geochim. Cosmochim. Acta 179: 53-75. [doi.org/10.1016/j.gca.2016.01.016] [2] DiMarzio, J., Georgiev, S.V., Stein, H.J., and Hannah, J.L. (in press) Residency of rhenium and osmium in a heavy crude oil: Geochim. Cosmochim. Acta. [3] Hurtig, N.C., Georgiev, S.V., Stein, H.J., and Hannah, J.L. (in review) Re-Os in oil - in the company of water. [4] Fichler, C., Odinsen, T., Rueslåtten, H., Olesen, O., Vingstad, J.-E., Wienecke, S. (2011) Crustal inhomogenities in the northern North Sea from potential field modeling: inherited structure and serpentinites: Tectonophysics 510: 172-185. [doi:10.1016/j.tecto.2011.06.026

  7. Phosphorescent heterobimetallic complexes involving platinum(iv) and rhenium(vii) centers connected by an unsupported μ-oxido bridge.

    PubMed

    Molaee, Hajar; Nabavizadeh, S Masoud; Jamshidi, Mahboubeh; Vilsmeier, Max; Pfitzner, Arno; Samandar Sangari, Mozhgan

    2017-11-28

    Heterobimetallic compounds [(C^N)LMe 2 Pt(μ-O)ReO 3 ] (C^N = ppy, L = PPh 3 , 2a; C^N = ppy, L = PMePh 2 , 2b; C^N = bhq, L = PPh 3 , 2c; C^N = bhq, L = PMePh 2 , 2d) containing a discrete unsupported Pt(iv)-O-Re(vii) bridge have been synthesized through a targeted synthesis route. The compounds have been prepared by a single-pot synthesis in which the Pt(iv) precursor [PtMe 2 I(C^N)L] complexes are allowed to react easily with AgReO 4 in which the iodide ligand of the starting Pt(iv) complex is replaced by an ReO 4 - anion. In these Pt-O-Re complexes, the Pt(iv) centers have an octahedral geometry, completed by a cyclometalated bidentate ligand (C^N), two methyl groups and a phosphine ligand, while the Re(vii) centers have a tetrahedral geometry. Elemental analysis, single crystal X-ray diffraction analysis and multinuclear NMR spectroscopy are used to establish their identities. The new complexes exhibit phosphorescence emission in the solid and solution states at 298 and 77 K, which is an uncommon property of platinum complexes with an oxidation state of +4. According to DFT calculations, we found that this emission behavior in the new complexes originates from ligand centered 3 LC (C^N) character with a slight amount of metal to ligand charge transfer ( 3 MLCT). The solid-state emission data of the corresponding cycloplatinated(iv) precursor complexes [PtMe 2 I(C^N)L], 1a-1d, pointed out that the replacement of I - by an ReO 4 - anion helps enhancing the emission efficiency besides shifting the emission wavelengths.

  8. Rhenium - osmium heterogeneity of enriched mantle basalts explained by composition and behaviour of mantle-derived sulfides

    NASA Astrophysics Data System (ADS)

    Harvey, J.; Dale, C. W.; Gannoun, A.; Burton, K. W.

    2010-12-01

    Analyses of enriched mantle (EM) -basalts, using lithophile element-based isotope systems have long provided evidence for discrete, but variable mantle reservoirs [1]. Upon partial melting, the isotopic fingerprint of each reservoir is imparted upon the partial melt produced. However, recent work involving the Re-Os isotope systematics of EM-basalts [2] suggests that it may not be so simple to delimit these previously well defined mantle reservoirs; the “mantle zoo” [3] may contain more reservoirs than previously envisaged. However, a simple model, with varying contributions from two populations of compositionally distinct mantle sulfides can readily account for the observed heterogeneities in Re-Os isotope systematics of such basalts without additional mantle reservoirs. Rhenium-osmium elemental and isotopic analyses of individual sulfide grains separated from spinel lherzolites from Kilbourne Hole, NM, USA demonstrate that two discrete populations of mantle sulfide exist in terms of both Re-Os systematics and textural relationship with co-existing silicates. One population, with a rounded morphology, is preserved in silicate grains and typically possesses high [Os], low [Re] with unradiogenic, typically sub-chondritic, 187Os/188Os attributable to long term isolation in a low-Re environment. By contrast, irregular-shaped sulfides, preserved along silicate grain boundaries, possess low [Os], higher [Re] and a wider range of, but generally supra-chondritic, 187Os/188Os ([Os] typically ≤ 1-2 ppm, 187Os/188Os ≤ 0.3729; this study). This population is thought to represent metasomatic sulfide (e.g. [4,5]). Uncontaminated silicate phases contain negligible Os (<100 ppt) therefore the Os elemental and isotope composition of basalts is dominated by volumetrically insignificant sulfide ([Os] ≤ 37 ppm, this study). During the early stages of partial melting, supra-chondritic interstitial sulfides are mobilized and incorporated into the melt, adding their radiogenic 187Os/188Os signature. Only when sulfides armored within silicates are exposed to the melt through continued partial melting will enclosed sulfides add their high [Os] and unradiogenic 187Os/188Os to the aggregate melt. Platinum-group element data for whole rocks are also consistent with this scenario. The sequence of (i) addition of all the metasomatic sulfide, followed by (ii) the incorporation of small amounts of armored sulfide can thus account for the range of both [Os] and 187Os/188Os of EM-basalts worldwide without the need for contributions from additional silicate mantle reservoirs. References: [1] Zindler & Hart, (1986) Annu. Rev. Earth Planet. Sci. 14, 493-571. [2] Class et al. (2009) Earth Planet. Sci. Lett. 284, 219-227. [3] Stracke, et al. (2005) Geochem., Geophys., Geosys. 6, doi:10.1029/2004GC000824. [4] Burton et al., Earth Planet. Sci. Lett. (1999) 172, 311-322. [5] Alard et al., (2002) Earth Planet. Sci. Lett. 203, 651-663

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

    PubMed

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

    2016-12-01

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

  10. Characterising molecules for fundamental physics: an accurate spectroscopic model of methyltrioxorhenium derived from new infrared and millimetre-wave measurements.

    PubMed

    Asselin, Pierre; Berger, Yann; Huet, Thérèse R; Margulès, Laurent; Motiyenko, Roman; Hendricks, Richard J; Tarbutt, Michael R; Tokunaga, Sean K; Darquié, Benoît

    2017-02-08

    Precise spectroscopic analysis of polyatomic molecules enables many striking advances in physical chemistry and fundamental physics. We use several new high-resolution spectroscopic devices to improve our understanding of the rotational and rovibrational structure of methyltrioxorhenium (MTO), the achiral parent of a family of large oxorhenium compounds that are ideal candidate species for a planned measurement of parity violation in chiral molecules. Using millimetre-wave and infrared spectroscopy in a pulsed supersonic jet, a cryogenic buffer gas cell, and room temperature absorption cells, we probe the ground state and the Re[double bond, length as m-dash]O antisymmetric and symmetric stretching excited states of both CH 3 187 ReO 3 and CH 3 185 ReO 3 isotopologues in the gas phase with unprecedented precision. By extending the rotational spectra to the 150-300 GHz range, we characterize the ground state rotational and hyperfine structure up to J = 43 and K = 41, resulting in refinements to the rotational, quartic and hyperfine parameters, and the determination of sextic parameters and a centrifugal distortion correction to the quadrupolar hyperfine constant. We obtain rovibrational data for temperatures between 6 and 300 K in the 970-1015 cm -1 range, at resolutions down to 8 MHz and accuracies of 30 MHz. We use these data to determine more precise excited-state rotational, Coriolis and quartic parameters, as well as the ground-state centrifugal distortion parameter D K of the 187 Re isotopologue. We also account for hyperfine structure in the rovibrational transitions and hence determine the upper state rhenium atom quadrupole coupling constant eQq'.

  11. Preparation and evaluation of rhenium-188-pamidronate as a palliative treatment in bone metastasis.

    PubMed

    Erfani, Mostafa; Rahmani, Nasim; Doroudi, Alireza; Shafiei, Mohammad

    2017-06-01

    Rhenium-188-hydroxyethylidene diphosphonate ( 188 Re-HEDP) as a first generation bisphosphonate has been widely used for bone seeking radiopharmaceutical in cases of metastatic bone disease. No study has been yet reported on preparing a complex of 188 Re with pamidronate (3-aminohydroxypropylidene-1,1-bisphosphonic acid) (PMA) as a second generation bisphosphonate. Based on this fact, it was hypothesized that a bone-seeking 188 Re-PMA radiopharmaceutical could be developed as an agent for palliative radiotherapy of bone pain due to skeletal metastases. Pamidronate was labeled with 188 ReO 4 - eluted from the alumina based 188 W/ 188 Re generator. Labeling was optimized, and radiochemical analysis was performed by thin layer chromatography (TLC) and high performance liquid chromatography (HPLC). Biodistribution of this radioconjugate was evaluated and verified further in mice. 188 Re-PMA was prepared successfully in a high labeling yield (˃95%) corresponding to a specific activity of 124MBq/μmol and good in vitro stability, but it is likely to consist of multiple species. In biodistribution studies selective uptake and retention of activity in the skeletal system (0.81±0.25% ID/g and 0.57±0.16 at 4 and 48h in bone post injection respectively) followed by clearance in the soft tissues were observed. These results show that due to its biological capabilities it would be advantageous to use 188 Re-PMA for bone pain palliation therapy. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Glass microspheres for medical applications

    NASA Astrophysics Data System (ADS)

    Conzone, Samuel David

    Radioactive dysprosium lithium borate glass microspheres have been developed as biodegradable radiation delivery vehicles for the radiation synovectomy treatment of rheumatoid arthritis. Once injected into a diseased joint, the microspheres deliver a potent dose of radiation to the diseased tissue, while a non-uniform chemical reaction converts the glass into an amorphous, porous, hydrated dysprosium phosphate reaction product. The non-radioactive, lithium-borate component is dissolved from the glass (up to 94% weight loss), while the radioactive 165Dy reacts with phosphate anions in the body fluids, and becomes "chemically" trapped in a solid, dysprosium phosphate reaction product that has the same size as the un-reacted glass microsphere. Ethylene diamine tetraacetate (EDTA) chelation therapy can be used to dissolve the dysprosium phosphate reaction product after the radiation delivery has subsided. The dysprosium phosphate reaction product, which formed in vivo in the joint of a Sprague-Dawley rat, was dissolved by EDTA chelation therapy in <1 week, without causing any detectable joint damage. The combination of dysprosium lithium borate glass microspheres and EDTA chelation therapy provides an unique "tool" for the medical community, which can deliver a large dose (>100 Gy) of localized beta radiation to a treatment site within the body, followed by complete biodegradability. The non-uniform reaction process is a desirable characteristic for a biodegradable radiation delivery vehicle, but it is also a novel material synthesis technique that can convert a glass to a highly porous materials with widely varying chemical composition by simple, low-temperature, glass/solution reaction. The reaction product formed by nonuniform reaction occupies the same volume as the un-reacted glass, and after drying for 1 h at 300°C, has a specific surface area of ≈200 m2/g, a pore size of ≈30 nm, and a nominal crushing strength of ≈10 MPa. Finally, rhenium glass microspheres, composed of micron-sized, metallic rhenium particles dispersed within a magnesium alumino borate glass matrix were produced by sintering ReO2 powder and glass frit at 1050°C. A 50 mg injection of radioactive rhenium glass microspheres containing 3.7 GBq of 186Re and 8.5 GBq of 188Re could be used to deliver a 100 Gy dose to a cancerous tumor, while limiting the total body dose caused by rhenium dissolution to approximately 1 mGy.

  13. Tellurite glasses for vitrification of technetium-99 from pyrochemical processing

    NASA Astrophysics Data System (ADS)

    Pyo, Jae-Young; Lee, Cheong Won; Park, Hwan-Seo; Yang, Jae Hwan; Um, Wooyong; Heo, Jong

    2017-09-01

    A new alkali-alumino tellurite glass composition was developed to immobilize highly-volatile technetium (Tc) wastes generated from the pyrochemical processing technology. Tellurite glass can incorporate up to 7 mass% of rhenium (Re, used as a surrogate for Tc) with an average retention of 86%. Normalized elemental releases evaluated by seven-day product consistency test (PCT) satisfied the immobilized low activity waste requirements of United States when concentration of Ca(ReO4)2 in the glass was <12 mass%. Re ions form Re7+ and are coordinated with four oxygens to form ReO4- tetrahedra. These tetrahedra bond to modifiers such as Ca2+ or Na+ that are further connected to the tellurite glass network by Ca2+ (or Na+) - non-bridging oxygen bonds.

  14. Room temperature synthesis of ReS2 through aqueous perrhenate sulfidation

    NASA Astrophysics Data System (ADS)

    Borowiec, Joanna; Gillin, William P.; Willis, Maureen A. C.; Boi, Filippo S.; He, Y.; Wen, J. Q.; Wang, S. L.; Schulz, Leander

    2018-02-01

    In this study, a direct sulfidation reaction of ammonium perrhenate (NH4ReO4) leading to a synthesis of rhenium disulfide (ReS2) is demonstrated. These findings reveal the first example of a simplistic bottom-up approach to the chemical synthesis of crystalline ReS2. The reaction presented here takes place at room temperature, in an ambient and solvent-free environment and without the necessity of a catalyst. The atomic composition and structure of the as-synthesized product were characterized using several analysis techniques including energy dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, x-ray diffraction, transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis and differential scanning calorimetry. The results indicated the formation of a lower symmetry (1Tʹ) ReS2 with a low degree of layer stacking.

  15. Room temperature synthesis of ReS2 through aqueous perrhenate sulfidation.

    PubMed

    Borowiec, Joanna; Gillin, William P; Willis, Maureen A C; Boi, Filippo S; He, Y; Wen, J Q; Wang, S L; Schulz, Leander

    2018-01-11

    In this study, a direct sulfidation reaction of ammonium perrhenate (NH 4 ReO 4 ) leading to a synthesis of rhenium disulfide (ReS 2 ) is demonstrated. These findings reveal the first example of a simplistic bottom-up approach to the chemical synthesis of crystalline ReS 2 . The reaction presented here takes place at room temperature, in an ambient and solvent-free environment and without the necessity of a catalyst. The atomic composition and structure of the as-synthesized product were characterized using several analysis techniques including energy dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, x-ray diffraction, transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis and differential scanning calorimetry. The results indicated the formation of a lower symmetry (1T') ReS 2 with a low degree of layer stacking.

  16. Fractionation of rhenium from osmium during noble metal alloy formation in association with sulfides: Implications for the interpretation of model ages in alloy-bearing magmatic rocks

    NASA Astrophysics Data System (ADS)

    Fonseca, Raúl O. C.; Brückel, Karoline; Bragagni, Alessandro; Leitzke, Felipe P.; Speelmanns, Iris M.; Wainwright, Ashlea N.

    2017-11-01

    Although Earth's continental crust is thought to derive from melting of the Earth's mantle, how the crust has formed and the timing of its formation are not well understood. The main difficulty in understanding how the crust was extracted from the Earth's mantle is that most isotope systems recorded in mantle rocks have been disturbed by crustal recycling, metasomatic activity and dilution of the signal by mantle convection. In this regard, important age constraints can be obtained from Re-Os model ages in platinum group minerals (PGM), as Re-poor and Os-rich PGM show evidence of melting events up to 4.1 Ga. To constrain the origin of the Re-Os fractionation and Os isotope systematics of natural PGM, we have investigated the linkage between sulfide and PGM grains of variable composition via a series of high-temperature experiments carried out at 1 bar. We show that with the exception of laurite, all experimentally-produced PGM, in particular Pt3Fe (isoferroplatinum) and Pt-Ir metal grains, are systematically richer in Re than their sulfide precursors and will develop radiogenic 187Os /188Os signatures over time relative to their host base metal sulfides. Cooling of an PGM-saturated sulfide assemblage shows a tendency to amplify the extent of Re-Os fractionation between PGM and the different sulfide phases present during cooling. Conversely, laurite grains (RuS2) are shown to accept little to no Re in them and their Os isotope composition changes little over time as a result. Laurite is therefore the PGM that provides the most robust Re-depletion ages in mantle lithologies. Our results are broadly consistent with observations made on natural PGM, where laurites are systematically less radiogenic than Pt-rich PGM. These experimental results highlight the need for the acquisition of large datasets for both mantle materials and ophiolite-derived detrital grains that include measurements of the Os isotope composition of minerals rich in highly siderophile elements at the grain scale (i.e. PGM and base metal sulfides). Only with such datasets is it possible to identify past episodes of mantle melting.

  17. Ka Whanau mai te Reo: Honouring Whanau, Upholding Reo Maori

    ERIC Educational Resources Information Center

    Bright, Nicola; Barnes, Alex; Hutchings, Jessica

    2013-01-01

    This is the first report from a 3-year (2012-2015) kaupapa Maori research project that investigates how best to support the continuity of reo Maori development of whanau as they transition between kohanga reo, kura kaupapa primary, wharekura, secondary and beyond. It aims to provide useful information about the reo Maori education options that are…

  18. Evaluation of chromosomal aberrations induced by 188Re-dendrimer nanosystem on B16f1 melanoma cells.

    PubMed

    Tassano, Marcos; Oddone, Natalia; Fernández, Marcelo; Porcal, Williams; García, María Fernanda; Martínez-López, Wilner; Benech, Juan Claudio; Cabral, Pablo

    2018-06-19

    To study the rhenium-188 labeling of polyamidoamine (PAMAM) generation 4 (G4) dendrimer and its evaluation on biodistribution and chromosomal aberrations in melanoma cells induced by ionizing radiation as potential treatment agent. Dendrimers were first conjugated with Suc-HYNIC (succinimidyl 6-hydrazinopyridine-3-carboxylic acid hydrochloride). Dendrimer-HYNIC was then incubated with 188 ReO 4 - . Biodistribution was performed administrating 188 Re-dendrimer to normal (NM) or melanoma-bearing mice (MBM). Chromosome aberration test was conducted in order to measure treatment capacity of 188 Re-dendrimer in melanoma cells. Radiolabeling yield of dendrimer was approx. 70%. Biodistribution studies in NM showed blood clearance with hepatic and renal depuration. MBM showed a similar pattern of biodistribution with tumor uptake of 6% of injected dose. Aberrant metaphases quantified in control cells were 7%, increasing to 29.5% in cells treated with 15μCi (0.555 MBq) of 188 Re-dendrimer for 24 h. 188 Re-dendrimer can produce double-stranded breaks in DNA induced by ionizing radiation in melanoma cells in vitro.

  19. 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

  20. Rhenium Complexes and Clusters Supported on c-Al2O3: Effects of Rhenium Oxidation State and Rhenium Cluster Size on Catalytic Activity for n-butane Hydrogenolysis

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

    Lobo Lapidus, R.; Gates, B

    2009-01-01

    Supported metals prepared from H{sub 3}Re{sub 3}(CO){sub 12} on {gamma}-Al{sub 2}O{sub 3} were treated under conditions that led to various rhenium structures on the support and were tested as catalysts for n-butane conversion in the presence of H{sub 2} in a flow reactor at 533 K and 1 atm. After use, two samples were characterized by X-ray absorption edge positions of approximately 5.6 eV (relative to rhenium metal), indicating that the rhenium was cationic and essentially in the same average oxidation state in each. But the Re-Re coordination numbers found by extended X-ray absorption fine structure spectroscopy (2.2 and 5.1)more » show that the clusters in the two samples were significantly different in average nuclearity despite their indistinguishable rhenium oxidation states. Spectra of a third sample after catalysis indicate approximately Re{sub 3} clusters, on average, and an edge position of 4.5 eV. Thus, two samples contained clusters approximated as Re{sub 3} (on the basis of the Re-Re coordination number), on average, with different average rhenium oxidation states. The data allow resolution of the effects of rhenium oxidation state and cluster size, both of which affect the catalytic activity; larger clusters and a greater degree of reduction lead to increased activity.« less

  1. 187Re - 187Os Nuclear Geochronometry: A New Dating Method Applied to Old Ores

    NASA Astrophysics Data System (ADS)

    Roller, Goetz

    2015-04-01

    187Re - 187Os nuclear geochronometry is a newly developed dating method especially (but not only) for PGE hosting magmatic ore deposits. It combines ideas of nuclear astrophysics with geochronology. For this, the concept of sudden nucleosynthesis [1-3] is used to calculate so-called nucleogeochronometric Rhenium-Osmium two-point-isochrone (TPI) ages. Here, the method is applied to the Sudbury Igneous Complex (SIC) and the Stillwater Complex (SC), using a set of two nuclear geochronometers. They are named the BARBERTON ( Re/Os = 0.849, 187Os/186Os = 10.04 ± 0.015 [4]) and the IVREA (Re/Os = 0.951, 187Os/186Os = 1.9360 ± 0.0015 [5]) nuclear geochronometer. Calculated TPI ages are consistent with results from Sm-Nd geochronology, a previously published Re-Os Molybdenum age of 2740 ± 80 Ma for the G-chromitite of the SC [6] and a Re-Os isochrone age of 1689 ± 160 Ma for the Strathcona ores of the SIC [7]. This leads to an alternative explanation of the peculiar and enigmatic 187Os/186Osi isotopic signatures reported from both ore deposits. For example, for a TPI age of 2717 ± 100 Ma the Ultramafic Series of the SC contains both extremely low (subchrondritic) 187Os/186Osi ratios (187Os/186Osi = 0.125 ± 0.067) and extremely radiogenic isotopic signatures (187Os/186Osi = 6.55 ± 1.7, [6]) in mineral separates (chromites) and whole rock samples, respectively. Within the Strathcona ores of the SIC, even more pronounced radiogenic 187Os/186Os initial ratios can be calculated for TPI ages between 1586 ± 63 Ma (187Os/186Osi = 8.998 ± 0.045) and 1733 ± 84 Ma (187Os/186Osi = 8.901 ± 0.059). These results are in line with the recalculated Re-Os isochrone age of 1689 ± 160 Ma (187Os/186Osi = 8.8 ± 2.3 [7]). In the light of nuclear geochronometry, the occurrence of such peculiar isotopic 187Os/186Osi signatures within one and the same lithological horizon are plausible if explained by mingling of the two nucleogeochronometric (BARBERTON and IVREA) reservoirs containing very old rapid (r) neutron-capture process signatures from (at least) two different events. In this scenario, intermediate 187Os/186Osi ratios are due to mixing, resulting from the interaction of the two ancient components. Since there is a striking agreement between the nucleogeochronometric TPI ages and the conventional isochrone and mineral ages for the SC and SIC, respectively, nuclear geochronometry may offer an enormous potential for exploration purposes in mining industry, especially if additional geochemical and petrologic cross-correlations are taken into account. Furthermore, there might be now a new and promising opportunity to understand the link between magmatic ore forming processes and global geodynamics. [1] Burbidge et al. (1957) Revs. Mod. Phys. 29, 547 - 650. [2] Cameron (1957), CRL-41, Atomic Energy of Canada Limited, Chalk River, Ontario. [3] Hoyle et al. (1960) ApJ 132, 565 - 590. [4] Birck et al. (1994) EPSL 124, 139-148. [5] Roller (1997), PhD Thesis, RKP N+T, Munich. [6] Marcantonio et al. (1993), GCA 57, 4029 - 4037. [7] Walker et al. (1991) EPSL 105, 416 - 429.

  2. Arsenic trioxide mediates HAPI microglia inflammatory response and subsequent neuron apoptosis through p38/JNK MAPK/STAT3 pathway

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

    Mao, Jiamin

    Arsenic is a widely distributed toxic metalloid all over the world. Inorganic arsenic species are supposed to affect astrocytic functions and to cause neuron apoptosis in CNS. Microglias are the key cell type involved in innate immune responses in CNS, and microglia activation has been linked to inflammation and neurotoxicity. In this study, using ELISA, we showed that Arsenic trioxide up-regulated the expression and secretion of IL-1β in a dose-dependent manner and a time-dependent manner in cultured HAPI microglia cells. The secretion of IL-1β caused the apoptosis of SH-SY5Y. These pro-inflammatory responses were inhibited by the STAT3 blocker, AG490 andmore » P38/JNK MAPK blockers SB202190, SP600125. Further, Arsenic trioxide exposure could induce phosphorylation and activation of STAT3, and the translocation of STAT3 from the cytosol to the nucleus in this HAPI microglia cell line. Thus, the STAT3 signaling pathway can be activated after Arsenic trioxide treatment. However, P38/JNK MAPK blockers SB202190, SP600125 also obviously attenuated STAT3 activation and transnuclear transport induced by Arsenic trioxide. In concert with these results, we highlighted that the secretion of IL-1β and STAT3 activation induced by Arsenic trioxide can be mediated by elevation of P38/JNK MAPK in HAPI microglia cells and then induced the toxicity of neurons. - Highlights: • Arsenic trioxide exposure induced expression of IL-β in HAPI microglia. • Arsenic trioxide exposure induced activation of MAPK pathways in HAPI microglia. • Arsenic trioxide exposure induced activation of STAT3 pathways in HAPI microglia. • The expression of IL-β though P38/JNK MAPK/STAT3 pathways in HAPI microglia.« less

  3. Mechanical properties of electron-beam-melted molybdenum and dilute molybdenum-rhenium alloys

    NASA Technical Reports Server (NTRS)

    Klopp, W. D.; Witzke, W. R.

    1972-01-01

    A study of molybdenum and three dilute molybdenum-rhenium alloys was undertaken to determine the effects of rhenium on the low temperature ductility and other mechanical properties of molybdenum. Alloys containing 3.9, 5.9, and 7.7 atomic percent rhenium exhibited lower ductile-brittle transition temperatures than did the unalloyed molybdenum. The maximum improvement in the annealed condition was observed for molybdenum - 7.7 rhenium, which had a ductile-brittle transition temperature approximately 200 C (360 F) lower than that for unalloyed molybdenum. Rhenium additions also increased the low and high temperature tensile strengths and the high temperature creep strength of molybdenum. The mechanical behavior of dilute molybdenum-rhenium alloys is similar to that observed for dilute tungsten-rhenium alloys.

  4. High inflammogenic potential of rare earth oxide nanoparticles: the New Hazardous Entity.

    PubMed

    Han, Youngju; Lee, Dong-Keon; Kim, Sung-Hyun; Lee, Seonghan; Jeon, Soyeon; Cho, Wan-Seob

    2018-05-30

    Due to the exponential increase in the development and utilization of rare earth oxide nanoparticles (REO NPs) in various fields, the possibility of exposure in humans by inhalation has increased. However, there are little information about hazards of REO NPs and its mechanisms of toxicity. In this study, we evaluated the acute pulmonary inflammation using 10 REO NPs (Dy 2 O 3 , Er 2 O 3 , Eu 2 O 3 , Gd 2 O 3 La 2 O 3 , Nd 2 O 3 , Pr 6 O 11 , Sm 2 O 3 , Tb 4 O 7 , and Y 2 O 3 ) and four well-known toxic particles (CuO, NiO, ZnO, and DQ12). Minimum three doses per NP were instilled into the lungs of female Wistar rats at surface area dose metric and lung inflammation was evaluated at 24 h post-instillation by bronchoalveolar lavage fluid (BALF) analysis and histopathological observation. All types of REO NPs showed common pathological changes including mild to moderate infiltration of neutrophils and activated macrophages in the alveoli, peribronchial, and perivascular region. The inflammogenic potential evaluated by the number of granulocytes divided by the treated surface area dose showed all types of REO NPs has much higher inflammogenic potential than DQ12, ZnO, and NiO NPs. The correlation plot between the number of granulocytes and the potential for reactive oxygen species (ROS) generation showed a good correlation with exception of Pr 6 O 11 . The higher inflammogenic potential of REO NPs than that of well-known highly toxic particles imply that REO NPs need special attention for inhalation exposure and more studies are needed. In addition, the potential of ROS generation is one of the key factors producing lung inflammation by REO NPs.

  5. Diamond growth beneath Letlhakane established by Re-Os and Sm-Nd systematics of individual eclogitic sulphide, garnet and clinopyroxene inclusions

    NASA Astrophysics Data System (ADS)

    Gress, Michael U.; Pearson, D. Graham; Timmerman, Suzette; Chinn, Ingrid L.; Koornneef, Janne M.; Davies, Gareth R.

    2017-04-01

    The diamondiferous Letlhakane kimberlites are part of the Orapa kimberlite cluster (˜ 93.1 Ma) in north-eastern Botswana, located on the edge of the Zimbabwe Craton, close to the Proterozoic Magondi Mobile Belt. Here we report the first Re-Os ages of six individual eclogitic sulphide inclusions (3.0 to 35.7μg) from Letlhakane diamonds along with their rhenium, osmium, iridium and platinum concentrations, and carbon isotope, nitrogen content and N-aggregation data from the corresponding growth zones of the host diamonds. For the first time, Re-Os data will be compared to Sm-Nd ages of individual eclogitic silicate inclusions recovered from the same diamonds using a Triton Plus equipped with four 1013Ω amplifiers. The analysed inclusion set currently encompasses pairs of individual sulphides from two diamonds (LK040 sf4 & 5, LK113 sf1 & 2) and two sulphide inclusions from separate diamonds (LK048, LK362). Ongoing work will determine the Sm-Nd ages and element composition of multiple individual eclogitic garnets (LK113/LK362, n=4) and an eclogitic clinopyroxene (LK040) inclusion. TMA ages of the six sulphides range from 1.06 to 2.38 Ga (± 0.1 to 0.54 Ga) with Re and Os contents between 7 and 68 ppb and 0.03 and 0.3 ppb, respectively. The host diamond growth zones have low nitrogen abundances (21 to 43 ppm N) and high N-aggregation (53 to 90% IaB). Carbon isotope data suggests the involvement of crustal carbon (δ13C between -19.3 to -22.7 ± 0.2 per mill) during diamond precipitation. Cathodoluminescence imaging of central plates from LK040 and LK113 displays homogenous internal structure with no distinct zonation. The two sulphide inclusions from LK040 define an 'isochron' of 0.92 ± 0.23 Ga (2SD) with initial 187Os/188Os = 1.31 ± 0.24. Sulphides from LK113 have clear imposed diamond morphology and indicate diamond formation at 0.93 ± 0.36 Ga (2SD) with initial 187Os/188Os = 0.69 ± 0.44. The variation in the initial 187Os/188Os does not justify including these inclusions (or any from other diamonds) on the same isochron and implies an extremely heterogeneous diamond crystallisation environment that incorporated recycled Os. C1-normalized osmium, iridium and platinum (PGE) compositions from the analysed sulphide inclusions display enrichment in Ir (3.4 to 33) and Pt (2.3 to 28.1) in comparison to eclogitic xenolith data from Orapa that are depleted relative to chondrite. The Re-Os isochrons determined in this study are within error of previously reported ages from the adjacent (˜40km) Orapa diamond mine (1.0 to 2.9 Ga) based on sulphide inclusions and a multi-point 990 ± 50 Ma (2SD) isochron for composite (n=730) silicate inclusions. Together with additional new Sm-Nd isochron age determinations from individual silicate inclusions from Letlhakane (2.3 ± 0.02 (n = 3); 1.0 ± 0.14 (n = 4) and 0.25 ± 0.04 Ga (n = 3), all 2SE) these data suggest a phase of Mesoproterozoic diamond formation as well as Neoarchean/Paleoproterozoic and Mesozoic diamond growth, in punctuated events spanning >2.0 Ga.

  6. Rhenium-osmium systematics of calcium-aluminium-rich inclusions in carbonaceous chondrites

    USGS Publications Warehouse

    Becker, H.; Morgan, J.W.; Walker, R.J.; MacPherson, G.J.; Grossman, J.N.

    2001-01-01

    The Re-Os isotopic systematics of calcium-aluminium-rich inclusions (CAIs) in chondrites were investigated in order to shed light on the behavior of the Re-Os system in bulk chondrites, and to constrain the timing of chemical fractionation in primitive chondrites. CAIs with relatively unfractionated rare earth element (REE) patterns (groups I, III, V, VI) define a narrow range of 187Re/188Os (0.3764-0.4443) and 187Os/188Os (0.12599-0.12717), and high but variable Re and Os abundances (3209-41,820 ppb Os). In contrast, CAIs that show depletions in highly refractory elements and strongly fractionated REE patterns (group II) also show a much larger range in 187Re/188Os (0.409-0.535) and 187Os/188Os (0.12695-0.13770), and greater than an order of magnitude lower Re and Os abundances than other groups (e.g., 75.7-680.2 ppb Os). Sixteen bulk CAIs and CAI splits plot within analytical uncertainty of a 4558 Ga reference isochron, as is expected for materials of this antiquity. Eight samples, however, plot off the isochron. Several possible reasons for these deviations are discussed. Data for multiple splits of one CAI indicate that the nonisochronous behavior for at least this CAI is the result of Re-Os reequilibration at approximately 1.6 Ga. Thus, the most likely explanation for the deviations of most of the nonisochronous CAIs is late-stage open-system behavior of Re and Os in the asteroidal environment. The 187Os/188Os-Os systematics of CAIs are consistent with previous models that indicate group II CAIs are mixtures of components that lost the bulk of their highly refractory elements in a previous condensation event and a minor second component that provided refractory elements at chondritic relative proportions. The high Re/Os of group II CAIs relative to other CAIs and chondrite bulk rocks may have been caused by variable mobilization of Re and Os during medium- to low-temperature parent body alteration ??4.5 Ga ago. This model is favored over nebular models, which pose several difficulties. The narrow range of 187Os/188Os in group I, III, V, and VI bulk CAIs, and the agreement with 187Os/188Os of whole rock carbonaceous chondrites suggest that on a bulk inclusion scale, secondary alteration only modestly fractionated Re/Os in these CAIs. The average of 187Os/188Os for group I, III, V, and VI CAIs is indistinguishable from average CI chondrites, indicating a modern solar system value for 187Os/188Os of 0.12650, corresponding to a 187Re/188Os of 0.3964. Copyright ?? 2001 Elsevier Science Ltd.

  7. Rhenium-Foil Witness Cylinders

    NASA Technical Reports Server (NTRS)

    Knight, B. L.

    1992-01-01

    Cylindrical portion of wall of combustion chamber replaced with rhenium foil mounted on holder. Rhenium oxidizes without melting, indicating regions of excess oxidizer in combustion-chamber flow. Rhenium witness foils also useful in detecting excess oxygen and other oxidizers at temperatures between 2,000 and 3,600 degrees F in burner cores of advanced gas-turbine engines.

  8. Re-Os isotopic evidence for an enriched-mantle source for the Noril'sk-type, ore-bearing intrusions, Siberia

    USGS Publications Warehouse

    Walker, R.J.; Morgan, J.W.; Horan, M.F.; Czamanske, G.K.; Krogstad, E.J.; Fedorenko, V.A.; Kunilov, V.E.

    1994-01-01

    Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Noril'sk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Noril'sk I intrusion have ??Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have ??Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have ??Os values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Noril'sk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also have relatively uniform ??{lunate}Nd values that range only from -0.8 to + 1.1. This limited variation in neodymium isotopic composition may reflect the characteristics of the mantle sources of the rocks, or it may indicate that somehow similar proportions of crust contaminated the parental melts. The osmium, lead, and neodymium isotopic data for these rocks most closely resemble the mantle sources of certain ocean island basalts (OIB), such as some Hawaiian basalts. Hence, these data are consistent with derivation of primary melts from a mantle source similar to that of some types of hotspot activity. The long-term Re/Os enrichment of this and similar mantle sources, relative to chondritic upper mantle, may reflect 1. (1) incorporation of recycled oceanic crust into the source more than 1 Ga ago, 2. (2) derivation from a mantle plume that originated at the outer core-lower mantle interface, or 3. (3) persistence of primordial stratification of rhenium and osmium in the mantle. ?? 1994.

  9. Waste form evaluation for RECl 3 and REO x fission products separated from used electrochemical salt

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

    Riley, Brian J.; Pierce, David A.; Crum, Jarrod V.

    The work presented here is based off the concept that the rare earth chloride (RECl 3) fission products within the used electrorefiner (ER) salt can be selectively removed as RECl 3 (not yet demonstrated) or precipitated out as a mixture of REOCl and REO x through oxygen sparging (has been demonstrated). This paper presents data showing the feasibility of immobilizing a mixture of RECl 3s at 10 mass% into a 78%TeO 2-22%PbO glass while also showing that this same mixture of RECl 3s can be oxidized to REOCl at 300 °C and then to REO x by 1200 °C, evolvingmore » Cl 2(g). When the REO x mixture is heated at temperatures >1200 °C, the ratios of REO xs change. The mixture of REO x was then immobilized in a lanthanide borosilicate (LABS) glass at a high loading of 60 mass%. Both the 78%TeO 2-22%PbO glass and LABS glass systems show good chemical durability. In conclusion, the advantages and disadvantages of tellurite and LABS glasses are compared.« less

  10. Waste form evaluation for RECl 3 and REO x fission products separated from used electrochemical salt

    DOE PAGES

    Riley, Brian J.; Pierce, David A.; Crum, Jarrod V.; ...

    2017-09-22

    The work presented here is based off the concept that the rare earth chloride (RECl 3) fission products within the used electrorefiner (ER) salt can be selectively removed as RECl 3 (not yet demonstrated) or precipitated out as a mixture of REOCl and REO x through oxygen sparging (has been demonstrated). This paper presents data showing the feasibility of immobilizing a mixture of RECl 3s at 10 mass% into a 78%TeO 2-22%PbO glass while also showing that this same mixture of RECl 3s can be oxidized to REOCl at 300 °C and then to REO x by 1200 °C, evolvingmore » Cl 2(g). When the REO x mixture is heated at temperatures >1200 °C, the ratios of REO xs change. The mixture of REO x was then immobilized in a lanthanide borosilicate (LABS) glass at a high loading of 60 mass%. Both the 78%TeO 2-22%PbO glass and LABS glass systems show good chemical durability. In conclusion, the advantages and disadvantages of tellurite and LABS glasses are compared.« less

  11. Determination of rhenium in molybdenite by X-ray fluorescence: A combined chemical-spectrometric technique.

    PubMed

    Solt, M W; Wahlberg, J S; Myers, A T

    1969-01-01

    Rhenium in molybdenite is separated from molybdenum by distillation of rhenium heptoxide from a perchloric-sulphuric acid mixture. It is concentrated by precipitation of the sulphide and then determined by X-ray fluorescence. From 3 to 1000 microg of rhenium can be measured with a precision generally within 2%. The procedure tolerates larger amounts of molybdenum than the usual colorimetric methods.

  12. Rhenium-catalysed dehydrogenative borylation of primary and secondary C(sp3)-H bonds adjacent to a nitrogen atom.

    PubMed

    Murai, Masahito; Omura, Tetsuya; Kuninobu, Yoichiro; Takai, Kazuhiko

    2015-03-18

    Rhenium-catalysed C(sp(3))-H bond borylation in the absence of any oxidant, hydrogen acceptor, or external ligand, with the generation of H2 as the sole byproduct is described. The transformation, which represents a rare example of rhenium-catalysed C(sp(3))-H bond functionalisation, features high atom efficiency and simple reaction conditions.

  13. Tissue deposition and toxicological effects of commercially significant rare earth oxide nanomaterials: Material and physical properties.

    PubMed

    Das, Soumen; Reed McDonagh, Philip; Selvan Sakthivel, Tamil; Barkam, Swetha; Killion, Kelsey; Ortiz, Julian; Saraf, Shashank; Kumar, Amit; Gupta, Ankur; Zweit, Jamal; Seal, Sudipta

    2017-03-01

    Rare earth oxide (REO) materials are found naturally in earth's crust and at the nanoscale these REO nanoparticles exhibit unique thermal, electrical, and physicochemical properties. REO nanoparticles are widely used in different industrial sectors for ceramics, glass polishing, metallurgy, lasers, and magnets. Recently, some of these REO nanoparticles have been identified for their potential application in medicine, including therapy, imaging, and diagnostics. Concurrent research into the REO nanomaterials' toxicities has also raised concern for their environmental impacts. The correlation of REO nanoparticles mediated toxicity with their physiochemical properties can help to design nanoparticles with minimal effect on the environment and living organisms. In vitro assay revealed toxicity toward Human squamous epithelial cell line (CCL30) and Human umbilical vascular endothelial cells (HUVEC) at a concentration of 100 µM and higher. In vivo results showed, with the exception of CeO 2 and Gd 2 O 3 , most of the naoparticles did not clear or had minimum clearance (10-20%) from the system. Elevated levels of alanine transferase were seen for animals given each different nanoparticle, however the increases were not significant for CeO 2 and Dy 2 O 3 . Nephrotoxicity was only seen in case of Dy 2 O 3 and Gd 2 O 3 . Lastly, histological examination revealed presence of swollen hepatocytes which further confirms toxicity of the commercial REO nanomaterials. The in vivo toxicity is mainly due to excessive tissue deposition (70-90%) due to the commercial REO nanoparticles' poor physical properties (shape, stability, and extent of agglomeration). Therefore, optimization of nanoparticles physical properties is very important. © 2016 Wiley Periodicals, Inc. Environ Toxicol 32: 904-917, 2017. © 2016 Wiley Periodicals, Inc.

  14. Evaluation of the rhenium-osmium geochronometer in the Phosphoria petroleum system, Bighorn Basin of Wyoming and Montana, USA

    USGS Publications Warehouse

    Lillis, Paul G.; Selby, David

    2013-01-01

    Rhenium-osmium (Re-Os) geochronometry is applied to crude oils derived from the Permian Phosphoria Formation of the Bighorn Basin in Wyoming and Montana to determine whether the radiogenic age reflects the timing of petroleum generation, timing of migration, age of the source rock, or the timing of thermochemical sulfate reduction (TSR). The oils selected for this study are interpreted to be derived from the Meade Peak Phosphatic Shale and Retort Phosphatic Shale Members of the Phosphoria Formation based on oil-oil and oil-source rock correlations utilizing bulk properties, elemental composition, δ13C and δ34S values, and biomarker distributions. The δ34S values of the oils range from -6.2‰ to +5.7‰, with oils heavier than -2‰ interpreted to be indicative of TSR. The Re and Os isotope data of the Phosphoria oils plot in two general trends: (1) the main trend (n = 15 oils) yielding a Triassic age (239 ± 43 Ma) with an initial 187Os/188Os value of 0.85 ± 0.42 and a mean square weighted deviation (MSWD) of 1596, and (2) the Torchlight trend (n = 4 oils) yielding a Miocene age (9.24 ± 0.39 Ma) with an initial 187Os/188Os value of 1.88 ± 0.01 and a MSWD of 0.05. The scatter (high MSWD) in the main-trend regression is due, in part, to TSR in reservoirs along the eastern margin of the basin. Excluding oils that have experienced TSR, the regression is significantly improved, yielding an age of 211 ± 21 Ma with a MSWD of 148. This revised age is consistent with some studies that have proposed Late Triassic as the beginning of Phosphoria oil generation and migration, and does not seem to reflect the source rock age (Permian) or the timing of re-migration (Late Cretaceous to Eocene) associated with the Laramide orogeny. The low precision of the revised regression (±21 Ma) is not unexpected for this oil family given the long duration of generation from a large geographic area of mature Phosphoria source rock, and the possible range in the initial 187Os/188Os values of the Meade Peak and Retort source units. Effects of re-migration may have contributed to the scatter, but thermal cracking and biodegradation likely have had minimal or no effect on the main-trend regression. The four Phosphoria-sourced oils from Torchlight and Lamb fields yield a precise Miocene age Re-Os isochron that may reflect the end of TSR in the reservoir due to cooling below a threshold temperature in the last 10 m.y. from uplift and erosion of overlying rocks. The mechanism for the formation of a Re-Os isotopic relationship in a family of crude oils may involve multiple steps in the petroleum generation process. Bitumen generation from the source rock kerogen may provide a reset of the isotopic chronometer, and incremental expulsion of oil over the duration of the oil window may provide some of the variation seen in 187Re/188Os values from an oil family.

  15. Effect of rosemary essential oil and modified-atmosphere packaging (MAP) on meat quality and survival of pathogens in poultry fillets

    PubMed Central

    Kahraman, Tolga; Issa, Ghassan; Bingol, Enver Baris; Kahraman, Beren Basaran; Dumen, Emek

    2015-01-01

    The effect of rosemary (Rosmarinus officinalis L.) essential oil (REO) and modified-atmosphere packaging (MAP) on the survival of certain pathogens (Salmonella Typhimurium and Listeria monocytogenes) in poultry fillets and on their meat quality during 7 days of refrigerated storage were investigated. Because REO at 0.05% and 0.1% had weak antibacterial activity and REO at 0.3%, 0.5% and 1.0% imparted unacceptable organoleptic properties, only REO at 0.2% was used to treat the poultry meat. The results showed that adding 0.2% REO to poultry fillets did not reduce the size of the population of S. Typhimurium and L. monocytogenes. However, REO treatment significantly decreased the L* (lightness) value and increased the a* (redness) value of stored fillets, and adding REO in combination with MAP reduced the level of lipid oxidation. In conclusion, in a suitable combination, REO can be applied to improve the quality of meat, but further studies should be conducted to determine the appropriate commercial level for different meat products. PMID:26273279

  16. Determination of rhenium in molybdenite by X-ray fluorescence. A combined chemical-spectrometric technique

    USGS Publications Warehouse

    Solt, M.W.; Wahlberg, J.S.; Myers, A.T.

    1969-01-01

    Rhenium in molybdenite is separated from molybdenum by distillation of rhenium heptoxide from a perchloric-sulphuric acid mixture. It is concentrated by precipitation of the sulphide and then determined by X-ray fluorescence. From 3 to 1000 ??g of rhenium can be measured with a precision generally within 2%. The procedure tolerates larger amounts of molybdenum than the usual colorimetric methods. ?? 1969.

  17. Effect of Silicon on the Activity Coefficient of Rhenium in Fe-Si Liquids: Implications for HSE and Os Isotopes in Planetary Mantles

    NASA Technical Reports Server (NTRS)

    Righter, K.; Pando, K.; Yang, S.; Humayun, M.

    2018-01-01

    Metallic cores contain light alloying elements that can be a combination of S, C, Si, and O, all of which have important chemical and physical influences. For Earth, Si may be the most abundant light element in the core. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE), and thus the partitioning behavior of those elements between core and mantle. The effect of Si on the highly siderophile elements is only beginning to be studied and the effects on Au, Pd and Pt are significant. Here we report new experiments designed to quantify the effect of Si on the partitioning of Re between metal and silicate melt. A solid understanding of Re partitioning is required for a complete understanding of the Re-Os isotopic systems. The results will be applied to understanding the HSEs and Os isotopic data for planetary mantles, and especially Earth.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  19. Lung-resident eosinophils represent a distinct regulatory eosinophil subset

    PubMed Central

    Mesnil, Claire; Raulier, Stéfanie; Paulissen, Geneviève; Xiao, Xue; Birrell, Mark A.; Pirottin, Dimitri; Janss, Thibaut; Henket, Monique; Schleich, Florence N.; Radermecker, Marc; Thielemans, Kris; Gillet, Laurent; Thiry, Marc; Belvisi, Maria G.; Louis, Renaud; Desmet, Christophe; Bureau, Fabrice

    2016-01-01

    Increases in eosinophil numbers are associated with infection and allergic diseases, including asthma, but there is also evidence that eosinophils contribute to homeostatic immune processes. In mice, the normal lung contains resident eosinophils (rEos), but their function has not been characterized. Here, we have reported that steady-state pulmonary rEos are IL-5–independent parenchymal Siglec-FintCD62L+CD101lo cells with a ring-shaped nucleus. During house dust mite–induced airway allergy, rEos features remained unchanged, and rEos were accompanied by recruited inflammatory eosinophils (iEos), which were defined as IL-5–dependent peribronchial Siglec-FhiCD62L–CD101hi cells with a segmented nucleus. Gene expression analyses revealed a more regulatory profile for rEos than for iEos, and correspondingly, mice lacking lung rEos showed an increase in Th2 cell responses to inhaled allergens. Such elevation of Th2 responses was linked to the ability of rEos, but not iEos, to inhibit the maturation, and therefore the pro-Th2 function, of allergen-loaded DCs. Finally, we determined that the parenchymal rEos found in nonasthmatic human lungs (Siglec-8+CD62L+IL-3Rlo cells) were phenotypically distinct from the iEos isolated from the sputa of eosinophilic asthmatic patients (Siglec-8+CD62LloIL-3Rhi cells), suggesting that our findings in mice are relevant to humans. In conclusion, our data define lung rEos as a distinct eosinophil subset with key homeostatic functions. PMID:27548519

  20. Probing surface sites of TiO2: reactions with [HRe(CO)5] and [CH3Re(CO)5].

    PubMed

    Lobo-Lapidus, Rodrigo J; Gates, Bruce C

    2010-10-04

    Two carbonyl complexes of rhenium, [HRe(CO)(5)] and [CH(3)Re(CO)(5)], were used to probe surface sites of TiO(2) (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O(2) or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti(+3)-OH and Ti(+4)-OH. IR and extended X-ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface-bound rhenium tricarbonyls, when [HRe(CO)(5)] was adsorbed, or rhenium tetracarbonyls, when [CH(3)Re(CO)(5)] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti(+3) and Ti(+4) ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)(5)] or [CH(3)Re(CO)(5)] determined a ranking of the reactivity of the surface OH sites, with the Ti(+3)-OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.

  1. Re-Os isotopic systematics of primitive lavas from the Lassen region of the Cascade arc, California

    USGS Publications Warehouse

    Borg, L.E.; Brandon, A.D.; Clynne, M.A.; Walker, R.J.

    2000-01-01

    Rhenium-osmium isotopic systematics of primitive calc-alkaline lavas from the Lassen region appear to be controlled by mantle wedge processes. Lavas with a large proportion of slab component have relatively low Re and Os abundances, and have radiogenic Os and mid ocean ridge basalt-like Sr and Pb isotopic compositions. Lavas with a small proportion of slab component have higher Re and Os elemental abundances and display mantle-like Os, Sr, Nd, and Pb isotopic compositions. Assimilation with fractional crystallization can only generate the Re-Os systematics of the Lassen lavas from a common parent if the distribution coefficient for Re in sulfide is ~40-1100 times higher than most published estimates and if most incompatible element abundances decrease during differentiation. High Re/Os ratios in mid ocean ridge basalts makes subducted oceanic crust a potential source of radiogenic Os in volcanic arcs. The slab beneath the southernmost Cascades is estimated to have 187Os/188Os ratios as high as 1.4. Mixing between a slab component and mantle wedge peridotite can generate the Os isotopic systematics of the Lassen lavas provided the slab component has a Sr/Os ratio of ~7.5X105 and Os abundances that are 100-600 times higher than mid ocean ridge basalts. For this model to be correct, Os must be readily mobilized and concentrated in the slab component, perhaps as a result of high water and HCl fugacities in this subduction environment. Another possible mechanism to account for the correlation between the magnitude of the subduction geochemical signature and Os isotopic composition involves increasing the stability of an Os-bearing phase in mantle wedge peridotites as a result of fluxing with the slab component. Melting of such a source could yield low Os magmas that are more susceptible to crustal contamination, and hence have more radiogenic Os isotopic compositions, than magmas derived from sources with a smaller contribution from the slab. Thus, the addition of the slab component to the mantle wedge appears to result in either the direct or indirect addition of radiogenic Os to arc magmas. (C) 2000 Elsevier Science B.V. All rights reserved.

  2. Chemical composition and biological activities of the essential oil from Rubus pungens var. oldhamii.

    PubMed

    Zhang, Yaojie; Chen, Jiajing; Wang, Lizhi; Cao, Jingjing; Xu, Lishan

    2017-06-01

    This paper presents a study on chemical composition, antimicrobial, antioxidant and tyrosinase inhibitory properties of the essential oil from leaves of Rubus pungens var. oldhamii (REO). The major component of the REO is sesquiterpenes (36.04%), which consists of 1,5-Cyclooctadiene,3-(1-me thylallyl)-(8CI)(17.66%), 5,6-Diethenyl-1-methylcyclohexene (12%), (+) - γ-Elemene (10.48%) and β-Caryophyllene (8.39%).The REO is shown to be moderately active against Staphylococcus aureus, Aspergillus niger and Penicillium glaucum, and has weak antioxidant activity in 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay. Furthermore, tyrosinase inhibition was investigated against monophenolase (L-tyrosine). IC 50 values of REO and arbutin were found 0.923 and 0.657 mg/mL, respectively. The REO exerted potential antityrosinase activity. Our test results indicated that the REO was rich in sesquiterpenes, and also exhibited good antityrosinase activity, and moderate antimicrobial activity against pathogenic micro-organisms. The REO can be used as a natural source of promising antimicrobial and tyrosinase inhibiting agent.

  3. EFFECTS OF ARSENIC TRIOXIDE INHALATION EXPOSURE ON PULMONARY ANTIBACTERIAL DEFENSES IN MICE

    EPA Science Inventory

    The effects of single and multiple (5 and 20) 3 hr inhalation exposures to aerosols of arsenic trioxide on the pulmonary defense system of mice were investigated. Arsenic trioxide mist was generated from an aqueous solution and dried to produce particulate aerosols of 0.4 microme...

  4. Electronic structure of trioxide, oxoperoxide, oxosuperoxide, and ozonide clusters of the 3d elements: density functional theory study.

    PubMed

    Uzunova, Ellie L

    2011-03-03

    The trioxide clusters with stoichiometry MO3, and the structural isomers with side-on and end-on bonded oxygen atoms, are studied by DFT with the B1LYP functional. For the first half of the 3d elements row (Sc to Cr), pyramidal or distorted pyramidal structures dominate among the trioxide and oxoperoxide ground states, while the remaining elements form planar trioxides, oxoperoxides, oxosuperoxides, and ozonides. Low-lying trioxide clusters are formed by Ti, V, Cr, and Mn, among which the distorted pyramidal VO3 in the (2)A'' state, the pyramidal CrO3 in the (1)A1 state, and the planar MnO3 in the (2)A1' state are global minima. With the exception of the middle-row elements Mn, Fe, and Co, the magnetic moment of the ground-state clusters is formed with a major contribution from unpaired electrons located at the oxygen atoms. The stability of trioxides and oxoperoxides toward release of molecular oxygen is significantly higher for Sc, Ti, and V than for the remaining elements of the row. A trend of increasing the capability to dissociate one oxygen molecule is observed from Cr to Cu, with the exception of OFe(O2) being more reactive than OCo(O2). A gradual increase of reactivity from Ti to Cu is observed for the complete fragmentation reaction M + O + O2.

  5. Rhenium-coated glass beads for intracolonic administration attenuate TNBS-induced colitis in mice: Proof-of-Concept Study.

    PubMed

    Siczek, Krzysztof; Zatorski, Hubert; Pawlak, Wojciech; Fichna, Jakub

    2015-01-01

    In search for novel effective treatments in inflammatory bowel diseases, a new strategy employing glass beads coated with rhenium nanolayer has been developed and validated in the mouse model of 2,4,6-trinitrobenzene sulfonic acid (TNBS)-induced colitis. Briefly, mice were randomly divided into 5 experimental groups: control (vehicle alone, Group 1); control treated with rhenium-coated glass beads (Group 2); TNBS (Group 3); TNBS treated with rhenium-coated glass beads (Group 4); and TNBS treated with uncoated glass beads (Group 5). Mice from Group 2, 4 and 5 were treated with respective beads (once daily, 5 beads / animal, i.c.) between D3-D6 post-TNBS/vehicle and evaluation of colonic damage was performed on D7, based on macroscopic scoring and clinical parameters. Severe colonic inflammation developed in post-TNBS mice (Group 3) [P <0.001 vs. control (Group 1) for macroscopic score], which was significantly attenuated by treatment with rhenium-coated glass beads (Group 4) [P <0.01 vs. TNBS (Group 3), for macroscopic score]. Neither rhenium-coated glass beads had any effect in control animals (Group 2), nor uncoated glass beads influenced TNBS-induced colitis (Group 5). In conclusion, a novel and attractive strategy for the treatment of colonic inflammation has been proposed; therapy with rhenium-coated glass beads already proved effective in the mouse model of TNBS-induced colitis, now requires further characterization in clinical conditions.

  6. Synthesis of rhenium nitride crystals with MoS2 structure

    NASA Astrophysics Data System (ADS)

    Kawamura, Fumio; Yusa, Hitoshi; Taniguchi, Takashi

    2012-06-01

    Rhenium nitride (ReN2) crystals were synthesized from a metathesis reaction between ReCl5 and Li3N under high pressure. The reaction was well controlled by the addition of a large amount of NaCl as reaction inhibitor to prevent a violent exothermic reaction. The largest rhenium nitride crystals obtained had a millimeter-order size with a platelet shape. X-ray diffraction analysis revealed that rhenium nitride has MoS2 structure similar to hexagonal rhenium diboride (ReB2) which has recently been investigated as an ultra-hard material. The structure was different from any structures previously predicted for ReN2 by theoretical calculations.

  7. [Influence of antitumor system rhenium-platinum on biochemical state of the liver].

    PubMed

    Ivchuk, V V; Polishko, T M; Golichenko, O A; Shtemenko, O V; Shtemenko, N I

    2011-01-01

    Influence of the antitumour rhenium-platinum system on biochemical liver characteristics in the model of tumor growth (Guerin carcinoma) was studied and possible hepatoprotective activity of rhenium cluster compounds when introducing them in different forms was shown, that was confirmed by decreasing of diagnostic enzymes activity in blood (aminotransferase--AST 6 times and ALT 5.6 times, lactatedehydrogenase 4.9 times, gamma-glutamyltranspeptidase 3.6 times) and normalization of morphological state of the liver cells. The hepatoprotective activity of the cluster rhenium compound with adamanthyl ligands was confirmed in the model of acute toxic hepatitis. Introduction of this compound led to reduction of the concentration of MDA in homogenates of liver tissue (2 times), and in blood plasma (3.8 times); to reduction of levels of diagnostic liver enzymes in blood--AST and ALT 5.8 and 5.5 times respectively in comparison with control group. Some aspects of the mechanism of hepatoprotection were discussed, that included the presence of conjugated systems around the quadrupol rhenium-rhenium bond and alkyl radicals with significant positive inductive effects.

  8. Arsenic induces functional re-expression of estrogen receptor α by demethylation of DNA in estrogen receptor-negative human breast cancer.

    PubMed

    Du, Juan; Zhou, Nannan; Liu, Hongxia; Jiang, Fei; Wang, Yubang; Hu, Chunyan; Qi, Hong; Zhong, Caiyun; Wang, Xinru; Li, Zhong

    2012-01-01

    Estrogen receptor α (ERα) is a marker predictive for response of breast cancers to endocrine therapy. About 30% of breast cancers, however, are hormone- independent because of lack of ERα expression. New strategies are needed for re-expression of ERα and sensitization of ER-negative breast cancer cells to selective ER modulators. The present report shows that arsenic trioxide induces reactivated ERα, providing a target for therapy with ER antagonists. Exposure of ER-negative breast cancer cells to arsenic trioxide leads to re-expression of ERα mRNA and functional ERα protein in in vitro and in vivo. Luciferase reporter gene assays and 3-(4,5-dimethylthiazol-2-yl)- 5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium (MTS) assays show that, upon exposure to arsenic trioxide, formerly unresponsive, ER-negative MDA-MB-231 breast cancer cells become responsive to ER antagonists, 4-hydroxytamoxifen and ICI 182,780. Furthermore, methylation- specific PCR and bisulfite-sequencing PCR assays show that arsenic trioxide induces partial demethylation of the ERα promoter. A methyl donor, S-adenosylmethionine (SAM), reduces the degree of arsenic trioxide-induced re-expression of ERα and demethylation. Moreover, Western blot and ChIP assays show that arsenic trioxide represses expression of DNMT1 and DNMT3a along with partial dissociation of DNMT1 from the ERα promoter. Thus, arsenic trioxide exhibits a previously undefined function which induces re-expression ERα in ER-negative breast cancer cells through demethylation of the ERα promoter. These findings could provide important information regarding the application of therapeutic agents targeting epigenetic changes in breast cancers and potential implication of arsenic trioxide as a new drug for the treatment of ER-negative human breast cancer.

  9. Rhenium(VII) Catalysis of Prins Cyclization Reactions

    PubMed Central

    Tadpetch, Kwanruthai; Rychnovsky, Scott D.

    2009-01-01

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

  10. Effect of Iron and Carbonation of the Diffusion of Iodine and Rhenium in Waste Encasement Concrete and Soil Fill Material under Hydraulically Unsaturated Conditions

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

    Wellman, Dawn M.; Parker, Kent E.; Powers, Laura

    2008-07-31

    Assessing long-term performance of Category 3 cement wasteforms and accurate prediction for radionuclide encasement requires knowledge of the radionuclide-cement interactions and mechanisms of retention (i.e. sorption or precipitation). A set of sediment-concrete half-cell diffusion experiments was conducted under unsaturated conditions (4% and 7% by weight moisture content) using carbonated and non-carbonated concrete-soil half-cells. Results indicate the behavior of rhenium and iodine release was comparable within a given half-cell test. Diffusivity in soil is a function of moisture content; a 3% increase in moisture content affords a one to two order of magnitude increase in diffusivity. Release of iodine and rheniummore » was 1 to 3 orders of magnitude less from non-carbonated, relative to carbonated, concrete monoliths. Inclusion of iron in non-carbonate monoliths resulted in the lowest concrete diffusivity values for both iodine and rhenium. This suggests that in the presence of iron, iodine and rhenium are converted to reduced species, which are less soluble and better retained within the concrete monolith. The release of iodine and rhenium was greatest from iron-bearing, carbonated concrete monoliths, suggesting carbonation negates the effect of iron on the retention of iodine and rhenium within concrete monoliths. This is likely due to enhanced formation of microcracks in the presence of iron, which provide preferential paths for contaminant migration. Although the release of iodine and rhenium were greatest from carbonated concrete monoliths containing iron, the migration of iodine and rhenium within a given half-cell is dependent on the moisture content, soil diffusivity, and diffusing species.« less

  11. Rhenium and technetium tricarbonyl, {M(CO)3} (+) (M = Tc, Re), binding to mammalian metallothioneins: new insights into chemical and radiopharmaceutical implications.

    PubMed

    Lecina, Joan; Palacios, Òscar; Atrian, Sílvia; Capdevila, Mercè; Suades, Joan

    2015-04-01

    This paper deals with the binding of the four mammalian metallothioneins (MTs) to the organometallic metal fragment {fac-M(CO)3}(+) (M = (99)Tc, Re), which is highly promising for the preparation of second-generation radiopharmaceuticals. The study of the transmetallation reaction between zinc and rhenium in Zn7-MT1 by means of UV-vis and CD spectroscopy demonstrated the incorporation of the {fac-Re(CO)3}(+) fragment to the MTs. This reaction should be performed at 70 °C to accelerate the reaction rate, a result that is consistent with the reported reactivity of the rhenium fragment. ESI-TOF MS demonstrated the formation of mixed-metal species as Zn6,{Re(CO)3}-MT, Zn6,{Re(CO)3}2-MT, and Zn5,{Re(CO)3}3-MT, as well as the different reactivity of the four MT isoforms. Hence, Zn-MT3 showed the highest reactivity, in agreement with its high Cu-thionein character, whereas Zn-MT2 exhibited the lowest reactivity, in line with its high Zn-thionein character. The reactivity of the Zn-loaded forms of MT1 and MT4 is intermediate between those of MT3 and MT2. The study of the binding of the {fac-(99)Tc(CO)3}(+) fragment to MTs showed a significant and very interesting different reactivity in relation to rhenium. The transmetallation reaction is much more effective with technetium than with rhenium and significant amounts of mixed Zn x ,{(99)Tc(CO)3} y -MT species were formed with the four MT isoforms whereas only MT3 rendered similar amounts of rhenium derivatives. The results obtained in this study support the possible use of technetium for labelling mammalian metallothioneins and also for possible radiopharmaceutical applications.

  12. Novel carboxymethyl cellulose-polyvinyl alcohol blend films stabilized by Pickering emulsion incorporation method.

    PubMed

    Fasihi, Hadi; Fazilati, Mohammad; Hashemi, Mahdi; Noshirvani, Nooshin

    2017-07-01

    The aim of this study was to investigate the possibility of increasing the antimicrobial and antioxidant properties of biodegradable active films stabilized via Pickering emulsions. The blend films were prepared from carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA), emulsified with oleic acid (OL) and incorporated with rosemary essential oil (REO). Formation of Pickering emulsion was confirmed by scanning electron microscopy (SEM), optical microscopy, mean droplet size and emulsion stability. Morphological, optical, physical, mechanical, thermal, antifungal and antioxidant properties of the films incorporated with different concentrations of REO (0.5, 1.5 and 3%) were determined. The results showed an increase in UV absorbance and elongation at break but, a decrease in tensile strength and thermal stability of the films. Interestingly, films containing REO exhibited considerable antioxidant and antimicrobial properties. In vitro microbial tests exhibited 100% fungal inhibition against Penicillium digitatum in the films containing 3% REO. In addition, no fungal growth were observed after 60days of storage at 25°C in bread slices were stored with active films incorporated with 3% REO, could attributed to the slow and regular release of REO caused by Pickering emulsions. The results of this study suggest that Pickering emulsion is a very promising method, which significantly affects antioxidant and antimicrobial activities of the films. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Re-Os Systematics and HSE Distribution in Metal from Ochansk (H4) Chondrite

    NASA Technical Reports Server (NTRS)

    Smoliar, M. I.; Horan, M. F.; Alexander, C. M. OD.; Walker, R. J.

    2003-01-01

    Previous studies of the Re-Os systematics of chondrites have documented considerable variation in the Re/Os ratios of whole rock samples. For some whole rock chondrites, Re-Os systematics display large deviations from the primitive isochron that are considerably larger than deviations in other isotope systems. Possible interpretation of these facts is that the Re-Os system in chondrites is particularly sensitive to post-formation alteration processes, thus providing a useful tool to examine such processes. Significant variations that have been detected in highly siderophile element (HSE) patterns for ordinary chondrites support this conclusion. We report Re-Os isotope data for metal separates from the Ochansk H4 chondrite coupled with abundance data for Ru, Pd, Ir, and Pt, determined in the same samples by isotope dilution. We chose this meteorite mainly because it is an observed fall with minimal signs of weathering, and its low metamorphic grade (H4) and shock stage (S3).

  14. New Estimates of Rhenium in the Crust: Implications for Mantle Re-Os Budgets

    NASA Astrophysics Data System (ADS)

    Bennett, V. C.; Sun, W.

    2002-12-01

    The 187Re-187Os isotopic system has provided a new probe of mantle chemical structure with, for example, now numerous studies balancing estimates of the Os isotopic compositions of the upper modern mantle with sizes and ages of proposed conjugate reservoirs stored within the deep mantle. This style of modeling is dependent upon estimates of the parent Re in the various reservoirs including total crust, upper mantle, MORB and ocean island basalts. New laser ICP-MS in situ and ID whole rock results from OIB, arc and back-arc basalts suggest Re concentrations in oceanic and crustal domains may have been greatly underestimated. For example Hawaiian OIBs show a clear distinction between subaerial and submarine erupted samples with the latter having Re much closer to the higher MORB estimates (1) than to previous OIB estimates. This difference has been attributed to Re volatility and loss during syn- and post-eruption degassing of subaerial samples. Recent work has produced similar results for submarine arc samples using both dredged glasses and melt inclusions in olivines from primitive basalts. Both have much higher average Re (ca. 1.5 and 3.4 ppb; 2,3) than literature values for arcs (ca. 0.30ppb) determined largely from sub-aerial samples, or for average crust estimated from loess (0.2 ppb; 4). If the undegassed arc samples are representative, then the total crust may have more than 5 times the Re previously estimated. Re lost during arc eruptions may ultimately be concentrated in anoxic seafloor sediments. Prior under-estimates may be linked to the extremely heterogeneous concentration (> 5 orders of magnitude) of the chalcophile, redox sensitive Re in crustal environments. If the residence time of high Re in the crust is long (>1 Ga) then, 1) much smaller reservoirs of stored Re in the deep mantle are required to balance Re depletions in the upper mantle, and 2) significant portions of the upper mantle are likely Re depleted. Alternatively Re may be rapidly recycled in oceanic sediments (short residence time) resulting in a smaller affect on Re-Os budgets, but creating areas of extreme Re heterogeneity in the upper mantle. Refs: 1. Bennett, Norman and Garcia, EPSL 2000. 2. Sun et al. (in press, Chemical Geology) 3. Sun et al. (submitted). 4. Peucker-Ehrenbrink and Jahn, G3, 2001.

  15. Photochemical preparation of pyrimidin-2(1H)-ones by rhenium(I) complexes with visible light.

    PubMed

    Liu, Qiang; Li, Ya-Nan; Zhang, Hui-Hui; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu

    2011-03-04

    With visible light irradiation (λ > 400 nm) of rhenium(I) complexes (P1-P4), a photochemical conversion from 3,4-dihydropyrimidin-2(1H)-ones to pyrimidin-2(1H)-ones at room temperature has been achieved with good to excellent yields in CH(3)CN-H(2)O solution containing CCl(4) and K(2)CO(3). Luminescence quenching study and product analysis reveal that photoinduced electron transfer between rhenium(I) complex P and 3,4-dihydropyrimidin-2(1H)-ones plays an important role in the initial event.

  16. Design Parameters Affecting the Accuracy of Isothermal Thermocouples

    DTIC Science & Technology

    1975-01-02

    Design Parameters Lead Wire Length intekference Accuracy Askew Installation Tungsten / Rhenium Wire Diameter Trajectory Insulation Thickness Heatshield...Summary ................. 73 A-3 Thermodynamic Properties of Tungsten / Rhenium Therm ocouples ............................ 75 A-4 Thermodynamic Properties...were tungsten / rhenium , chromel/alumel, and iron/constbntan, which covered the 0 to 5000, 0 to 2200, and 0 to I-00°F temperatut- ranges, resoectively. in

  17. Re-Os systematics and age of pyrite associated with stratiform Zn-Pb mineralization in the Howards Pass district, Yukon and Northwest Territories, Canada

    NASA Astrophysics Data System (ADS)

    Kelley, Karen D.; Selby, David; Falck, Hendrik; Slack, John F.

    2017-03-01

    Stratiform Zn-Pb deposits hosted in unmetamorphosed carbonaceous and siliceous mudstones of the Ordovician to Silurian Duo Lake Formation define the Howards Pass district in Yukon Territory and Northwest Territories, western Canada. Collectively, the deposits are amongst the largest in the world, containing drill-indicated and inferred resources of 423 Mt at 4.84 % Zn and 1.59 % Pb. Sulphide textures include (a) fine-scale laminations of sphalerite, galena, and pyrite from <0.05 mm to 1 cm thick, interbedded with carbonaceous sedimentary rock; (b) layers of coarse sulphide that are structurally controlled by microfolds; and (c) veins that cut bedding and sulphide laminations. The finely interlaminated nature of sulphides with mudstone has been used as evidence for syngenetic mineralizing processes, whereas paleomagnetic data determined on coarse layered sulphides suggest a Middle Jurassic age of mineralization. Here, we present new rhenium-osmium (Re-Os) isotopic data for 12 pyrite separates obtained from 4 laminated sulphide-rich samples from the XY Central (XYC) and Don (DON) deposits and for 1 unmineralized organic-rich mudstone ˜20 m stratigraphically below the sulphide-bearing zone. Pyrite separates that lack mudstone inclusions ("pure") from the XYC deposit contain 2.2 to 4.0 ppb Re and 93.4 to 123.4 ppt Os; pure pyrite from the DON deposit is significantly more enriched in Re and Os (34-37 ppb Re; 636.8-694.9 ppt Os). The 187Re/188Os values of pure pyrite separates from the XYC and DON deposits range from 137.6 to 197 and 182.1 to 201.4, respectively. Regression of all pure pyrite Re-Os data from both deposits yields an isochron age of 442 ± 14 Ma (MSWD = 7.4) and an initial 187Os/188Os (Osi) value of 0.71 ± 0.07. The Re-Os age indicates that the early phase of pyrite precipitation (and by inference, sphalerite and galena) occurred during the early Silurian, consistent with biostratigraphic ages of the host rocks. The Osi value of ˜0.8 for earliest Silurian seawater recorded from organic-rich shale in the basal Silurian Global Stratotype Section and Point (GSSP) at Dobs Linn, Scotland is very similar to that provided by the Howards Pass pyrite regression and hence suggests a hydrogenous (seawater) source of Os for the pyrite. Therefore, two possible sources of Os are (1) the Zn- and Pb-bearing hydrothermal fluid that leached Os from footwall sedimentary rocks, which were deposited in seawater, or (2) directly from seawater during precipitation of the pyrite, which suggests that the Os content of the hydrothermal fluid was minor relative to that of seawater.

  18. Intracellular distribution and stability of a luminescent rhenium(i) tricarbonyl tetrazolato complex using epifluorescence microscopy in conjunction with X-ray fluorescence imaging.

    PubMed

    Wedding, J L; Harris, H H; Bader, C A; Plush, S E; Mak, R; Massi, M; Brooks, D A; Lai, B; Vogt, S; Werrett, M V; Simpson, P V; Skelton, B W; Stagni, S

    2017-04-19

    Optical epifluorescence microscopy was used in conjunction with X-ray fluorescence imaging to monitor the stability and intracellular distribution of the luminescent rhenium(i) complex fac-[Re(CO) 3 (phen)L], where phen = 1,10-phenathroline and L = 5-(4-iodophenyl)tetrazolato, in 22Rv1 cells. The rhenium complex showed no signs of ancillary ligand dissociation, a conclusion based on data obtained via X-ray fluorescence imaging aligning iodine and rhenium distributions. A diffuse reticular localisation was detected for the complex in the nuclear/perinuclear region of cells, by either optical or X-ray fluorescence imaging techniques. X-ray fluorescence also showed that the rhenium complex disrupted the homeostasis of some biologically relevant elements, such as chlorine, potassium and zinc.

  19. Mineral Trioxide Aggregate and Portland Cement for Direct Pulp Capping in Dog: A Histopathological Evaluation

    PubMed Central

    Bidar, Maryam; Naghavi, Neda; Mohtasham, Nooshin; Sheik-Nezami, Mahshid; Fallahrastegar, Amir; Afkhami, Farzaneh; Attaran Mashhadi, Negin; Nargesi, Iman

    2014-01-01

    Background and aims. Mineral trioxide aggregate and calcium hydroxide are considered the gold standard pulp-capping materials. Recently, Portland cement has been introduced with properties similar to those of mineral trioxide aggregate. Histopathological effects of direct pulp capping using mineral trioxide aggregate and Portland cements on dog dental pulp tissue were evaluated in the present study. Materials and methods. This histopatological study was carried out on 64 dog premolars. First, the pulp was exposed with a sterile bur. Then, the exposed pulp was capped with white or gray mineral trioxide aggregates and white or gray Portland cements in each quadrant and sealed with glass-ionomer. The specimens were evaluated under a light microscope after 6 months. Statistical analysis was carried out using Kruskal-Wallis test. Statistical significance was defined at α=5%. Results. There was no acute inflammation in any of the specimens. Chronic inflammation in white and gray mineral trioxide aggregates and white and gray Portland cements was reported to be 45.5%, 27.3%, 57.1% and 34.1%, respectively. Although the differences were not statistically significant, severe inflammation was observed mostly adjacent to white mineral trioxide aggregate. The largest extent of increased vascularization (45%) and the least increase in fibrous tissue were observed adjacent to white mineral trioxide aggregate, with no significant differences. In addition, the least calcified tissue formed adjacent to white mineral trioxide aggregate, although the difference was not significant. Conclusion. The materials used in this study were equally effective as pulp protection materials following direct pulp capping in dog teeth. PMID:25346831

  20. Rhenium

    USGS Publications Warehouse

    John, David A.; Seal, Robert R.; Polyak, Désirée E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Rhenium is one of the rarest elements in Earth’s continental crust; its estimated average crustal abundance is less than 1 part per billion. Rhenium is a metal that has an extremely high melting point and a heat-stable crystalline structure. More than 80 percent of the rhenium consumed in the world is used in high-temperature superalloys, especially those used to make turbine blades for jet aircraft engines. Rhenium’s other major application is in platinum-rhenium catalysts used in petroleum refining.Rhenium rarely occurs as a native element or as its own sulfide mineral; most rhenium is present as a substitute for molybdenum in molybdenite. Annual world mine production of rhenium is about 50 metric tons. Nearly all primary rhenium production (that is, rhenium produced by mining rather than through recycling) is as a byproduct of copper mining, and about 80 percent of the rhenium obtained through mining is recovered from the flue dust produced during the roasting of molybdenite concentrates from porphyry copper deposits. Molybdenite in porphyry copper deposits can contain hundreds to several thousand grams per metric ton of rhenium, although the estimated rhenium grades of these deposits range from less than 0.1 gram per metric ton to about 0.6 gram per metric ton.Continental-arc porphyry copper-(molybdenum-gold) deposits supply most of the world’s rhenium production and have large inferred rhenium resources. Porphyry copper mines in Chile account for about 55 percent of the world’s mine production of rhenium; rhenium is also recovered from porphyry copper deposits in the United States, Armenia, Kazakhstan, Mexico, Peru, Russia, and Uzbekistan. Sediment-hosted strata-bound copper deposits in Kazakhstan (of the sandstone type) and in Poland (of the reduced-facies, or Kupferschiefer, type) account for most other rhenium produced by mining. These types of deposits also have large amounts of identified rhenium resources. The future supply of rhenium is likely to depend largely on the capacity of the specialized processing facilities needed to recover rhenium from molybdenite concentrates.The environmental consequences of rhenium recovery are closely linked to the consequences of mining large porphyry copper and strata-bound copper deposits; no additional environmental impact from recovery of rhenium from these deposits has been identified. No information is available regarding the potential toxic effects of rhenium on humans, partly because of the low natural abundance of rhenium.

  1. Photosensitized generation of singlet oxygen by rhenium(I) complex

    NASA Astrophysics Data System (ADS)

    Burchinov, A. N.; Kiselev, V. M.; Penni, A. A.; Khistyaeva, V. V.

    2015-12-01

    The photosensitized generation of singlet oxygen in solutions of rhenium(I) complex fac-[Re(bipy)(CO)3NCCH3]+OTf-, where bipy=2,2'-bipyridine, in chloride methylene and carbon tetrachloride under continuous LED irradiation in the UV and visible ranges has been investigated.

  2. Oxide strengthened molybdenum-rhenium alloy

    DOEpatents

    Bianco, Robert; Buckman, Jr., R. William

    2000-01-01

    Provided is a method of making an ODS molybdenum-rhenium alloy which includes the steps of: (a) forming a slurry containing molybdenum oxide and a metal salt dispersed in an aqueous medium, the metal salt being selected from nitrates or acetates of lanthanum, cerium or thorium; (b) heating the slurry in the presence of hydrogen to form a molybdenum powder comprising molybdenum and an oxide of the metal salt; (c) mixing rhenium powder with the molybdenum powder to form a molybdenum-rhenium powder; (d) pressing the molybdenum-rhenium powder to form a molybdenum-rhenium compact; (e) sintering the molybdenum-rhenium compact in hydrogen or under a vacuum to form a molybdenum-rhenium ingot; and (f) compacting the molybdenum-rhenium ingot to reduce the cross-sectional area of the molybdenum-rhenium ingot and form a molybdenum-rhenium alloy containing said metal oxide. The present invention also provides an ODS molybdenum-rhenium alloy made by the method. A preferred Mo--Re-ODS alloy contains 7-14 weight % rhenium and 2-4 volume % lanthanum oxide.

  3. Effect of the electronegativity on the electrosorption selectivity of anions during capacitive deionization.

    PubMed

    Sun, Zhumei; Chai, Liyuan; Liu, Mingshi; Shu, Yude; Li, Qingzhu; Wang, Yunyan; Qiu, Dingfan

    2018-03-01

    The effect of electronegativity on the electrosorption selectivity of anions during capacitive deionization was investigated via a combination of experimental and theoretical studies. A model was developed based on chemical thermodynamics and the classic Stern's model to reveal the role of the anode potential and to describe electrosorption selectivity behavior during capacitive deionization. The effects of the anode potential on the adsorption of Cl - and ReO 4 - were studied and the obtained data were used to validate the model. Using the validated model, the effects of the anode potential and electronegativity of various anions, including Cl - , ReO 4 - , SO 4 2- and NO 3 - were assessed. The experimental results for the electrosorption of Cl - and ReO 4 - corresponded well with the developed model. The electrosorption capacity demonstrates a logarithmic relationship with the anode potential. The model showed that the electronegativity significantly affects the selectivity. In a mixed Cl - , ReO 4 - , SO 4 2- and NO 3 - solution, ReO 4 - was preferentially adsorbed over the other three anions, and the following selectivity was exhibited: ReO 4 -  > NO 3 -  > Cl -  > SO 4 2- . The results showed that the effect of flow rates on the electrosorption selectivity can be considered negligible when the flow rates are higher than 112 mL min -1 . The anions selectivity can be further enhanced by increasing the anode potential, and electrosorption selectivity is no appreciable decline after 6 experiments. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH 3 ) 4 ](ReO 4 ) 2 on γ-Al 2 O 3

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

    Thompson, Simon T.; Lamb, H. Henry

    The double complex salt [Pd(NH3)4](ReO4)2 was employed as precursor of supported bimetallic catalysts for selective hydrogenation of furfural. Direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 in flowing H2 at 400 °C yields bimetallic nanoparticles 1–2 nm in size that exhibit significant interaction between the metals, as evidenced by temperature-programmed hydride decomposition (complete suppression of β-PdHx formation), extended X-ray absorption fine structure spectroscopy at the Pd K and Re LIII edges (PdRe distance = 2.72 Å), and scanning transmission electron microscopy with energy dispersive X-ray analysis. In contrast, calcination of [Pd(NH3)4](ReO4)2 on γ-Al2O3 at 350 °C in air and subsequent reduction inmore » H2 at 400 °C results in metal segregation and formation of large (>50 nm) supported Pd particles; Re species cover the Pd particles and γ-Al2O3 support. A PdRe 1:2 catalyst prepared by sequential impregnation and calcination using HReO4 and [Pd(NH3)4](NO3)2 has a similar morphology. The catalyst derived by direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 exhibits remarkably high activity for selective hydrogenation of furfural to furfuryl alcohol (FAL) at 150 °C and 1 atm. Suppression of H2 chemisorption via elimination of Pd threefold sites, as evidenced by CO diffuse-reflectance infrared Fourier transform spectroscopy, correlates with increased FAL selectivity.« less

  5. EMISSIONS OF SULFUR TRIOXIDE FROM COAL-FIRED POWER PLANTS

    EPA Science Inventory

    Emissions of sulfur trioxide (SO3) are a key component of plume opacity and acid deposition. Consequently, these emissions need to be low enough not to cause opacity violations and acid deposition. Generally, a small fraction of sulfur in coal is converted to SO3 in coal-fired co...

  6. Multiple bonds between transition metals and main-group elements. 73. Synthetic routes to rhenium(V) alkyl and rhenium(VII) alkylidyne complexes. X-ray crystal structures of (. eta. sup 5 -C sub 5 Me sub 5 )Re( double bond O)(CH sub 3 )(CH sub 2 C(CH sub 3 ) sub 3 ) and (. eta. sup 5 -C sub 5 Me sub 5 )(Br) sub 3 Re triple bond CC(CH sub 3 ) sub 3

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

    Herrmann, W.A.; Felixberger, J.K.; Anwander, R.

    1990-05-01

    Dialkyloxo({eta}{sup 5}pentamethylcyclopentadienyl)rhenium(V) complexes ({eta}{sup 5}-C{sub 5}Me{sub 5})Re({double bond}O)(CH{sub 3})R{prime}(R{prime} = C{sub 2}H{sub 5}, CH{sub 2}Si(CH{sub 3}){sub 3}, CH{sub 2}C(CH{sub 3}){sub 3}), 1c-e, have become accessible through alkylation of ({eta}{sup 5}-C{sub 5}Me{sub 5})Re({double bond}O)(Cl)(CH{sub 3}) (7) with R{prime}MgCl. 1c-e are the first rhenium complexes containing different alkyl ligands. The neopentyl derivative 1e (R{prime} = CH{sub 2}C(CH{sub 3}){sub 3}) crystallizes in the orthorhombic space group Pbca with a = 960.7 (2), b = 2.844.5 (4), c = 1,260.7 (2) pm, and Z = 8. The X-ray crystal structure was refined to R{sub W} = 3.9%. The chiral molecule shows a distorted tetrahedralmore » geometry around the rhenium center. The tribromide 3b has been structurally characterized. Brown crystals of 3b belong to space group P2{sub 1}/c with unit cell dimensions a = 1,311.5 (2), b = 723.0 (1), c = 1,901.6 (2) pm, {beta} = 92.68 (1){degree}, and Z = 4. The structure exhibits a four-legged piano stool geometry with no trans influence of the neopentylidyne ligand to the bromine atom.« less

  7. In house development of (99m)Tc-Rhenium sulfide colloidal nanoparticles for sentinel lymph node detection.

    PubMed

    Dar, Ume-Kalsoom; Khan, Irfanullah; Javed, Muhammad; Ali, Muhammad; Hyder, Syed Waqar; Murad, Sohail; Anwar, Jamil

    2013-03-01

    In this study, rhenium sulfide colloidal nanoparticles were developed as radiopharmaceutical for sentinel lymph node detection. We directly used rhenium sulfide as a starting material for the preparation of colloidal nanoparticles. UV-visible spectrophotometry was used for characterization of in house developed colloidal particles. The size distribution of radioactive particles was studied by using membrane filtration method. The percentage of radiolabeled colloidal nanoparticles was determined by paper chromatography (PC). The study also includes in vitro stability, protein binding in human blood and bioevaluation in a rabbit model. The results indicate that 77.27 ± 3.26 % particles of size less than 20nm (suitable for lymphoscintigraphy) were radiolabeled. (99m)Tc labeled rhenium sulfide labeling efficacy with the radiometal is 98.5 ± 0.5%, which remains considerably stable beyond 5h at room temperature. Furthermore, it was observed that 70.2 ± 1.3% radiolabeled colloid complex showed binding with the blood protein. Bioevaluation results show the remarkable achievement of our radiopharmaceutical. The in house prepared (99m)Tc labeled rhenium sulfide colloidal nanoparticles reached the sentinel node within 15 min of post injection. These results indicate that (99m)Tc labeled rhenium sulfide colloid nanoparticles kit produced by a novel procedure seems of significant potential as a feasible candidate for further development to be used in clinical practice.

  8. Constraints on the timing of Marinoan ``Snowball Earth'' glaciation by 187Re-187Os dating of a Neoproterozoic, post-glacial black shale in Western Canada

    NASA Astrophysics Data System (ADS)

    Kendall, Brian S.; Creaser, Robert A.; Ross, Gerald M.; Selby, David

    2004-06-01

    New Re-Os isotopic data were obtained from chlorite-grade black shales from the upper Old Fort Point Formation (Windermere Supergroup), a post-glacial Neoproterozoic marker horizon in western Canada. A Re-Os isochron date of 634±57 Ma (MSWD=65, n=5) was determined using the conventional inverse aqua regia digestion medium. However, dissolution of the same samples with a new CrO 3-H 2SO 4 dissolution technique [Chem. Geol. 200 (2003) 225] yielded a much more precise date of 607.8±4.7 Ma (MSWD=1.2). Both dates are in agreement with existing U-Pb age constraints that bracket the Old Fort Point Formation between ˜685 and ˜570 Ma. The distinctive Re-Os systematics recorded by the two analytical protocols is explained by dissolution of a variably radiogenic, detrital Os component by the aqua regia method. In contrast, the CrO 3-H 2SO 4 technique minimizes this detrital component by selectively dissolving organic matter that is dominated by hydrogenous (seawater) Re and Os. The date of 607.8±4.7 Ma is thus interpreted as the depositional age for the upper Old Fort Point Formation providing a minimum age constraint for the timing of the second Windermere glaciation in western Canada. This ice age is correlative with the Marinoan (˜620-600 Ma) ice age and older than the ˜580-Ma Gaskiers glaciation of northeastern North America. The new Re-Os age determined from the CrO 3-H 2SO 4 digestion technique thus provides further support to a growing body of evidence for a global Marinoan glacial episode. Such an interpretation would not be discernable from the imprecise Re-Os date obtained with the aqua regia protocol. These results also indicate the potential for Re-Os radiometric dating of black shales that was not previously recognized. Importantly, neither chlorite-grade metamorphism nor the low organic content (TOC <1%) of the Old Fort Point Formation precluded the determination of a precise Re-Os depositional age using the CrO 3-H 2SO 4 analytical protocol.

  9. PREVENTION REFERENCE MANUAL: CHEMICAL SPECIFIC. VOL. 15: CONTROL OF ACCIDENTAL RELEASES OF SULFUR TRIOXIDE

    EPA Science Inventory

    The report, discussing sulfur trioxide (SO3), is one of a series addressing the prevention of accidental releases of toxic chemicals. SO3, a clear oily liquid or solid at typical ambient conditions, has an Immediately Dangerous to Life and Health (IDLH) concentration of 20 ppm, w...

  10. Mechanistic Study of Oxygen Atom Transfer Catalyzed by Rhenium Compounds

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

    Shan, Xiaopeng

    2003-01-01

    Two ionic and one neutral methyl(oxo)rhenium(V) compounds were synthesized and structurally characterized. They were compared in reactivity towards the ligands triphenylphosphane, pyridines, pyridine N-oxides. Assistance from Broensted bases was found on ligand displacement of ionic rhenium compounds as well as nucleophile assistance on oxidation of all compounds. From the kinetic data, crystal structures, and an analysis of the intermediates, a structural formula of PicH +3 - and mechanisms of ligand displacement and oxidation were proposed.

  11. Rhenium and technetium tricarbonyl complexes of 1,4-Substituted pyridyl-1,2,3-triazole bidentate 'click' ligands conjugated to a targeting RGD peptide.

    PubMed

    Connell, Timothy U; Hayne, David J; Ackermann, Uwe; Tochon-Danguy, Henri J; White, Jonathan M; Donnelly, Paul S

    2014-04-01

    New 1,4-substituted pyridyl-1,2,3-triazole ligands with pendent phenyl isothiocyanate functional groups linked to the heterocycle through a short methylene or longer polyethylene glycol spacers were prepared and conjugated to a peptide containing the arginine-glycine-aspartic acid peptide motif. Rhenium and technetium carbonyl complexes, [M(CO)3 L(x) (py)](+) (where M = Re(I) or (99m) Tc(I) ; L(x)  = 1,4-substituted pyridyl-1,2,3-triazole ligands and py = pyridine) were prepared. One rhenium complex has been characterized by X-ray crystallography, and the luminescent properties of [M(CO)3 L(x) (py)](+) are reported. Copyright © 2013 John Wiley & Sons, Ltd.

  12. Re-Os sulfide geochronology of the Red Dog sediment-hosted Zn-Pb-Ag deposit, Brooks Range, Alaska

    USGS Publications Warehouse

    Morelli, R.M.; Creaser, R.A.; Selby, D.; Kelley, K.D.; Leach, D.L.; King, A.R.

    2004-01-01

    The Red Dog sediment-hosted deposit in the De Long Mountains of northern Alaska is the largest Zn producer in the world. Main stage mineralization is characterized by massive sulfide ore and crosscutting subvertical veins. Although the vein mineralization is clearly younger than the massive ore, the exact temporal relationship between the two is unclear. Re-Os geochronology of pyrite is used to determine the absolute age of main stage ore at Red Dog. A 10-point isochron on both massive and vein pyrite yields an age of 338.3 ?? 5.8 Ma and is interpreted to represent the age of main stage ore. The Re-Os data indicate that both massive and vein ore types are coeval within the resolution of the technique. Formation of the Red Dog deposit was associated with extension along a passive continental margin, and therefore the Re-Os age of main stage ore constrains the timing of rifting as well as the age of the host sedimentary rocks. Sphalerite from both massive and vein ore yields imprecise ages and shows a high degree of scatter compared to pyrite. We suggest that the Re-Os systematics of sphalerite can be disturbed and that this mineral is not reliable for Re-Os geochronology. ?? 2004 by Economic Geology.

  13. 7 CFR 3560.505 - Agency loans to finance purchases of REO properties.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 15 2014-01-01 2014-01-01 false Agency loans to finance purchases of REO properties... Disposition of Real Estate Owned (REO) Properties § 3560.505 Agency loans to finance purchases of REO properties. (a) Agency loans to finance the purchase of REO property designated to be sold as program...

  14. 7 CFR 3560.505 - Agency loans to finance purchases of REO properties.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 15 2011-01-01 2011-01-01 false Agency loans to finance purchases of REO properties... Disposition of Real Estate Owned (REO) Properties § 3560.505 Agency loans to finance purchases of REO properties. (a) Agency loans to finance the purchase of REO property designated to be sold as program...

  15. 7 CFR 3560.505 - Agency loans to finance purchases of REO properties.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 15 2013-01-01 2013-01-01 false Agency loans to finance purchases of REO properties... Disposition of Real Estate Owned (REO) Properties § 3560.505 Agency loans to finance purchases of REO properties. (a) Agency loans to finance the purchase of REO property designated to be sold as program...

  16. 7 CFR 3560.505 - Agency loans to finance purchases of REO properties.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 15 2012-01-01 2012-01-01 false Agency loans to finance purchases of REO properties... Disposition of Real Estate Owned (REO) Properties § 3560.505 Agency loans to finance purchases of REO properties. (a) Agency loans to finance the purchase of REO property designated to be sold as program...

  17. High glutamate attenuates S100B and LDH outputs from rat cortical slices enhanced by either oxygen-glucose deprivation or menadione.

    PubMed

    Demircan, Celaleddin; Gül, Zülfiye; Büyükuysal, R Levent

    2014-07-01

    One hour incubation of rat cortical slices in a medium without oxygen and glucose (oxygen-glucose deprivation, OGD) increased S100B release to 6.53 ± 0.3 ng/ml/mg protein from its control value of 3.61 ± 0.2 ng/ml/mg protein. When these slices were then transferred to a medium containing oxygen and glucose (reoxygenation, REO), S100B release rose to 344 % of its control value. REO also caused 192 % increase in lactate dehydrogenase (LDH) leakage. Glutamate added at millimolar concentration into the medium decreased OGD or REO-induced S100B release and REO-induced LDH leakage. Alpha-ketoglutarate, a metabolic product of glutamate, was found to be as effective as glutamate in decreasing the S100B and LDH outputs. Similarly lactate, 2-ketobutyrate and ethyl pyruvate, a lipophilic derivative of pyruvate, also exerted a glutamate-like effect on S100B and LDH outputs. Preincubation with menadione, which produces H2O2 intracellularly, significantly increased S100B and LDH levels in normoxic medium. All drugs tested in the present study, with the exception of pyruvate, showed a complete protection against menadione preincubation. Additionally, each OGD-REO, menadione or H2O2-induced mitochondrial energy impairments determined by 2,3,5-triphenyltetrazolium chloride (TTC) staining and OGD-REO or menadione-induced increases in reactive oxygen substances (ROS) determined by 2,7-dichlorofluorescin diacetate (DCFH-DA) were also recovered by glutamate. Interestingly, H2O2-induced increase in fluorescence intensity derived from DCFH-DA in a slice-free physiological medium was attenuated significantly by glutamate and alpha-keto acids. All these drug actions support the conclusion that high glutamate, such as alpha-ketoglutarate and other keto acids, protects the slices against OGD- and REO-induced S100B and LDH outputs probably by scavenging ROS in addition to its energy substrate metabolite property.

  18. 7 CFR 3560.506 - Conversion of single family type REO property to MFH use.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 15 2014-01-01 2014-01-01 false Conversion of single family type REO property to MFH... and Disposition of Real Estate Owned (REO) Properties § 3560.506 Conversion of single family type REO property to MFH use. Single family type REO property may be sold for conversion to MFH program use under...

  19. 7 CFR 3560.506 - Conversion of single family type REO property to MFH use.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 15 2012-01-01 2012-01-01 false Conversion of single family type REO property to MFH... and Disposition of Real Estate Owned (REO) Properties § 3560.506 Conversion of single family type REO property to MFH use. Single family type REO property may be sold for conversion to MFH program use under...

  20. 7 CFR 3560.506 - Conversion of single family type REO property to MFH use.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 15 2013-01-01 2013-01-01 false Conversion of single family type REO property to MFH... and Disposition of Real Estate Owned (REO) Properties § 3560.506 Conversion of single family type REO property to MFH use. Single family type REO property may be sold for conversion to MFH program use under...

  1. 7 CFR 3560.506 - Conversion of single family type REO property to MFH use.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 15 2011-01-01 2011-01-01 false Conversion of single family type REO property to MFH... and Disposition of Real Estate Owned (REO) Properties § 3560.506 Conversion of single family type REO property to MFH use. Single family type REO property may be sold for conversion to MFH program use under...

  2. 7 CFR 3560.506 - Conversion of single family type REO property to MFH use.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 15 2010-01-01 2010-01-01 false Conversion of single family type REO property to MFH... and Disposition of Real Estate Owned (REO) Properties § 3560.506 Conversion of single family type REO property to MFH use. Single family type REO property may be sold for conversion to MFH program use under...

  3. Preservation of an Archaean whole rock Re-Os isochron for the Venetia lithospheric mantle: Evidence for rapid crustal recycling and lithosphere stabilisation at 3.3 Ga

    NASA Astrophysics Data System (ADS)

    van der Meer, Quinten H. A.; Klaver, Martijn; Reisberg, Laurie; Riches, Amy J. V.; Davies, Gareth R.

    2017-11-01

    Re-Os and platinum group element analyses are reported for peridotite xenoliths from the 533 Ma Venetia kimberlite cluster situated in the Limpopo Mobile Belt, the Neoarchaean collision zone between the Kaapvaal and Zimbabwe Cratons. The Venetian xenoliths provide a rare opportunity to examine the state of the cratonic lithosphere prior to major regional metasomatic disturbance of Re-Os systematics throughout the Phanerozoic. The 32 studied xenoliths record Si-enrichment that is characteristic of the Kaapvaal lithospheric mantle and can be subdivided into five groups based on Re-Os analyses. The most pristine group I samples (n = 13) display an approximately isochronous relationship and fall on a 3.28 ± 0.17 Ga (95 % conf. int.) reference line that is based on their mean TMA age. This age overlaps with the formation age of the Limpopo crust at 3.35-3.28 Ga. The group I samples derive from ∼50 to ∼170 km depth, suggesting coeval melt depletion of the majority of the Venetia lithospheric mantle column. Group II and III samples have elevated Re/Os due to Re addition during kimberlite magmatism. Group II has otherwise undergone a similar evolution as the group I samples with overlapping 187Os/188Os at eruption age: 187Os/188OsEA, while group III samples have low Os concentrations, unradiogenic 187Os/188OsEA and were effectively Re-free prior to kimberlite magmatism. The other sample groups (IV and V) have disturbed Re-Os systematics and provide no reliable age information. A strong positive correlation is recorded between Os and Re concentrations for group I samples, which is extended to groups II and III after correction for kimberlite addition. This positive correlation precludes a single stage melt depletion history and indicates coupled remobilisation of Re and Os. The combination of Re-Os mobility, preservation of the isochronous relationship, correlation of 187Os/188Os with degree of melt depletion and lack of radiogenic Os addition puts tight constraints on the formation and subsequent evolution of Venetia lithosphere. First, melt depletion and remobilisation of Re and Os must have occurred within error of the 3.28 Ga mean TMA age. Second, the refractory peridotites contain significant Re despite recording >40 % melt extraction. Third, assuming that Si-enrichment and Re-Os mobility in the Venetia lithospheric mantle were linked, this process must have occurred within ∼100 Myr of initial melt depletion in order to preserve the isochronous relationship. Based on the regional geological evolution, we propose a rapid recycling model with initial melt depletion at ∼3.35 Ga to form a tholeiitic mafic crust that is recycled at ∼3.28 Ga, resulting in the intrusion of a TTG suite and Si-enrichment of the lithospheric mantle. The non-zero primary Re contents of the Venetia xenoliths imply that TRD model ages significantly underestimate the true depletion age even for highly depleted peridotites. The overlap of the ∼2.6 Ga TRD ages with the time of the Kaapvaal-Limpopo collision is purely fortuitous and has no geological significance. Hence, this study underlines the importance of scrutiny if age information is to be derived from whole rock Re-Os analyses.

  4. Development of chemically vapor deposited rhenium emitters of (0001) preferred crystal orientation

    NASA Technical Reports Server (NTRS)

    Yang, L.; Hudson, R. G.

    1973-01-01

    Rhenium thermionic emitters were prepared by the pyrolysis of rhenium chlorides formed by the chlorination of rhenium pellets. The impurity contents, microstructures, degrees of (0001) preferred crystal orientation, and vacuum electron work functions of these emitters were determined as a function of deposition parameters, such as substrate temperature, rhenium pellet temperature and chlorine flow rate. A correlation between vacuum electron work function and degree of (0001) preferred crystal orientation was established. Conditions for depositing porosity-free rhenium emitters of high vacuum electron work functions were defined. Finally, three cylindrical rhenium emitters were prepared under the optimum deposition conditions.

  5. Therapeutic and scintigraphic applications of polymeric micelles: combination of chemotherapy and radiotherapy in hepatocellular carcinoma

    PubMed Central

    Shih, Ying-Hsia; Peng, Cheng-Liang; Chiang, Ping-Fang; Lin, Wuu-Jyh; Luo, Tsai-Yueh; Shieh, Ming-Jium

    2015-01-01

    This study evaluated a multifunctional micelle simultaneously loaded with doxorubicin (Dox) and labeled with radionuclide rhenium-188 (188Re) as a combined radiotherapy and chemotherapy treatment for hepatocellular carcinoma. We investigated the single photon emission computed tomography, biodistribution, antitumor efficacy, and pathology of 188Re-Dox micelles in a murine orthotopic luciferase-transfected BNL tumor cells hepatocellular carcinoma model. The single photon emission computed tomography and computed tomography images showed high radioactivity in the liver and tumor, which was in agreement with the biodistribution measured by γ-counting. In vivo bioluminescence images showed the smallest size tumor (P<0.05) in mice treated with the combined micelles throughout the experimental period. In addition, the combined 188Re-Dox micelles group had significantly longer survival compared with the control, 188ReO4 alone (P<0.005), and Dox micelles alone (P<0.01) groups. Pathohistological analysis revealed that tumors treated with 188Re-Dox micelles had more necrotic features and decreased cell proliferation. Therefore, 188Re-Dox micelles may enable combined radiotherapy and chemotherapy to maximize the effectiveness of treatment for hepatocellular carcinoma. PMID:26719687

  6. Formation of self-ordered porous anodized alumina template for growing tungsten trioxide nanowires

    NASA Astrophysics Data System (ADS)

    Hussain, Tajamal; Shah, Asma Tufail; Shehzad, Khurram; Mujahid, Adnan; Farooqi, Zahoor Hussain; Raza, Muhammad Hamid; Ahmed, Mirza Nadeem; Nisa, Zaib Un

    2015-12-01

    Uniform porous anodized aluminum oxide (AAO) membrane has been synthesized by two-step anodization for fabricating tungsten trioxide (WO3) nanowires. Under assayed conditions, uniform porous structure of alumina (Al2O3) membrane with long range ordered hexagonal arrangements of nanopores was achieved. The self-assembled template possesses pores of internal diameter of 50 nm and interpore distance ( d int) of 80 nm with a thickness of about 80 µm, i.e., used for fabrication of nanostructures. WO3 nanowires have been fabricated by simple electroless deposition method inside Al2O3 nanopores. SEM images show tungsten trioxide nanowire with internal diameter of about 50 nm, similar to porous diameter of AAO template. XRD results showed that nanowires exist in cubic crystalline state with minor proportion of monoclinic phase.

  7. Effects of Rosmarinus officinalis L. essential oils supplementation on digestion, colostrum production of dairy ewes and lamb mortality and growth.

    PubMed

    Smeti, Samir; Joy, Margalida; Hajji, Hadhami; Alabart, José Luis; Muñoz, Fernando; Mahouachi, Mokhtar; Atti, Naziha

    2015-07-01

    The aim of this study was to evaluate the effect of rosemary essential oils (REO) and the forage nature on ewes' performances, immune response and lambs' growth and mortality. Forty-eight dairy ewes (Sicilo-Sarde) were fed oat-hay or oat-silage supplemented with 400 g of concentrate during pregnancy and 600 g during postpartum. The experimental concentrate contained the same mixture as the control (barley, soybean meal and mineral vitamin supplement) more 0.6 g/kg of REO. Two groups were obtained with each forage (Hay groups: H-C and H-REO; Silage groups: S-C and S-REO). REO increased the dry matter (DM) intake, the nitrogen intake and retention being higher with the silage groups (P < 0.05). REO increased solid non-fat (P = 0.004) and fat contents of colostrum which was higher with hay (P = 0.002). REO decreased lamb mortality (P < 0.05) which averaged 21% for control groups and 6% for H-REO, while no mortality was recorded with S-REO. REO dietary supply improved forage intake and tended to ameliorate colostrum production; it could be a natural additive to improve ewes' performances. © 2015 Japanese Society of Animal Science.

  8. Solution and diffusion of hydrogen isotopes in tungsten-rhenium alloy

    NASA Astrophysics Data System (ADS)

    Ren, Fei; Yin, Wen; Yu, Quanzhi; Jia, Xuejun; Zhao, Zongfang; Wang, Baotian

    2017-08-01

    Rhenium is one of the main transmutation elements forming in tungsten under neutron irradiation. Therefore, it is essential to understand the influence of rhenium impurity on hydrogen isotopes retention in tungsten. First-principle calculations were used to study the properties of hydrogen solution and diffusion in perfect tungsten-rhenium lattice. The interstitial hydrogen still prefers the tetrahedral site in presence of rhenium, and rhenium atom cannot act directly as a trapping site of hydrogen. The presence of rhenium in tungsten raises the solution energy and the real normal modes of vibration on the ground state and the transition state, compared to hydrogen in pure tungsten. Without zero point energy corrections, the presence of rhenium decreases slightly the migration barrier. It is found that although the solution energy would tend to increase slightly with the rising of the concentration of rhenium, but which does not influence noticeably the solution energy of hydrogen in tungsten-rhenium alloy. The solubility and diffusion coefficient of hydrogen in perfect tungsten and tungsten-rhenium alloy have been estimated, according to Sievert's law and harmonic transition state theory. The results show the solubility of hydrogen in tungsten agrees well the experimental data, and the presence of Re would decrease the solubility and increase the diffusivity for the perfect crystals.

  9. Intracellular distribution and stability of a luminescent rhenium(I) tricarbonyl tetrazolato complex using epifluorescence microscopy in conjunction with X-ray fluorescence imaging

    DOE PAGES

    Wedding, Jason L.; Harris, Hugh H.; Bader, Christie A.; ...

    2016-11-23

    Optical fluorescence microscopy was used in conjunction with X-ray fluorescence microscopy to monitor the stability and intracellular distribution of the luminescent rhenium(I) complex fac-[Re(CO) 3(phen)L], where phen = 1,10-phenathroline and L = 5-(4-iodophenyl)tetrazolato, in 22Rv1 cells. The rhenium complex showed no signs of ancillary ligand dissociation, a conclusion based on data obtained via X-ray fluorescence imaging aligning iodine and rhenium distributions. A diffuse reticular localisation was detected for the complex, in the nuclear/perinuclear region of cells, by either optical or X-ray fluorescence techniques. Furthermore, X-ray fluorescence also showed that the Re-I complex disrupted the homeostasis of some biologically relevant elements,more » such as chlorine, potassium and zinc.« less

  10. The First Seven-Coordinated Triiodo Complex of Rhenium(III)

    NASA Astrophysics Data System (ADS)

    Schoultz, X.; Gerber, T. I. A.; Betz, R.; Hosten, E. C.

    2017-12-01

    The reaction of cis-[ReO2I(P Ph 3)2] with tert-butyl isocyanide in benzene led to the isolation of the complex [ReI3(CN- t-Bu)3(P Ph 3)] ( 1). The complex is unusual since it contains bulky ligands with large cone angles, i.e. three iodides, three isocyanides with tert-butyl groups and a triphenylphosphine as ligands in a seven-coordinate geometry around the rhenium(III) metal ion.

  11. Necroptosis-inducing rhenium(V) oxo complexes.

    PubMed

    Suntharalingam, Kogularamanan; Awuah, Samuel G; Bruno, Peter M; Johnstone, Timothy C; Wang, Fang; Lin, Wei; Zheng, Yao-Rong; Page, Julia E; Hemann, Michael T; Lippard, Stephen J

    2015-03-04

    Rhenium(V) oxo complexes of general formula [ReO(OMe)(N^N)Cl2], where N^N = 4,7-diphenyl-1,10-phenanthroline, 1, or 3,4,7,8-tetramethyl-1,10-phenanthroline, 2, effectively kill cancer cells by triggering necroptosis, a non-apoptotic form of cell death. Both complexes evoke necrosome (RIP1-RIP3)-dependent intracellular reactive oxygen species (ROS) production and propidium iodide uptake. The complexes also induce mitochondrial membrane potential depletion, a possible downstream effect of ROS production. Apparently, 1 and 2 are the first rhenium complexes to evoke cellular events consistent with programmed necrosis in cancer cells. Furthermore, 1 and 2 display low acute toxicity in C57BL/6 mice and reasonable stability in fresh human blood.

  12. Necroptosis-Inducing Rhenium(V) Oxo Complexes

    PubMed Central

    Suntharalingam, Kogularamanan; Awuah, Samuel G.; Bruno, Peter M.; Johnstone, Timothy C.; Wang, Fang; Lin, Wei; Zheng, Yao-Rong; Page, Julia E.; Hemann, Michael T.; Lippard, Stephen J.

    2015-01-01

    Rhenium(V) oxo complexes of general formula [ReO(OMe)(N^N)Cl2], where N^N = 4,7-diphenyl-1,10-phenanthroline, 1, or 3,4,7,8-tetramethyl-1,10-phenanthroline, 2, effectively kill cancer cells by triggering necroptsosis, a non-apoptotic form of cell death. Both complexes evoke necrosome (RIP1-RIP3)-dependent intracellular ROS production and propidium iodide uptake. The complexes also induce mitochondrial membrane potential depletion, a possible downstream effect of ROS production. Apparently, 1 and 2 are the first rhenium complexes to evoke cellular events consistent with programmed necrosis in cancer cells. Furthermore, 1 and 2 display low acute toxicity in C57BL/6 mice and reasonable stability in fresh human blood. PMID:25698398

  13. Thermodynamic and kinetic studies of As2O3 toxicological effects on human insulin in generation diabetes mellitus

    NASA Astrophysics Data System (ADS)

    Mohsennia, Mohsen; Motaharinejad, Atieh; Rafiee-Pour, Hossain-Ali; Torabbeigi, Marzieh

    2017-12-01

    The interaction of arsenic trioxide with human insulin was investigated by circular dichroism (CD), cyclic voltammetry and electrophoresis techniques. The interfacial behavior of insulin in presence of As2O3 onto the Ag electrode surface was studied at 310 K in phosphate buffer solution (PBS). According to Far-UV CD spectroscopy results, As2O3 caused to decrease in structural compactness and variety of alpha helix into beta structures. Near-UV CD indicated that As2O3 dissociates disulfide linkage in insulin structure. The kinetic parameters, including charge-transfer coefficient and apparent heterogeneous electron transfer rate constant were also determined. The thermodynamic parameters of insulin denaturation in presence of arsenic trioxide were calculated and reported. The obtained results indicated strong adsorption of insulin in presence of arsenic trioxide onto the Ag surface via chemisorptions.

  14. An isotopic study of the Ni-Cu-PGE-rich Wellgreen intrusion of the Wrangellia Terrane: Evidence for hydrothermal mobilization of rhenium and osmium

    NASA Astrophysics Data System (ADS)

    Marcantonio, Franco; Reisberg, Laurie; Zindler, Alan; Wyman, Derek; Hulbert, Larry

    1994-01-01

    Re-Os, Sm-Nd, Rb-Sr, and oxygen isotope systematics of the Wellgreen intrusion in the Wrangellia terrane were investigated in an effort to deduce the origin of this mafic-ultramafic sill and its attendant Ni-Cu-PGE deposit. Radiogenic initial Os ratios (1.06-1.82) and Sr ratios (0.7044-0.7062), and heavy δ18O (7.3-7.9%.) suggest alteration of the intrusion by hydrothermal fluids that carried radiogenic 187Os and 87Sr from the surrounding country rocks. The great majority (>99%) of the Os, however, and by inference the other PGEs, derived from a mantle-derived magma that suffered little or no interaction with the crust prior to crystallization. Initial Nd isotope ratios are not as variable ( ɛNd( t) ranges from 2.02-4.49) and suggest that the rocks were derived from a light-rare-earth-element depleted mantle source. The Nd results, together with Os data from relatively undisturbed wehrlites, are compatible with either a plume ( RICHARDS et al., 1991) or island arc ( SAMSON et al., 1990) model for Wrangellia. This study contributes to a growing body of evidence that documents the ready mobilization of Os in hydrothermal fluids. The potential effects of this mobility must be carefully evaluated prior to invoking crustal assimilation to explain variable and radiogenic Os initial ratios in layered intrusions.

  15. Contribution to the photometric determination of small amounts of boron trioxide in glasses

    NASA Technical Reports Server (NTRS)

    Markova, D.

    1985-01-01

    The photometric determination for boron trioxide is described in amounts of 0-75 micrograms B2O3 with an azomethin H reagent. The yellow colored complex which occurs in a medium held at a pH of 4.5 was measured in light of a wavelength of 415 nm.

  16. Structural, morphological, gas sensing and photocatalytic characterization of MoO3 and WO3 thin films prepared by the thermal vacuum evaporation technique

    NASA Astrophysics Data System (ADS)

    Arfaoui, A.; Touihri, S.; Mhamdi, A.; Labidi, A.; Manoubi, T.

    2015-12-01

    Thin films of molybdenum trioxide and tungsten trioxide were deposited on glass substrates using a simplified thermal evaporation under vacuum method monitored by heat treatment in flowing oxygen at 500 °C for 1 h. The structural and morphological properties of the films were investigated using X-ray diffraction, Raman spectroscopy, atomic force microscopy and scanning electron microscopy. The X-ray diffraction analysis shows that the films of MoO3 and WO3 were well crystallized in orthorhombic and monoclinic phase respectively with the crystallites preferentially oriented toward (2 0 0) direction parallel a-axis for both samples. In literature, we have shown in previous papers that structural and surface morphology of metal thin films play an important role in the gas detection mechanism. In this article, we have studied the response evolution of MoO3 and WO3 thin films sensors ethanol versus time, working temperature and the concentration of the ethanol. It was found that these films had high sensitivity to ethanol, which made them as a good candidate for the ethanol sensor. Finally, the photocatalytic activity of the samples was evaluated with respect to the degradation reaction of a wastewater containing methylene blue (MB) under UV-visible light irradiation. The molybdenum trioxide exhibits a higher degradation rate than the tungsten trioxide thin films under similar experimental conditions.

  17. Rhenium-osmium isotopes and highly siderophile elements in ultramafic rocks from the Eoarchean Saglek Block, northern Labrador, Canada: implications for Archean mantle evolution

    NASA Astrophysics Data System (ADS)

    Ishikawa, Akira; Suzuki, Katsuhiko; Collerson, Kenneth D.; Liu, Jingao; Pearson, D. Graham; Komiya, Tsuyoshi

    2017-11-01

    We determined highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, and Re) concentrations and 187Os/188Os ratios for ultramafic rocks distributed over the Eoarchean gneiss complex of the Saglek-Hebron area in northern Labrador, Canada in order to constrain to what extent variations in HSE abundances are recorded in Early Archean mantle that have well-resolved 182W isotope anomalies relative to the present-day mantle (∼+11 ppm: Liu et al., 2016). The samples analysed here have been previously classified into two suites: mantle-derived peridotites occurring as tectonically-emplaced slivers of lithospheric mantle, and metakomatiites comprising mostly pyroxenitic layers in supracrustal units dominated by amphibolites. Although previous Sm-Nd and Pb-Pb isotope studies provided whole-rock isochrons indicative of ∼3.8 Ga protolith formation for both suites, our whole-rock Re-Os isotope data on a similar set of samples yield considerably younger errorchrons with ages of 3612 ± 130 Ma (MSWD = 40) and 3096 ± 170 Ma (MSWD = 10.2) for the metakomatiite and lithospheric mantle suites, respectively. The respective initial 187Os/188Os = 0.10200 ± 18 for metakomatiites and 0.1041 ± 18 for lithospheric mantle rocks are within the range of chondrites. Re-depletion Os model ages for unradiogenic samples from the two suites are consistent with the respective Re-Os errorchrons (metakomatiite TRD = 3.4-3.6 Ga; lithospheric mantle TRD = 2.8-3.3 Ga). These observations suggest that the two ultramafic suites are not coeval. However, the estimated mantle sources for the two ultramafics suites are similar in terms of their broadly chondritic evolution of 187Os/188Os and their relative HSE patterns. In detail, both mantle sources show a small excess of Ru/Ir similar to that in modern primitive mantle, but a ∼20% deficit in absolute HSE abundances relative to that in modern primitive mantle (metakomatiite 74 ± 18% of PUM; lithospheric mantle 82 ± 10% of PUM), consistent with the ∼3.8 Ga Isua mantle source and Neoarchean komatiite sources around the world (∼70-86% of PUM). This demonstrates that the lower HSE abundances are not unique to the sources of komatiites, but rather might be a ubiquitous feature of Archean convecting mantle. This tentatively suggests that chondritic late accretion components boosted the convecting mantle HSE inventory after core separation in the Hadean, and that the Eoarchean to Neoarchean convecting mantle was depleted in its HSE content relative to that of today. Further investigation of Archean mantle-derived rocks is required to explore this hypothesis.

  18. Evaluation of Rhenium Joining Methods

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.; Morren, Sybil H.

    1995-01-01

    Coupons of rhenium-to-Cl03 flat plate joints, formed by explosive and diffusion bonding, were evaluated in a series of shear tests. Shear testing was conducted on as-received, thermally-cycled (100 cycles, from 21 to 1100 C), and thermally-aged (3 and 6 hrs at 1100 C) joint coupons. Shear tests were also conducted on joint coupons with rhenium and/or Cl03 electron beam welded tabs to simulate the joint's incorporation into a structure. Ultimate shear strength was used as a figure of merit to assess the effects of the thermal treatment and the electron beam welding of tabs on the joint coupons. All of the coupons survived thermal testing intact and without any visible degradation. Two different lots of as-received, explosively-bonded joint coupons had ultimate shear strengths of 281 and 310 MPa and 162 and 223 MPa, respectively. As-received, diffusion-bonded coupons had ultimate shear strengths of 199 and 348 MPa. For the most part, the thermally-treated and rhenium weld tab coupons had shear strengths slightly reduced or within the range of the as-received values. Coupons with Cl03 weld tabs experienced a significant reduction in shear strength. The degradation of strength appeared to be the result of a poor heat sink provided during the electron beam welding. The Cl03 base material could not dissipate heat as effectively as rhenium, leading to the formation of a brittle rhenium-niobium intermetallic.

  19. Slip casting and extruding shapes of rhemium with metal oxide additives. Part 2: Development of grain stabilized rhenium parts for resistojets

    NASA Technical Reports Server (NTRS)

    Barr, Francis A.; Page, Russell J.

    1987-01-01

    The adaptation of the powdered particle process used for pure metal oxides to the coprocessing of rhenium oxides suitable to produce pure miniature resistojet hardware has been successful. Both slip casting and extrusion processes were used. The metal oxide ZrO2 was stabilized into the cubic phase with Y2O3, for use as a potentially grain stabilizing additive to rhenium. Straight meter long tubing in two sizes are reported. Tubing suitable for resistojet ohmic heater use of fully fired dimensions of nominally 3.8 mm o.d. x 2.2 mm i.d.. and 1.26 mm o.d. x .45 mm i.d. with 0, 0.5, 1.0 and 5.0% zirconia additives were produced for further study. Photomicrographs of these are discussed. The addition of the metal oxide zirconia to rhenium resulted in more dense and less porous parts. The additions of phase stabilized zirconia most likely act as a sintering aid. Tubes of varying diameter were slip cast which were representative of miniature pressure cases.

  20. Technetium and rhenium pentacarbonyl complexes with C₂ and C₁₁ ω-isocyanocarboxylic acid esters.

    PubMed

    Miroslavov, Alexander E; Polotskii, Yuriy S; Gurzhiy, Vladislav V; Ivanov, Alexander Yu; Lumpov, Alexander A; Tyupina, Margarita Yu; Sidorenko, Georgy V; Tolstoy, Peter M; Maltsev, Daniil A; Suglobov, Dmitry N

    2014-08-04

    Technetium(I) and rhenium(I) pentacarbonyl complexes with ethyl 2-isocyanoacetate and methyl 11-isocyanoundecanoate, [M(CO)5(CNCH2COOEt)]ClO4 (M = Tc (1) and Re (2)) and [M(CO)5(CN(CH2)10COOMe)]ClO4 (M = Tc (3) and Re (4)), were prepared and characterized by IR, (1)H NMR, and (13)C{(1)H} NMR spectroscopy. The crystal structures of 1 and 2 were determined using single-crystal X-ray diffraction. The kinetics of thermal decarbonylation of technetium complexes 1 and 3 in ethylene glycol was studied by IR spectroscopy. The rate constants and activation parameters of this reaction were determined and compared with those for [Tc(CO)6](+). It was found that rhenium complexes 2 and 4 were stable with respect to thermal decarbonylation. Histidine challenge reaction of complexes 1 and 2 in phosphate buffer was examined by IR spectroscopy. In the presence of histidine, the rhenium pentacarbonyl isocyanide complex partially decomposes to form an unidentified yellow precipitate. Technetium analogue 1 is more stable under these conditions.

  1. A study of scandia and rhenium doped tungsten matrix dispenser cathode

    NASA Astrophysics Data System (ADS)

    Wang, Jinshu; Li, Lili; Liu, Wei; Wang, Yanchun; Zhao, Lei; Zhou, Meiling

    2007-10-01

    Scandia and rhenium doped tungsten powders were prepared by solid-liquid doping combined with two-step reduction method. The experimental results show that scandia was distributed evenly on the surface of tungsten particles. The addition of scandia and rhenium could decrease the particle size of doped tungsten, for example, the tungsten powders doped with Sc 2O 3 and Re had the average size of about 50 nm in diameter. By using this kind of powder, scandia and rhenium doped tungsten matrix with the sub-micrometer sized tungsten grains was obtained. This kind of matrix exhibited good anti-bombardment insensitivity at high temperature. The emission property result showed that high space charge limited current densities of more than 60 A/cm 2 at 900 °C could be obtained for this cathode. A Ba-Sc-O multilayer about 100 nm in thickness formed at the surface of cathode after activation led to the high emission property.

  2. Rhemium-186-monoaminemonoamidedithiol-conjugated bisphosphonate derivatives for bone pain palliation.

    PubMed

    Ogawa, Kazuma; Mukai, Takahiro; Arano, Yasushi; Otaka, Akira; Ueda, Masashi; Uehara, Tomoya; Magata, Yasuhiro; Hashimoto, Kazuyuki; Saji, Hideo

    2006-05-01

    To develop a radiopharmaceutical for the palliation of painful bone metastases based on the concept of bifunctional radiopharmaceuticals, we synthesized a bisphosphonate derivative labeled with rhenium-186 (186Re) that contains a hydroxyl group at the central carbon of its bisphosphonate structure, we attached a stable 186Re-MAMA chelate to the amino group of a 4-amino butylidene-bisphosphonate derivative [N-[2-[[4-[(4-hydroxy-4,4-diphosphonobutyl)amino]-4-oxobutyl]-2-thioethylamino]acetyl]-2-aminoethanethiolate] oxorhenium (V) (186Re-MAMA-HBP) and we investigated the effect of a hydroxyl group at the central carbon of its bisphosphonate structure on affinity for hydroxyapatite and on biodistribution by conducting a comparative study with [N-[2-[[3-(3,3-diphosphonopropylcarbamoyl)propyl]-2-thioethylamino]acetyl]-2-aminoethanethiolate] oxorhenium (V) (186Re-MAMA-BP). The precursor of 186Re-MAMA-HBP, trityl (Tr)-MAMA-HBP, was obtained by coupling a Tr-MAMA derivative to 4-amino-1-hydroxybutylidene-1,1-bisphosphonate. 186Re-MAMA-HBP was prepared by a reaction with 186ReO(4-) and SnCl2 in citrate buffer after the deprotection of the Tr groups of Tr-MAMA-HBP. After reversed-phase high-performance liquid chromatography, 186Re-MAMA-HBP had a radiochemical purity of over 95%. Compared with 186Re-MAMA-BP, 186Re-MAMA-HBP showed a greater affinity for hydroxyapatite beads in vitro and accumulated a significantly higher level in the femur in vivo. Thus, the introduction of a hydroxyl group into 186Re complex-conjugated bisphosphonates would be effective in enhancing accumulation in bones. These findings provide useful information on the design of bone-seeking therapeutic radiopharmaceuticals.

  3. Investigations on microstructure, electrical and magnetic properties of copper spinel ferrite with WO3 addition for applications in the humidity sensors

    NASA Astrophysics Data System (ADS)

    Tudorache, Florin

    2018-04-01

    In the present study we report the structural, electrical, magnetic and humidity characteristics of copper ferrite with different percent on tungsten trioxide addition. The aim of this study was to obtain more stable and sensitive active materials for humidity sensors. In order to highlight the influence of tungsten on the structural, electrical and magnetic properties, the ferrite samples were fabricated via sol-gel self-combustion method and sintered for 30 min at 1000 °C with percent between 0 and 20% tungsten trioxide additions. The X-ray diffraction investigations showed the copper ferrite phase composition. The scanning electron microscopy revealed the influence of the substitution on characteristics of the crystallites and the profilometry showed the surface topography of samples. The investigation was focused on the variation of permittivity and electrical conductivity, in relation with tungsten trioxide addition, frequency and humidity. We have also, investigated the relevant magnetic characteristics of the copper ferrite material by highlighting the influence of tungsten trioxide addition on to Curie temperature and the permeability frequency characteristics. The data suggests that the copper ferrite with tungsten trioxide addition can be used as active material for humidity sensors.

  4. Dose- and Time-Dependent Response of Human Leukemia (HL-60) Cells to Arsenic Trioxide Treatment

    PubMed Central

    Yedjou, Clement G.; Moore, Pamela; Tchounwou, Paul B.

    2006-01-01

    The treatment of acute promyelocytic leukemia (APL) has been based on the administration of all-trans retinoic acid plus anthracycline chemotherapy, which is very effective as first line therapy; however 25 to 30% of patients will relapse with their disease becoming refractory to conventional therapy. Recently, studies have shown arsenic trioxide to be effective in the treatment of acute promyelocytic leukemia. In this study, we used the human leukemia (HL-60) cell line as a model to evaluate the cytoxicity of arsenic trioxide based on the MTT assay. Data obtained from this assay indicated that arsenic trioxide significantly reduced the viability of HL-60 cells, showing LD50 values of 14.26 ± 0.5μg/mL, 12.54 ± 0.3μg/mL, and 6.4 ± 0.6μg/mL upon 6, 12, and 24 hours of exposure, respectively; indicating a dose- and time-dependent response relationship. Findings from the present study indicate that arsenic trioxide is highly cytotoxic to human leukemia (HL-60) cells, supporting its use as an effective therapeutic agent in the management of acute promyelocytic leukemia. PMID:16823087

  5. Facile Solution Synthesis of Tungsten Trioxide Doped with Nanocrystalline Molybdenum Trioxide for Electrochromic Devices.

    PubMed

    Hasani, Amirhossein; Le, Quyet Van; Nguyen, Thang Phan; Choi, Kyoung Soon; Sohn, Woonbae; Kim, Jang-Kyo; Jang, Ho Won; Kim, Soo Young

    2017-10-16

    A facile, highly efficient approach to obtain molybdenum trioxide (MoO 3 )-doped tungsten trioxide (WO 3 ) is reported. An annealing process was used to transform ammonium tetrathiotungstate [(NH 4 ) 2 WS 4 ] to WO 3 in the presence of oxygen. Ammonium tetrathiomolybdate [(NH 4 ) 2 MoS 4 ] was used as a dopant to improve the film for use in an electrochromic (EC) cell. (NH 4 ) 2 MoS 4 at different concentrations (10, 20, 30, and 40 mM) was added to the (NH 4 ) 2 WS 4 precursor by sonication and the samples were annealed at 500 °C in air. Raman, X-ray diffraction, and X-ray photoelectron spectroscopy measurements confirmed that the (NH 4 ) 2 WS 4 precursor decomposed to WO 3 and the (NH 4 ) 2 MoS 4 -(NH 4 ) 2 WS 4 precursor was transformed to MoO 3 -doped WO 3 after annealing at 500 °C. It is shown that the MoO 3 -doped WO 3 film is more uniform and porous than pure WO 3 , confirming the doping quality and the privileges of the proposed method. The optimal MoO 3 -doped WO 3 used as an EC layer exhibited a high coloration efficiency of 128.1 cm 2 /C, which is larger than that of pure WO 3 (74.5 cm 2 /C). Therefore, MoO 3 -doped WO 3 synthesized by the reported method is a promising candidate for high-efficiency and low-cost smart windows.

  6. Re-Os dating of maltenes and asphaltenes within single samples of crude oil

    NASA Astrophysics Data System (ADS)

    Georgiev, Svetoslav V.; Stein, Holly J.; Hannah, Judith L.; Galimberti, Roberto; Nali, Micaela; Yang, Gang; Zimmerman, Aaron

    2016-04-01

    Re-Os geochronology of oil may constrain the timing of oil formation and improve oil-source and oil-oil correlations. Typically, asphaltene (ASPH), the heaviest and most Re-Os rich oil fraction, from multiple oils within an oil field or a larger petroleum system are analyzed to obtain sufficient spread in Re-Os isotopic ratios, a mathematical necessity for precise Re-Os isochrons. Here we offer a new approach for Re-Os geochronology of oil based on isotopic analyses of different fractions within a single sample of crude oil. We studied three oils from the Gela oil field, southern Sicily, Italy, recovered from Triassic-Jurassic stratigraphic intervals (Streppenosa, Noto, and Sciacca Formations) within the Gela-1 well. ASPH (insoluble in n-alkane) and maltene (MALT, soluble in n-alkane) fractions of oil were separated using n-pentane, n-hexane, n-heptane and n-decane solvents. The ASPH contents of the Sciacca and Noto oils (26-33 wt%) are notably higher compared to the Streppenosa oil (7-12 wt% ASPH). We present an optimized Re-Os procedure with sample digestion in a high-pressure asher, followed by isotopic measurements using negative thermal ionization mass spectrometry. Very high metal contents of Gela oils allowed acquisition of precise Re-Os data. Systematic variations between the type of solvent used for ASPH precipitation and the ASPH content of the oil (also known from the literature) and the Re-Os contents of the ASPH and MALT fractions (first observed in this study) provide important practical applications for Re-Os analyses of oil. Most Re and Os (∼96-98%) in the Noto oil are hosted in the ASPH fraction. In contrast, a significant portion of Re and Os (∼33-34%) is stored in the MALT fraction of the lighter, but heavily biodegraded Streppenosa oil. Collectively, our new data on alkane distribution, hopane and sterane biomarkers, major and trace element contents, and Re-Os concentrations and isotopic ratios of the oils and their fractions support the presence of two oil families. Streppenosa oil, a heavily biodegraded oil generated at an early stage of thermal maturation from a shaly source rock, is clearly distinct from the Noto and Sciacca oils, both generated at peak maturation from a carbonate source rock with no subsequent biodegradation. Two Re-Os ages were obtained. Crude oil and ASPH from Noto and Sciacca oil yield a Model 1 isochron age of 27.5 ± 4.6 Ma with an initial 187Os/188Os of 3.89 ± 0.43 (MSWD = 1.6, n = 19). We interpret this Oligocene age as the time of initial oil generation, that was probably related to the onset of regional collisional tectonics in southern Sicily. ASPH and crude oil from the Streppenosa oil yield scattered data, perhaps related to effects of biodegradation. Streppenosa MALT yield a Model 1 age of 200.0 ± 5.2 Ma and initial 187Os/188Os of 1.39 ± 0.11 (MSWD = 0.52; n = 4). This age and initial Os-isotopic composition are consistent with rapid oil generation shortly after Late Triassic source-rock formation, perhaps driven by magmatic-related heating. Here we document a potentially powerful geochronological tool that can be applied to single samples of crude oil. Within each oil, the 187Os/188Os and most of the 187Re/188Os ratios in the MALT fractions are lower than in the corresponding ASPH fractions. Crude oils, being physical mixtures of ASPH and MALT, have intermediate Re-Os isotopic ratios. Hence, the needed spread in data points for a Re-Os isochron is obtained by analyzing components of a single crude oil. This approach eliminates pitfalls in interpretation of Re-Os data from multiple oils with possibly different generation, migration, or reservoir modification history.

  7. NTP Toxicology and Carcinogenesis Studies of Molybdenum Trioxide (CAS No. 1313-27-5) in F344 Rats and B6C3F1 Mice (Inhalation Studies).

    PubMed

    1997-04-01

    Molybdenum is an essential element for the function of nitrogenase in plants and as a cofactor for enzymes including xanthine oxidoreductase, aldehyde oxidase, and sulfide oxidase in animals. Molybdenum trioxide is used primarily as an additive to steel and corrosion-resistant alloys. It is also used as a chemical intermediate for molybdenum products; an industrial catalyst; a pigment; a crop nutrient; components of glass, ceramics, and enamels; a flame retardant for polyester and polyvinyl chloride resins; and a reagent in chemical analyses. Molybdenum trioxide was nominated by the NCI for toxicity and carcinogenicity studies as a representative inorganic molybdenum compound. The production of molybdenum trioxide is the largest of all the molybdenum compounds examined. Male and female F344/N rats and B6C3F1 mice were exposed to molybdenum trioxide (approximately 99% pure) by inhalation for 14 days, 13 weeks, or 2 years. Genetic toxicology studies were conducted in Salmonella typhimurium and cultured Chinese hamster ovary cells. 14-DAY STUDY IN RATS: Groups of five male and five female F344/N rats were exposed to 0, 3, 10, 30, 100, or 300 mg molybdenum trioxide/m(3). Rats were exposed for 6 hours per day, 5 days per week, for a total of 10 exposure days during a 14-day period. All rats survived to the end of the study. The final mean body weights of male rats exposed to 100 mg/m(3) and male and female rats exposed to 300 mg/m(3) were significantly lower than those of the control groups. Male rats exposed to 300 mg/m(3) lost weight during the study. There were no clinical findings related to exposure to molybdenum trioxide. No chemical-related lesions were observed. 14-DAY STUDY IN MICE: Groups of five male and five female B6C3F1 mice were exposed to 0, 3, 10, 30, 100, or 300 mg molybdenum trioxide/m(3). Mice were exposed 6 hours per day, 5 days per week, for a total of 10 exposure days during a 14-day period. All mice survived to the end of the study. Final mean body weights of male and female mice exposed to 300 mg/m(3) were significantly lower than those of the control groups. Male mice exposed to 300 mg/m(3) lost weight during the study. There were no clinical findings related to exposure to molybdenum trioxide. No chemical-related lesions were observed. 13-WEEK STUDY IN RATS: Groups of 10 male and 10 female F344/N rats were exposed to molybdenum trioxide by inhalation at concentrations of 0, 1, 3, 10, 30, or 100 mg/m(3) for 6.5 hours per day, 5 days per week, for 13 weeks. All rats survived to the end of the study. The final mean body weights of exposed rats were similar to those of the control groups. No clinical findings related to molybdenum trioxide exposure were observed. There were no significant chemical-related differences in absolute or relative organ weights, hematology or clinical chemistry parameters, sperm counts or motility, or liver copper concentrations between control and exposed rats. No chemical-related lesions were observed. 13-WEEK STUDY IN MICE: Groups of 10 male and 10 female B6C3F1 mice were exposed to molybdenum trioxide by inhalation at concentrations of 0, 1, 3, 10, 30, or 100 mg/m(3) for 6.5 hours per day, 5 days per week, for 13 weeks. All mice survived to the end of the study. The final mean body weights of exposed mice were similar to those of the control groups. There were no chemical-related clinical findings. There were no significant differences in absolute or relative organ weights or sperm counts or motility between control and exposed mice. There were significant increases in liver copper concentrations in female mice exposed to 30 mg/m(3) and in male and female mice exposed to 100 mg/m(3) compared to those of the control groups. No chemical-related lesions were observed. 2-YEAR STUDIES IN RATS: Groups of 50 male and 50 female F344/N rats were exposed to molybdenum trioxide by inhalation at concentrations of 0, 10, 30, or 100 mg/m(3). Rats were exposed for 6 hours per day, 5 days per week, for 106 weeks. Survival, Body Weights, and Special Studies: Survival rates of exposed maleed male and female rats were similar to those of the control groups. Mean body weights of exposed groups of male and female rats were similar to those of the control groups throughout the study. There was a significant exposure-dependent increase in blood molybdenum concentration in exposed rats. Blood concentrations of molybdenum in exposed male rats were greater than those in exposed female rats. There were no toxicologically significant differences in bone density or curvature between control and exposed rats. Pathology Findings: The incidences of alveolar/bronchiolar adenoma or carcinoma (combined) were increased in male rats with a marginally significant positive trend. No increase in the incidences of lung neoplasms occurred in female rats. Incidences of chronic alveolar inflammation in male and female rats exposed to 30 or 100 mg/m(3) were significantly greater than those in the control groups. No nasal or laryngeal neoplasms were attributed to exposure to molybdenum trioxide. Incidences of hyaline degeneration in the nasal respiratory epithelium in 30 and 100 mg/m(3) males and in all exposed groups of females were significantly greater than those in the control groups. The incidences of hyaline degeneration in the nasal olfactory epithelium of all exposed groups of females were significantly greater than that in the control group. In the larynx, incidences of squamous metaplasia of the epithelium lining the base of the epiglottis in all exposed groups of male and female rats were significantly greater than those in the control groups and increased with increasing exposure concentration. 2-YEAR STUDY IN MICE: Groups of 50 male and 50 female B6C3F1 mice were exposed to molybdenum trioxide by inhalation at concentrations of 0, 10, 30, or 100 mg/m(3). Mice were exposed for 6 hours per day, 5 days per week, for 105 weeks. Survival, Body Weights, and Special Studies: The survival rate of male mice exposed to 30 mg/m(3) was marginally lower than that of the control group; survival rates of 10 and 100 mg/m(3) males and of all exposed groups of females were similar to those of the control groups. Mean body weights of exposed male mice were generally similar to those of the control group throughout the study. Mean body weights of exposed female mice were generally greater than those of the control group from week 11 until the end of the study. There was a significant exposure-dependent increase in blood molybdenum concentration in exposed mice. There were no toxicologically significant differences in bone density or curvature between control and exposed mice. Pathology Findings: The incidences of alveolar/bronchiolar carcinoma in all exposed groups of males were significantly greater than that in the control group. Incidences of alveolar/bronchiolar adenoma in females in the 30 and 100 mg/m(3) groups were significantly greater than that in the control group. Incidences of alveolar/bronchiolar adenoma or carcinoma (combined) in 10 and 30 mg/m(3) males and in 100 mg/m(3) females were significantly greater than those in the control groups and exceeded the historical control ranges for 2-year NTP inhalation studies. Incidences of metaplasia of the alveolar epithelium of minimal severity in the centriacinar region of the lung were significantly increased in all exposed groups of mice. The incidences of histiocyte cellular infiltration in all exposed groups of males were significantly greater than that in the control group. Incidences of hyaline degeneration of the respiratory epithelium of the nasal cavity in 100 mg/m(3) males and females and hyaline degeneration of the olfactory epithelium of the nasal cavity in 100 mg/m(3) females were significantly greater than those in the control groups. The incidences of squamous metaplasia of the epithelium lining the base of the epiglottis were significantly increased in all exposed groups of males and females. In both male and female mice, the incidences of hyperplasia of the laryngeal epithelium in level II of the larynx increased with increasing exposure concentration. The increase was statistically significant only in mice exposed to 100 mg/m(3) with 82% of male and 70% of female mice affected. GENETIC TOXICOLOGY: Molybdenum trioxide was not mutagenic in any of five strains of Salmonella typhimurium, and it did not induce sister chromatid exchanges or chromosomal aberrations in cultured Chinese hamster ovary cells in vitro. All tests were conducted with and without S9 metabolic activation enzymes. CONCLUSIONS: Under the conditions of these 2-year inhalation studies, there was equivocal evidence of carcinogenic activity of molybdenum trioxide in male F344/N rats based on a marginally significant positive trend of alveolar/bronchiolar adenoma or carcinoma (combined). There was no evidence of carcinogenic activity of molybdenum trioxide in female F344/N rats exposed to 10, 30, or 100 mg/m(3). There was some evidence of carcinogenic activity of molybdenum trioxide in male B6C3F1 mice based on increased incidences of alveolar/bronchiolar carcinoma and adenoma or carcinoma (combined). There was some evidence of carcinogenic activity of molybdenum trioxide in female B6C3F1 mice based on increased incidences of alveolar/bronchiolar adenoma and adenoma or carcinoma (combined). Exposure of male and female rats to molybdenum trioxide by inhalation resulted in increased incidences of chronic alveolar inflammation, hyaline degeneration of the respiratory epithelium, hyaline degeneration of the olfactory epithelium (females), and squamous metaplasia of the epiglottis. Exposure of male and female mice to molybdenum trioxide by inhalation resulted in increased incidences of metaplasia of the alveolar epithelium, histiocyte cellular infiltration (males), hyaline degeneration of the respiratory epithelium, hyaline degeneration of the olfactory epithelium (females), squamous metaplasia of the epiglottis, and hyperplasia of the larynx. Synonyms: Molybdic oxide; molybdic trioxide; molybdic anhydride; molybdenum (VI) oxide; molybdenum peroxide; molybdic acid anhydride; molybdenum anhydride; natural molybdite; molybdena

  8. Characterization of Rhenium Oxides Using ESCA

    NASA Technical Reports Server (NTRS)

    Panda, Binayak; Jones, Clyde S. (Technical Monitor)

    2001-01-01

    Rhenium as an engineering material has the following properties: (1) high melting point (one of the refractory metals); (2) high strength at elevated temperatures; (3) excellent toughness at room temperature; (4) low vapor pressure at melting point; (5) low coefficient of thermal expansion; (6) high impact and wear resistance; (7) compatibility with elements such as carbon and platinum; (8) conservation of properties in the presence of hydrogen, water vapor, and nitrogen oxides; and (9) poor oxidation resistance. This viewgraph presentation gives an overview of rhenium oxide characterization, including details on its history, experimental procedure using ESCA, and the analysis of the oxides (spectra and effects of ion sputtering).

  9. Metal oxide films on metal

    DOEpatents

    Wu, Xin D.; Tiwari, Prabhat

    1995-01-01

    A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

  10. Effect of rhenium on the structure and properties of the weld metal of a molybdenum alloy

    NASA Technical Reports Server (NTRS)

    Dyachenko, V. V.; Morozov, B. P.; Tylkina, M. A.; Savitskiy, Y. M.; Nikishanov, V. V.

    1984-01-01

    The structure and properties of welds made in molybdenum alloy VM-1 as a function of rhenium concentrations in the weld metal were studied. Rhenium was introduced into the weld using rhenium wire and tape or wires of Mo-47Re and Mo-52Re alloys. The properties of the weld metal were studied by means of metallographic techniques, electron microscopy, X-ray analysis, and autoradiography. The plasticity of the weld metal sharply was found to increase with increasing concentration of rhenium up to 50%. During welding, a decarburization process was observed which was more pronounced at higher concentrations of rhenium.

  11. 40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

  12. 40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

  13. 40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

  14. 40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

  15. 40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

  16. 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.

  17. Fac-Re(bpy)(CO){sub 3}(COOMe): A model metallocarboxylate complex of rhenium with a bipyridyl ligand

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

    Gibson, D.H.; Sleadd, B.A.; Vij, A.

    1999-05-01

    The title compound fac-(2,2{prime}-bipyridyl)(carbomethoxy)rhenium tricarbonyl, crystallizes in the monoclinic system, space group P2{sub 1}/c with the following crystal data: a = 8.37551(1), b = 6.6934(1), c = 26.2098(1) {angstrom}, V({angstrom}{sup 3}) = 1,535.93(3), Z = 4, and {beta} = 90.0971(2). The metal environment is slightly distorted octahedral with a chelating bipyridyl ligand and a facial arrangement of the carbon monoxide ligands.

  18. Slip casting and extruding shapes of rhenium with metal oxide additives. 1: Feasibility demonstration

    NASA Technical Reports Server (NTRS)

    Barr, F. A.; Page, R. J.

    1986-01-01

    The feasibility of fabricating small rhenium parts with metal oxide additives by means of slip casting and extrusion techniques is described. The metal oxides, ZrO2 and HfO2 were stabilized into the cubic phase with Y2O3. Additions of metal oxide to the rhenium of up to 15 weight percent were used. Tubes of 17 mm diameter with 0.5 mm walls were slip cast by adapting current ceramic oxide techniques. A complete cast double conical nozzle demonstrated the ability to meet shapes and tolerances. Extrusion of meter long tubing lengths of 3.9 mm o.d. x 2.3 mm i.d. final dimension is documented. Sintering schedules are presented to produce better than 95% of theoretical density parts. Finished machining was found possible were requried by electric discharge machining and diamond grinding.

  19. Superconductivity in REO0.5F0.5BiS2 with high-entropy-alloy-type blocking layers

    NASA Astrophysics Data System (ADS)

    Sogabe, Ryota; Goto, Yosuke; Mizuguchi, Yoshikazu

    2018-05-01

    We synthesized new REO0.5F0.5BiS2 (RE: rare earth) superconductors with high-entropy-alloy-type (HEA-type) REO blocking layers. The lattice constant a systematically changed in the HEA-type samples with the RE concentration and the RE ionic radius. A sharp superconducting transition was observed in the resistivity measurements for all the HEA-type samples, and the transition temperature of the HEA-type samples was higher than that of typical REO0.5F0.5BiS2. The sharp superconducting transition and the enhanced superconducting properties of the HEA-type samples may indicate the effectiveness of the HEA states of the REO blocking layers in the REO0.5F0.5BiS2 system.

  20. Near-Net Shape Powder Metallurgy Rhenium Thruster

    NASA Technical Reports Server (NTRS)

    Leonhardt, Todd; Hamister, Mark; Carlen, Jan C.; Biaglow, James; Reed, Brian

    2001-01-01

    This paper describes the development of a method to produce a near-net shape (NNS) powder metallurgy (PM) rhenium combustion chamber of the size 445 N (100 lbf) used in a high performance liquid apogee engine. These engines are used in low earth Orbit and geostationary orbit for satellite positioning systems. The developments in near-net shape powder metallurgy rhenium combustion chambers reported in this paper will reduce manufacturing cost of the rhenium chambers by 25 percent, and reduce the manufacturing time by 30 to 40 percent. The quantity of rhenium metal powder used to produce a rhenium chamber is reduced by approximately 70 percent and the subsequent reduction in machining schedule and costs is nearly 50 percent.

  1. Photoinduced hydrogen evolution in supramolecular devices with a rhenium photosensitizer linked to FeFe-hydrogenase model complexes.

    PubMed

    Liu, Jianhui; Jiang, Weina

    2012-08-28

    Coordination of the pyridyl-attached diiron azadithiolate hexacarbonyl complexes (2 and 3) through the pyridyl nitrogen to the Re on 10-phenanthroline rhenium (5a) and 2,9-diphenyl-1,10-phenanthroline rhenium (5b) forms novel [Re-Fe] complexes 7a, 7b and 8 respectively. Under visible light illumination using triethylamine as a sacrificial electron donor and [Re-Fe] type complexes (7a, 7b or 8) as catalysts, remarkably increased efficiency was observed for photoinduced hydrogen production with a turnover number reaching 11.8 from complex 7a and 8.75 from 7b. To the best of our knowledge, these are the best values compared to other [Re-Fe] photocatalysts reported so far. In contrast to the parent molecules, the turnover number by the intermolecular combination of complexes 6a and 2 showed a value of 5.23, and that from 6b and 2 is 3.8, while no H(2) was detected from 8a and 3 under the same experimental conditions. Obviously, the intramolecular combination of rhenium(I) and [2Fe2S] as a catalyst is promising for efficient H(2) evolution, and it is better than the intermolecular multi-component system.

  2. Mono- and Dinuclear Phosphorescent Rhenium(I) Complexes: Impact of Subcellular Localization on Anticancer Mechanisms.

    PubMed

    Ye, Rui-Rong; Tan, Cai-Ping; Chen, Mu-He; Hao, Liang; Ji, Liang-Nian; Mao, Zong-Wan

    2016-06-01

    Elucidation of relationship among chemical structure, cellular uptake, localization, and biological activity of anticancer metal complexes is important for the understanding of their mechanisms of action. Organometallic rhenium(I) tricarbonyl compounds have emerged as potential multifunctional anticancer drug candidates that can integrate therapeutic and imaging capabilities in a single molecule. Herein, two mononuclear phosphorescent rhenium(I) complexes (Re1 and Re2), along with their corresponding dinuclear complexes (Re3 and Re4), were designed and synthesized as potent anticancer agents. The subcellular accumulation of Re1-Re4 was conveniently analyzed by confocal microscopy in situ in live cells by utilizing their intrinsic phosphorescence. We found that increased lipophilicity of the bidentate ligands could enhance their cellular uptake, leading to improved anticancer efficacy. The dinuclear complexes were more potent than the mononuclear counterparts. The molecular anticancer mechanisms of action evoked by Re3 and Re4 were explored in detail. Re3 with a lower lipophilicity localizes to lysosomes and induces caspase-independent apoptosis, whereas Re4 with higher lipophilicity specially accumulates in mitochondria and induces caspase-independent paraptosis in cancer cells. Our study demonstrates that subcellular localization is crucial for the anticancer mechanisms of these phosphorescent rhenium(I) complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Rhenium material properties

    NASA Technical Reports Server (NTRS)

    Biaglow, James A.

    1995-01-01

    Tensile data were obtained from four different types of rhenium at ambient and elevated temperatures. The four types of rhenium included chemical vapor deposition (CVD) and three powder metallurgy (PM) types, i.e., rolled sheet and pressed and sintered bars, with and without hot isostatic pressure (HIP) treatment. Results revealed a wide range of values with ultimate strengths at ambient temperatures varying from 663 MPa for CVD rhenium to 943 MPa for rolled sheet. A similar spread was also obtained for material tested at 1088 K and 1644 K. The wide variance observed with the different materials indicated that the rhenium manufacturing process, material composition and prior handling strongly dictated its properties. In addition to tensile properties, CVD, pressed and sintered material and HIP rhenium successfully completed 100 cycles of low cycle fatigue. Creep data were also obtained showing that CVD and pressed and sintered rhenium could sustain five hours of testing under a tension of 27.5 MPa at 1922 K.

  4. Corrosion Behavior of Nuclear Waste Storage Canister Materials

    NASA Astrophysics Data System (ADS)

    Grant, John

    The nature of interaction of mild steel nuclear waste storage containers with technetium ions is not fully known. Technetium is formed during nuclear processing and some of this technetium has leaked at the Hanford nuclear waste storage site in Washington State. It is often found as highly oxidized pertechnetate (TeO4-) anions at these storage sites which also happen to be highly alkaline and contain a significant amount of nitrate. Theoretically, pertechnetate anions can act as electron acceptors and interact with the mild steel containers and accelerate the oxidation (corrosion) of steel. It is of interest to identify if pertechnetate anions pose a corrosion hazard to the mild steel nuclear waste storage tanks, under the conditions of the storage sites, as that can accelerate the degradation of the tanks and lead to further contamination. In this thesis, the interaction of two relevant container materials, namely, steel alloys A285 and A537 with a technetium surrogate, rhenium was studied. Perrhenate was used as an analog for pertechnetate. As all isotopes of technetium are radioactive, rhenium was chosen as the experimental surrogate due to its chemical similarity to technetium. Electrochemical behavior was evaluated using potentiodynamic polarization tests, and the surface morphology was studied using optical microscopy and scanning electron microscopy. Potentiodynamic polarization tests were conducted in 1.0M NaNO3 + 0.1M NaOH and 1.0M NaNO3 + 0.1M NaOH + 0.02M NaReO4. Tests were performed at three different temperatures, namely, (i) room temperature, (ii) 50°C and (iii) 80°C to study the effect of higher temperatures found in the storage sites. Corrosion current, corrosion potential, anodic and cathodic Tafel slopes, polarization resistance and corrosion rates were obtained from electrochemical testing and evaluated. Increasing temperatures was found to lead to increasing corrosion rates for all samples. The data also revealed increased corrosion from sodium perrhenate on the mild steel A285 samples. The perrhenate anion (ReO4-) formed a redox couple with iron in the mild steel and accelerated metal dissolution that increased with temperature. Pitting and uniform corrosion was observed in the A285 and A537 mild steel samples. The A537 mild steel, however, displayed lower corrosion rates in the presence of perrhenate compared in the absence of perrhenate. A hypothesis has been proposed to explain the differences between the two alloys.

  5. Re-Os geochronology of a Mesoproterozoic sedimentary succession, Taoudeni basin, Mauritania: Implications for basin-wide correlations and Re-Os organic-rich sediments systematics

    NASA Astrophysics Data System (ADS)

    Rooney, Alan D.; Selby, David; Houzay, Jean-Pierre; Renne, Paul R.

    2010-01-01

    The exceptionally well-preserved sedimentary rocks of the Taoudeni basin, NW Africa represent one of the world's most widespread (> 1 M km 2) Proterozoic successions. Hitherto, the sedimentary rocks were considered to be Mid Tonian based on Rb-Sr illite and glauconite geochronology of the Atar Group. However, new Re-Os organic-rich sediment (ORS) geochronology from two drill cores indicates that the Proterozoic Atar Group is ˜ 200 Ma older (1107 ± 12 Ma, 1109 ± 22 Ma and 1105 ± 37 Ma). The Re-Os geochronology suggests that the Rb-Sr geochronology records the age of diagenetic events possibly associated with the Pan African collision. The new Re-Os geochronology data provide absolute age constraints for recent carbon isotope chemostratigraphy which suggests that the Atar Group is Mesoproterozoic and not Neoproterozoic. The new Re-Os ORS geochronology supports previous studies that suggest that rapid hydrocarbon generation (flash pyrolysis) from contact metamorphism of a dolerite sill does not significantly disturb the Re-Os ORS systematics. Modelled contact conditions suggest that the Re-Os ORS systematics remain undisturbed at ˜ 650 °C at the sill/shale contact and ≥ 280 °C 20 m from the sill/shale contact. Moreover, the Re-Os geochronology indicates that the West African craton has a depositional history that predates 1100 Ma and that ORS can be correlated on a basin-wide scale. In addition, the Re-Os depositional ages for the ORS of the Taoudeni basin are comparable to those of ORS from the São Francisco craton, suggesting that these cratons are correlatable. This postulate is further supported by identical Os i values for the Atar Group and the Vazante Group of the São Francisco craton.

  6. Multiple episodes of mineralization revealed by Re-Os molybdenite geochronology in the Lala Fe-Cu deposit, SW China

    NASA Astrophysics Data System (ADS)

    Zhu, Zhimin; Tan, Hongqi; Liu, Yingdong; Li, Chao

    2018-03-01

    The Lala Fe-Cu deposit is one of the largest iron oxide-copper-gold (IOCG) deposits in the Kangdian copper belt, southwest China. The paragenetic sequence of the Lala deposit includes six hydrothermal stages: pre-ore pervasive Na alteration (I); magnetite stage with K-feldspar and apatite (II); polymetallic disseminated/massive magnetite-sulfide stage (III); banded magnetite-sulfide stage (IV); sulfide vein stage (V); and late quartz-carbonate vein stage (VI). Fifteen molybdenite separates from stages III to VI were analyzed for Re-Os dating. Our new Re-Os data, together with previous studies, identify four distinct hydrothermal events at the Lala deposit. Molybdenite from the stage III disseminated to massive chalcopyrite-magnetite ores yielded a weighted average Re-Os age of 1306 ± 8 Ma (MSWD = 1.1, n = 6) which represents the timing of main ore formation. Molybdenite from the stage IV-banded magnetite-chalcopyrite ores yielded a weighted average Re-Os age of 1086 ± 8 Ma (MSWD = 2.2, n = 7), i.e., a second ore-forming event. Molybdenite from the stage V sulfide veins yielded a weighted average Re-Os age of 988 ± 8 Ma (MSWD = 1.3, n = 7) which represents the timing of a third hydrothermal event. Molybdenite from the quartz-carbonate veins (stage VI) yielded a weighted average Re-Os age at 835 ± 4 Ma (MSWD = 0.66, n = 10) and documented the timing of a late hydrothermal event. Our results indicate that the Lala deposit formed during multiple, protracted mineralization events over several hundred million years. The first three Mesoproterozoic mineralization events are coeval with intra-continental rifting (breakup of the supercontinent Nuna) and share a temporal link to other IOCG-style deposits within the Kangdian Copper Belt, and the last Neoproterozoic hydrothermal event is coeval with the Sibao orogeny which culminated with the amalgamation of the Yangtze Block with the Cathaysia Block at 860-815 Ma.

  7. ITEP MEVVA ion beam for rhenium silicide production.

    PubMed

    Kulevoy, T; Gerasimenko, N; Seleznev, D; Kropachev, G; Kozlov, A; Kuibeda, R; Yakushin, P; Petrenko, S; Medetov, N; Zaporozhan, O

    2010-02-01

    The rhenium silicides are very attractive materials for semiconductor industry. In the Institute for Theoretical and Experimental Physics (ITEP) at the ion source test bench the research program of rhenium silicide production by ion beam implantation are going on. The investigation of silicon wafer after implantation of rhenium ion beam with different energy and with different total dose were carried out by secondary ions mass spectrometry, energy-dispersive x-ray microanalysis, and x-ray diffraction analysis. The first promising results of rhenium silicide film production by high intensity ion beam implantation are presented.

  8. Inter-diffusion analysis of joint interface of tungsten-rhenium couple

    NASA Astrophysics Data System (ADS)

    Hua, Y. F.; Li, Z. X.; Zhang, X.; Du, J. H.; Huang, C. L.; Du, M. H.

    2011-09-01

    The tungsten-rhenium couple was prepared by using glow plasma physical vapor deposition (PVD) on the isotropic fine grained graphite (IG) substrates. Diffusion anneals of the tungsten-rhenium couple were conducted at the temperature from 1100 °C to 1400 °C to investigate the inter-diffusion behaviors. The results showed that the thickness of the inter-diffusion zone increased with increasing annealing temperature. The relationship between the inter-diffusion coefficient and the annealing temperature accorded with the Arrhenius manner. The value of inter-diffusion activation energies was 189 kJ/mole (1.96 eV). The service time of tungsten-rhenium multilayer diffusion barrier was limited by the inter-diffusion for rhenium and tungsten rather than the diffusion of carbon in rhenium.

  9. Rhenium Redefined

    NASA Technical Reports Server (NTRS)

    2001-01-01

    Through a Small Business Innovation Research (SBIR) contract with NASA's Glenn Research Center, Rhenium Alloys, Inc., of Elyria, Ohio, developed a new method for producing rhenium combustion chambers. Using room temperature isostatic pressing, Rhenium Alloys, Inc., compacted rhenium powder to a high density and into the approximated end shape and dimension of the rocket thruster. The item was then subjected to sintering and containerless hot isostatic pressing, increasing the density of the powder metallurgy part. With the new manufacturing process, both production time and costs are reduced while quality is significantly increased. The method enabled the company to deliver two chemical rocket thrusters to Glenn Research Center. The company makes rhenium a practical choice in manufacturing fields, including the aerospace, nuclear, and electronic industries, with upcoming opportunities projected in medical instrumentation.

  10. Rhenium-osmium isotope systematics in meteorites I: Magmatic iron meteorite groups IIAB and IIIAB

    USGS Publications Warehouse

    Morgan, J.W.; Walker, R.J.; Grossman, J.N.

    1992-01-01

    Using resonance ionization mass spectrometry (RIMS), Re and Os abundances were determined by isotope dilution (ID) and 187Os 186Os ratios measured in nineteen iron meteorites: eight from group IIAB, ten from group IIIAB, and Treysa (IIIB anomalous). Abundances range from 1.4 to 4800 ppb Re, and from 13 to 65000 ppb Os, and generally agree well with previous ID and neutron activation (NAA) results. The Re and Os data suggest that abundance trends in these iron groups may be entirely explained by fractional crystallization. Addition of late-formed metal to produce ReOs variation in the B subgroups is not essential but cannot be excluded. Whole-rock isochrons for the IIAB and IIIAB groups are statistically indistinguishable. Pooled data yield an initial 187Os 186Os of 0.794 ?? 0.010, with a slope of (7.92 ?? 0.20) ?? 10-2 corresponding to a magmatic iron meteorite age of 4.65 ?? 0.11 Ga (using a decay constant of 1.64 ?? 10-11 a-1). Given the errors in the slope and half life, this age does not differ significantly from the canonical chondrite age of 4.56 Ga, but could be as young as 4.46 Ga. ?? 1992.

  11. Nipponium as a new element (Z=75) separated by the Japanese chemist, Masataka Ogawa: a scientific and science historical re-evaluation.

    PubMed

    Yoshihara, H Kenji

    2008-01-01

    This review article deals with a new element 'nipponium' reported by Masataka Ogawa in 1908, and with its scientific and science historical background. Ogawa positioned nipponium between molybdenum and ruthenium in the periodic table. From a modern chemical viewpoint, however, nipponium is ascribable to the element with Z=75, namely rhenium, which was unknown in 1908. The reasons for this corrected assignment of nipponium are (1) its optical spectra, (2) its atomic weight when corrected, (3) its relative abundance in molybdenite, the same being true with rhenium. Recently some important evidence was found among the Ogawa's personal collection preserved by his family. Deciphering the X-ray spectra revealed that the measured spectra of the nipponium sample that Ogawa brought from University College, London clearly showed the presence of the element 75 (rhenium). Thus was resolved the mysterious story of nipponium, which had continued for almost a century. It is concluded that nipponium was identical to rhenium.

  12. Nipponium as a new element (Z = 75) separated by the Japanese chemist, Masataka Ogawa: a scientific and science historical re-evaluation

    PubMed Central

    Yoshihara, H. Kenji

    2008-01-01

    This review article deals with a new element ‘nipponium’ reported by Masataka Ogawa in 1908, and with its scientific and science historical background. Ogawa positioned nipponium between molybdenum and ruthenium in the periodic table. From a modern chemical viewpoint, however, nipponium is ascribable to the element with Z = 75, namely rhenium, which was unknown in 1908. The reasons for this corrected assignment of nipponium are (1) its optical spectra, (2) its atomic weight when corrected, (3) its relative abundance in molybdenite, the same being true with rhenium. Recently some important evidence was found among the Ogawa’s personal collection preserved by his family. Deciphering the X-ray spectra revealed that the measured spectra of the nipponium sample that Ogawa brought from University College, London clearly showed the presence of the element 75 (rhenium). Thus was resolved the mysterious story of nipponium, which had continued for almost a century. It is concluded that nipponium was identical to rhenium. PMID:18941300

  13. Arsenic trioxide and all-trans retinoic acid treatment for acute promyelocytic leukaemia in all risk groups (AML17): results of a randomised, controlled, phase 3 trial.

    PubMed

    Burnett, Alan K; Russell, Nigel H; Hills, Robert K; Bowen, David; Kell, Jonathan; Knapper, Steve; Morgan, Yvonne G; Lok, Jennie; Grech, Angela; Jones, Gail; Khwaja, Asim; Friis, Lone; McMullin, Mary Frances; Hunter, Ann; Clark, Richard E; Grimwade, David

    2015-10-01

    Acute promyelocytic leukaemia is a chemotherapy-sensitive subgroup of acute myeloid leukaemia characterised by the presence of the PML-RARA fusion transcript. The present standard of care, chemotherapy and all-trans retinoic acid (ATRA), results in a high proportion of patients being cured. In this study, we compare a chemotherapy-free ATRA and arsenic trioxide treatment regimen with the standard chemotherapy-based regimen (ATRA and idarubicin) in both high-risk and low-risk patients with acute promyelocytic leukaemia. In the randomised, controlled, multicentre, AML17 trial, eligible patients (aged ≥16 years) with acute promyelocytic leukaemia, confirmed by the presence of the PML-RARA transcript and without significant cardiac or pulmonary comorbidities or active malignancy, and who were not pregnant or breastfeeding, were enrolled from 81 UK hospitals and randomised 1:1 to receive treatment with ATRA and arsenic trioxide or ATRA and idarubicin. ATRA was given to participants in both groups in a daily divided oral dose of 45 mg/m(2) until remission, or until day 60, and then in a 2 weeks on-2 weeks off schedule. In the ATRA and idarubicin group, idarubicin was given intravenously at 12 mg/m(2) on days 2, 4, 6, and 8 of course 1, and then at 5 mg/m(2) on days 1-4 of course 2; mitoxantrone at 10 mg/m(2) on days 1-4 of course 3, and idarubicin at 12 mg/m(2) on day 1 of the final (fourth) course. In the ATRA and arsenic trioxide group, arsenic trioxide was given intravenously at 0·3 mg/kg on days 1-5 of each course, and at 0·25 mg/kg twice weekly in weeks 2-8 of course 1 and weeks 2-4 of courses 2-5. High-risk patients (those presenting with a white blood cell count >10 × 10(9) cells per L) could receive an initial dose of the immunoconjugate gemtuzumab ozogamicin (6 mg/m(2) intravenously). Neither maintenance treatment nor CNS prophylaxis was given to patients in either group. All patients were monitored by real-time quantitative PCR. Allocation was by central computer minimisation, stratified by age, performance status, and de-novo versus secondary disease. The primary endpoint was quality of life on the European Organisation for Research and Treatment of Cancer (EORTC) QLQ-C30 global health status. All analyses are by intention to treat. This trial is registered with the ISRCTN registry, number ISRCTN55675535. Between May 8, 2009, and Oct 3, 2013, 235 patients were enrolled and randomly assigned to ATRA and idarubicin (n=119) or ATRA and arsenic trioxide (n=116). Participants had a median age of 47 years (range 16-77; IQR 33-58) and included 57 high-risk patients. Quality of life did not differ significantly between the treatment groups (EORTC QLQ-C30 global functioning effect size 2·17 [95% CI -2·79 to 7·12; p=0·39]). Overall, 57 patients in the ATRA and idarubicin group and 40 patients in the ATRA and arsenic trioxide group reported grade 3-4 toxicities. After course 1 of treatment, grade 3-4 alopecia was reported in 23 (23%) of 98 patients in the ATRA and idarubicin group versus 5 (5%) of 95 in the ATRA and arsenic trioxide group, raised liver alanine transaminase in 11 (10%) of 108 versus 27 (25%) of 109, oral toxicity in 22 (19%) of 115 versus one (1%) of 109. After course 2 of treatment, grade 3-4 alopecia was reported in 25 (28%) of 89 patients in the ATRA and idarubicin group versus 2 (3%) of 77 in the ATRA and arsenic trioxide group; no other toxicities reached the 10% level. Patients in the ATRA and arsenic trioxide group had significantly less requirement for most aspects of supportive care than did those in the ATRA and idarubicin group. ATRA and arsenic trioxide is a feasible treatment in low-risk and high-risk patients with acute promyelocytic leukaemia, with a high cure rate and less relapse than, and survival not different to, ATRA and idarubicin, with a low incidence of liver toxicity. However, no improvement in quality of life was seen. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Physical and antimicrobial properties of starch-carboxy methyl cellulose film containing rosemary essential oils encapsulated in chitosan nanogel.

    PubMed

    Mohsenabadi, Nafiseh; Rajaei, Ahmad; Tabatabaei, Meisam; Mohsenifar, Afshin

    2018-06-01

    This study was set to prepare a new active film by using a biodegradable bio-based source, i.e., corn starch. To achieve that, benzoic acid (BA) and chitosan (CS) were covalently bound and CS-BA nanogel was then obtained using self-assembly method. Subsequently, rosemary essential oil (REO) was encapsulated in CS-BA nanogel. Finally, REO in both free and encapsulated forms were incorporated in starch-carboxy methyl cellulose (CMC) films and their physical, mechanical and antimicrobial properties were studied. The films incorporating CS-BA nanogel had a higher water vapor permeability compared with the films containing REO. Moreover, film containing 0.2% CS-BA nanogel had the highest transparency and tensile strength. The REO and nanogel alone had inhibitory effects against Staphylococcus aureus (S. aureus) and by encapsulation, the inhibitory effect of REO was increased. By encapsulating REO in nanogel, both immediately (REO) and gradual (Nanogel) antimicrobial effect against S. aureus in the starch-CMC suspensions were obtained. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Arsenic trioxide-mediated growth inhibition in gallbladder carcinoma cells via down-regulation of Cyclin D1 transcription mediated by Sp1 transcription factor

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

    Ai, Zhilong; Lu, Weiqi; Ton, Saixiong

    2007-08-31

    Gallbladder carcinoma (GBC), an aggressive and mostly lethal malignancy, is known to be resistant to a number of drug stimuli. Here, we demonstrated that arsenic trioxide inhibited the proliferation of gallbladder carcinoma in vivo and in vitro as well as the transcription of cell cycle-related protein Cyclin D1. And, Cyclin D1 overexpression inhibited the negative role of arsenic trioxide in cell cycle progression. We further explored the mechanisms by which arsenic trioxide affected Cyclin D1 transcription and found that the Sp1 transcription factor was down-regulated by arsenic trioxide, with a corresponding decrease in Cyclin D1 promoter activity. Taken together, thesemore » results suggested that arsenic trioxide inhibited gallbladder carcinoma cell proliferation via down-regulation of Cyclin D1 transcription in a Sp1-dependent manner, which provided a new mechanism of arsenic trioxide-involved cell proliferation and may have important therapeutic implications in gallbladder carcinoma patients.« less

  16. Synthesis and characterization of WO3 nanowires and metal nanoparticle-WO3 nanowire composites

    NASA Astrophysics Data System (ADS)

    Szabó, Mária; Pusztai, Péter; Leino, Anne-Riikka; Kordás, Krisztián; Kónya, Zoltán; Kukovecz, Ákos

    2013-07-01

    Tungsten-trioxide nanowire bundles were prepared using a simple hydrothermal method. Sodium-tungstate was used as precursor and sodium-sulfate as structure directing agent. All the reflections of the X-ray diffractogram of the synthesized wires belong to the hexagonal phase of the tungsten trioxide. The nanowires were successfully decorated with metal nanoparticles by wet impregnation. The TEM investigation showed that using different metal precursors resulted in different particle sizes and coverage on the surface.

  17. Method for removing sulfur oxide from waste gases and recovering elemental sulfur

    DOEpatents

    Moore, Raymond H.

    1977-01-01

    A continuous catalytic fused salt extraction process is described for removing sulfur oxides from gaseous streams. The gaseous stream is contacted with a molten potassium sulfate salt mixture having a dissolved catalyst to oxidize sulfur dioxide to sulfur trioxide and molten potassium normal sulfate to solvate the sulfur trioxide to remove the sulfur trioxide from the gaseous stream. A portion of the sulfur trioxide loaded salt mixture is then dissociated to produce sulfur trioxide gas and thereby regenerate potassium normal sulfate. The evolved sulfur trioxide is reacted with hydrogen sulfide as in a Claus reactor to produce elemental sulfur. The process may be advantageously used to clean waste stack gas from industrial plants, such as copper smelters, where a supply of hydrogen sulfide is readily available.

  18. In vitro comparison of the antiproliferative effects of rhenium-186 and rhenium-188 on human aortic endothelial cells.

    PubMed

    Sauter, Alexander; Arthasana, Daniel; Dittmann, Helmut; Pritzkow, Maren; Wiesinger, Benjamin; Schmehl, Joerg; Brechtel, Klaus; Bantleon, Rüdiger; Claussen, Claus; Kehlbach, Rainer

    2011-08-01

    Rhenium-186 ((186)Re) and rhenium-188 ((188)Re) are promising radionuclides for the inhibition of restenosis after percutaneous transluminal angioplasty or other vascular interventions. Until now the maximal dose tolerance of endothelial cells has not been clearly known. To characterize the effects of local irradiation treatment, human aortic endothelial cells (ECs) were incubated with different doses of (186)Re and (188)Re. Two days after plating, ECs received treatment for a period of 5 days. The total radiation doses applied were 1, 4, 8, 16, and 32 Gy. On days 1, 3, 5, 7, and 12 after initial rhenium incubation, cell growth, clonogenic activity, cell-cycle distribution, and cytoskeletal architecture were evaluated. From the first day on, a dose-dependent growth inhibition was observed. Cumulative doses of ≥32 Gy caused a weak colony formation and significant alterations in the cytoskeletal architecture. An increased fraction of cells in G2/M phase was seen for cumulative radiation doses of ≥16 Gy. Interestingly, there were no significant differences between (186)Re and (188)Re. Even for low dose rates of β particles a dose-dependent proliferation inhibition of ECs is seen. Doses beyond 32 Gy alter the cytoskeletal architecture with possibly endothelial dysfunction and late thrombosis.

  19. New rhenium complexes with ciprofloxacin as useful models for understanding the properties of [99mTc]-ciprofloxacin radiopharmaceutical.

    PubMed

    Lecina, Joan; Cortés, Pilar; Llagostera, Montserrat; Piera, Carlos; Suades, Joan

    2014-07-01

    Rhenium complexes with the antibiotic ciprofloxacin have been prepared to be studied as models of technetium radiopharmaceuticals. With this aim, the new rhenium complexes 1 {[ReO(Cpf)2]Cl}, 2 {[ReO(CpfH)2]Cl3} and 3 {fac-[Re(CO)3(H2O)(Cpf)]} with ciprofloxacin (CpfH=ciprofloxacin; Cpf=conjugated base of ciprofloxacin) have been synthesised and characterised by elemental analyses, IR, NMR ((1)H, (19)F and (13)C CP-MAS) spectroscopy, as well as MS measurements. All spectroscopic data are consistent with the coordination of ciprofloxacin in all these complexes through the carbonyl and the carboxylate oxygen atoms with the formation of a six member chelate ring. The study of a Tc-ciprofloxacin solution by ESI-MS reveals the presence of [TcO(Cpf)2](+) cations, which agrees with the hypothesis that complexes 1 and 2 can be seen as model rhenium complexes of this radiopharmaceutical. Antimicrobial and DNA gyrase inhibition studies performed with complexes 2 and 3 have shown a very similar behaviour between complex 2 and the free antibiotic, whereas complex 3 exhibit a lower antimicrobial activity. Based on a joint analysis of the data reported in the literature and the chemical and biological results obtained in this study, a tentative proposal to explain some aspects of the behaviour of Tc-ciprofloxacin radiopharmaceutical has been made. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Arsenic Trioxide Injection

    MedlinePlus

    Arsenic trioxide is used to treat acute promyelocytic leukemia (APL; a type of cancer in which there ... worsened following treatment with other types of chemotherapy. Arsenic trioxide is in a class of medications called ...

  1. Spectrophotometric catalytic determination of small amounts of rhenium in mineralized rocks and molybdenite

    USGS Publications Warehouse

    Simon, F.O.; Grimaldi, F.S.

    1962-01-01

    Rhenium is determined by spectrophotometry of the tellurium sol formed by the reduction of tellurate by stannous chloride under the catalytic influence of rhenium. A detailed investigation of the conditions for high sensitivity and stability at lowest concentration levels of rhenium is presented as well as the behavior of 26 ions. The method is applied to the determination of some tenths of 1 p.p.m. or more of rhenium in a 1-mg. aliquot of mineralized rocks, mixtures of molybdenite and rocks, and molybdenite concentrates. The practical quantity limit of detection is 2 ?? 10-10 gram of rhenium. Samples are decomposed with a mixture of CaO, CaCl2, and MgO. On leaching, most constituents of the sample are precipitated either as calcium salts or hydroxides, except for rhenium and a small amount of molybdenum which pass into the filtrate. Residual molybdenum is removed by extraction with 8-quinolinol in chloroform. Better than 95% recoveries are obtained with two fusions with flux.

  2. Broad Detection Range Rhenium Diselenide Photodetector Enhanced by (3-Aminopropyl)Triethoxysilane and Triphenylphosphine Treatment.

    PubMed

    Jo, Seo-Hyeon; Park, Hyung-Youl; Kang, Dong-Ho; Shim, Jaewoo; Jeon, Jaeho; Choi, Seunghyuk; Kim, Minwoo; Park, Yongkook; Lee, Jaehyeong; Song, Young Jae; Lee, Sungjoo; Park, Jin-Hong

    2016-08-01

    The effects of triphenylphosphine and (3-aminopropyl)triethoxysilane on a rhenium diselenide (ReSe2 ) photodetector are systematically studied by comparing with conventional MoS2 devices. This study demonstrates a very high performance ReSe2 photodetector with high photoresponsivity (1.18 × 10(6) A W(-1) ), fast photoswitching speed (rising/decaying time: 58/263 ms), and broad photodetection range (possible above 1064 nm). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. High Temperature Oxidation-Resistant Thruster Research

    DTIC Science & Technology

    1990-02-01

    substrates: Refractory metals, ! Ceramics, Composites and I Carbon - carbon . Rhenium and hafnium carbide were selected based on their properties I and... carbon . Rhenium was selected as the primary refractory metal candidate because of its high melting point, no ductile-to- brittle transition in the...of rhenium (Re) with those of other refractory metals. Rhenium has the second highest melting point of the elements, 3013 C, second only to tungsten

  4. Re-Os in Lunar Soils and Meteoritic Siderophiles on the Lunar Surface

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Papanastassiou, D. A.; Wasserburg, G. J.

    2001-01-01

    Re-Os isotopes in lunar soils indicate approximately chondritic Re, Os, and Os isotopic compositions and substantial Re/Os fractionation, possibly due to the terminal lunar cataclysm. Additional information is contained in the original extended abstract.

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

    Wedding, Jason L.; Harris, Hugh H.; Bader, Christie A.

    Optical fluorescence microscopy was used in conjunction with X-ray fluorescence microscopy to monitor the stability and intracellular distribution of the luminescent rhenium(I) complex fac-[Re(CO) 3(phen)L], where phen = 1,10-phenathroline and L = 5-(4-iodophenyl)tetrazolato, in 22Rv1 cells. The rhenium complex showed no signs of ancillary ligand dissociation, a conclusion based on data obtained via X-ray fluorescence imaging aligning iodine and rhenium distributions. A diffuse reticular localisation was detected for the complex, in the nuclear/perinuclear region of cells, by either optical or X-ray fluorescence techniques. Furthermore, X-ray fluorescence also showed that the Re-I complex disrupted the homeostasis of some biologically relevant elements,more » such as chlorine, potassium and zinc.« less

  6. Retroperitoneal Extraskeletal Osteosarcoma: Imaging Findings and Transarterial Chemoembolization

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

    Zhang Huojun, E-mail: chyyzhj@hotmail.com; Yang Jijin, E-mail: yangjijin@live.com; Lu Jianping

    2010-04-15

    Extraskeletal osteosarcoma (EOS) is an uncommon and usually highly aggressive mesenchymal tumor. Retroperitoneal extraskeletal osteosarma (REOS) is exceedingly rare. Due to the rare nature of the disease, both the diagnosis and the management of REOS can be challenging. We present the clinical history, CT findings, angiographic manifestations, and use of transarterial chemoembolization for treatment in a case of REOS. To our knowledge, the angiographic features of and attempt at transarterial treatment of REOS have not been reported in the literature.

  7. Tiny Molybdenites Tell Diffusion Tales

    NASA Astrophysics Data System (ADS)

    Stein, H. J.; Hannah, J. L.

    2014-12-01

    Diffusion invokes micron-scale exchange during crystal growth and dissolution in magma chambers on short time-scales. Fundamental to interpreting such data are assumptions on magma-fluid dynamics at all scales. Nevertheless, elemental diffusion profiles are used to estimate time scales for magma storage, eruption, and recharge. An underutilized timepiece to evaluate diffusion and 3D mobility of magmatic fluids is high-precision Re-Os dating of molybdenite. With spatially unique molybdenite samples from a young ore system (e.g., 1 Ma) and a double Os spike, analytical errors of 1-3 ka unambiguously separate events in time. Re-Os ages show that hydrous shallow magma chambers locally recharge and expel Cu-Mo-Au-silica as superimposed stockwork vein networks at time scales less than a few thousand years [1]. Re-Os ages provide diffusion rates controlled by a dynamic crystal mush, accumulation and expulsion of metalliferous fluid, and magma reorganization after explosive crystallization events. Importantly, this approach has broad application far from ore deposits. Here, we use Re-Os dating of molybdenite to assess time scales for generating and diffusing metals through the deep crust. To maximize opportunity for chemical diffusion, we use a continental-scale Sveconorwegian mylonite zone for the study area. A geologically constrained suite of molybdenite samples was acquired from quarry exposures. Molybdenite, previously unreported, is extremely scarce. Tiny but telling molybdenites include samples from like occurrences to assure geologic accuracy in Re-Os ages. Ages range from mid-Mesoproterozoic to mid-Neoproterozoic, and correspond to early metamorphic dehydration of a regionally widespread biotite-rich gneiss, localized melting of gneiss to form cm-m-scale K-feldspar ± quartz pods, development of vapor-rich, vuggy mm stringers that serve as volatile collection surfaces in felsic leucosomes, and low-angle (relative to foliation) cross-cutting cm-scale quartz veins. Re-Os ages and detailed geologic observation document a 200 m.y. history of metal liberation and diffusion through oxidation. [1] Stein, H.J. (2014) Dating and Tracing the History of Ore Formation, in Holland, H.D. & Turekian, K.K. (eds) Treatise on Geochemistry, 2nd Ed. 13: 87-118, Oxford: Elsevier.

  8. Re-Os systematics of early proterozoic ferropicrites, Pechenga Complex, northwestern Russia: Evidence for ancient 187Os-enriched plumes

    NASA Astrophysics Data System (ADS)

    Walker, Richard J.; Morgan, John W.; Hanski, Eero J.; Smolkin, Valery F.

    1997-08-01

    The Re-Os isotopic systematics of various ferropicritic flows and sills of the Pechenga Complex, Russia, have been examined. During crystallization about 1.98 Ga ago, many of these bodies became highly differentiated. In addition, some of the larger igneous units are associated with major NiCu ore deposits. The melts that produced these rocks have been termed ferropicritic because of their high FeO and MgO contents. They are also enriched in light rare earth elements (LREEs), TiO 2, Zr, and many other incompatible trace elements. Previous studies have concluded that the ferropicrites were most likely derived from an Fe-rich mantle plume that had a complex history of long-term LREE depletion (initial ɛNd = + 1.4), but that also experienced a LREE enrichment event within 200 Ma of the generation of the rocks. Whole rock samples believed to be most representative of primary melt compositions indicate that initial melt concentrations of rhenium and osmium were approximately 1.1 ppb and 0.5 ppb, respectively. The high primary melt concentrations presumably made the osmium contained in the melts relatively immune to the effects of crustal contamination. Nonetheless, all ore-bearing intrusions examined show osmium isotopic evidence for crustal contamination. For example, the initial γOs for some primary magmatic sulfides from the Pilgujärvi intrusion average +46. Other ore-bearing intrusions, such as the Kammikivi sill, appear to have been similarly contaminated by crustal osmium during the injection of magma, with initial yo, values as high as +251. The seemingly high levels of crustal osmium may be attributed to the rapidly diminishing concentrations of osmium in the melts as the larger bodies differentiated, combined with localized in situ assimilation of the metasedimentary rocks that comprise the country rocks. The Re-Os systematics of some whole rock samples of both mineralized and sulfide-poor intrusions were affected by post-magmatic events, especially the greenschist grade metamorphism that impacted the rocks between about 1.7 and 1.8 Ga ago. The metamorphic effects are reflected in the recrystallization of many of the primary sulfides. As a consequence of this open-system behavior in many whole rock samples, the primary igneous Re-Os systematics of these rocks are best examined via analysis of magmatic phases such as chromite, olivine, clinopyroxene, and primary sulfides. Chromite and ilmenite+sulfide separates from two sulfide-poor lava flows, the Lammas and Keskitunturi, have characteristically low 187Re/ 188Os ( < l), and because of the limited age correction, precisely define the initial γOs of these systems to be +6.0±0.7. Because of the identical initial compositions of the two, spatially distinct lava flows, and the fact that these flows were extruded onto only slightly older volcanic rocks, we conclude that the +6.0 value reflects the composition of the mantle source and not minor crustal contamination. Although 187Os-enriched, plume-derived systems are common during the Phanerozoic, this is the earliest known evidence for the existence of long-term, Re-enriched mantle reservoirs. The most commonly invoked model to explain 187Os enrichments in Phanerozoic systems, oceanic crustal recycling, in this instance requires that very large proportions of oceanic crust were recycled into the mantle source and that the event was likely very ancient. Other options, such as core-mantle interaction and a stratified mantle, are also discussed.

  9. Accelerator Production and Separations for High Specific Activity Rhenium-186

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

    Jurisson, Silvia S.; Wilbur, D. Scott

    2016-04-01

    Tungsten and osmium targets were evaluated for the production of high specific activity rhenium-186. Rhenium-186 has potential applications in radiotherapy for the treatment of a variety of diseases, including targeting with monoclonal antibodies and peptides. Methods were evaluated using tungsten metal, tungsten dioxide, tungsten disulfide and osmium disulfide. Separation of the rhenium-186 produced and recycling of the enriched tungsten-186 and osmium-189 enriched targets were developed.

  10. Reestablishing Strategic and Critical Material Security in the Department of Defense

    DTIC Science & Technology

    2011-05-11

    Nickel >700% Tungsten 300% Titanium 600% Cobalt 325% Germanium 300% Chromium 500% Molybdenum 500% Indium 300% Manganese 350% Rhenium > 1000% Peak...CHAIN LEADERSHIP New Mission Example • Currently working with Tinker Air Force Base on a rhenium availability issue – Rhenium is a super alloy used in...acquisitions to assure industrial base capability – Titanium – Rare Earth Elements – Germanium – Rhenium / nickel super-alloys – Other materials as supply chain

  11. Volatile molecule PuO 3 observed from subliming plutonium dioxide

    NASA Astrophysics Data System (ADS)

    Ronchi, C.; Capone, F.; Colle, J. Y.; Hiernaut, J. P.

    2000-06-01

    Mass spectrometric measurements of effusing vapours over PuO 2 and (U, Pu)O 2 indicate the presence of volatile PuO 3 (g) molecules. The formation of plutonium trioxide vapour is due to a chemical process involving oxygen adsorbed during oxidation of the sample. Although in the examined samples, the fraction of trioxide effusing in vacuo was of the order of 0.02 ppm of the plutonium content, under steady-state oxidation conditions it has been shown that the process can have a relevant effect on the sublimation rate of the dioxide.

  12. Synthesis and redox properties of fac-BrRe(CO)3[1,2-(PPh2)2-closo-1,2-C2B10H10]: The first structurally characterized rhenium carbonyl containing a carboranyl-based diphosphine ligand

    NASA Astrophysics Data System (ADS)

    Lin, Chen-Hao; Nesterov, Vladimir N.; Richmond, Michael G.

    2018-03-01

    The diphosphine 1,2-(PPh2)2-closo-1,2-C2B10H10 reacts with BrRe(CO)5 and fac-BrRe(CO)3(THF)2 to give fac-BrRe(CO)3[1,2-(PPh2)2-closo-1,2-C2B10H10] (1) in high yields (>80%). Compound 1 is the first structurally characterized rhenium carbonyl that contains an ancillary carborane-based diphosphine ligand. 1 has been characterized in solution by IR and NMR spectroscopies (1H and 31P), and the solid-state structure has been determined by X-ray diffraction analysis. The electrochemical properties of 1 have been investigated by cyclic voltammetry, and the composition of the DFT-computed HOMO and LUMO levels are discussed relative to the electrochemical data. The thermodynamics for the formation of 1 from the rhenium precursors BrRe(CO)5 and fac-BrRe(CO)3(THF)2 have been evaluated by DFT calculations.

  13. Photodetectors: Broad Detection Range Rhenium Diselenide Photodetector Enhanced by (3-Aminopropyl)Triethoxysilane and Triphenylphosphine Treatment (Adv. Mater. 31/2016).

    PubMed

    Jo, Seo-Hyeon; Park, Hyung-Youl; Kang, Dong-Ho; Shim, Jaewoo; Jeon, Jaeho; Choi, Seunghyuk; Kim, Minwoo; Park, Yongkook; Lee, Jaehyeong; Song, Young Jae; Lee, Sungjoo; Park, Jin-Hong

    2016-08-01

    The effects of triphenylphosphine (PPh3 ) and (3-amino-propyl)triethoxysilane (APTES) on a rhenium diselenide (ReSe2 ) photodetector are systematically studied by J.-H. Park and co-workers on page 6711 in comparison with a conventional MoS2 device. A very high performance ReSe2 photodetector is demonstrated, which has a broad photodetection range, high photoresponsivity (1.18 × 10(6) A W(-1) ), and fast photoswitching speed (rising/decaying time: 58/263 ms). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis, characterization, and photophysical properties of a thiophene-functionalized bis(pyrazolyl) pyridine (BPP) tricarbonyl rhenium(I) complex.

    PubMed

    Lytwak, Lauren A; Stanley, Julie M; Mejía, Michelle L; Holliday, Bradley J

    2010-09-07

    A bromo tricarbonyl rhenium(I) complex with a thiophene-functionalized bis(pyrazolyl) pyridine ligand (L), ReBr(L)(CO)(3) (1), has been synthesized and characterized by variable temperature and COSY 2-D (1)H NMR spectroscopy, single-crystal X-ray diffraction, and photophysical methods. Complex 1 is highly luminescent in both solution and solid-state, consistent with phosphorescence from an emissive (3)MLCT excited state with an additional contribution from a LC (3)(pi-->pi*) transition. The single-crystal X-ray diffraction structure of the title ligand is also reported.

  15. 78 FR 52975 - Amended Certification Regarding Eligibility To Apply for Worker Adjustment Assistance

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-08-27

    ... Servicing, Inc., Power Reo Management Services, Inc., and Stratus Asset Management Coppell, Texas; Homeward... Servicing, Inc., Power Reo Management Services, Inc., and Stratus Asset Management Addison, Texas; Homeward... Servicing, Inc., Power Reo Management Services, Inc., and Stratus Asset Management Jacksonville, Florida In...

  16. Combination of three metals for the treatment of cancer: gallium, rhenium and platinum. 1. Determination of the optimal schedule of treatment.

    PubMed

    Collery, Philippe; Mohsen, Ahmed; Kermagoret, Anthony; D'Angelo, Jean; Morgant, Georges; Desmaele, Didier; Tomas, Alain; Collery, Thomas; Wei, Ming; Badawi, Abdelfattah

    2012-07-01

    Platinum is well known for its anticancer activity, firstly used as cis-diaminedichloroplatinum (II) (CDDP), with a wide range of activity. Its main mechanism of action involves its binding to DNA. Gallium, another metal, has also demonstrated apoptotic effects on malignant cells, but through interaction with targets other than DNA, such as the membrane, cytoskeleton and proteasome, and on enzyme activities. An antitumor synergism between CDDP and both gallium and rhenium compounds has been demonstrated. For these reasons, we proposed to combine these three metals and to determine at which doses each compound could be administered without major toxicity. CDDP, tetrakis(1-octanol) tris(5-aminosalicylate)gallium(III), and a diseleno-ether rhenium(I) complex were used in this experimental study in breast cancer MCF-7 tumor-bearing mice. CDDP was administered intraperitoneally (i.p.) twice a week at the dose of 3 mg/kg. Tetrakis(1-octanol) tris(5-aminosalicylate) gallium (III) and rhenium(I) diseleno-ether complexes were administered orally, daily, five days a week for three weeks, at doses ranging from 20 to 100 mg/kg for the gallium compound and from 10 to 50 mg/kg for the rhenium compound. Doses of 10 mg/kg of rhenium(I) diseleno-ether, and 100 mg/kg of the salicylate gallium compound, in combination with CDDP induced a significant decrease of 50% of the tumor volume, by comparison with the control group. In contrast, the decrease of the tumor volume in mice treated by CDDP alone was less than 25%. Changes in the sequence of administration of the three metals will be discussed to improve the therapeutic index.

  17. Use of arsenic trioxide in remission induction and consolidation therapy for acute promyelocytic leukaemia in the Australasian Leukaemia and Lymphoma Group (ALLG) APML4 study: a non-randomised phase 2 trial.

    PubMed

    Iland, Harry J; Collins, Marnie; Bradstock, Ken; Supple, Shane G; Catalano, Alberto; Hertzberg, Mark; Browett, Peter; Grigg, Andrew; Firkin, Frank; Campbell, Lynda J; Hugman, Amanda; Reynolds, John; Di Iulio, Juliana; Tiley, Campbell; Taylor, Kerry; Filshie, Robin; Seldon, Michael; Taper, John; Szer, Jeff; Moore, John; Bashford, John; Seymour, John F

    2015-09-01

    Initial treatment of acute promyelocytic leukaemia traditionally involves tretinoin (all-trans retinoic acid) combined with anthracycline-based risk-adapted chemotherapy, with arsenic trioxide being the treatment of choice at relapse. To try to reduce the relapse rate, we combined arsenic trioxide with tretinoin and idarubicin in induction therapy, and used arsenic trioxide with tretinoin as consolidation therapy. Patients with previously untreated genetically confirmed acute promyelocytic leukaemia were eligible for this study. Eligibilty also required Eastern Cooperative Oncology Group performance status 0-3, age older than 1 year, normal left ventricular ejection fraction, Q-Tc interval less than 500 ms, absence of serious comorbidity, and written informed consent. Patients with genetic variants of acute promyelocytic leukaemia (fusion of genes other than PML with RARA) were ineligible. Induction comprised 45 mg/m(2) oral tretinoin in four divided doses daily on days 1-36, 6-12 mg/m(2) intravenous idarubicin on days 2, 4, 6, and 8, adjusted for age, and 0·15 mg/kg intravenous arsenic trioxide once daily on days 9-36. Supportive therapy included blood products for protocol-specified haemostatic targets, and 1 mg/kg prednisone daily as prophylaxis against differentiation syndrome. Two consolidation cycles with tretinoin and arsenic trioxide were followed by maintenance therapy with oral tretinoin, 6-mercaptopurine, and methotrexate for 2 years. The primary endpoints of the study were freedom from relapse and early death (within 36 days of treatment start) and we assessed improvement compared with the 2 year interim results. To assess durability of remission we compared the primary endpoints and disease-free and overall survival at 5 years in APML4 with the 2 year interim APML4 data and the APML3 treatment protocol that excluded arsenic trioxide. This study is registered with the Australian New Zealand Clinical Trials Registry, number ACTRN12605000070639. 124 patients were enrolled between Nov 10, 2004, and Sept 23, 2009, with data cutoff of March 15, 2012. Four (3%) patients died early. After a median follow-up of 4·2 years (IQR, 3·2-5·2), the 5 year freedom from relapse was 95% (95% CI 89-98), disease-free survival was 95% (89-98), event-free survival was 90% (83-94), and overall survival was 94% (89-97). The comparison with APML3 data showed that hazard ratios were 0·23 (95% CI 0·08-0·64, p=0·002) for freedom from relapse, 0·21 (0·07-0·59, p=0·001) for disease-free survival, 0·34 (0·16-0·69, p=0·002) for event-free survival, and 0·35 (0·14-0·91, p=0·02) for overall survival. Incorporation of arsenic trioxide in initial therapy induction and consolidation for acute promyelocytic leukaemia reduced the risk of relapse when compared with historical controls. This improvement, together with a non-significant reduction in early deaths and absence of deaths in remission, translated into better event-free and overall survival. Phebra. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. 24 CFR 291.200 - Future REO acquisition method.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 24 Housing and Urban Development 2 2014-04-01 2014-04-01 false Future REO acquisition method. 291.200 Section 291.200 Housing and Urban Development Regulations Relating to Housing and Urban... Sales Procedures § 291.200 Future REO acquisition method. (a) Under this method of property disposition...

  19. 24 CFR 291.200 - Future REO acquisition method.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 24 Housing and Urban Development 2 2010-04-01 2010-04-01 false Future REO acquisition method. 291.200 Section 291.200 Housing and Urban Development Regulations Relating to Housing and Urban... Sales Procedures § 291.200 Future REO acquisition method. (a) Under this method of property disposition...

  20. Scientific communications: Re-Os sulfide (bornite, chalcopyrite, and pyrite) systematics of the carbonate-hosted copper deposits at ruby creek, southern brooks range, Alaska

    USGS Publications Warehouse

    Selby, D.; Kelley, K.D.; Hitzman, M.W.; Zieg, J.

    2009-01-01

    New Re-Os data for chalcopyrite, bornite, and pyrite from the carbonate-hosted Cu deposit at Ruby Creek (Bornite), Alaska, show extremely high Re abundances (hundreds of ppb, low ppm) and contain essentially no common Os. The Re-Os data provide the first absolute ages of ore formation for the carbonate-hosted Ruby Creek Cu-(Co) deposit and demonstrate that the Re-Os systematics of pyrite, chalcopyrite, and bornite are unaffected by greenschist metamorphism. The Re-Os data show that the main phase of Cu mineralization pre dominantly occurred at 384 ?? 4.2 Ma, with an earlier phase possibly at ???400 Ma. The Re-Os data are consistent with the observed paragenetic sequence and coincide with zircon U-Pb ages from igneous rocks within the Ambler metallogenic belt, some of which are spatially and genetically associated with regional volcanogenic massive sulfide deposits. The latter may suggest a temporal link between regional magmatism and hydrothermal mineralization in the Ambler district. The utility of bornite and chalcopyrite, in addition to pyrite, contributes to a new understanding of Re-Os geochronology and permits a refinement of the genetic model for the Ruby Creek deposit. ?? 2009 Society of Economices Geologists, Inc.

  1. Gondola-shaped tetra-rhenium metallacycles modified evanescent wave infrared chemical sensors for selective determination of volatile organic compounds.

    PubMed

    Huang, Genin Gary; Lee, Chung-Jay; Tsai, Bo-Chan; Yang, Jyisy; Sathiyendiran, Malaichamy; Lu, Kuang-Lieh

    2011-07-15

    Water-stable and cavity-contained rhenium metallacycles were synthesized, and their ability to selectively interact with volatile organic compounds (VOCs) systematically studied using attenuated total reflection infrared (ATR-IR) spectroscopy. Integrating the unique properties of rhenium metallacycles into optical sensing technologies significantly improves selectivity in detecting aromatic compounds. To explore the interaction of rhenium metallacycles with VOCs, the surface of ATR sensing elements was modified with the synthesized rhenium metallacycles and used to detect VOCs. The results indicate that rhenium metallacycles have crown ether-like recognition sites, which can selectively interact with aromatic compounds, especially those bearing polar functional groups. The IR absorption bands of rhenium metallacycles shift significantly upon adsorption of aromatic VOCs, revealing a strong interaction between the tetra-rhenium metallacycles and guest aromatic compounds. Optimizing the thickness of the metallacycles coated on the surface of the sensing element led to rapid response in detection. The dynamic range of response was generally up to 30 mg/L with detection limits ca. 30 μg/L. Further studies of the effect of interferences indicate that recovery can be higher than 95% for most of the compounds tested. The results on the flow-cell device indicated that the performances were similar to a static detection system but the detection of VOCs can be largely simplified. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Mineral trioxide aggregate: part 2 - a review of the material aspects.

    PubMed

    Malhotra, Neeraj; Agarwal, Antara; Mala, Kundabala

    2013-03-01

    The purpose of this two-part series is to review the composition, properties, and products of mineral trioxide aggregate (MTA) materials. PubMed and MedLine electronic databases were used to identify scientific papers from January 1991 to May 2010. Based on the selected inclusion criteria, citations were referenced from the scientific peer-reviewed dental literature. Mineral trioxide aggregate is a refined form of the parent compound, Portland cement (PC), and demonstrates a strong biocompatibility due to the high pH level and the material's ability to form hydroxyapatite. Mineral trioxide aggregate materials provide better microleakage protection than traditional endodontic materials as observed in findings from dye-leakage, fluid-filtration, protein-leakage, and bacterial penetration-leakage studies and has been recognized as a bioactive material. Various MTA commercial products are available, including gray mineral trioxide aggregate (GMTA), white mineral trioxide aggregate (WMTA), and mineral trioxide aggregate-Angelus (AMTA). Although these materials are indicated for various dental uses and applications, long-term in-vivo clinical studies are needed. Part 1 of this article highlighted and discussed the composition and characteristics of the material. Part 2 provides an overview of commercially available MTA materials.

  3. Re-Os ages for Archean molybdenite and pyrite, Kuittila-Kivisuo, Finland and Proterozoic molybdenite, Kabeliai, Lithuania: Testing the chronometer in a metamorphic and metasomatic setting

    USGS Publications Warehouse

    Stein, H.J.; Sundblad, K.; Markey, R.J.; Morgan, J.W.; Motuza, G.

    1998-01-01

    Seven 187Re-187Os ages were determined for molybdenite and pyrite samples from two well-dated Precambrian intrusions in Fennoscandia to examine the sustainability of the Re-Os chronometer in a metamorphic and metasomatic setting. Using a new 187Re decay constant (1.666 x 10-11y-1) with a much improved uncertainty (±0.31%), we determined replicate Re-Os ages for molybdenite and pyrite from the Kuittila and Kivisuo prospects in easternmost Finland and for molybdenite from the Kabeliai prospect in southernmost Lithuania. These two localities contain some of the oldest and youngest plutonic activity in Fennoscandia and are associated with newly discovered economic Au mineralization (Ilomantsi, Finland) and a Cu-Mo prospect (Kabeliai, Lithuania). Two Re-Os ages for veinhosted Kabeliai molybdenite average 1486 ± 5 Ma, in excellent agreement with a 1505 ± 11 Ma U-Pb zircon age for the hosting Kabeliai granite pluton. The slightly younger age suggests the introduction of Cu-Mo mineralization by a later phase of the Kabeliai magmatic system. Mean Re-Os ages of 2778 ± 8 Ma and 2781 ± 8 Ma for Kuittila and Kivisuo molybdenites, respectively, are in reasonable agreement with a 2753 ± 5 Ma weighted mean U-Pb zircon age for hosting Kuittila tonalite. These Re-Os ages agree well with less precise ages of 2789 ± 290 Ma for a Rb-Sr whole-rock isochron and 2771 ± 75 Ma for the average of six Sm-Nd T(DM) model ages for Kuittila tonalite. Three Re-Os analyses of a single pyrite mineral separate, from the same sample of Kuittila pluton that yielded a molybdenite separate, provide individual model ages of 2710 ± 27, 2777 ± 28, and 2830 ± 28 Ma (Re = 17.4, 12.1, and 8.4 ppb, respectively), with a mean value of 2770 ± 120 Ma in agreement with the Kuittila molybdenite age. The Re and 187Os abundances in these three pyrite splits are highly correlated (r = 0.9994), and provide a 187Re-187Os isochron age of 2607 ± 47 Ma with an intercept of 21 ppt 187Os (MSWD = 1.1). It appears that the Re-Os isotopic system in pyrite has been reset on the millimeter scale and that the 21 ppt 187Os intercept reflects the in situ decay of 187Re during the ~160 to 170 m.y. interval from ~2778 Ma (time of molybdenite ± pyrite deposition) to ~2607 Ma (time of pyrite resetting). When the Re-Os data for molybdenites from the nearby Kivisuo prospect are plotted together with the Kuittila molybdenite and pyrite data, a well-constrained five-point isochron with an age of 2780 ± 8 Ma and a 187Os intercept (-2.4 ± 3.8 ppt) of essentially zero results (MSWD = 1.5). We suggest that the pyrite isochron age records a regional metamorphic and/or hydrothermal event, possibly the time of Au mineralization. A proposed Re-Os age of ~2607 Ma for Au mineralization is in good agreement with radiometric ages by other methods that address the timing of Archean Au mineralization in deposits worldwide (so-called 'late Au model'). Molybdenite, in contrast, provides a robust Re-Os chronometer, retaining its original formation age of ~2780 Ma, despite subsequent metamorphic disturbances in Archean and Proterozoic time.

  4. Self-assembled flower-like antimony trioxide microstructures with high infrared reflectance performance

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

    Ge, Shengsong, E-mail: geshengsong@126.com; Yang, Xiaokun; Shao, Qian

    A simple hydrothermal process was adopted to self-assembly prepare high infrared reflective antimony trioxide with three-dimensional flower-like microstructures. The morphologies of antimony trioxide microstructures were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM) respectively. It is also found that experimental parameters, such as NaOH concentration, surfactant concentration and volume ratio of ethanol–water played crucial roles in controlling the morphologies of Sb{sub 2}O{sub 3} microstructures. A possible growth mechanism of flower-like Sb{sub 2}O{sub 3} microstructure was proposed based on the experimental data. UV–vis–NIR spectra verified that the near infraredmore » reflectivity of the obtained flower-like microstructures could averagely achieve as 92% with maximum reflectivity of 98%, obviously higher than that of other different morphologies of antimony trioxide microstructures. It is expected that the flower-like Sb{sub 2}O{sub 3} nanostructures have some applications in optical materials and heat insulation coatings. - Graphical abstract: Flower-like Sb{sub 2}O{sub 3} microstructures that composed of nanosheets with thickness of ca. 100 nm exhibit high reflectivity under UV–vis–NIR spectra. Highlights: ► Uniform flower-like microstructures were synthesized via simple hydrothermal reaction. ► The flower-like Sb{sub 2}O{sub 3} microstructures exhibited higher reflectivity than other morphologies under the UV–vis–NIR light. ► Influencing parameters on the Sb{sub 2}O{sub 3} morphologies have been discussed in detail. ► Possible mechanism leading to flower-like microstructures was proposed.« less

  5. Robust Hydrophobic Surfaces from Suspension HVOF Thermal Sprayed Rare-Earth Oxide Ceramics Coatings.

    PubMed

    Bai, M; Kazi, H; Zhang, X; Liu, J; Hussain, T

    2018-05-03

    This study has presented an efficient coating method, namely suspension high velocity oxy-fuel (SHVOF) thermal spraying, to produce large super-hydrophobic ceramic surfaces with a unique micro- and nano-scale hierarchical structures to mimic natural super-hydrophobic surfaces. CeO 2 was selected as coatings material, one of a group of rare-earth oxide (REO) ceramics that have recently been found to exhibit intrinsic hydrophobicity, even after exposure to high temperatures and abrasive wear. Robust hydrophobic REO ceramic surfaces were obtained from the deposition of thin CeO 2 coatings (3-5 μm) using an aqueous suspension with a solid concentration of 30 wt.% sub-micron CeO 2 particles (50-200 nm) on a selection of metallic substrates. It was found that the coatings' hydrophobicity, microstructure, surface morphology, and deposition efficiency were all determined by the metallic substrates underneath. More importantly, it was demonstrated that the near super-hydrophobicity of SHVOF sprayed CeO 2 coatings was achieved not only by the intrinsic hydrophobicity of REO but also their unique hierarchically structure. In addition, the coatings' surface hydrophobicity was sensitive to the O/Ce ratio, which could explain the 'delayed' hydrophobicity of REO coatings.

  6. Quantitative experimental determination of the solid solution hardening potential of rhenium, tungsten and molybdenum in single-crystal nickel-based superalloys

    DOE PAGES

    Fleischmann, Ernst; Miller, Michael K.; Affeldt, Ernst; ...

    2015-01-31

    Here, the solid-solution hardening potential of the refractory elements rhenium, tungsten and molybdenum in the matrix of single-crystal nickel-based superalloys was experimentally quantified. Single-phase alloys with the composition of the nickel solid-solution matrix of superalloys were cast as single crystals, and tested in creep at 980 °C and 30–75 MPa. The use of single-phase single-crystalline material ensures very clean data because no grain boundary or particle strengthening effects interfere with the solid-solution hardening. This makes it possible to quantify the amount of rhenium, tungsten and molybdenum necessary to reduce the creep rate by a factor of 10. Rhenium is moremore » than two times more effective for matrix strengthening than either tungsten or molybdenum. The existence of rhenium clusters as a possible reason for the strong strengthening effect is excluded as a result of atom probe tomography measurements. If the partitioning coefficient of rhenium, tungsten and molybdenum between the γ matrix and the γ' precipitates is taken into account, the effectiveness of the alloying elements in two-phase superalloys can be calculated and the rhenium effect can be explained.« less

  7. Diverse roles of hydrogen in rhenium carbonyl chemistry: hydrides, dihydrogen complexes, and a formyl derivative.

    PubMed

    Li, Nan; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2010-11-04

    Rhenium carbonyl hydride chemistry dates back to the 1959 synthesis of HRe(CO)₅ by Hieber and Braun. The binuclear H₂Re₂(CO)₈ was subsequently synthesized as a stable compound with a central Re₂(μ-H)₂ unit analogous to the B₂(μ-H)₂ unit in diborane. The complete series of HRe(CO)(n) (n = 5, 4, 3) and H₂Re₂(CO)(n) (n = 9, 8, 7, 6) derivatives have now been investigated by density functional theory. In contrast to the corresponding manganese derivatives, all of the triplet rhenium structures are found to lie at relatively high energies compared with the corresponding singlet structures consistent with the higher ligand field splitting of rhenium relative to manganese. The lowest energy HRe(CO)₅ structure is the expected octahedral structure. Low-energy structures for HRe(CO)(n) (n = 4, 3) are singlet structures derived from the octahedral HRe(CO)₅ structure by removal of one or two carbonyl groups. For H₂Re₂(CO)₉ a structure HRe₂(CO)₉(μ-H), with one terminal and one bridging hydrogen atom, lies within 3 kcal/mol of the structure Re₂(CO)₉(η²-H₂), similar to that of Re₂(CO)₁₀. For H₂Re₂(CO)(n) (n = 8, 7, 6) the only low-energy structures are doubly bridged singlet Re₂(μ-H)₂(CO)(n) structures. Higher energy dihydrogen complex structures are also found.

  8. enantio-Enriched CPL-active helicene-bipyridine-rhenium complexes.

    PubMed

    Saleh, Nidal; Srebro, Monika; Reynaldo, Thibault; Vanthuyne, Nicolas; Toupet, Loïc; Chang, Victoria Y; Muller, Gilles; Williams, J A Gareth; Roussel, Christian; Autschbach, Jochen; Crassous, Jeanne

    2015-03-04

    The incorporation of a rhenium atom within an extended helical π-conjugated bi-pyridine system impacts the chiroptical and photophysical properties of the resulting neutral or cationic complexes, leading to the first examples of rhenium-based phosphors that exhibit circularly polarized luminescence.

  9. Rhenium/Oxygen Interactions at Elevated Temperatures

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan; Myers, Dwight; Zhu, Dong-Ming; Humphrey, Donald

    2000-01-01

    The oxidation of pure rhenium is examined from 600-1400 C in oxygen/argon mixtures. Linear weight loss kinetics are observed. Gas pressures, flow rates, and temperatures are methodically varied to determine the rate controlling steps. The reaction at 600 and 800 C appears to be controlled by a chemical reaction step at the surface; whereas the higher temperature reactions appear to be controlled by gas phase diffusion of oxygen to the rhenium surface. Attack of the rhenium appears to be along grain boundaries and crystallographic planes.

  10. Synthesis, structure, and photochemistry of a novel rhenium (I) enolate and photochemistry and second harmonic generation in Langmuir-Blodgett films

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

    Gron, L.U.

    1987-01-01

    A background of cyclopentadienyl ring-slippage reactions is presented along with a brief discussion of the transformations of the related indenyl and fluorenyl ligands. Subsequently a review of oxygen-bonded transition metal enolate complexes is given. Synthesis, structure, and photochemistry of fac-(CO)/sub 3/(P(CH/sub 3/)/sub 3/)/sub 2/Re(OC(CH/sub 3/)C/sub 5/H/sub 4/), 5, is presented. The Re(I) enolate complex was prepared from the reaction of (eta/sup 5/-C/sub 5/H/sub 4/C(O)CH/sub 3/)Re(CO)/sub 3/, 4, with P(CH/sub 3/)/sub 3/. Compound 5 was characterized structurally in the solid state by x-ray crystallography and in solution by ir, and /sup 1/H, /sup 13/C, and /sup 31/P NMR spectroscopy. Photolysis ofmore » 5 at 337 nm in CH/sub 2/Cl/sub 2/ solution cleaves the Re-O bond: smooth conversion to fac-(CO)/sub 3/(P(CH/sub 3/)/sub 3/)/sub 2/ReCl, 6, is observed with a quantum yield of 0.04. The photochemistry of 5 in benzene solution and the synthesis and photochemistry of fac-(CO)/sub 3/(P(CH/sub 3/)/sub 2/-Re(OC(CH/sub 3/)C/sub 5/H/sub 3/CH/sub 3/), 14, is also presented. The Langmuir-Blodgett method of monolayer film formation, characteristics of good film formation and structure of the supported film are reviewed. The basics of second harmonic generation are also presented along with useful applications of the Langmuir-Blodgett films to these studies. Synthesis, structure, and photochemistry of Langmuir-Blodgett stearate films incorporated the emissive Eu/sup 3 +/ and UO/sub 2//sup 2 +/ cations are described. A mixed film containing UO/sub 2/2/sup +//stearate and Eu/sup 3 +//stearate in alternating layers exhibited energy transfer from the UO/sub 2//sup 2 +/ ions to the Eu/sup 3 +/ ions.« less

  11. Absolute timing of sulfide and gold mineralization: A comparison of Re-Os molybdenite and Ar-Ar mica methods from the Tintina Gold Belt, Alaska

    USGS Publications Warehouse

    Selby, D.; Creaser, R.A.; Hart, C.J.R.; Rombach, C.S.; Thompson, J.F.H.; Smith, Moira T.; Bakke, A.A.; Goldfarb, R.J.

    2002-01-01

    New Re-Os molybdenite dates from two lode gold deposits of the Tintina Gold Belt, Alaska, provide direct timing constraints for sulfide and gold mineralization. At Fort Knox, the Re-Os molybdenite date is identical to the U-Pb zircon age for the host intrusion, supporting an intrusive-related origin for the deposit. However, 40Ar/39Ar dates from hydrothermal and igneous mica are considerably younger. At the Pogo deposit, Re-Os molybdenite dates are also much older than 40Ar/39Ar dates from hydrothermal mica, but dissimilar to the age of local granites. These age relationships indicate that the Re-Os molybdenite method records the timing of sulfide and gold mineralization, whereas much younger 40Ar/39Ar dates are affected by post-ore thermal events, slow cooling, and/or systemic analytical effects. The results of this study complement a growing body of evidence to indicate that the Re-Os chronometer in molybdenite can be an accurate and robust tool for establishing timing relations in ore systems.

  12. Effect of Rosmarinus officinalis L. essential oil combined with different packaging conditions to extend the shelf life of refrigerated beef meat.

    PubMed

    Sirocchi, Veronica; Devlieghere, Frank; Peelman, Nanou; Sagratini, Gianni; Maggi, Filippo; Vittori, Sauro; Ragaert, Peter

    2017-04-15

    Rosemary essential oil (REO) contains bioactives having antioxidant and antimicrobial properties. This work investigated the effect of REO combined with modified atmosphere packaging conditions (MAP), in our case, aerobic, vacuum or high O 2 , to extend the shelf life of beef. Beef slices were wrapped in special three-layer sheets of packaging material, some with a coating of REO (active packaging, AP), and some without REO (non active packaging, NAP), and stored at 4°C for 20days. The use of REO proved efficacious in every storage condition, as seen in the lower counts of psychrotrophics, Brochothrix thermosphacta, Pseudomonas spp., and Enterobacteriaceae in AP meat compared to NAP meat. Sensory and colourimetric analyses showed that the best packaging conditions were high-O 2 atmosphere in combination with REO. Based on microbiological data, shelf life of beef was 5-6days for AP samples packaged under aerobic conditions and 14-15days for AP samples in high-O 2 conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Online High Temporal Resolution Measurement of Atmospheric Sulfate and Sulfur Trioxide with a Light Emitting Diode and Liquid Core Waveguide-Based Sensor.

    PubMed

    Tian, Yong; Shen, Huiyan; Wang, Qiang; Liu, Aifeng; Gao, Wei; Chen, Xu-Wei; Chen, Ming-Li; Zhao, Zongshan

    2018-06-13

    High temporal resolution components analysis is still a great challenge for the frontier of atmospheric aerosol research. Here, an online high time resolution method for monitoring soluble sulfate and sulfur trioxide in atmospheric aerosols was developed by integrating a membrane-based parallel plate denuder, a particle collector, and a liquid waveguide capillary cell into a flow injection analysis system. The BaCl 2 solution (containing HCl, glycerin, and ethanol) was enabled to quantitatively transform sulfate into a well-distributed BaSO 4 solution for turbidimetric detection. The time resolution for monitoring the soluble sulfate and sulfur trioxide was 15 h -1 . The limits of detection were 86 and 7.3 μg L -1 ( S/ N = 3) with a 20 and 200 μL SO 4 2- solution injection, respectively. Both the interday and intraday precision values (relative standard deviation) were less than 6.0%. The analytical results of the certificated reference materials (GBW(E)08026 and GNM-M07117-2013) were identical to the certified values (no significant difference at a 95% confidence level). The validity and practicability of the developed device were also evaluated during a firecracker day and a routine day, obviously revealing the continuous variance in atmospheric sulfate and sulfur trioxide in both interday and intraday studies.

  14. enantio-Enriched CPL-active helicene–bipyridine–rhenium complexes†

    PubMed Central

    Saleh, Nidal; Srebro, Monika; Reynaldo, Thibault; Vanthuyne, Nicolas; Toupet, Loïc; Chang, Victoria Y.; Muller, Gilles; Gareth Williams, J. A.; Roussel, Christian

    2016-01-01

    The incorporation of a rhenium atom within an extended helical π-conjugated bi-pyridine system impacts the chiroptical and photophysical properties of the resulting neutral or cationic complexes, leading to the first examples of rhenium-based phosphors that exhibit circularly polarized luminescence. PMID:25643941

  15. Extended X-ray Absorption Fine Structure (EXAFS) Analysis of Vitreous Rare Earth Sodium Phosphates

    NASA Astrophysics Data System (ADS)

    Yoo, Changhyeon; Marasinghe, Kanishka; Segre, Carlo; Shibata, Tomohiro

    2015-03-01

    The local structure around rare-earth ions (RE3+) in rare-earth ultraphosphate (REUP) glasses has been studied using RE LIII edge (RE = Nd, Er, Dy, and Eu) and K edge (RE = Nd, Pr, Dy, and Eu) extended X-ray absorption fine structure (EXAFS) spectroscopy. (RE2O3)x (Na2O)y(P2O5) 1 - x - y glasses in the compositional range 0 <= x <= 0.14 and x + y = 0.3 and 0.4 were studied. RE-oxygen (RE-O) coordination number decreases from ~ 10 to ~ 7.5 with increasing RE-content for Nd, Pr, Eu, and Dy. For Er, RE-O coordination number increases from ~ 8.7 to ~ 10 with increasing RE-content. For the first oxygen shell, the RE-O distance ranges between 2.41-2.43 Å, 2.44-2.46 Å, 2.24-2.26 Å, 2.28-2.32 Å, and 2.32-2.36 Å for Nd, Pr, Er, Dy, and EU glasses, respectively. Second shell around RE ions consists of phosphorus atoms, with RE-P distance about 3.0-3.5 Å and coordination number ranging from 1 to 3. The third shell primarily contains oxygen and is at a distance about 4.0-4.1 Å from RE ions.

  16. Liquid fluorine/hydrazine rhenium thruster update

    NASA Technical Reports Server (NTRS)

    Appel, M. A.; Kaplan, R. B.; Tuffias, R. H.

    1983-01-01

    The status of a fluorine/hydrazine thruster development program is discussed. A solid rhenium metal sea-level thrust chamber was successfully fabricated and tested for a total run duration of 1075 s with 17 starts. Rhenium fabrication methods are discussed. A test program was conducted to evaluate performance and chamber cooling. Acceptable performance was reached and cooling was adequate. A flight-type injector was fabricated that achieved an average extrapolated performance value of 3608 N-s/kg (368 lbf-s/lbm). Altitude thrust chambers were fabricated. One chamber incorporates a rhenium combustor and nozzle with an area ratio of 15:1, and a columbium nozzle extension with area ratios from 15:1 to 60:1. The other chamber was fabricated completely with a carbon/carbon composite. Because of the attributes of rhenium for use in high-temperature applications, a program to provide the materials and processes technology needed to reliably fabricate and/or repair vapor-deposited rhenium parts of relatively large size and complex shape is recommended.

  17. Atom Probe Tomography Analysis of the Distribution of Rhenium in Nickel Alloys

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

    Mottura, A.; Warnken, N; Miller, Michael K

    2010-01-01

    Atom probe tomography (APT) is used to characterise the distributions of rhenium in a binary Ni-Re alloy and the nickel-based single-crystal CMSX-4 superalloy. A purpose-built algorithm is developed to quantify the size distribution of solute clusters, and applied to the APT datasets to critique the hypothesis that rhenium is prone to the formation of clusters in these systems. No evidence is found to indicate that rhenium forms solute clusters above the level expected from random fluctuations. In CMSX-4, enrichment of Re is detected in the matrix phase close to the matrix/precipitate ({gamma}/{gamma}{prime}) phase boundaries. Phase field modelling indicates that thismore » is due to the migration of the {gamma}/{gamma}{prime} interface during cooling from the temperature of operation. Thus, neither clustering of rhenium nor interface enrichments can be the cause of the enhancement in high temperature mechanical properties conferred by rhenium alloying.« less

  18. [Antioxidant properties of cluster rhenium compounds and their effect on erythropoiesis of rats with guerin carcinoma].

    PubMed

    Voronkova, Y S; Babiy, S O; Ivans'kar, L V; Shtemenko, O V; Shtemenko, N I

    2015-01-01

    Biochemical characteristics of kidneys, pe- ripheral blood and bone marrow of rats in model of tumor growth under introduction of cisplatin and cis-tetrachlorodi-μ-isobutyratodirhenium(III), cis-Re2(i-C3H7COO)2Cl4 (I) have been investigated. It was shown that introduction of I alone and together with cisplatin led to decrease of biochemical markers of oxidation of lipids and proteins in tissue homogenates of the kidneys, change of enzyme activity in the urea and tissue homogenates of the kidneys, by a decrease of filtration function of kidneys. Introduction of nanoliposomal forms of the rhenium cluster compound led to a practically normal morphological picture of bone marrow and increase of the RBC (by 60%) with normalization of hematocrit counts, and decrease of quantities of destructed RBC (3.2 times) in comparison with the tumor-bearing animals. A tentative scheme of influence of cluster rhenium compound on erythropoiesis through regulation of synthesis of erythropoietin in kidneys has been proposed.

  19. Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects

    PubMed Central

    Pastor, María Jesús; Cuerva, Cristián; Campo, José A.; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes

    2016-01-01

    Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOOR(n)pyH]+ and BF4−, ReO4−, NO3−, CF3SO3−, CuCl42− counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOOR(12)pyH][ReO4] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl42− salts exhibit the best LC properties followed by the ReO4− ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO4−, and CuCl42− families, and for the solid phase in one of the non-mesomorphic Cl− salts. The highest ionic conductivity was found for the smectic mesophase of the ReO4− containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure. PMID:28773485

  20. Clustering of transmutation elements tantalum, rhenium and osmium in tungsten in a fusion environment

    NASA Astrophysics Data System (ADS)

    You, Yu-Wei; Kong, Xiang-Shan; Wu, Xuebang; Liu, C. S.; Fang, Q. F.; Chen, J. L.; Luo, G.-N.

    2017-08-01

    The formation of transmutation solute-rich precipitates has been reported to seriously degrade the mechanical properties of tungsten in a fusion environment. However, the underlying mechanisms controlling the formation of the precipitates are still unknown. In this study, first-principles calculations are therefore performed to systemically determine the stable structures and binding energies of solute clusters in tungsten consisting of tantalum, rhenium and osmium atoms as well as irradiation-induced vacancies. These clusters are known to act as precursors for the formation of precipitates. We find that osmium can easily segregate to form clusters even in defect-free tungsten alloys, whereas extremely high tantalum and rhenium concentrations are required for the formation of clusters. Vacancies greatly facilitate the clustering of rhenium and osmium, while tantalum is an exception. The binding energies of vacancy-osmium clusters are found to be much higher than those of vacancy-tantalum and vacancy-rhenium clusters. Osmium is observed to strongly promote the formation of vacancy-rhenium clusters, while tantalum can suppress the formation of vacancy-rhenium and vacancy-osmium clusters. The local strain and electronic structure are analyzed to reveal the underlying mechanisms governing the cluster formation. Employing the law of mass action, we predict the evolution of the relative concentration of vacancy-rhenium clusters. This work presents a microscopic picture describing the nucleation and growth of solute clusters in tungsten alloys in a fusion reactor environment, and thereby explains recent experimental phenomena.

  1. 7 CFR 3560.505 - Agency loans to finance purchases of REO properties.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 15 2010-01-01 2010-01-01 false Agency loans to finance purchases of REO properties. 3560.505 Section 3560.505 Agriculture Regulations of the Department of Agriculture (Continued) RURAL HOUSING SERVICE, DEPARTMENT OF AGRICULTURE DIRECT MULTI-FAMILY HOUSING LOANS AND GRANTS Management and Disposition of Real Estate Owned (REO)...

  2. Aromatic sulfonation with sulfur trioxide: mechanism and kinetic model.

    PubMed

    Moors, Samuel L C; Deraet, Xavier; Van Assche, Guy; Geerlings, Paul; De Proft, Frank

    2017-01-01

    Electrophilic aromatic sulfonation of benzene with sulfur trioxide is studied with ab initio molecular dynamics simulations in gas phase, and in explicit noncomplexing (CCl 3 F) and complexing (CH 3 NO 2 ) solvent models. We investigate different possible reaction pathways, the number of SO 3 molecules participating in the reaction, and the influence of the solvent. Our simulations confirm the existence of a low-energy concerted pathway with formation of a cyclic transition state with two SO 3 molecules. Based on the simulation results, we propose a sequence of elementary reaction steps and a kinetic model compatible with experimental data. Furthermore, a new alternative reaction pathway is proposed in complexing solvent, involving two SO 3 and one CH 3 NO 2 .

  3. Equation of state of rhenium and application for ultra high pressure calibration

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

    Anzellini, Simone; Dewaele, Agnès; Occelli, Florent

    2014-01-28

    The isothermal equation of state of rhenium has been measured by powder X-ray diffraction experiments up to 144 GPa at room temperature in a diamond anvil cell. A helium pressure transmitting medium was used to minimize the non-hydrostatic stress on the sample. The fit of pressure-volume data yields a bulk modulus K{sub 0} = 352.6 GPa and a pressure derivative of the bulk modulus K′{sub 0}=4.56. This equation of state differs significantly from a recent determination [Dubrovinsky et al., Nat. Commun. 3, 1163 (2012)], giving here a lower pressure at a given volume. The possibility of using rhenium gasket X-ray diffraction signal, with themore » present equation of state, to evaluate multi-Mbar pressures in the chamber of diamond anvil cells is discussed.« less

  4. Preparation and certification of Re-Os dating reference materials: Molybdenites HLP and JDC

    USGS Publications Warehouse

    Du, A.; Wu, S.; Sun, D.; Wang, Shaoming; Qu, W.; Markey, R.; Stain, H.; Morgan, J.; Malinovskiy, D.

    2004-01-01

    Two Re-Os dating reference material molybdenites were prepared. Molybdenite JDC and molybdenite HLP are from a carbonate vein-type molybdenum-(lead)- uranium deposit in the Jinduicheng-Huanglongpu area of Shaanxi province, China. The samples proved to be homogeneous, based on the coefficient of variation of analytical results and an analysis of variance test. The sampling weight was 0.1 g for JDC and 0.025 g for HLP. An isotope dilution method was used for the determination of Re and Os. Sample decomposition and preconcentration of Re and Os prior to measurement were accomplished using a variety of methods: acid digestion, alkali fusion, ion exchange and solvent extraction. Negative thermal ionisation mass spectrometry and inductively coupled plasma-mass spectrometry were used for the determination of Re and 187Os concentration and isotope ratios. The certified values include the contents of Re and Os and the model ages. For HLP, the Re content was 283.8 ?? 6.2 ??g g-1, 187Os was 659 ?? 14 ng g-1 and the Re-Os model age was 221.4 ?? 5.6 Ma. For JDC, the Re content was 17.39 ?? 0.32 ng g-1, 187Os was 25.46 ?? 0.60 ng g-1 and the Re-Os model age was 139.6 ?? 3.8 Ma. Uncertainties for both certified reference materials are stated at the 95% level of confidence. Three laboratories (from three countries: P.R. China, USA, Sweden) joined in the certification programme. These certified reference materials are primarily useful for Re-Os dating of molybdenite, sulfides, black shale, etc.

  5. Development of Improved Rhenium Coatings for Fluorine Engine Thrust Chambers. [hydrazine-fluorine rocket engines

    NASA Technical Reports Server (NTRS)

    Barton, K. J.; Yurkewycz, R.; Harada, Y.; Daniels, I.

    1981-01-01

    Coating trials were undertaken to evaluate the application of rhenium to carbon-carbon composite sheet by plasma spraying. Optimum spray parameters and coating thickness were identified for production of coatings free from continuous defects and with adequate adherence to the substrate. A tungsten underlayer was not beneficial and possibly detracted from coating integrity. Stress calculations indicated that the proposed operating cycle of the rocket engine would not cause spalling of the rhenium coating. Calculations indicated that permeation of gases through the coating would not be significant during the expected life of the thrust chamber. The feasibility of applying rhenium coatings by laser melting was also studied. Poor wetting of the composite surface by the liquid rhenium precluded production of uniform coatings. Borate/carborate fluxes did not improve wetting characteristics.

  6. Toward hypoxia-selective rhenium and technetium tricarbonyl complexes.

    PubMed

    North, Andrea J; Hayne, David J; Schieber, Christine; Price, Katherine; White, Anthony R; Crouch, Peter J; Rigopoulos, Angela; O'Keefe, Graeme J; Tochon-Danguy, Henri; Scott, Andrew M; White, Jonathan M; Ackermann, Uwe; Donnelly, Paul S

    2015-10-05

    With the aim of preparing hypoxia-selective imaging and therapeutic agents, technetium(I) and rhenium(I) tricarbonyl complexes with pyridylhydrazone, dipyridylamine, and pyridylaminocarboxylate ligands containing nitrobenzyl or nitroimidazole functional groups have been prepared. The rhenium tricarbonyl complexes were synthesized with short reaction times using microwave irradiation. Rhenium tricarbonyl complexes with deprotonated p-nitrophenyl pyridylhydrazone ligands are luminescent, and this has been used to track their uptake in HeLa cells using confocal fluorescent microscopy. Selected rhenium tricarbonyl complexes displayed higher uptake in hypoxic cells when compared to normoxic cells. A (99m)Tc tricarbonyl complex with a dipyridylamine ligand bearing a nitroimidazole functional group is stable in human serum and was shown to localize in a human renal cell carcinoma (RCC; SK-RC-52) tumor in a mouse.

  7. Vapor deposition of thin films

    DOEpatents

    Smith, David C.; Pattillo, Stevan G.; Laia, Jr., Joseph R.; Sattelberger, Alfred P.

    1992-01-01

    A highly pure thin metal film having a nanocrystalline structure and a process of preparing such highly pure thin metal films of, e.g., rhodium, iridium, molybdenum, tungsten, rhenium, platinum, or palladium by plasma assisted chemical vapor deposition of, e.g., rhodium(allyl).sub.3, iridium(allyl).sub.3, molybdenum(allyl).sub.4, tungsten(allyl).sub.4, rhenium(allyl).sub.4, platinum(allyl).sub.2, or palladium(allyl).sub.2 are disclosed. Additionally, a general process of reducing the carbon content of a metallic film prepared from one or more organometallic precursor compounds by plasma assisted chemical vapor deposition is disclosed.

  8. Synthesis, molecular structure and magnetic properties of a rhenium(IV) compound with catechol

    NASA Astrophysics Data System (ADS)

    Cuevas, A.; Geis, L.; Pintos, V.; Chiozzone, R.; Sanchíz, J.; Hummert, M.; Schumann, H.; Kremer, C.

    2009-03-01

    A novel Re(IV) complex containing catechol as ligand has been prepared and characterized. The crystal structure of (HNEt 3)(NBu 4)[ReCl 4(cat)]·H 2cat was determined. The rhenium ion presents a distorted octahedral geometry, being bonded to a bidentate catecholate group and four chloride anions. The magnetic properties of the complex were studied, a /2 D/ (the energy gap between ±3/2 and ±1/2 Kramers doublets) value of 190(10) cm -1. This is the largest /2 D/ value reported for Re(IV) up to now.

  9. Facile rhenium-peptide conjugate synthesis using a one-pot derived Re(CO)3 reagent.

    PubMed

    Chanawanno, Kullapa; Kondeti, Vinay; Caporoso, Joel; Paruchuri, Sailaja; Leeper, Thomas C; Herrick, Richard S; Ziegler, Christopher J

    2016-03-21

    We have synthesized two Re(CO)3-modified lysine complexes (1 and 2), where the metal is attached to the amino acid at the Nε position, via a one-pot Schiff base formation reaction. These compounds can be used in the solid phase synthesis of peptides, and to date we have produced four conjugate systems incorporating neurotensin, bombesin, leutenizing hormone releasing hormone, and a nuclear localization sequence. We observed uptake into human umbilical vascular endothelial cells as well as differential uptake depending on peptide sequence identity, as characterized by fluorescence and rhenium elemental analysis.

  10. Bench to bedside development of GMP grade Rhenium-188-HEDP, a radiopharmaceutical for targeted treatment of painful bone metastases.

    PubMed

    ter Heine, Rob; Lange, Rogier; Breukels, Oscar B; Bloemendal, Haiko J; Rummenie, Rob G; Wakker, Antoinette M; de Graaf, Hilly; Beekman, Freek J; van der Westerlaken, Monique M L; Malingré, Mirte M; Wielders, Jos P M; van den Berg, Leo; Hendrikse, N Harry; de Klerk, John M H

    2014-04-25

    Bone-targeting therapeutic radiopharmaceuticals are effective agents for treatment of painful bone metastases. Rhenium-188-HEDP is such a therapeutic radiopharmaceutical and has advantages over commercially available alternatives in terms of efficacy, safety and the ability to be produced on-site, allowing rapid treatment upon presentation of patients with pain. Unlike many other radiopharmaceuticals, there are no standardized preparation methods for Rhenium-188-HEDP. It is known, however, that drug composition may not only affect stability of the final drug product, but it may also influence bone affinity and, thus, efficacy. Furthermore, for support of clinical studies with Rhenium-188-HEDP as an investigational medicinal product, preparation of this radiopharmaceutical has to be performed under GMP conditions. To our knowledge, no group has reported on the preparation of Rhenium-188-HEDP under GMP conditions or on stock production of sterile non-radioactive starting materials. We present the production of GMP grade Rhenium-188-HEDP for application of this therapeutic radiopharmaceutical in routine clinical practice and for support of clinical studies. In addition, bio-distribution data of Rhenium-188-HEDP in mice and in patients with bone metastases originating from prostate cancer are presented. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Theoretical studies on the electronic structures and photoelectron spectra of tri-rhenium oxide clusters: Re3O(n)(-) and Re3O(n) (n=1-6).

    PubMed

    Zhou, Qi; Gong, Wei-Chao; Xie, Lu; Zheng, Cun-Gong; Zhang, Wei; Wang, Bin; Zhang, Yong-Fan; Huang, Xin

    2014-01-03

    Density functional theory (DFT) calculations are performed to study the structural and electronic properties of tri-rhenium oxide clusters Re3On(-/0) (n=1-6). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level are carried out to search for the global minima for both the anions and the neutrals. For the anions, the first two O atoms prefer the same corner position of a Re3 triangle. Whereas, Re3O3(-) possesses a C2v symmetry with one bridging and two terminal O atoms. The next three O atoms (n=4-6) are adding sequentially on the basis of Re3O3(-) motif, i.e., adding one terminal O atom for Re3O4(-), one terminal and one bridging O atoms for Re3O5(-), and one terminal and two bridging O atoms for Re3O6(-), respectively. Their corresponding neutral species are similar to the anions in geometry except Re3O4 and Re3O5. Molecular orbital analyses are employed to investigate the chemical bonding and structural evolution in these tri-rhenium oxide clusters. Copyright © 2013 Elsevier B.V. All rights reserved.

  12. Oral arsenic plus retinoic acid versus intravenous arsenic plus retinoic acid for non-high-risk acute promyelocytic leukaemia: a non-inferiority, randomised phase 3 trial.

    PubMed

    Zhu, Hong-Hu; Wu, De-Pei; Du, Xin; Zhang, Xi; Liu, Lin; Ma, Jun; Shao, Zong-Hong; Ren, Han-Yun; Hu, Jian-Da; Xu, Kai-Lin; Wang, Jing-Wen; Song, Yong-Ping; Fang, Mei-Yun; Li, Juan; Yan, Xiao-Yan; Huang, Xiao-Jun

    2018-06-05

    Intravenous arsenic trioxide plus all-trans retinoic acid (ATRA) without chemotherapy is the standard of care for non-high-risk acute promyelocytic leukaemia (white blood cell count ≤10 × 10 9 per L), resulting in cure in more than 95% of cases. However, a pilot study of treatment with oral arsenic realgar-Indigo naturalis formula (RIF) plus ATRA without chemotherapy, which has a more convenient route of administration than the standard intravenous regimen, showed high efficacy. In this study, we compare an oral RIF plus ATRA treatment regimen with the standard intravenous arsenic trioxide plus ATRA treatment regimen in patients with non-high-risk acute promyelocytic leukaemia. We did a multicentre, non-inferiority, open-label, randomised, controlled phase 3 trial at 14 centres in China. Patients aged 18-70 years with newly diagnosed (within 7 days) non-high-risk acute promyelocytic leukaemia, and a WHO performance status of 2 or less were eligible. Patients were randomly assigned (2:1) to receive treatment with RIF-ATRA or arsenic trioxide-ATRA as the induction and consolidation therapy. Randomisation was done centrally with permuted blocks and stratification according to trial centre and was implemented through an interactive web response system. RIF (60 mg/kg bodyweight daily in an oral divided dose) or arsenic trioxide (0·15 mg/kg daily in an intravenous dose) and ATRA (25 mg/m 2 daily in an oral divided dose) were used until complete remission was achieved. The home-based consolidation therapy was RIF (60 mg/kg daily in an oral divided dose) or intravenous arsenic trioxide (0·15 mg/kg daily in an intravenous dose) in a 4-week on 4-week off regimen for four cycles and ATRA (25 mg/m 2 daily in an oral divided dose) in a 2-week on 2-week off regimen for seven cycles. Patients and treating physicians were not masked to treatment allocation. The primary outcome was event-free survival at 2 years. A non-inferiority margin of -10% was used to assess non-inferiority. Primary analyses were done in a modified intention-to-treat population of all patients who received at least one dose of their assigned treatment and the per-protocol population. This study was registered with the Chinese Clinical Trial Registry (ChiCTR-TRC-13004054), and the trial is complete. Between Feb 13, 2014, and Aug 31, 2015, 109 patients were enrolled and assigned to RIF-ATRA (n=72) or arsenic trioxide-ATRA (n=37). Three patients in the RIF-ATRA and one in the arsenic trioxide-ATRA did not receive their assigned treatment. After a median follow-up of 32 months (IQR 27-36), 67 (97%) of 69 patients in the RIF-ATRA group and 34 (94%) of 36 in the arsenic trioxide-ATRA group had achieved 2-year event-free survival in the modified intention-to-treat population. The percentage difference in event-free survival was 2·7% (95% CI, -5·8 to 11·1). The lower limit of the 95% CI for the difference in event-free survival was greater than the -10% non-inferiority margin, confirming non-inferiority (p=0·0017). Non-inferiority was also confirmed in the per-protocol population. During induction therapy, grade 3-4 hepatic toxic effects (ie, increased liver aspartate aminotransferase or alanine transaminase concentrations) were reported in six (9%) of 69 patients in the RIF-ATRA group versus five (14%) of 36 patients in the arsenic trioxide-ATRA group; grade 3-4 infection was reported in 15 (23%) of 64 versus 15 (42%) of 36 patients. Two patients in the arsenic trioxide-ATRA group died during induction therapy (one from haemorrhage and one from thrombocytopenia). Oral RIF plus ATRA is not inferior to intravenous arsenic trioxide plus ATRA for the treatment of patients with non-high-risk acute promyelocytic leukaemia. This study suggests that a completely oral, chemotherapy-free model might be an alternative to the standard intravenous treatment for patients with non-high-risk acute promyelocytic leukaemia. Foundation for innovative research group of the National Natural Science Foundation of China, the Beijing Municipal Science and Technology Commission, the National Key R&D Program of China, and the National Natural Science Foundation of China. Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Pyrometallurgical Extraction of Valuable Elements in Ni-Metal Hydride Battery Electrode Materials

    NASA Astrophysics Data System (ADS)

    Jiang, Yin-ju; Deng, Yong-chun; Bu, Wen-gang

    2015-10-01

    Gas selective reduction-oxidation (redox) and melting separation were consecutively applied to electrode materials of AB5-type Ni-metal hydride batteries leading to the production of a Ni-Co alloy and slag enriched with rare earth oxides (REO). In the selective redox process, electrode materials were treated with H2/H2O at 1073 K and 1173 K (800 °C and 900 °C). Active elements such as REs, Al, and Mn were oxidized whereas relatively inert elements such as Ni and Co were transformed into their elemental states in the treated materials. SiO2 and Al2O3 powders were added into the treated materials as fluxes which were then melted at 1823 K (1550 °C) to yield a Ni-Co alloy and a REO-SiO2-Al2O3-MnO slag. The high-purity Ni-Co alloy produced can be used as a raw material for AB5-type hydrogen-storage alloy. The REO content in slag was very high, i.e., 48.51 pct, therefore it can be used to recycle rare earth oxides.

  14. Speech Language Assessments in Te Reo in a Primary School Maori Immersion Unit

    ERIC Educational Resources Information Center

    Naidoo, Kershni

    2012-01-01

    This research originated from the need for a speech and language therapy assessment in te reo Maori for a particular child who attended a Maori immersion unit. A Speech and Language Therapy te reo assessment had already been developed but it needed to be revised and normative data collected. Discussions and assessments were carried out in a…

  15. Learning Te Reo Maori via Online Distance Education: A Case Study

    ERIC Educational Resources Information Center

    Jeurissen, Maree

    2015-01-01

    Despite some gains in the regeneration of te reo Maori, the indigenous language of Aotearoa New Zealand, its long-term survival remains threatened. One avenue for regeneration seldom considered is the English-medium secondary school. This article reports on a case study where students in one such school chose te reo Maori as an option and, and,…

  16. Sulfide and whole rock Re-Os systematics of eclogite and pyroxenite xenoliths from the Slave Craton, Canada

    NASA Astrophysics Data System (ADS)

    Aulbach, Sonja; Creaser, Robert A.; Pearson, Norm J.; Simonetti, Stefanie S.; Heaman, Larry M.; Griffin, William L.; Stachel, Thomas

    2009-06-01

    We characterized single sulfides in eclogite and pyroxenite xenoliths from the Diavik kimberlites (central Slave Craton, Canada) with regard to their petrography, major-element composition and Re-Os isotope systematics. Together with trace-element and Re-Os isotope compositions of whole rocks, these data allow identification of the major Re-Os host phases and provide constraints on the origin(s) of sulfides in these samples. The majority of sulfide minerals contain 8 to 28 at.% Ni, with intragranular sulfides having on average significantly lower contents (~ 6 at.%) than intergranular sulfides (~ 12 at.%). These high Ni-sulfides are not in equilibrium with an eclogitic assemblage and were likely introduced from a peridotitic source subsequent to eclogite formation. In contrast, their Re-Os abundances and Re/Os ratios (average ~ 825 ppb, 190 ppb and 10, respectively) overlap those of primary eclogitic sulfides. These conflicting compositional characteristics may document open-system disequilibrium processes accompanying the introduction of sulfides into eclogites. The general association of high 187Os/ 188Os with high 187Re/ 188Os of sulfides in three low-temperature eclogite xenoliths suggests that the addition is not young. In contrast, sulfides in a high-temperature eclogite plot on a ~ 90 Ma errorchron with radiogenic initial 187Os/ 188Os, perhaps indicative of young introduction of sulfides from a deep enriched source. Sulfides in a single pyroxenite xenolith have Ni, Re and Os contents intermediate between pristine eclogitic and peridotitic sulfides, and correlated Re-Os isotope systematics defining an age of 1.84 ± 0.14 Ga with a radiogenic 187Os/ 188Os i (0.16 ± 0.01). The age and 187Os/ 188Os i are identical to those obtained for eclogitic sulfide inclusions in diamonds from Diavik, thus supporting a link between eclogite and pyroxenite formation. Several eclogite and pyroxenite whole rocks show evidence for addition of secondary sulfides, but many plot on Paleoproterozoic Re-Os age arrays - particularly so at low Re/Os - coincident with previously determined ages using Lu-Hf and Pb-Pb techniques. They may represent sulfide-poor varieties that did not suffer secondary sulfide addition and that may be best suited to yielding meaningful Re-Os ages.

  17. Differences between the macroscopic and tracer level chemistry of rhenium and technetium: contrasting cage isomerisation behaviour of Re(I) and Tc(I) carborane complexes.

    PubMed

    Armstrong, Andrea F; Valliant, John F

    2010-09-21

    Carboranes form stable complexes with the [M(CO)(3)](+) (M = (99m)Tc, Re) core and are viable ligands for the development of targeted radiopharmaceuticals. (99m)Tc-carborane complexes were found to exhibit substantially different 1,2-->1,7 cage isomerisation behaviour than their Re counterparts, challenging the validity of the routine use of rhenium as a surrogate for the development of technetium-99m based molecular imaging agents.

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

    PubMed

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

    2017-01-01

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

  19. Te Reo Maori as a Subject: The Impact of Language Ideology, Language Practice, and Language Management on Secondary School Students' Decision Making

    ERIC Educational Resources Information Center

    Jeurissen, Maree

    2014-01-01

    Te reo Maori, the Indigenous language of Aotearoa (New Zealand), remains 'endangered' despite concentrated ongoing efforts to reverse declining numbers of speakers. Most of these efforts have focused on te reo Maori immersion education settings as these were considered the most effective means to ensure the survival of the language (May &…

  20. Absolute mass of neutrinos and the first unique forbidden {beta} decay of {sup 187}Re

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

    Dvornicky, Rastislav; Simkovic, Fedor; Bogoliubov Laboratory of Theoretical Physics, JINR Dubna, 141980 Dubna, Moscow region

    2011-04-15

    The planned rhenium {beta}-decay experiment, called the ''Microcalorimeter Arrays for a Rhenium Experiment'' (MARE), might probe the absolute mass scale of neutrinos with the same sensitivity as the Karlsruhe tritium neutrino mass (KATRIN) experiment, which will take commissioning data in 2011 and will proceed for 5 years. We present the energy distribution of emitted electrons for the first unique forbidden {beta} decay of {sup 187}Re. It is found that the p-wave emission of electron dominates over the s wave. By assuming mixing of three neutrinos, the Kurie function for the rhenium {beta} decay is derived. It is shown that themore » Kurie plot near the end point is within a good accuracy linear in the limit of massless neutrinos like the Kurie plot of the superallowed {beta} decay of {sup 3}H.« less

  1. Determination of rhenium in molybdenite by neutron-activation analysis.

    PubMed

    Terada, K; Yoshimura, Y; Osaki, S; Kiba, T

    1967-01-01

    A neutron-activation method is described for the determination of rhenium in molybdenite. Radiochemical separation by a carrier technique was carried out very rapidly by means of successive liquid-liquid extraction processes. The recovery of rhenium, which was determined by a spectrophotometric method, was about 93%. About 10 samples could be analysed within 6 hr in parallel runs.

  2. Rhenium: a rare metal critical in modern transportation

    USGS Publications Warehouse

    John, David A.

    2015-01-01

    Rhenium rarely occurs as a native element or as its own sulfide mineral—rheniite (ReS2)—and often occurs as a substitute for molybdenum in molybdenite (MoS2). Most extracted rhenium is a byproduct of copper mining, with about 80 percent recovered from flue dust during the processing of molybdenite concentrates from porphyry copper deposits.

  3. Mineral of the month: rhenium

    USGS Publications Warehouse

    Magyar, Michael J.

    2005-01-01

    Rhenium, an exotic, heat-resistant metal, has grown in importance since its discovery nearly 80 years ago. First isolated by a team of German chemists studying a platinum ore, the mineral was named for the Rhine River. From then until the 1960s, only 2 metric tons of rhenium were produced worldwide. In 2004, worldwide production was 40 metric tons.

  4. Ethanol Reduced Molybdenum Trioxide for Li-ion Capacitors

    DOE PAGES

    Li, Tianqi; Beidaghi, Majid; Xiao, Xu; ...

    2016-05-06

    Orthorhombic molybdenum trioxide (α-MoO 3) is a layered oxide with promising performance as electrode material for Li-ion capacitors. In this study, we show that expansion of the interlayer spacing (by ~0.32 Å) of the structure along the b-axis, introduced by partial reduction of α-MoO 3 and formation of MoO 3-x (x=0.06–0.43), results in enhanced diffusion of Li ions. Binder-free hybrid electrodes made of MoO 3-x nanobelts and carbon nanotubes show excellent electrical conductivity. The combination of increased interlayer spacing and enhanced electron transport leads to high gravimetric and volumetric capacitances of about 420 F/g or F/cm 3 and excellent cyclemore » life of binder-free MoO 3-x electrodes.« less

  5. Drug composition matters: the influence of carrier concentration on the radiochemical purity, hydroxyapatite affinity and in-vivo bone accumulation of the therapeutic radiopharmaceutical 188Rhenium-HEDP.

    PubMed

    Lange, R; de Klerk, J M H; Bloemendal, H J; Ramakers, R M; Beekman, F J; van der Westerlaken, M M L; Hendrikse, N H; Ter Heine, R

    2015-05-01

    (188)Rhenium-HEDP is an effective bone-targeting therapeutic radiopharmaceutical, for treatment of osteoblastic bone metastases. It is known that the presence of carrier (non-radioactive rhenium as ammonium perrhenate) in the reaction mixture during labeling is a prerequisite for adequate bone affinity, but little is known about the optimal carrier concentration. We investigated the influence of carrier concentration in the formulation on the radiochemical purity, in-vitro hydroxyapatite affinity and the in-vivo bone accumulation of (188)Rhenium-HEDP in mice. The carrier concentration influenced hydroxyapatite binding in-vitro as well as bone accumulation in-vivo. Variation in hydroxyapatite binding with various carrier concentrations seemed to be mainly driven by variation in radiochemical purity. The in-vivo bone accumulation appeared to be more complex: satisfactory radiochemical purity and hydroxyapatite affinity did not necessarily predict acceptable bio-distribution of (188)Rhenium-HEDP. For development of new bisphosphonate-based radiopharmaceuticals for clinical use, human administration should not be performed without previous animal bio-distribution experiments. Furthermore, our clinical formulation of (188)Rhenium-HEDP, containing 10 μmol carrier, showed excellent bone accumulation that was comparable to other bisphosphonate-based radiopharmaceuticals, with no apparent uptake in other organs. Radiochemical purity and in-vitro hydroxyapatite binding are not necessarily predictive of bone accumulation of (188)Rhenium-HEDP in-vivo. The formulation for (188)Rhenium-HEDP as developed by us for clinical use exhibits excellent bone uptake and variation in carrier concentration during preparation of this radiopharmaceutical should be avoided. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. Monte Carlo Criticality Analysis of Simple Geometrics COntaining Tungsten Rhenium Alloys Engrained with Uranium Dioxide and Uranium Mononitride

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

    Jonathan A. Webb; Indrajit Charit

    2011-08-01

    The critical mass and dimensions of simple geometries containing highly enriched uraniumdioxide (UO2) and uraniummononitride (UN) encapsulated in tungsten-rhenium alloys are determined using MCNP5 criticality calculations. Spheres as well as cylinders with length to radius ratios of 1.82 are computationally built to consist of 60 vol.% fuel and 40 vol.% metal matrix. Within the geometries the uranium is enriched to 93 wt.% uranium-235 and the rhenium content within the metal alloy was modeled over a range of 0 to 30 at.%. The spheres containing UO2 were determined to have a critical radius of 18.29 cm to 19.11 cm and amore » critical mass ranging from 366 kg to 424 kg. The cylinders containing UO2 were found to have a critical radius ranging from 17.07 cm to 17.844 cm with a corresponding critical mass of 406 kg to 471 kg. Spheres engrained with UN were determined to have a critical radius ranging from 14.82 cm to 15.19 cm and a critical mass between 222 kg and 242 kg. Cylinders which were engrained with UN were determined to have a critical radius ranging from 13.811 cm to 14.155 cm with a corresponding critical mass of 245 kg to 267 kg. The critical geometries were also computationally submerged in a neutronaically infinite medium of fresh water to determine the effects of rhenium addition on criticality accidents due to water submersion. The monte carlo analysis demonstrated that rhenium addition of up to 30 at.% can reduce the excess reactivity due to water submersion by up to $5.07 for UO2 fueled cylinders, $3.87 for UO2 fueled spheres and approximately $3.00 for UN fueled spheres and cylinders.« less

  7. Fluorescent rhenium-naphthalimide conjugates as cellular imaging agents.

    PubMed

    Langdon-Jones, Emily E; Symonds, Nadine O; Yates, Sara E; Hayes, Anthony J; Lloyd, David; Williams, Rebecca; Coles, Simon J; Horton, Peter N; Pope, Simon J A

    2014-04-07

    A range of biologically compatible, fluorescent rhenium-naphthalimide conjugates, based upon the rhenium fac-tricarbonyl core, has been synthesized. The fluorescent ligands are based upon a N-functionalized, 4-amino-derived 1,8-naphthalimide core and incorporate a dipicolyl amine binding unit to chelate Re(I); the structural variations accord to the nature of the alkylated imide with ethyl ester glycine (L(1)), 3-propanol (L(2)), diethylene glycol (L(3)), and benzyl alcohol (L(4)) variants. The species are fluorescent in the visible region between 505 and 537 nm through a naphthalimide-localized intramolecular charge transfer, with corresponding fluorescent lifetimes of up to 9.8 ns. The ligands and complexes were investigated for their potential as imaging agents for human osteoarthritic cells and protistan fish parasite Spironucleus vortens using confocal fluorescence microscopy. The results show that the specific nature of the naphthalimide structure serves to control the uptake and intracellular localization of these imaging agents. Significant differences were noted between the free ligands and complexes, with the Re(I) complex of L(2) showing hydrogenosomal localization in S. vortens.

  8. A randomised, phase II study of repeated rhenium-188-HEDP combined with docetaxel and prednisone versus docetaxel and prednisone alone in castration-resistant prostate cancer (CRPC) metastatic to bone; the Taxium II trial.

    PubMed

    van Dodewaard-de Jong, Joyce M; de Klerk, John M H; Bloemendal, Haiko J; Oprea-Lager, Daniela E; Hoekstra, Otto S; van den Berg, H Pieter; Los, Maartje; Beeker, Aart; Jonker, Marianne A; O'Sullivan, Joe M; Verheul, Henk M W; van den Eertwegh, Alfons J M

    2017-08-01

    Rhenium-188-HEDP is a beta-emitting radiopharmaceutical used for palliation of metastatic bone pain. We investigated whether the addition of rhenium-188-HEDP to docetaxel/prednisone improved efficacy of chemotherapy in patients with CRPC. Patients with progressive CRPC and osteoblastic bone metastases were randomised for first-line docetaxel 75 mg/m 2 3-weekly plus prednisone with or without 2 injections of rhenium-188-HEDP after the third (40 MBq/kg) and after the sixth (20 MBq/kg) cycle of docetaxel. Primary endpoint was progression-free survival (PFS), defined as either PSA, radiographic or clinical progression. Patients were stratified by extent of bone metastases and hospital. Forty-two patients were randomised for standard treatment and 46 patients for combination therapy. Median number of cycles of docetaxel was 9 in the control group and 8 in the experimental group. Median follow-up was 18.4 months. Two patients from the experimental group did not start treatment after randomisation. In the intention to treat analysis no differences in PFS, survival and PSA became apparent between the two groups. In an exploratory per-protocol analysis median overall survival was significantly longer in the experimental group (33.8 months (95%CI 31.75-35.85)) than in the control group (21.0 months (95%CI 13.61-28.39); p 0.012). Also median PFS in patients with a baseline phosphatase >220U/L was significantly better with combination treatment (9.0 months (95%CI 3.92-14.08) versus 6.2 months (95%CI 3.08-9.32); log rank p 0.005). As expected, thrombocytopenia (grade I/II) was reported more frequently in the experimental group (25% versus 0%). Combined treatment with rhenium-188-HEDP and docetaxel did not prolong PFS in patients with CRPC. The observed survival benefit in the per-protocol analysis warrants further studies in the combined treatment of chemotherapy and radiopharmaceuticals.

  9. Mass spectrometry of rhenium complexes: a comparative study by using LDI-MS, MALDI-MS, PESI-MS and ESI-MS.

    PubMed

    Petroselli, Gabriela; Mandal, Mridul Kanti; Chen, Lee Chuin; Ruiz, Gustavo T; Wolcan, Ezequiel; Hiraoka, Kenzo; Nonami, Hiroshi; Erra-Balsells, Rosa

    2012-03-01

    A group of rhenium (I) complexes including in their structure ligands such as CF(3)SO(3)-, CH(3)CO(2)-, CO, 2,2'-bipyridine, dipyridil[3,2-a:2'3'-c]phenazine, naphthalene-2-carboxylate, anthracene-9-carboxylate, pyrene-1-carboxylate and 1,10-phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF-ESI-CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M](+·) and to produce their reduction yielding the gas species [M](-·). It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV-visible region, particularly at 355 nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix-assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor-harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M](-·) species. Results obtained with 2-[(2E)-3-(4-tert-buthylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones. Copyright © 2012 John Wiley & Sons, Ltd.

  10. Thermal reduction of MoO3 in sub- and supercritical water: Insights on redox conditions in Hydrothermal Diamond Anvil Cell (HDAC) experiments

    NASA Astrophysics Data System (ADS)

    Solferino, G.; Anderson, A. J.

    2011-12-01

    The Hydrothermal Diamond Anvil Cell (HDAC) is a key tool used in the study of volatile bearing melts and solute-rich fluids at the pressure and temperatures existent in the crust and shallow upper mantle (100-1500 MPa). Oxygen fugacity is among the key parameters that must be constrained in phase equilibrium and speciation studies of melt and aqueous fluid systems. It is however difficult to assess fO2 during HDAC experiments due to decomposition of water, interaction of fluid with gasket materials and the diamond themselves. In this study the temperature at which molybdenum trioxide was thermally reduced to molybdenum dioxide in the presence of deoxygenated water was measured in order to constrain the oxygen fugacity in the HDAC experiment. The sample was contained within either a rhenium gasket between two diamond anvils or within a laser-milled recess in the culet face of one of the diamond anvils (i.e. no gasket). Experiments consisted of loading a MoO3 crystal and deoxygenated water into the sample chamber and then holding the system at a temperature for the desired amount of time. MoO3 dissolved in large part or completely after 30-60 minutes at high temperature. In most experiments tugarinovite (MoO2) precipitated directly from solution once the temperature of thermal reduction was attained. MicroRaman spectroscopy was used to characterize run products. The temperature at which tugarinovite appeared varied depending on the experimental setup, and was 315 ± 2.0 °C in experiments where a gasket was used and 344 ± 2.5 °C in the experiments without a gasket. This implies that the presences of a Re gasket resulted in more reducing conditions of log(fO2) = -20.6 ± 0.5, compared to log(fO2) = -19.5 ± 0.2 for the series without gasket. Moreover, in some of the experiments performed below the transition temperature to tugarinovite, and when MoO3 crystals were not dissolved completely, an additional Raman peak at 854 cm-1 was observed that is not present in pure orthorhombic molybdite (α-MoO3). This feature, which is attributed to the presence of metastable monoclinic MoO3, is absent or poorly developed in runs where no gasket was used but was very intense in experiments where a gasket was used. According to previous studies, monoclinic MoO3 is formed in reducing conditions. The results indicate that for very simple systems, where water is the only or the dominating fluid medium, a Re gasket has a significant reducing effect on the fO2 at relatively low temperatures (200-400 °C). Furthermore, the fO2 conditions appear to be imposed (mainly) by the fluid and not by the noble metal gasket. Despite the reducing effect of the rhenium metal on the fluid, fO2 values for the Re-ReO2 buffer are much smaller than those extrapolated for our runs (i.e. log (fO2) = -27 to -29).

  11. Development and research of a rhenium-free high-temperature nickel superalloy for the turbine rotor blades in aviation GTE

    NASA Astrophysics Data System (ADS)

    Shmotin, Yu. N.; Logunov, A. V.; Leshchenko, I. A.; Danilov, D. V.

    2016-12-01

    The studies directed on designing an advanced rhenium-free nickel superalloy, which is an analog of ZhS32VI alloy, are performed. The chemical composition of the alloy has been found and an experimental alloy batch has been melted (10 kg). Microstructural and metallographic studies and strength tests are carried out. The new single-crystal superalloy has a long-term strength σ1000 100= 238-248 MPa at a density of 8.87 g/cm3.

  12. AC conductivity and dielectric properties of bulk tungsten trioxide (WO3)

    NASA Astrophysics Data System (ADS)

    El-Nahass, M. M.; Ali, H. A. M.; Saadeldin, M.; Zaghllol, M.

    2012-11-01

    AC conductivity and dielectric properties of tungsten trioxide (WO3) in a pellet form were studied in the frequency range from 42 Hz to 5 MHz with a variation of temperature in the range from 303 K to 463 K. AC conductivity, σac(ω) was found to be a function of ωs where ω is the angular frequency and s is the frequency exponent. The values of s were found to be less than unity and decrease with increasing temperature, which supports the correlated barrier hopping mechanism (CBH) as the dominant mechanism for the conduction in WO3. The dielectric constant (ε‧) and dielectric loss (ε″) were measured. The Cole-Cole diagram determined complex impedance for different temperatures.

  13. Isotopic determinations of rhenium and osmium in meteorites by using fusion, distillation and ion-exchange separations

    USGS Publications Warehouse

    Morgan, J.W.; Walker, R.J.

    1989-01-01

    A stable isotope-dilution method using resonance ionization mass spectrometry is suitable for the determination of rhenium and osmium abundances and osmium isotopic composition in carbonaceous chondrites and iron meteorites. The chemical procedure involves sodium peroxide fusion, followed by distillation of osmium from sulfuric acid/hydrogen peroxide and subsequent anion-exchange separation of rhenium from the same solution. ?? 1989.

  14. Dzhezkazgan and associated sandstone copper deposits of the Chu-Sarysu basin, Central Kazakhstan

    USGS Publications Warehouse

    Box, Stephen E.; Seltmann, Reimar; Zientek, Michael L.; Syusyura, Boris; Creaser, Robert A.; Dolgopolova, Alla

    2012-01-01

    Sandstone-hosted copper (sandstone Cu) deposits occur within a 200-km reach of the northern Chu-Sarysu basin of central Kazakhstan (Dzhezkazgan and Zhaman-Aibat deposits, and the Zhilandy group of deposits). The deposits consist of Cu sulfide minerals as intergranular cement and grain replacement in 10 ore-bearing members of sandstone and conglomerate within a 600- to 1,000-m thick Pennsylvanian fluvial red-bed sequence. Copper metal content of the deposits ranges from 22 million metric tons (Mt, Dzehzkazgan) to 0.13Mt (Karashoshak in the Zhilandy group), with average grades of 0.85 to 1.7% Cu and significant values for silver (Ag) and rhenium (Re). Broader zones of iron reduction (bleaching) of sandstones and conglomerates of the red-bed sequence extend over 10 km beyond each of the deposits along E-NE-trending anticlines, which began to form in the Pennsylvanian. The bleached zones and organic residues within them are remnants of ormer petroleum fluid accumulations trapped by these anticlines. Deposit sites along these F1anticlines are localized at and adjacent to the intersections of nearly orthogonal N-NW-trending F2synclines. These structural lows served to guide the flow of dense ore brines across the petroleum-bearing anticlines, resulting in ore sulfide precipitation where the two fluids mixed. The ore brine was sourced either from the overlying Early Permian lacustrine evaporitic basin, whose depocenter occurs between the major deposits, or from underlying Upper Devonian marine evaporites. Sulfur isotopes indicate biologic reduction of sulfate but do not resolve whether the sulfate was contributed from the brine or from the petroleum fluids. New Re-Os age dates of Cu sulfides from the Dzhezkazgan deposit indicate that mineralization took place between 299 to 309 Ma near the Pennsylvanian-Permian age boundary. At the Dzhezkazgan and some Zhilandy deposits, F2fold deformation continued after ore deposition. Copper orebodies in Lower Permian shale near the Zhaman-Aibat deposit indicate that at least some of the mineralization there is younger than at Dzhezkazgan, consistent with the Re-Os age and with differences in their ore Pb isotopes.

  15. Re-Os Isotopic Characteristics of the Earth's Oldest Preserved Oceanic Crustal Fragments (Isua Supracrustals Belt, W Greenland); A Vastly Disturbed System.

    NASA Astrophysics Data System (ADS)

    Frei, R.; Frei, R.; Jensen, B. K.

    2001-12-01

    Variably preserved pillow lavas from the Isua Supracrustals Belt (ISB; Western Greenland) exhibit strongly supra-chondritic Re/Os (range from 2 to 45) and highly radiogenic 187Os/188Os isotopic compositions (range from 0.3 to 20.5). Re-Os model ages are geologically meaningless and reflect the disturbances invoked by post-formational metamorphic overprinting and by metasomatic events that were associated with the intrusion of various generations of the precursors of tonalitic gneisses into the ISB. Most prominently, a late Archean (c. 2.8 Ga) tectono-metamorphic event has locally reset the Re-Os clock in high strain domains of the ISB. Disturbance of the Re-Os system was initially caused by Re addition in connection with metasomatic fluid flow during the early Archean (3.65 to 3.81 Ga) emplacement of central dome gneiss precursors and tonalite sheets into the supracrustals sequences. The effects of open system behaviour of the Re-Os system are similarly recorded by the U-Pb and Sm-Nd systems of these meta-basalts, principally revealing the influx of U, Th, Re; LREE and alkaline-rich fluids from the gneisses into the oceanic crustal sequences preserved at Isua (Blichert-Toft and Frei, 2001; Frei et al., in press; Frei and Rosing, in press). Ultramafic lenses with komatiitic chemical affinities within the ISB are equally affected by early addition of Re, but the very much higher Os concentrations (more than an order of magnitude higher than those of the meta-basalts with values ranging from 30 to 150 ppt) did efficiently mask the disturbances in the Os isotope compositions, so that reasonable Re depletion ages (TRD) can still be deduced. The least altered of these ultramafic lenses revealed a TRD) of 3725 Ma and a mantle extraction (TMA) age of 3807 Ma, dates which are compatible with independent U-Pb zircon ages from intrusive tonaltic gneisses (Nutman et al., 1997) and Pb-Pb age constraints from metasomatic minerals of strongly altered meta-basalts (Frei and Rosing, in press). They can be regarded as minimum ages of deposition of the supracrustals. The complexity of post-formational overprinting however makes it difficult to investigate and explore the Earth's mantle geochemical evolution before this time. Blichert-Toft, J. and Frei, R. (2001) Geochim. Cosmochim. Acta, 65, 3177-3187. Frei, R., Rosing, M.T., Waight, T.E., and Ulfbeck, D.G. (in press) Geochim. Cosmochim. Acta Frei,R. and Rosing, M.T. (in press) Chem. Geol. Nutman, A.P., Bennett, V.C., Friend, C.R.L., and Rosing, M.T. (1997) Chem. Geol., 141, 271-287.

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

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

    AA KRUGER; A GOEL; CP RODRIGUEZ

    2012-08-13

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

  17. Rhenium Concentration Variations in the Non-flood Period of the Yangtze River Water and Estimation of the Oxidation Rate of Organic Carbon

    NASA Astrophysics Data System (ADS)

    Xu, P.; Chen, Y.; Li, S.; Wang, K.

    2017-12-01

    In geological history, the uplift of the Tibet plateau has accelerated the silicate weathering and organic carbon burial at the same time, which made great influence on the global carbon cycle by increasing the carbon sink. Because of the vital connection between tectonic uplift and carbon cycle, more and more attention was casted on rivers originating from orogens. The Yangtze River, as an important large river in the world, is one of them. However, although silicate weathering has been studied thoroughly, researches on organic carbon cycle are much less, and oxidation of fossil organic carbon remained poorly constrained. In this study, we try to use rhenium(Re) as a proxy to estimate the oxidation rate of fossil organic carbon and thus proceed our understanding towards the carbon cycle, the silicate weathering. This is because Re has a close relationship with organic carbon in the sediments and will be released into hydrological network in the mountain river catchments by being oxidized and exist as soluble ReO4-, so that we can use Re concentration in river water to estimate the oxidation rate of organic carbon. We collected water samples from the Yangtze River fortnightly at Banqiao Ferry and the sampling date cover the non-flood period. In this way, we are able to have a rough estimate of the amount of carbon dioxide that released to the atmosphere by the oxidation of organic carbon, using the data of non-flood period we got. We found that Re concentration in Yangtze River ranges approximately from 45 to 85 pmol/L. The rate of organic carbon weathering is estimated using the expression, ΦCO2,fossil=[Re]×runoff×[OC/Re]rock, and according to researches on the black shale of Yangtze River, the value 2.86×106 is chosen as the ratio OC(organic carbon) to Re in the black shale. The result is a really high flux, up to 152×109mol/y, just a little less than of the CO2 consumption rates from silicate weathering which is 191×109mol/y and about 166×109mol/y in non-flood period. Our result indicates that in the Yangtze Basin, oxidation of fossil organic carbon can very likely offset the carbon dioxide that removed by silicate weathering.

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

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

    Pierce, Eric M.; Lukens, Wayne W.; Fitts, Jeff. P.

    2013-12-01

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

  19. A biography of arsenic and medicine in Hong Kong and China.

    PubMed

    Au, W Y

    2011-12-01

    Arsenic trioxide has been used in traditional Chinese medicine for over 5000 years, but lost its appeal due to its toxicity. It was rediscovered in western medicine and enjoyed a renaissance from 1830 to 1930, as the first effective chemotherapy against syphilis, parasites and leukaemia. These years were also a time of political turmoil in China. The Nanking treaty (29 August 1842) turned Hong Kong into a colony, while the Xinhai Revolution (10 October 1911) gave birth to a republic of China. Arsenic returned to China and Hong Kong with the establishment of the first medical schools from 1887 to 1920. Until 1950, oral arsenic trioxide was the standard anti-leukaemic treatment in Queen Mary Hospital. The advent of alkylating chemotherapeutic agents replaced arsenic trioxide in Hong Kong and around the world. In the 1970s, however, the specific activity of arsenic trioxide against acute promyelocytic leukaemia was re-discovered during the Cultural Revolution in Harbin, China. In 1997, Hong Kong was returned to China. In the same year, arsenic trioxide returned to the world stage. Intravenous arsenic trioxide became the worldwide standard therapy for relapsed acute promyelocytic leukaemia. Oral administration of arsenic trioxide was revived in Hong Kong in 2000. This resulted in the first locally produced, registered, patented prescription drug in Hong Kong. Pending imminent manufacture, this product is poised to revolutionise acute promyelocytic leukaemia care and may hold the key to saving the lives of acute promyelocytic leukaemia patients worldwide. The remarkable journey of arsenic in the setting of medical history of China and Hong Kong is reviewed.

  20. Rhenium Rocket Manufacturing Technology

    NASA Technical Reports Server (NTRS)

    1997-01-01

    The NASA Lewis Research Center's On-Board Propulsion Branch has a research and technology program to develop high-temperature (2200 C), iridium-coated rhenium rocket chamber materials for radiation-cooled rockets in satellite propulsion systems. Although successful material demonstrations have gained much industry interest, acceptance of the technology has been hindered by a lack of demonstrated joining technologies and a sparse materials property data base. To alleviate these concerns, we fabricated rhenium to C-103 alloy joints by three methods: explosive bonding, diffusion bonding, and brazing. The joints were tested by simulating their incorporation into a structure by welding and by simulating high-temperature operation. Test results show that the shear strength of the joints degrades with welding and elevated temperature operation but that it is adequate for the application. Rhenium is known to form brittle intermetallics with a number of elements, and this phenomena is suspected to cause the strength degradation. Further bonding tests with a tantalum diffusion barrier between the rhenium and C-103 is planned to prevent the formation of brittle intermetallics.

  1. Evaluation of the Re-Os Geochronometer in Organic-rich Mudrocks as a Method for Constraining the Absolute Ages of Neoproterozoic Glaciogenic Deposits

    NASA Astrophysics Data System (ADS)

    Kendall, B. S.; Creaser, R. A.; Ross, G. M.

    2002-12-01

    Absolute-age constraints on the Neoproterozoic glaciations are generally poor due to a paucity of suitable plutonic and volcanic igneous rocks that are temporally and spatially related to Neoproterozoic glaciogenic deposits and are amenable to radiometric dating methods. In this study, the Re-Os isotope systematics of dark gray, sulfidic slates from the Old Fort Point Formation (OFP) of the Windermere Supergroup (near Jasper, Alberta) were examined to test the ability of the Re-Os geochronometer to provide an absolute age constraint for a Neoproterozoic glaciogenic deposit. The OFP has been interpreted as the deep water expression of post-glacial sea level rise and therefore is comparable stratigraphically to cap carbonates that immediately overlie glaciogenic deposits worldwide. Despite the relatively low Re (6-16 ppb) and Os (0.07-0.14 ppb) concentrations and total organic contents (~ 0.5% TOC) of the slates compared to other organic-rich mudrocks used in previous Re-Os isotope studies, precise well-fitted Re-Os isochrons have been obtained with two different dissolution methods. An age of 620.8 +/- 8.1 Ma (MSWD = 0.9; initial 187Os/188Os = 0.68 +/- 0.06) is obtained using conventional aqua regia dissolution. Using a method designed to selectively dissolve organic matter alone, an age of 609.0 +/- 8.3 Ma (MSWD = 1.5; initial 187Os/188Os = 0.62 +/- 0.05) is obtained. These absolute age results are in accord with existing age constraints (e.g., stratigraphically younger Hamill Group with a U-Pb zircon age of 569 Ma). The well-defined Re-Os systematics of the OFP slates demonstrates for the first time that the Re-Os system is not disturbed in organic-rich sediments during lower greenschist (-chlorite) grade metamorphic conditions. The whole-rock analysis of each individual sample yields consistently higher initial 187Os/188Os isotope ratios than the corresponding organic matter analysis and suggests that a significant radiogenic detrital Os component is present within the OFP slates. Because organic matter is likely dominated by the hydrogenous (seawater) Os budget, the initial 187Os/188Os ratio of 0.62 +/- 0.05 calculated from the organic matter regression represents the best estimate of the Os isotopic composition of the contemporaneous seawater at the time of sediment deposition. The corresponding age of 609.0 +/- 8.3 Ma is then considered to be the best depositional age determination for the OFP and provides a minimum absolute age constraint on the stratigraphically underlying glaciogenic Mount Vreeland Formation (northeastern British Columbia) and the correlative Ice Brook diamictites (Mackenzie Mountains, northwestern Canada). Thus, we conclude that the Mount Vreeland and Ice Brook diamictites are older than the ~ 580-570 Ma glaciogenic deposits of Eastern North America and may thus be considered as lower Marinoan in age. Further application of the Re-Os geochronometer to other organic-rich mudrock horizons spatially and temporally related to Neoproterozoic glaciogenic deposits will allow further opportunities for their correlation and provide better age constraints on the timing, number, and duration of the Neoproterozoic glaciations. This will allow a further assessment of the Snowball Earth Theory and its prediction of global, synchronous glaciations.

  2. New constraints on the Paleoarchean meteorite bombardment of the Earth - Geochemistry and Re-Os isotope signatures of spherule layers in the BARB5 ICDP drill core from the Barberton Greenstone Belt, South Africa

    NASA Astrophysics Data System (ADS)

    Schulz, Toni; Koeberl, Christian; Luguet, Ambre; van Acken, David; Mohr-Westheide, Tanja; Ozdemir, Seda; Reimold, Wolf Uwe

    2017-08-01

    Archean spherule layers, resulting from impacts by large extraterrestrial objects, to date represent the only remnants of the early meteorite, asteroid, and comet bombardment of the Earth. Only few Archean impact debris layers have been documented, all of them embedded in the 3.23-3.47 billion year old successions of the Barberton Greenstone Belt (BGB) in South Africa and the Pilbara Craton in Western Australia. Some of them might be correlated with each other. Given the scarcity of Archean spherule deposits, four spherule layer intersections from the recently recovered BARB5 drill core from the central Barberton Greenstone Belt, analyzed in this study, provide an opportunity to gain new insight into the early terrestrial impact bombardment. Despite being hydrothermally overprinted, siderophile element abundance signatures of spherule-rich samples from the BARB5 drill core, at least in part, retained a meteoritic fingerprint. The impact hypothesis for the generation of the BARB5 spherule layers is supported by correlations between the abundances of moderately (Cr, Co, Ni) and highly siderophile (Re, Os, Ir, Pt, Ru and Pd) elements, whose peak concentrations and interelement ratios are within the range of those for chondrites. Rhenium-Osmium isotope evidence further support the impact hypothesis. Collectively, this study provides evidence for extraterrestrial admixtures ranging between ∼40 and up to 100% to three of the four analyzed BARB5 spherule layers, and a scenario for their genesis involving (i) impact of a chondritic bolide into a sedimentary target, (ii) varying admixtures of meteoritic components to target materials, (iii) spherule formation via condensation in an impact vapor plume, (iv) transportation of the spherules and sedimentation under submarine conditions, followed by (v) moderate post-impact remobilization of transition metals and highly siderophile elements.

  3. New Advances in Re-Os Geochronology of Organic-rich Sedimentary Rocks.

    NASA Astrophysics Data System (ADS)

    Creaser, R. A.; Selby, D.; Kendall, B. S.

    2003-12-01

    Geochronology using 187Re-187Os is applicable to limited rock and mineral matrices, but one valuable application is the determination of depositional ages for organic-rich clastic sedimentary rocks like black shales. Clastic sedimentary rocks, in most cases, do not yield depositional ages using other radioactive isotope methods, but host much of Earth's fossil record upon which the relative geological timescale is based. As such, Re-Os dating of black shales has potentially wide application in timescale calibration studies and basin analysis, if sufficiently high precision and accuracy could be achieved. This goal requires detailed, systematic studies and evaluation of factors like standard compound stoichiometry, geologic effects, and the 187Re decay constant. Ongoing studies have resulted in an improved understanding of the abilities, limitations and systematics of the Re-Os geochronometer in black shales. First-order knowledge of the effects of processes like hydrocarbon maturation and low-grade metamorphism is now established. Hydrocarbon maturation does not impact the ability of the Re-Os geochronometer to determine depositional ages from black shales. The Re-Os age determined for the Exshaw Fm of western Canada is accurate within 2σ analytical uncertainty of the known age of the unit (U-Pb monazite from ash, conodont biostratigraphy). This suggests that the large improvement in precision attained for Re-Os dating of black shales by Cohen et al (ESPL 1999) over the pioneering work of Ravizza & Turekian (GCA 1989), relates to advances in analytical methodologies and sampling strategies, rather than a lack of disturbance by hydrocarbon maturation. We have found that a significant reduction in isochron scatter can be achieved by using an alternate dissolution medium, which preferentially attacks organic matter in which Re and Os are largely concentrated. This likely results from a more limited release of detrital Os and Re held in silicate materials during dissolution, compared with the inverse aqua regia medium used for Carius tube analysis. Using these "organic-selective" dissolution techniques, precise depositional ages have now been obtained from samples with very low TOC contents ( ˜0.5%), meaning that a greater range of clastic sedimentary rocks is amenable for Re-Os age dating. Well-fitted Re-Os isochrons of plausible geological age have also been determined from low-TOC shales subjected to chlorite-grade regional metamorphism. These results further illustrate the wide, but currently underutilized, potential of the Re-Os geochronometer in shales. The precision of age data attainable by the Re-Os system directly from black shales can be better than +/- 1% uncertainty (2σ , derived from isochron regression analysis), and the derived ages are demonstrably accurate.

  4. Capping a Pulpotomy with Calcium Aluminosilicate Cement: Comparison to Mineral Trioxide Aggregates

    PubMed Central

    Kramer, Phillip R.; Woodmansey, Karl F.; White, Robert; Primus, Carolyn M.; Opperman, Lynne A.

    2014-01-01

    Introduction Calcium aluminate cements have shown little affinity for bacterial growth, low toxicity, and immunogenicity when used as a restoration material, but calcium aluminate cements have not been tested in vivo in pulpotomy procedures. Methods To address this question, a calcium aluminate cement (Quick-Set) was tested along with 2 mineral trioxide aggregates, ProRoot MTA and MTA Plus. These cements were used as a capping agent after pulpotomy. Control rats had no pulpotomy, or the pulpotomy was not capped. Proinflammatory cytokines interleukin (IL)-1β and IL-1α were measured, and histology was performed at 30 and 60 days after capping. The nociceptive response was determined by measuring the lengthening of the rat's meal duration. Results and Conclusions: IL-1β and IL-1α concentrations were reduced in the capped teeth, but no differences were observed among the 3 cements. Dentinal bridging could be detected at both 30 and 60 days with each of the 3 cements, and the pulps were still vital 60 days after capping. Meal duration significantly shortened after placement of the 3 different cements, indicating a nociceptive response, but there were no differences among the materials. Calcium aluminate cements had similar properties to mineral trioxide aggregates and is a viable option for pulpotomy procedures. PMID:25146026

  5. Mineral resource of the month: rhenium

    USGS Publications Warehouse

    Polyak, Désirée E.

    2012-01-01

    Rhenium, a silvery-white, heat resistant metal, has increased significantly in importance since its discovery in 1925. First isolated by a team of German chemists studying platinum ore, the mineral was named for the Rhine River. From 1925 until the 1960s, only two metric tons of rhenium were produced worldwide. Since then, its uses have steadily increased, including everything from unleaded gasoline to jet engines, and worldwide annual production now tops 45 metric tons.

  6. Rhenium-Oxygen Interactions at High Temperatures

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Myers, Dwight L.; Zhu, Dongming; Humphrey, Donald

    2000-01-01

    The reaction of pure rhenium metal with dilute oxygen/argon mixtures was studied from 600 to 1400 C. Temperature, oxygen pressure, and flow rates were systematically varied to determine the rate-controlling steps. At lower temperatures the oxygen/rhenium chemical reaction is rate limiting; at higher temperatures gas-phase diffusion of oxygen through the static boundary layer is rate limiting. At all temperatures post-reaction microstructures indicate preferential attack along certain crystallographic planes and defects.

  7. Effect of thalidomide and arsenic trioxide on the release of tumor necrosis factor-α and vascular endothelial growth factor from the KG-1a human acute myelogenous leukemia cell line.

    PubMed

    Girgis, Erian H; Mahoney, John P; Khalil, Rafaat H; Soliman, Magdi R

    2010-07-01

    Studies conducted in our lab have indicated that thalidomide cytotoxicity in the KG-1a human acute myelogenous leukemia (AML) cell line was enhanced by combining it with arsenic trioxide. The current investigation was conducted in order to evaluate the effect of thalidomide either alone or in combination with arsenic trioxide on the release of tumor necrosis factor-α (TNF-α) and vascular endothelial growth factor (VEGF) from this cell line in an attempt to clarify its possible cytotoxic mechanism(s). Human AML cell line KG-1a was used in this study. The cells were cultured for 48 h in the presence or absence of thalidomide (5 mg/l), and or arsenic trioxide (4 μM). The levels of TNF-α and VEGF in the supernatant were determined by ELISA. Results obtained indicate that the levels of TNF-α in the supernatant of KG-1a cell cultures incubated with thalidomide, arsenic trioxide, or combination were statistically lower than those observed in the supernatant of control cells (2.89, 5.07, 4.15 and 16.88 pg/ml, respectively). However, the levels of VEGF in the supernatant of thalidomide-treated cells were statistically higher than those in the supernatant of control cells (69.61 vs. 11.48 pg/l). Arsenic trioxide, whether alone or in combination with thalidomide, did not produce any statistically significant difference in the levels of VEGF as compared to the control or thalidomide-treated cell supernatant. These findings indicate that thalidomide and the arsenic trioxide inhibition of TNF-α production by KG-1a cells may play an important role in their cytotoxic effect.

  8. Environmentally relevant concentration of arsenic trioxide and humic acid promoted tumor progression of human cervical cancer cells: In vivo and in vitro studies.

    PubMed

    Tsai, Min-Ling; Yen, Cheng-Chieh; Lu, Fung-Jou; Ting, Hung-Chih; Chang, Horng-Rong

    2016-09-01

    In a previous study, treatment at higher concentrations of arsenic trioxide or co-exposure to arsenic trioxide and humic acid was found to be inhibited cell growth of cervical cancer cells (SiHa cells) by reactive oxygen species generation. However, treatment at lower concentrations slightly increased cell viability. Here, we investigate the enhancement of progression effects of environmentally relevant concentration of humic acid and arsenic trioxide in SiHa cell lines in vitro and in vivo by measuring cell proliferation, migration, invasion, and the carcinogenesis-related protein (MMP-2, MMP-9, and VEGF-A) expressions. SiHa cells treated with low concentrations of humic acid and arsenic trioxide alone or in co-exposure significantly increased reactive oxygen species, glutathione levels, cell proliferation, scratch wound-healing activities, migration abilities, and MMP-2 expression as compared to the untreated control. In vivo the tumor volume of either single drug (humic acid or arsenic trioxide) or combined drug-treated group was significantly larger than that of the control for an additional 45 days after tumor cell injection on the back of NOD/SCID mice. Levels of MMP-2, MMP-9, and VEGF-A, also significantly increased compared to the control. Histopathologic effects of all tumor cells appeared round in cell shape with high mitosis, focal hyperkeratosis and epidermal hyperplasia in the skin, and some tumor growth in the muscle were observed. Our results may indicate that exposure to low concentrations of arsenic trioxide and humic acid is associated with the progression of cervical cancer. © 2015 Wiley Periodicals, Inc. Environ Toxicol 31: 1121-1132, 2016. © 2015 Wiley Periodicals, Inc.

  9. Oncolytic reovirus as a combined antiviral and anti-tumour agent for the treatment of liver cancer.

    PubMed

    Samson, Adel; Bentham, Matthew J; Scott, Karen; Nuovo, Gerard; Bloy, Abigail; Appleton, Elizabeth; Adair, Robert A; Dave, Rajiv; Peckham-Cooper, Adam; Toogood, Giles; Nagamori, Seishi; Coffey, Matthew; Vile, Richard; Harrington, Kevin; Selby, Peter; Errington-Mais, Fiona; Melcher, Alan; Griffin, Stephen

    2018-03-01

    Oncolytic viruses (OVs) represent promising, proinflammatory cancer treatments. Here, we explored whether OV-induced innate immune responses could simultaneously inhibit HCV while suppressing hepatocellular carcinoma (HCC). Furthermore, we extended this exemplar to other models of virus-associated cancer. Clinical grade oncolytic orthoreovirus (Reo) elicited innate immune activation within primary human liver tissue in the absence of cytotoxicity and independently of viral genome replication. As well as achieving therapy in preclinical models of HCC through the activation of innate degranulating immune cells, Reo-induced cytokine responses efficiently suppressed HCV replication both in vitro and in vivo. Furthermore, Reo-induced innate responses were also effective against models of HBV-associated HCC, as well as an alternative endogenous model of Epstein-Barr virus-associated lymphoma. Interestingly, Reo appeared superior to the majority of OVs in its ability to elicit innate inflammatory responses from primary liver tissue. We propose that Reo and other select proinflammatory OV may be used in the treatment of multiple cancers associated with oncogenic virus infections, simultaneously reducing both virus-associated oncogenic drive and tumour burden. In the case of HCV-associated HCC (HCV-HCC), Reo should be considered as an alternative agent to supplement and support current HCV-HCC therapies, particularly in those countries where access to new HCV antiviral treatments may be limited. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

  10. Advanced Materials and Fabrication Techniques for the Orion Attitude Control Motor

    NASA Technical Reports Server (NTRS)

    Gorti, Sridhar; Holmes, Richard; O'Dell, John; McKechnie, Timothy; Shchetkovskiy, Anatoliy

    2013-01-01

    Rhenium, with its high melting temperature, excellent elevated temperature properties, and lack of a ductile-to-brittle transition temperature (DBTT), is ideally suited for the hot gas components of the ACM (Attitude Control Motor), and other high-temperature applications. However, the high cost of rhenium makes fabricating these components using conventional fabrication techniques prohibitive. Therefore, near-net-shape forming techniques were investigated for producing cost-effective rhenium and rhenium alloy components for the ACM and other propulsion applications. During this investigation, electrochemical forming (EL-Form ) techniques were evaluated for producing the hot gas components. The investigation focused on demonstrating that EL-Form processing techniques could be used to produce the ACM flow distributor. Once the EL-Form processing techniques were established, a representative rhenium flow distributor was fabricated, and samples were harvested for material properties testing at both room and elevated temperatures. As a lower cost and lighter weight alternative to an all-rhenium component, rhenium- coated graphite and carbon-carbon were also evaluated. The rhenium-coated components were thermal-cycle tested to verify that they could withstand the expected thermal loads during service. High-temperature electroforming is based on electrochemical deposition of compact layers of metals onto a mandrel of the desired shape. Mandrels used for electro-deposition of near-net shaped parts are generally fabricated from high-density graphite. The graphite mandrel is easily machined and does not react with the molten electrolyte. For near-net shape components, the inner surface of the electroformed part replicates the polished graphite mandrel. During processing, the mandrel itself becomes the cathode, and scrap or refined refractory metal is the anode. Refractory metal atoms from the anode material are ionized in the molten electrolytic solution, and are deposited onto the cathodic mandrel by electrochemical reduction. Rotation of the mandrel ensures uniform distribution of refractory material. The EL-Form process allows for manufacturing in an inert atmosphere with deposition rates from 0.0004 to 0.002 in./h (10.2 to 50.8 m/h). Thicknesses typically range from microns to greater than 0.5 in. (13 mm). The refractory component produced is fabricated, dependably, to within one micron of the desired tolerances with no shrinkage or distortion as in other refractory metal manufacture techniques. The electroforming process has been used to produce solid, nonporous deposits of rhenium, iridium, niobium, tungsten, and their alloys.

  11. 40 CFR 116.4 - Designation of hazardous substances.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., ammonium sulfocyanide Amly acetate 628637 Amylacetic ester iso- 123922 Pear oil sec- 626380 Banana oil tert... Antimony trifluoride 7783564 Antimony fluoride Antimony trioxide 1309644 Diantimony trioxide, flowers of...

  12. 40 CFR 116.4 - Designation of hazardous substances.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., ammonium sulfocyanide Amly acetate 628637 Amylacetic ester iso- 123922 Pear oil sec- 626380 Banana oil tert... Antimony trifluoride 7783564 Antimony fluoride Antimony trioxide 1309644 Diantimony trioxide, flowers of...

  13. 40 CFR 116.4 - Designation of hazardous substances.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., ammonium sulfocyanide Amly acetate 628637 Amylacetic ester iso- 123922 Pear oil sec- 626380 Banana oil tert... Antimony trifluoride 7783564 Antimony fluoride Antimony trioxide 1309644 Diantimony trioxide, flowers of...

  14. Low Cost, Net Shape Fabrication of Rhenium and High Temperature Materials for Rocket Engine Components

    DTIC Science & Technology

    2001-03-01

    tungsten thin wall nozzle liner removed from reusable mandrel. b) W and Re rocket, nozzle inserts (2 inserts per mandrel) for Air Force. Rhenium PPI...compares the fabrication time for the VPS nozzles with equivalent carbon / carbon composite (C/C) and forged tungsten materials. Table 5: Comparison of...UNCLASSIFIED Defense Technical Information Center Compilation Part Notice ADPO1 1181 TITLE: Low Cost, Net Shape Fabrication of Rhenium and High

  15. METHOD FOR FORMING A COATING OF MOLYBDENUM CARBIDE ON A CARBON BODY

    DOEpatents

    Simnad, M.T.

    1962-04-01

    A method is described for coating a carbon bodywith molybdenum carbide in such a manner that the carbon body is rendered less permeable to the flow of gases and has increased resistance to corrosion and erosion. The method includes coating a carbon body with molybdenum trioxide by contacting it at a temperature below the condensation temperature with molybdenum trioxide vapors and thereafter carburizing the molybdenum trioxide in situ in an inert atmosphere on the carhon body. (AEC)

  16. Determination of sulfur trioxide in engine exhaust.

    PubMed Central

    Arnold, D R

    1975-01-01

    Sulfur trioxide in the exhaust gas of an internal combustion engine is removed and concentrated by absorption in a solution of 80% isopropyl alcohol, which quantitatively absorbs it and inhibits the oxidation of any sulfur dioxide which may be absorbed. The absorbed sulfur trioxide (sulfuric acid) is determined by an absorption titration by using barium chloride as the titrant and thorin as the indicator. The sulfur dioxide content of the exhaust is measured continuously by means of a DuPont Model 411 ultraviolet photoanalyzer. PMID:50930

  17. Joint effects of microwave and chromium trioxide on root tip cells of Vicia faba *

    PubMed Central

    Qian, Xiao-Wei; Luo, Wei-Hua; Zheng, Ou-Xiang

    2006-01-01

    The mutagenic effects of microwave and chromium trioxide (CrO3) on Vicia faba root tip were studied. Micronucleus assay and chromosomal aberration assay were used to determine the mitotic index, the micronucleus frequency and chromosomal aberration frequency of Vicia faba root tip cells induced by microwave and CrO3. The results showed that the micronucleus frequency decreased, and that the mitotic index and chromosomal aberration frequency showed linear dose responses to CrO3, in treatment of microwave for 5 s. In microwave of 25 s, the mitotic index decreased, the micronucleus frequency and chromosomal aberration frequency increased with increase of CrO3 concentration. We concluded that microwave and CrO3 had antagonistic effect on the mitotic index of Vicia faba root tip cells, but had synergetic effect on micronucleus frequency and chromosomal aberration frequency of Vicia faba root tip cells. PMID:16502510

  18. Joint effects of microwave and chromium trioxide on root tip cells of Vicia faba.

    PubMed

    Qian, Xiao-wei; Luo, Wei-hua; Zheng, Ou-xiang

    2006-03-01

    The mutagenic effects of microwave and chromium trioxide (CrO(3)) on Vicia faba root tip were studied. Micronucleus assay and chromosomal aberration assay were used to determine the mitotic index, the micronucleus frequency and chromosomal aberration frequency of Vicia faba root tip cells induced by microwave and CrO(3). The results showed that the micronucleus frequency decreased, and that the mitotic index and chromosomal aberration frequency showed linear dose responses to CrO(3), in treatment of microwave for 5 s. In microwave of 25 s, the mitotic index decreased, the micronucleus frequency and chromosomal aberration frequency increased with increase of CrO(3) concentration. We concluded that microwave and CrO(3) had antagonistic effect on the mitotic index of Vicia faba root tip cells, but had synergetic effect on micronucleus frequency and chromosomal aberration frequency of Vicia faba root tip cells.

  19. Photodecomposition Profile of Curcumin in the Existence of Tungsten Trioxide Particles

    NASA Astrophysics Data System (ADS)

    Nandiyanto, A. B. D.; Zaen, R.; Oktiani, R.; Abdullah, A. G.

    2018-02-01

    The purpose of this study was to investigate the stability of curcumin solution in the existence of tungsten trioxide (WO3) particles under light illumination. In the experimental method, curcumin extracted from Indonesian local turmeric was added with WO3 microparticles and put into the photoreactor system. The photostability performance of curcumin was conducted for 22 hours using 100 W of Neon Lamp. The results showed that the curcumin solution was relatively stable. When curcumin without existence of WO3 was irradiated, no change in the curcumin concentration was found. However, when curcumin solution was mixed with WO3 particles, decreases in the concentration of curcumin was found. The concentration of curcumin with WO3 after light irradiation was about 73.58%. Based on the results, we concluded that the curcumin is relatively stable against light. However, its lightirradiation stability decreases with additional inorganic material.

  20. Thermocouples of tantalum and rhenium alloys for more stable vacuum-high temperature performance

    NASA Technical Reports Server (NTRS)

    Morris, J. F. (Inventor)

    1977-01-01

    Thermocouples of the present invention provide stability and performance reliability in systems involving high temperatures and vacuums by employing a bimetallic thermocouple sensor wherein each metal of the sensor is selected from a group of metals comprising tantalum and rhenium and alloys containing only those two metals. The tantalum, rhenium thermocouple sensor alloys provide bare metal thermocouple sensors having advantageous vapor pressure compatibilities and performance characteristics. The compatibility and physical characteristics of the thermocouple sensor alloys of the present invention result in improved emf, temperature properties and thermocouple hot junction performance. The thermocouples formed of the tantalum, rhenium alloys exhibit reliability and performance stability in systems involving high temperatures and vacuums and are adaptable to space propulsion and power systems and nuclear environments.

  1. Rhenium(I) polypyridine diamine complexes as intracellular phosphorogenic sensors: synthesis, characterization, emissive behavior, biological properties, and nitric oxide sensing.

    PubMed

    Choi, Alex Wing-Tat; Yim, Vicki Man-Wai; Liu, Hua-Wei; Lo, Kenneth Kam-Wing

    2014-07-28

    We report the development of a series of rhenium(I) polypyridine complexes appended with an electron-rich diaminoaromatic moiety as phosphorogenic sensors for nitric oxide (NO). The diamine complexes [Re(N^N)(CO)3 (py-DA)][PF6 ] (py-DA=3-(N-(2-amino-5-methoxyphenyl)aminomethyl)pyridine; N^N=1,10-phenanthroline (phen) (1 a), 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4 -phen) (2 a), 4,7-diphenyl-1,10-phenanthroline (Ph2 -phen) (3 a)) have been synthesized and characterized. In contrast to common rhenium(I) diimines, these diamine complexes were very weakly emissive due to quenching of the triplet metal-to-ligand charge-transfer ((3) MLCT) emission by the diaminoaromatic moiety through photoinduced electron transfer (PET). Upon treatment with NO, the complexes were converted into the triazole derivatives [Re(N^N)(CO)3 (py-triazole)][PF6 ] (py-triazole=3-((6-methoxybenzotriazol-1-yl)methyl)pyridine; N^N=phen (1 b), Me4 -phen (2 b), Ph2 -phen (3 b)), resulting in significant emission enhancement (I/I0 ≈60). The diamine complexes exhibited high reaction selectivity to NO, and their emission intensity was found to be independent on pH. Also, these complexes were effectively internalized by HeLa cells and RAW264.7 macrophages with negligible cytotoxicity. Additionally, the use of complex 3 a as an intracellular phosphorogenic sensor for NO has been demonstrated. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis, characterization and cellular location of cytotoxic constitutional organometallic isomers of rhenium delivered on a cyanocobalmin scaffold.

    PubMed

    Santoro, Giuseppe; Zlateva, Theodora; Ruggi, Albert; Quaroni, Luca; Zobi, Fabio

    2015-04-21

    Constitutional isomers of cyanocobalamin adducts based on a fluorescent rhenium tris-carbonyl diimine complex were prepared, characterized and tested against PC-3 cancer cells. The adducts differ only in the relative binding position of the organometallic species which is either bound at the cyano or the 5'-hydroxo group of vitamin B12. When tested for their cytotoxic potency, the species showed IC50 values in the low μM rage. Upon conjugation to the vitamin an energy transfer process causes an extremely low quantum yield of fluorescence emission, making the conjugates unsuitable for fluorescence imaging. However, by exploiting the vibrational signature of the fac-[Re(CO)3](+) core, their cellular distribution was evaluated via FTIR spectromicroscopy.

  3. 40 CFR 61.180 - Applicability and designation of sources.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... for Inorganic Arsenic Emissions From Arsenic Trioxide and Metallic Arsenic Production Facilities § 61... metallic arsenic production plant and to each arsenic trioxide plant that processes low-grade arsenic...

  4. 40 CFR 61.180 - Applicability and designation of sources.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... for Inorganic Arsenic Emissions From Arsenic Trioxide and Metallic Arsenic Production Facilities § 61... metallic arsenic production plant and to each arsenic trioxide plant that processes low-grade arsenic...

  5. Re-Os dating of 3AB iron meteorites

    NASA Technical Reports Server (NTRS)

    Esat, Tezer M.; Bennett, Victoria

    1993-01-01

    Recently, Creaser et al., and Volkening and Heumann, have demonstrated the efficient production of large (approximately 10 exp -11 A) ion beams by negative thermal ionization mass spectrometry (NTIMS) using standard laboratory solutions of Os compounds. Horan et al., have applied NTIMS to a group of 7 IIA iron meteorites and obtained a Re-Os closure age of 4596 +/- 152 million years. The initial Os-187/Os-186 ratio was 0.8007 plus or minus 0.0029. In addition they analyzed 3 IIIA meteorite samples which indicated an age of 4554 +/- 180 million years and Os initial of 0.8120 +/- 0.0075 which does not overlap with the initial for the IIA irons. We have been independently pursuing a similar program with the direct aim of determining possible variations in the initial (Os-187)/(Os-186) ratio or Re-Os closure age of different classes of iron meteorite. We have applied NTIMS to Os extracted from the most common group of iron meteorites the IIIAB. These meteorites are believed to be of magmatic origin, formed by fractional crystallization of molten cores of asteroidal bodies. The present results point to a significantly lower initial (Os-187)/(Os-186) ratio of 0.7731 plus or minus 0.0050 than previously determined.

  6. A study of the radiosynthesis of fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺ and its application in labeling 1,2,3-triazole analogs obtained by click chemistry.

    PubMed

    Wang, Cheng; Zhou, Wei; Yu, Junfeng; Zhang, Lan; Wang, Ni

    2012-01-01

    To optimize the conditions for the preparation of the organometallic precursor fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺ and to synthesize the radiolabeling compounds of tricarbonyl rhenium. 1,2,3-Triazole analogs were synthesized by click chemistry and labeled with fac-[ReCO₃(H₂O)₃]Br and fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺. The aim was to improve the methods for the synthesis of ¹⁸⁸Re-labeled radiopharmaceuticals for therapy. With potassium boranocarbonate as the CO source and ammonia borane as the reducing agent, fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺ was synthesized, and the click chemistry method was used to prepare the tricarbonyl rhenium complex. At the optimal reaction condition (the amounts of K₂[H₃BCO₂] and BH₃·NH₃ are 5 and 5 mg, respectively; reaction temperature is 75°C; and reaction time is 15 min), the radiochemical yields were 90%, and the labeling yield of bis(pyridin-2-ylmethyl) amine with fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺ was more than 99% in 1 h at 75°C; the conjugation yields of triazole analog obtained by click chemistry with 'cold' and 'radio' tricarbonyl rhenium were more than 80%. The organometallic precursor fac-[¹⁸⁸ReCO₃(H₂O)₃]⁺ was prepared under optimal reaction conditions with a yield of 90%, and the triazole analogs synthesized by click chemistry were suitable ligands for tricarbonyl rhenium.

  7. Sub-Micrometer Epitaxial Josephson Junctions for Quantum Circuits

    DTIC Science & Technology

    2011-10-31

    that the surface morphology of the Re base-electrode is independent of furnace treatment and miscut angle. At first we used a 165 nm thick rhenium ...substrate. Using this technique, we obtain crystalline rhenium films. We find that these film are characterized by ...... 100 nm diameter hexagonal islands...energy (1.9 J /m2) than rhenium (2.2 J /m2) and acts as a wetting layer, resulting in a significantly smoother surface, as shown in figures 1 (a) and

  8. 40 CFR 421.216 - Pretreatment standards for new sources.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... exceed the following values: (a) Molybdenum sulfide leachate. PSNS for the Primary Molybdenum and Rhenium...) Molybdic oxide leachate. PSNS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant...

  9. 40 CFR 421.216 - Pretreatment standards for new sources.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... exceed the following values: (a) Molybdenum sulfide leachate. PSNS for the Primary Molybdenum and Rhenium...) Molybdic oxide leachate. PSNS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant...

  10. 40 CFR 421.216 - Pretreatment standards for new sources.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... exceed the following values: (a) Molybdenum sulfide leachate. PSNS for the Primary Molybdenum and Rhenium...) Molybdic oxide leachate. PSNS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant...

  11. 40 CFR 421.216 - Pretreatment standards for new sources.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... exceed the following values: (a) Molybdenum sulfide leachate. PSNS for the Primary Molybdenum and Rhenium...) Molybdic oxide leachate. PSNS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant...

  12. 40 CFR 421.216 - Pretreatment standards for new sources.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... exceed the following values: (a) Molybdenum sulfide leachate. PSNS for the Primary Molybdenum and Rhenium...) Molybdic oxide leachate. PSNS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant...

  13. Studies of the fate of sulfur trioxide in coal-fired utility boilers based on modified selected condensation methods.

    PubMed

    Cao, Yan; Zhou, Hongcang; Jiang, Wu; Chen, Chien-Wei; Pan, Wei-Ping

    2010-05-01

    The formation of sulfur trioxide (SO(3)) in coal-fired utility boilers can have negative effects on boiler performance and operation, such as fouling and corrosion of equipment, efficiency loss in the air preheater (APH), increase in stack opacity, and the formation of PM(2.5). Sulfur trioxide can also compete with mercury when bonding with injected activated carbons. Tests in a lab-scale reactor confirmed there are major interferences between fly ash and SO(3) during SO(3) sampling. A modified SO(3) procedure to maximize the elimination of measurement biases, based on the inertial-filter-sampling and the selective-condensation-collecting of SO(3), was applied in SO(3) tests in three full-scale utility boilers. For the two units burning bituminous coal, SO(3) levels starting at 20 to 25 ppmv at the inlet to the selective catalytic reduction (SCR), increased slightly across the SCR, owing to catalytic conversion of SO(2) to SO(3,) and then declined in other air pollutant control device (APCD) modules downstream to approximately 5 ppmv and 15 ppmv at the two sites, respectively. In the unit burning sub-bituminous coal, the much lower initial concentration of SO(3) estimated to be approximately 1.5 ppmv at the inlet to the SCR was reduced to about 0.8 ppmv across the SCR and to about 0.3 ppmv at the exit of the wet flue gas desulfurization (WFGD). The SO(3) removal efficiency across the WFGD scrubbers at the three sites was generally 35% or less. Reductions in SO(3) across either the APH or the dry electrostatic precipitator (ESP) in units burning high-sulfur bituminous coal were attributed to operating temperatures being below the dew point of SO(3).

  14. Effects of freshwater exposure to arsenic trioxide on the parr-smolt transformation of coho salmon (Oncorhynchus kisutch)

    USGS Publications Warehouse

    Nichols, J.W.; Wedemeyer, G.A.; Mayer, F.L.; Dickhoff, Walton W.; Gregory, S.V.; Yasutake, W.T.; Smith, S.D.

    1984-01-01

    The effects of chronic (6 months) exposure to arsenic trioxide in fresh water on the Parr-smolt transformation of coho salmon (Oncorhynchus kisutch) were evaluated. Exposure to 300 μg As/L (as As2O3) appeared to delay the onset of the normal increase in plasma thyroxine concentration and cause a transient reduction of gill Na+,K+-ATPase activity. Fish exposed to 300 μg As/L also migrated to the sea less successfully than did nonexposed smolts, but there were no effects on the survival and growth of smolts held in 28‰ salt water for 6 months.

  15. Signal transduction pathways and transcription factors triggered by arsenic trioxide in leukemia cells

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

    Sumi, Daigo, E-mail: sdaigo@ph.bunri-u.ac.j; Shinkai, Yasuhiro; Kumagai, Yoshito

    2010-05-01

    Arsenic trioxide (As{sub 2}O{sub 3}) is widely used to treat acute promyelocytic leukemia (APL). Several lines of evidence have indicated that As{sub 2}O{sub 3} affects signal transduction and transactivation of transcription factors, resulting in the stimulation of apoptosis in leukemia cells, because some transcription factors are reported to associate with the redox condition of the cells, and arsenicals cause oxidative stress. Thus, the disturbance and activation of the cellular signaling pathway and transcription factors due to reactive oxygen species (ROS) generation during arsenic exposure may explain the ability of As{sub 2}O{sub 3} to induce a complete remission in relapsed APLmore » patients. In this report, we review recent findings on ROS generation and alterations in signal transduction and in transactivation of transcription factors during As{sub 2}O{sub 3} exposure in leukemia cells.« less

  16. Highly Selective Deoxydehydration of Tartaric Acid over Supported and Unsupported Rhenium Catalysts with Modified Acidities.

    PubMed

    Li, Xiukai; Zhang, Yugen

    2016-10-06

    The deoxydehydration (DODH) of sugar acids to industrially important carboxylic acids is a very attractive topic. Oxorhenium complexes are the most-often employed DODH catalysts. Because of the acidity of the rhenium catalysts, the DODH products of sugar acids were usually in the form of mixture of free carboxylic acids and esters. Herein, we demonstrate strategies for the selective DODH of sugar acids to free carboxylic acids by tuning the Lewis acidity or the Brønsted acidity of the rhenium-based catalysts. Starting from tartaric acid, up to 97 % yield of free maleic acid was achieved. Based on our strategies, functional polymer immobilized heterogeneous rhenium catalysts were also developed for the selective DODH conversion of sugar acids. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    USGS Publications Warehouse

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

    1991-01-01

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

  18. 2 x 2 Polyethylene Reflected and Moderated Highly Enriched Uranium System with Rhenium

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

    A. Nichole Ellis; Jesson Hutchinson; John D. Bess

    2010-09-01

    The 2 × 2 array HEU-Re experiment was performed on the Planet universal critical assembly machine on November 4th, 2003 at the Los Alamos Critical Experiments Facility (LACEF) at Los Alamos National Laboratory (LANL). For this experiment, there were 10 ½ units, each full unit containing four HEU foils and two rhenium foils. The top unit contained only two HEU foils and two rhenium foils. A total of 42 HEU foils were used for this experiment. Rhenium is a desirable cladding material for space nuclear power applications. This experiment consisted of HEU foils interleaved with rhenium foils and is moderatedmore » and reflected by polyethylene plates. A unit consisted of a polyethylene plate, which has a recess for rhenium foils, and four HEU foils in a single layer in the top recess of each polyethylene plate. The Planet universal criticality assembly machine has been previously used in experiments containing HEU foils interspersed with SiO2 (HEU-MET-THERM-001), Al (HEU-MET-THERM-008), MgO (HEU-MET-THERM-009), Gd foils (HEU-MET-THERM-010), 2 × 2 × 26 Al (HEU-MET-THERM-012), Fe (HEU-MET-THERM-013 and HEU-MET-THERM-015), 2 × 2 × 23 SiO2 (HEU-MET-THERM-014), 2 × 2 × 11 hastalloy plates (HEU-MET-THERM-016), and concrete (HEU-MET-THERM-018). The 2 × 2 array of HEU-Re is considered acceptable for use as a benchmark critical experiment.« less

  19. Pathogenesis and treatment of leukemia: an Asian perspective.

    PubMed

    Kwong, Yok-Lam

    2012-03-01

    Leukemias occur worldwide, but there are important geographic differences in incidences. Three leukemias with special Asian perspectives, acute promyelocytic leukemia (APL), T-cell large granular lymphocyte (T-LGL) leukemia and NK-cell leukemia. In APL, China has made contributions in discovering the efficacy of all-trans retinoic acid (ATRA) and arsenic trioxide. Some APL patients are potentially curable after treatment with ATRA or arsenic trioxide as a single agent. Combined treatment of APL with ATRA and arsenic trioxide induces remission with deeper molecular response. An oral formulation of arsenic trioxide is available, making outpatient treatment feasible. Future regimens for APL should examine how ATRA and arsenic trioxide can be optimally combined with other synergistic drugs. Asian patients with T-LGL leukemia present more frequently with pure red cell aplasia, but less frequently with neutropenia, recurrent infection, splenomegaly and rheumatoid arthritis as compared with Western patients. These differences have potential effects on treatment and disease pathogenesis. NK-cell leukemia is rapidly fatal and occurs almost exclusively in Asian and South American patients. Conventional anthracycline-based chemotherapy designed for B-cell lymphomas do not work in NK-cell leukemias. Novel therapeutic approaches targeting cellular signaling pathways or preferentially upregulated genes are needed to improve outcome.

  20. Solid-state thermolysis of a fac-rhenium(I) carbonyl complex with a redox non-innocent pincer ligand.

    PubMed

    Jurca, Titel; Chen, Wen-Ching; Michel, Sheila; Korobkov, Ilia; Ong, Tiow-Gan; Richeson, Darrin S

    2013-03-25

    The development of rhenium(I) chemistry has been restricted by the limited structural and electronic variability of the common pseudo-octahedral products fac-[ReX(CO)3L2] (L2 = α-diimine). We address this constraint by first preparing the bidentate bis(imino)pyridine complexes [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)3X] (X = Cl 2, Br 3), which were characterized by spectroscopic and X-ray crystallographic means, and then converting these species into tridentate pincer ligand compounds, [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)2X] (X = Cl 4, Br 5). This transformation was performed in the solid-state by controlled heating of 2 or 3 above 200 °C in a tube furnace under a flow of nitrogen gas, giving excellent yields (≥95 %). Compounds 4 and 5 define a new coordination environment for rhenium(I) carbonyl chemistry where the metal center is supported by a planar, tridentate pincer-coordinated bis(imino)pyridine ligand. The basic photophysical features of these compounds show significant elaboration in both number and intensity of the d-π* transitions observed in the UV/Vis spec tra relative to the bidentate starting materials, and these spectra were analyzed using time-dependent DFT computations. The redox nature of the bis(imino)pyridine ligand in compounds 2 and 4 was examined by electrochemical analysis, which showed two ligand reduction events and demonstrated that the ligand reduction shifts to a more positive potential when going from bidentate 2 to tridentate 4 (+160 mV for the first reduction step and +90 mV for the second). These observations indicate an increase in electrostatic stabilization of the reduced ligand in the tridentate conformation. Elaboration on this synthetic methodology documented its generality through the preparation of the pseudo-octahedral rhenium(I) triflate complex [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)2OTf] (7, 93 % yield). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Omega-3 and omega-6 polyunsaturated fatty acids enhance arsenic trioxide efficacy in arsenic trioxide-resistant leukemic and solid tumor cells.

    PubMed

    Wirtitsch, Melanie; Roth, Erich; Bachleitner-Hofmann, Thomas; Wessner, Barbara; Sturlan, Sanda

    2009-01-01

    Recently we showed that the polyunsaturated fatty acid (PUFA) docosahexaenoic acid (DHA) sensitizes arsenic trioxide (As2O3)-resistant tumor cells to a clinically achievable concentration (1 microM) of As2O3 via a reactive oxygen species (ROS)-dependent mechanism. The aim of the present study was to evaluate, whether this combined effect of As2O3 and DHA is also applicable to other PUFAs [i.e., eicospentaenoic acid (EPA), arachidonic acid (AA), and gamma-linolenic acid (GLA)]. Fourteen tumor cell lines were incubated with As2O3 (1 microM), PUFA (25-100 microM), or the combination thereof (+/- vitamin E). Cell viability (colorimetric), apoptosis (bivariate annexin V/propidium iodide staining, detection of hypodiploid DNA), and thiobarbituric acid reactive substances (TBARS) were evaluated. Twelve of 14 As2O3-resistant cell lines tested were resistant to PUFA monotherapy. However, combined treatment with As2O3 and either PUFA significantly reduced cell viability in a dose-dependent manner with AA being the most potent As2O3 enhancer. The combined cytotoxic effect of As2O3/AA treatment was due to induction of apoptosis, preceded by increased intracellular TBARS and was abolished by the antioxidant vitamin E. Importantly, the combined effect of As2O3 and AA was selectively toxic for malignant cells because no cytotoxic effect was observed in normal skin fibroblasts and human microvascular endothelial cells. In conclusion, our study shows that also other PUFAs than DHA-and in particular the omega-6-PUFA AA--can be used as effective modulators of tumor cell chemosensitivity to clinically achievable concentrations of As2O3. Enhanced lipid peroxidation most likely constitutes the key mechanism for the combined effect.

  2. Rhenium 2-oxoalkyl (enolate) complexes: Synthesis and carbon-carbon bond-forming reactions with nitriles

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

    Stack, J.G.; Doney, J.J.; Bergman, R.G.

    1990-02-01

    The (2-oxoalkyl)rhenium complexes (rhenium enolates) (CO){sub 5}ReCH{sub 2}COR{sup 1} (R{sup 1} = OEt, Me, Ph, 1-3) can be prepared on a multigram scale by alkylation of (CO){sub 5}ReNa with ClCH{sub 2}COR{sup 1}. The secondary enolate (CO){sub 5}ReCH(Me)CO{sub 2}Et (4) can also be prepared in a similar fashion with use of MsOCH(Me)CO{sub 2}Et (Ms = CH{sub 3}SO{sub 2}{sup {minus}}). The mono(phosphine) enolates cis-(Ph{sub 3}P)(CO){sub 4}ReCH{sub 2}R{sup 2}(R{sup 2} = CO{sub 2}Et, CO{sub 2}Bu{sup t}, CONEt{sub 2}, COMe, COPh, CN, 8-13) are prepared in high yield via alkylation of (Ph{sub 3}P)(CO){sub 4}ReNa with ClCH{sub 2}R{sup 2}. Synthesis of the secondary enolate cis-(Ph{submore » 3}P)(CO){sub 4}ReCH(Me)CO{sub 2}Et (14) is accomplished in 75% yield by alkylation with TfOCH(Me)CO{sub 2}Et (Tf = CF{sub 3}SO{sub 2}{sup {minus}}). The chelating phosphine complex is substitutionally inert under forcing thermal and photochemical conditions. Kinetic studies of the nitrile insertion reaction revealed a weak linear dependence of the rate constant of the reaction on the concentration of added CH{sub 3}CN in benzene; we believe this to be a medium effect.« less

  3. Synthesis, characterization and binding affinities of rhenium(I) thiosemicarbazone complexes for the estrogen receptor (α/β).

    PubMed

    Núñez-Montenegro, Ara; Carballo, Rosa; Vázquez-López, Ezequiel M

    2014-11-01

    The binding affinities towards estrogen receptors (ERs) α and β of a set of thiosemicarbazone ligands (HL(n)) and their rhenium(I) carbonyl complexes [ReX(HL(n))(CO)3] (X=Cl, Br) were determined by a competitive standard radiometric assay with [(3)H]-estradiol. The ability of the coordinated thiosemicarbazone ligands to undergo deprotonation and the lability of the ReX bond were used as a synthetic strategy to obtain [Re(hpy)(L(n))(CO)3] (hpy=3- or 4-hydroxypyridine). The inclusion of the additional hpy ligand endows the new thiosemicarbazonate complexes with an improved affinity towards the estrogen receptors and, consequently, the values of the inhibition constant (Ki) could be determined for some of them. In general, the values of Ki for both ER subtypes suggest an appreciable selectivity towards ERα. Copyright © 2014 Elsevier Inc. All rights reserved.

  4. Direct binding of arsenic trioxide to AMPK and generation of inhibitory effects on acute myeloid leukemia precursors

    PubMed Central

    Beauchamp, Elspeth M.; Kosciuczuk, Ewa M.; Serrano, Ruth; Nanavati, Dhaval; Swindell, Elden P.; Viollet, Benoit; O'Halloran, Thomas V.; Altman, Jessica K.; Platanias, Leonidas C.

    2014-01-01

    Arsenic trioxide (As2O3) exhibits potent antineoplastic effects and is used extensively in clinical oncology for the treatment of a subset of patients with acute myeloid leukemia (AML). Although As2O3 is known to regulate activation of several signaling cascades, the key events, accounting for its anti-leukemic properties, remain to be defined. We provide evidence that arsenic can directly bind to cysteine 299 in AMPKα and inhibit its activity. This inhibition of AMPK by arsenic is required in part for its cytotoxic effects on primitive leukemic progenitors from patients with AML, while concomitant treatment with an AMPK activator antagonizes in vivo the arsenic-induced antileukemic effects in a xenograft AML mouse model. A consequence of AMPK inhibition is activation of the mTOR pathway as a negative regulatory feedback loop. However, when AMPK expression is lost, arsenic-dependent activation of the kinase RSK downstream of MAPK activity compensates the generation of regulatory feedback signals through phosphorylation of downstream mTOR targets. Thus, therapeutic regimens with arsenic trioxide will need to include inhibitors of both the mTOR and RSK pathways in combination to prevent engagement of negative feedback loops and maximize antineoplastic responses. PMID:25344585

  5. Superfund Record of Decision (EPA region 8): North Dakota Arsenic Trioxide in Southeastern North Dakota, September 1986. Final report

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

    Not Available

    1986-09-26

    The North Dakota Arsenic Trioxide site consists of twenty townships in Richland, Ransom, and Sargent counties in southeastern North Dakota. Ground water use includes residential consumption, irrigation, and livestock watering. The contamination, limited to ground water, appears to have two sources; naturally occurring arsenic contained in shales native to the area; and an estimated 330,000 pounds of arsenic-laced bait used to control grasshopper infestations in the 1930s and 1940s. The primary contaminant of concern is arsenic trioxide.

  6. Oxide Protective Coats for Ir/Re Rocket Combustion Chambers

    NASA Technical Reports Server (NTRS)

    Fortini, Arthur; Tuffias, Robert H.

    2003-01-01

    An improved material system has been developed for rocket engine combustion chambers for burning oxygen/ hydrogen mixtures or novel monopropellants, which are highly oxidizing at operating temperatures. The baseline for developing the improved material system is a prior iridium/rhenium system for chambers burning nitrogen tetroxide/monomethyl hydrazine mixtures, which are less oxidizing. The baseline combustion chamber comprises an outer layer of rhenium that provides structural support, plus an inner layer of iridium that acts as a barrier to oxidation of the rhenium. In the improved material system, the layer of iridium is thin and is coated with a thermal fatigue-resistant refractory oxide (specifically, hafnium oxide) that serves partly as a thermal barrier to decrease the temperature and thus the rate of oxidation of the rhenium. The oxide layer also acts as a barrier against the transport of oxidizing species to the surface of the iridium. Tests in which various oxygen/hydrogen mixtures were burned in iridium/rhenium combustion chambers lined with hafnium oxide showed that the operational lifetimes of combustion chambers of the improved material system are an order of magnitude greater than those of the baseline combustion chambers.

  7. 40 CFR 421.214 - Standards of performance for new sources.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... leachate. NSPS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant property Maximum....5 to 10.0 at all times. (c) Molybdic oxide leachate. NSPS for the Primary Molybdenum and Rhenium...

  8. 40 CFR 421.214 - Standards of performance for new sources.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... leachate. NSPS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant property Maximum....5 to 10.0 at all times. (c) Molybdic oxide leachate. NSPS for the Primary Molybdenum and Rhenium...

  9. 40 CFR 421.214 - Standards of performance for new sources.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... leachate. NSPS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant property Maximum....5 to 10.0 at all times. (c) Molybdic oxide leachate. NSPS for the Primary Molybdenum and Rhenium...

  10. 40 CFR 421.214 - Standards of performance for new sources.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... leachate. NSPS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant property Maximum....5 to 10.0 at all times. (c) Molybdic oxide leachate. NSPS for the Primary Molybdenum and Rhenium...

  11. 40 CFR 421.214 - Standards of performance for new sources.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... leachate. NSPS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant property Maximum....5 to 10.0 at all times. (c) Molybdic oxide leachate. NSPS for the Primary Molybdenum and Rhenium...

  12. Photocatalytic Conversion of CO2 to CO using Rhenium Bipyridine Platforms Containing Ancillary Phenyl or BODIPY Moieties

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

    Andrade, Gabriel; Pistner, Allen; Yapp, Glenn P. A.

    2013-01-01

    Harnessing of solar energy to drive the reduction of carbon dioxide to fuels requires the development of efficient catalysts that absorb sunlight. In this work, we detail the synthesis, electrochemistry and photophysical properties of a set of homologous fac-ReI(CO)3 complexes containing either an ancillary phenyl (8) or BODIPY (12) substituent. These studies demonstrate that both the electronic properties of the rhenium center and BODIPY chromophore are maintained for these systems. Photolysis studies demonstrate that both assemblies 8 and 12 are competent catalysts for the photochemical reduction of CO2 to CO in DMF using triethanolamine (TEOA) as a sacrificial reductant. Bothmore » these systems display TOFs for photocatalytic CO production upon irradiation with light ( ex 400 nm) of ~5 hr 1 with TON values of approximately 20. Although structural and photophysical measurements demonstrate that electronic coupling between the BODIPY and fac-ReI(CO)3 units is limited for complex 12, this work clearly shows that the photoactive BODIPY moiety is tolerated during catalysis and does not interfere with the observed photochemistry. When taken together, these results provide a clear roadmap for the development of advanced rhenium bipyridine complexes bearing ancillary BODIPY groups for the efficient photocatalytic reduction of CO2 using visible light.« less

  13. Antimony trioxide

    Integrated Risk Information System (IRIS)

    Antimony trioxide ; CASRN 1309 - 64 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogeni

  14. Mechanistic insights into the rhenium-catalyzed alcohol-to-olefin dehydration reaction.

    PubMed

    Korstanje, Ties J; Jastrzebski, Johann T B H; Klein Gebbink, Robertus J M

    2013-09-23

    Rhenium-based complexes are powerful catalysts for the dehydration of various alcohols to the corresponding olefins. Here, we report on both experimental and theoretical (DFT) studies into the mechanism of the rhenium-catalyzed dehydration of alcohols to olefins in general, and the methyltrioxorhenium-catalyzed dehydration of 1-phenylethanol to styrene in particular. The experimental and theoretical studies are in good agreement, both showing the involvement of several proton transfers, and of a carbenium ion intermediate in the catalytic cycle. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Bone marrow necrosis in a patient with acute promyelocytic leukemia during re-induction therapy with arsenic trioxide.

    PubMed

    Ishitsuka, Kenji; Shirahashi, Akihiko; Iwao, Yasuhiro; Shishime, Mikiko; Takamatsu, Yasushi; Takatsuka, Yoshifusa; Utsunomiya, Atae; Suzumiya, Junji; Hara, Syuji; Tamura, Kazuo

    2004-04-01

    Arsenic trioxide (As2O3) therapy at a daily dose of 0.15 mg/kg was given to a 60-yr-old Japanese male with refractory acute promyelocytic leukemia. White blood cell (WBC) of 6.6 x 10(3)/microl increased to 134 x 10(3)/microl following the administration of As2O3. Daily hydroxyurea (HU), and 6-mercaptopurine (6-MP) were added on days 7 and 19, respectively. Both HU and 6-MP were discontinued on day 28, when WBC declined to 54.0 x 10(3)/microl. He developed unexplained fever and profound cytopenia requiring multiple blood products transfusions. Bone marrow examination on day 42 revealed massive necrosis. Pharmacokinetics confirmed a mean maximum plasma arsenic concentration (Cpmax) and a half-life time (t1/2) of 6.9 microm and 3.2 h, respectively, in the therapeutic range. This is the first case of bone marrow necrosis after standard-dose As2O3 therapy.

  16. Arsenic Trioxide – An Old Drug Rediscovered

    PubMed Central

    Emadi, Ashkan; Gore, Steven D.

    2010-01-01

    Over the last 17 years, clinical trials conducted worldwide have demonstrated the efficacy of arsenic trioxide (As2O3) in the treatment of relapsed acute promyelocytic leukemia (APL). Currently, the role of As2O3 in front-line therapy is under investigation. Recent trials in the US have demonstrated that the addition of As2O3 to standard treatment regimens improves survival outcomes in patients with APL and may allow a reduction in cytotoxic chemotherapy exposure. As2O3 has also shown efficacy in other malignancies, particularly multiple myeloma and myelodysplastic syndromes. Therapeutic doses of As2O3 are well tolerated, with no evidence of long-term toxicity. Adverse events include APL differentiation syndrome, electrocardiographic abnormalities, and mild elevations in liver enzymes. This review highlights trials investigating the role of As2O3 in induction and consolidation for newly diagnosed APL, as well as its role in other hematologic malignancies. The chemistry, mechanisms of action, and clinical side effects of As2O3 are also discussed. PMID:20471733

  17. Synthesis, structural characterization and photoluminescence properties of rhenium(I) complexes based on bipyridine derivatives with carbazole moieties.

    PubMed

    Li, Hong-Yan; Wu, Jing; Zhou, Xin-Hui; Kang, Ling-Chen; Li, Dong-Ping; Sui, Yan; Zhou, Yong-Hui; Zheng, You-Xuan; Zuo, Jing-Lin; You, Xiao-Zeng

    2009-12-21

    Three N,N-bidentate ligands, 5,5'-dibromo-2,2-bipyridine (L1) and two carbazole containing ligands of 5-bromo-5'-carbazolyl-2,2-bipyridine (L2), 5,5'-dicarbazolyl-2,2'-bipyridine (L3), and their corresponding rhenium Re(CO)3Cl(L) complexes (ReL1-ReL3) have been successfully synthesized and characterized by elemental analysis, 1H NMR and IR spectra. Their photophysical properties and thermal analysis, along with the X-ray crystal structure analysis of L3 and complexes ReL1 and ReL3 are also described. In CH2Cl2 solution at room temperature, all complexes display intense absorption bands at ca. 220-350 nm, which can be assigned to spin-allowed intraligand (pi-->pi*) transitions, and the low energy broad bands in the 360-480 nm region are attributed to the metal to ligand charge-transfer d(Re)-->pi* (diimine) (MLCT). The introduction of carbazole moieties improves the MLCT absorption and molar extinction coefficient of these complexes. Upon excitation at the peak maxima, all complexes show strong emissions around 620 nm, which are assigned to d(Re)-->pi* (diimine) MLCT phosphorescence. The photoluminescence lifetime decay of Re(I) complexes were measured and the quantum efficiencies of the rhenium(I) complexes were calculated by using air-equilibrated [Ru(bpy)3]2+ x 2 Cl- aqueous solution as standard (phi(std) = 0.028). The complexes with appended carbazole moieties exhibit enhanced luminescence performances relative to ReL1.

  18. Rhenium(I)-based Double-heterostranded Helicates.

    PubMed

    Saxena, Priya; Shankar, Bhaskaran; Sathyanarayana, Arruri; Prabusankar, Ganesan; Sathiyendiran, Malaichamy

    2015-01-01

    Rhenium(I)-based supramolecular coordination complexes were obtained using Re2(CO)10, (2-hydroxyphenyl)benzimidazole-derived bis-chelating N∩O donors and a benzimidazolyl-derived ditopic monodentate N-donor possessing Troger's base spacer in a one-pot approach.

  19. 188Re(V) Nitrido Radiopharmaceuticals for Radionuclide Therapy

    PubMed Central

    Boschi, Alessandra; Martini, Petra; Uccelli, Licia

    2017-01-01

    The favorable nuclear properties of rhenium-188 for therapeutic application are described, together with new methods for the preparation of high yield and stable 188Re radiopharmaceuticals characterized by the presence of the nitride rhenium core in their final chemical structure. 188Re is readily available from an 188W/188Re generator system and a parallelism between the general synthetic procedures applied for the preparation of nitride technetium-99m and rhenium-188 theranostics radiopharmaceuticals is reported. Although some differences between the chemical characteristics of the two metallic nitrido fragments are highlighted, it is apparent that the same general procedures developed for the labelling of biologically active molecules with technetium-99m can be applied to rhenium-188 with minor modification. The availability of these chemical strategies, that allow the obtainment, in very high yield and in physiological condition, of 188Re radiopharmaceuticals, gives a new attractive prospective to employ this radionuclide for therapeutic applications. PMID:28106830

  20. 188Re(V) Nitrido Radiopharmaceuticals for Radionuclide Therapy.

    PubMed

    Boschi, Alessandra; Martini, Petra; Uccelli, Licia

    2017-01-19

    The favorable nuclear properties of rhenium-188 for therapeutic application are described, together with new methods for the preparation of high yield and stable 188 Re radiopharmaceuticals characterized by the presence of the nitride rhenium core in their final chemical structure. 188 Re is readily available from an 188 W/ 188 Re generator system and a parallelism between the general synthetic procedures applied for the preparation of nitride technetium-99m and rhenium-188 theranostics radiopharmaceuticals is reported. Although some differences between the chemical characteristics of the two metallic nitrido fragments are highlighted, it is apparent that the same general procedures developed for the labelling of biologically active molecules with technetium-99m can be applied to rhenium-188 with minor modification. The availability of these chemical strategies, that allow the obtainment, in very high yield and in physiological condition, of 188 Re radiopharmaceuticals, gives a new attractive prospective to employ this radionuclide for therapeutic applications.

  1. Monoclonal Antibodies Radiolabeling with Rhenium-188 for Radioimmunotherapy

    PubMed Central

    Martini, Petra; Pasquali, Micol

    2017-01-01

    Rhenium-188, obtained from an alumina-based tungsten-188/rhenium-188 generator, is actually considered a useful candidate for labeling biomolecules such as antibodies, antibody fragments, peptides, and DNAs for radiotherapy. There is a widespread interest in the availability of labeling procedures that allow obtaining 188Re-labeled radiopharmaceuticals for various therapeutic applications, in particular for the rhenium attachment to tumor-specific monoclonal antibodies (Mo)Abs for immunotherapy. Different approaches have been developed in order to obtain 188Re-radioimmunoconjugates in high radiochemical purity starting from the generator eluted [188Re]ReO4−. The aim of this paper is to provide a short overview on 188Re-labeled (Mo)Abs, focusing in particular on the radiolabeling methods, quality control of radioimmunoconjugates, and their in vitro stability for radioimmunotherapy (RIT), with particular reference to the most important contributions published in literature in this topic. PMID:28951872

  2. Monoclonal Antibodies Radiolabeling with Rhenium-188 for Radioimmunotherapy.

    PubMed

    Uccelli, Licia; Martini, Petra; Pasquali, Micol; Boschi, Alessandra

    2017-01-01

    Rhenium-188, obtained from an alumina-based tungsten-188/rhenium-188 generator, is actually considered a useful candidate for labeling biomolecules such as antibodies, antibody fragments, peptides, and DNAs for radiotherapy. There is a widespread interest in the availability of labeling procedures that allow obtaining 188 Re-labeled radiopharmaceuticals for various therapeutic applications, in particular for the rhenium attachment to tumor-specific monoclonal antibodies (Mo)Abs for immunotherapy. Different approaches have been developed in order to obtain 188 Re-radioimmunoconjugates in high radiochemical purity starting from the generator eluted [ 188 Re]ReO 4 - . The aim of this paper is to provide a short overview on 188 Re-labeled (Mo)Abs, focusing in particular on the radiolabeling methods, quality control of radioimmunoconjugates, and their in vitro stability for radioimmunotherapy (RIT), with particular reference to the most important contributions published in literature in this topic.

  3. Mechanism of S100b release from rat cortical slices determined under basal and stimulated conditions.

    PubMed

    Gürsoy, Murat; Büyükuysal, R Levent

    2010-03-01

    Incubation of rat cortical slices in a medium that was not containing oxygen and glucose (oxygen-glucose deprivation, OGD) caused a 200% increase in the release of S100B. However, when slices were transferred to a medium containing oxygen and glucose (reoxygenation conditions, or REO), S100B release reached 500% of its control value. Neither inhibition of nitric oxide (NO) synthase by L-NAME nor addition of the NO donors sodium nitroprussid (SNP) or hydroxylamine (HA) to the medium altered basal S100B release. Similarly, the presence of SNP, HA or NO precursor L: -arginine in the medium, or inhibition of NO synthase by L-NAME also failed to alter OGD- and REO-induced S100B outputs. Moreover, individual inhibition of PKC, PLA(2) or PLC all failed to attenuate the S100B release determined under control condition or enhanced by either OGD or REO. Blockade of calcium channels with verapamil, chelating the Ca(+2) ions with BAPTA or blockade of sodium channels with tetrodotoxin (TTX) did not alter OGD- and REO-induced S100B release. In contrast to the pharmacologic manipulations mentioned above, glutamate and alpha-ketoglutarate added at high concentrations to the medium prevented both OGD- and REO-induced S100B outputs. These results indicate that neither NO nor the activation of PKC, PLA(2) or PLC seem to be involved in basal or OGD- and REO-induced S100B outputs. Additionally, calcium and sodium currents that are sensitive to verapamil and TTX, respectively, are unlikely to contribute to the enhanced S100B release observed under these conditions.

  4. Antimony Trioxide (ATO) - Summary of External Peer Review and Public Comments and Disposition

    EPA Pesticide Factsheets

    This document summarizes the public and external peer review comments that the EPA’s Office of Pollution Prevention and Toxics (OPPT) received for the draft work plan risk assessment for Antimony Trioxide (ATO).

  5. Tungstorhenate Heteropolyanions. 2. Synthesis and Characterization of Enneatungstorhenates(V), -(VI), and -(VII)

    USGS Publications Warehouse

    Ortega, F.; Pope, M.T.; Evans, H.T.

    1997-01-01

    The tungstorhenate(V) heteropolyanion [W9ReO32]5- has been isolated as guanidinium and cesium salts from reaction of [ReO2(PPh3)(py)3]+ with sodium tungstate. Crystallographic analysis of black Cs5[W9ReO32]??3H2O [triclinic, P1 or P1?? = 10.194(1), b = 11.503(2), c = 9.682(1) A??; a = 100.55(1), ??= 115.81(1), y = 99.13(1)??; Z = 1], based on 3743 reflections, shows the anion to be isostructural with decatungstate, [W10O32]4-. Refinement in P1 led to reliability indices R = 0.084, Rw = 0.046. Electrochemical investigation revealed the existence of ReVI and ReVII analogues, which were hydrolytically unstable in aqueous solution but which were isolated as crystalline tetra-n-butylammonium and tetra-n-heptylammonium salts, respectively, from nonaqueous solvents. The tetra-n-butylammonium salts of [W9ReVIO32]4- and [W10O32]4- were shown to be isomorphous by X-ray powder diffraction. Simulation of the Q-band ESR spectrum of [W9ReVIO32]4- (polycrystalline solid solution in [W10O32]4-) gave gx = 1.69(1), gy = 1.66(1), gz = 1.730(2) and 104Ax(185,187Re, I = 5/2) = (-)252(10), 104Ay = (-)398(10), 104Az = (-)653(5) cm-1. The orthorhombic ESR spectrum proves that the Re atom occupies one of the eight equivalent "equatorial" sites in the decatungstate structure.

  6. 21 CFR 184.1095 - Sulfuric acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... CONSUMPTION (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of Specific... (SO2) with oxygen and mixing the resultant sulfur trioxide (SO3) with water, or by reacting nitric...

  7. 21 CFR 184.1095 - Sulfuric acid.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... CONSUMPTION (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of Specific... (SO2) with oxygen and mixing the resultant sulfur trioxide (SO3) with water, or by reacting nitric...

  8. Submersion criticality safety of tungsten-rhenium urania cermet fuel for space propulsion and power applications

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

    A.E. Craft; R. C. O'Brien; S. D. Howe

    Nuclear thermal rockets are the preferred propulsion technology for a manned mission to Mars, and tungsten–uranium oxide cermet fuels could provide significant performance and cost advantages for nuclear thermal rockets. A nuclear reactor intended for use in space must remain subcritical before and during launch, and must remain subcritical in launch abort scenarios where the reactor falls back to Earth and becomes submerged in terrestrial materials (including seawater, wet sand, or dry sand). Submersion increases reflection of neutrons and also thermalizes the neutron spectrum, which typically increases the reactivity of the core. This effect is typically very significant for compact,more » fast-spectrum reactors. This paper provides a submersion criticality safety analysis for a representative tungsten/uranium oxide fueled reactor with a range of fuel compositions. Each submersion case considers both the rhenium content in the matrix alloy and the uranium oxide volume fraction in the cermet. The inclusion of rhenium significantly improves the submersion criticality safety of the reactor. While increased uranium oxide content increases the reactivity of the core, it does not significantly affect the submersion behavior of the reactor. There is no significant difference in submersion behavior between reactors with rhenium distributed within the cermet matrix and reactors with a rhenium clad in the coolant channels. The combination of the flooding of the coolant channels in submersion scenarios and the presence of a significant amount of spectral shift absorbers (i.e. high rhenium concentration) further decreases reactivity for short reactor cores compared to longer cores.« less

  9. CoMSIA and Docking Study of Rhenium Based Estrogen Receptor Ligand Analogs

    PubMed Central

    Wolohan, Peter; Reichert, David E.

    2007-01-01

    OPLS all atom force field parameters were developed in order to model a diverse set of novel rhenium based estrogen receptor ligands whose relative binding affinities (RBA) to the estrogen receptor alpha isoform (ERα) with respect to 17β-Estradiol were available. The binding properties of these novel rhenium based organometallic complexes were studied with a combination of Comparative Molecular Similarity Indices Analysis (CoMSIA) and docking. A total of 29 estrogen receptor ligands consisting of 11 rhenium complexes and 18 organic ligands were docked inside the ligand-binding domain (LBD) of ERα utilizing the program Gold. The top ranked pose was used to construct CoMSIA models from a training set of 22 of the estrogen receptor ligands which were selected at random. In addition scoring functions from the docking runs and the polar volume (PV) were also studied to investigate their ability to predict RBA ERα. A partial least-squares analysis consisting of the CoMSIA steric, electrostatic and hydrophobic indices together with the polar volume proved sufficiently predictive having a correlation coefficient, r2, of 0.94 and a cross-validated correlation coefficient, q2, utilizing the leave one out method of 0.68. Analysis of the scoring functions from Gold showed particularly poor correlation to RBA ERα which did not improve when the rhenium complexes were extracted to leave the organic ligands. The combined CoMSIA and polar volume model ranked correctly the ligands in order of increasing RBA ERα, illustrating the utility of this method as a prescreening tool in the development of novel rhenium based estrogen receptor ligands. PMID:17280694

  10. A polyhedron-based metal-organic framework with a reo-e net.

    PubMed

    Ren, Guojian; Liu, Shuxia; Wei, Feng; Ma, Fengji; Tang, Qun; Li, Shujun

    2012-10-14

    A polyhedron-based metal-organic framework has been designed and constructed with a reo-e net, which is constructed from trinuclear nickel clusters and mixed ligands (copolymerization pattern). It comprises three kinds of polyhedra, which are the hexahedron, cuboctahedron and rhombicuboctahedron.

  11. Enhancement of efficiencies for tandem green phosphorescent organic light-emitting devices with a p-type charge generation layer

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

    Yoo, Byung Soo; Jeon, Young Pyo; Lee, Dae Uk

    2014-10-15

    The operating voltage of the tandem green phosphorescent organic light-emitting device with a 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile layer was improved by 3% over that of the organic light-emitting device with a molybdenum trioxide layer. The maximum brightness of the tandem green phosphorescent organic light-emitting device at 21.9 V was 26,540 cd/m{sup 2}. The dominant peak of the electroluminescence spectra for the devices was related to the fac-tris(2-phenylpyridine) iridium emission. - Highlights: • Tandem OLEDs with CGL were fabricated to enhance their efficiency. • The operating voltage of the tandem OLED with a HAT-CN layer was improved by 3%. • The efficiency and brightnessmore » of the tandem OLED were 13.9 cd/A and 26,540 cd/m{sup 2}. • Efficiency of the OLED with a HAT-CN layer was lower than that with a MoO{sub 3} layer. - Abstract: Tandem green phosphorescent organic light-emitting devices with a 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile or a molybdenum trioxide charge generation layer were fabricated to enhance their efficiency. Current density–voltage curves showed that the operating voltage of the tandem green phosphorescent organic light-emitting device with a 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile layer was improved by 3% over that of the corresponding organic light-emitting device with a molybdenum trioxide layer. The efficiency and the brightness of the tandem green phosphorescent organic light-emitting device were 13.9 cd/A and 26,540 cd/m{sup 2}, respectively. The current efficiency of the tandem green phosphorescent organic light-emitting device with a 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile layer was lower by 1.1 times compared to that of the corresponding organic light-emitting device with molybdenum trioxide layer due to the decreased charge generation and transport in the 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile layer resulting from triplet–triplet exciton annihilation.« less

  12. Assuring Essential Industrial Base Requirements for Strategic & Critical Materials

    DTIC Science & Technology

    2012-05-23

    pilot project to reclaim rhenium containing super alloys from jet engines • Viewed as a method to offset substantial reliance on foreign sources of...be candidates for National Defense Stockpile inventory Rhenium Upgrade 13 WARFIGHTER SUPPORT ENHANCEMENT STEWARDSHIP

  13. Photoactivated in Vitro Anticancer Activity of Rhenium(I) Tricarbonyl Complexes Bearing Water-Soluble Phosphines.

    PubMed

    Marker, Sierra C; MacMillan, Samantha N; Zipfel, Warren R; Li, Zhi; Ford, Peter C; Wilson, Justin J

    2018-02-05

    Fifteen water-soluble rhenium compounds of the general formula [Re(CO) 3 (NN)(PR 3 )] + , where NN is a diimine ligand and PR 3 is 1,3,5-triaza-7-phosphaadamantane (PTA), tris(hydroxymethyl)phosphine (THP), or 1,4-diacetyl-1,3,7-triaza-5-phosphabicylco[3.3.1]nonane (DAPTA), were synthesized and characterized by multinuclear NMR spectroscopy, IR spectroscopy, and X-ray crystallography. The complexes bearing the THP and DAPTA ligands exhibit triplet-based luminescence in air-equilibrated aqueous solutions with quantum yields ranging from 3.4 to 11.5%. Furthermore, the THP and DAPTA complexes undergo photosubstitution of a CO ligand upon irradiation with 365 nm light with quantum yields ranging from 1.1 to 5.5% and sensitize the formation of 1 O 2 with quantum yields as high as 70%. In contrast, all of the complexes bearing the PTA ligand are nonemissive and do not undergo photosubstitution upon irradiation with 365 nm light. These compounds were evaluated as photoactivated anticancer agents in human cervical (HeLa), ovarian (A2780), and cisplatin-resistant ovarian (A2780CP70) cancer cell lines. All of the complexes bearing THP and DAPTA exhibited a cytotoxic response upon irradiation with minimal toxicity in the absence of light. Notably, the complex with DAPTA and 1,10-phenanthroline gave rise to an IC 50 value of 6 μM in HeLa cells upon irradiation, rendering it the most phototoxic compound in this library. The nature of the photoinduced cytotoxicity of this compound was explored in further detail. These data indicate that the phototoxic response may result from the release of both CO and the rhenium-containing photoproduct, as well as the production of 1 O 2 .

  14. The synthesis and toxicity of tripodal tricarbonyl rhenium complexes as radiopharmaceutical models

    PubMed Central

    Robenstine, Sarah; Barone, Natalie V.; Underwood, Adam C.; Milsted, Amy; Franklin, Brenton R.; Herrick, Richard S.; Ziegler, Christopher J.

    2012-01-01

    We report the synthesis and toxicity of a series of rhenium(I) tricarbonyl complexes incorporating the trisaminomethylethane (TAME) ligand. Compounds with the (TAME)Re(CO)3+ cation were synthesized via several routes, including by use of Re(CO)5X precursors as well as the aqueous cation Re(CO)3(H2O)3+. Salts of the formula [(TAME)Re(CO)3]X where X = Br−, Cl−, NO3−, PF6− and ClO4− were evaluated using two cell lines: the monoclonal S3 HeLa line and a vascular smooth muscle cell line harvested from mice. All compounds have isostructural cations and differ only in the identity of the non-coordinating anion. None of the complexes exhibited any appreciable toxicity in the HeLa line up to the solubility limit. In the vascular smooth muscle cell line, the bromide salt exhibited some cytotoxicity, but this observation most likely results from the presence of bromide anion, which has been shown to have limited toxicity. PMID:20362340

  15. Toxicological Profiling of Metal Oxide Nanoparticles in Liver Context Reveals Pyroptosis in Kupffer Cells and Macrophages versus Apoptosis in Hepatocytes.

    PubMed

    Mirshafiee, Vahid; Sun, Bingbing; Chang, Chong Hyun; Liao, Yu-Pei; Jiang, Wen; Jiang, Jinhong; Liu, Xiangsheng; Wang, Xiang; Xia, Tian; Nel, André E

    2018-04-24

    The liver and the mononuclear phagocyte system are a frequent target for engineered nanomaterials, either as a result of particle uptake and spread from primary exposure sites or systemic administration of therapeutic and imaging nanoparticles. In this study, we performed a comparative analysis of the toxicological impact of 29 metal oxide nanoparticles (NPs), some commonly used in consumer products, in transformed or primary Kupffer cells (KCs) and hepatocytes. We not only observed differences between KCs and hepatocytes, but also differences in the toxicological profiles of transition-metal oxides (TMOs, e. g., Co 3 O 4 ) versus rare-earth oxide (REO) NPs ( e. g., Gd 2 O 3 ). While pro-oxidative TMOs induced the activation of caspases 3 and 7, resulting in apoptotic cell death in both cell types, REOs induced lysosomal damage, NLRP3 inflammasome activation, caspase 1 activation, and pyroptosis in KCs. Pyroptosis was accompanied by cell swelling, membrane blebbing, IL-1β release, and increased membrane permeability, which could be reversed by knockdown of the pore forming protein, gasdermin D. Though similar features were not seen in hepatocytes, the investigation of the cytotoxic effects of REO NPs could also be seen to affect macrophage cell lines such as J774A.1 and RAW 264.7 cells as well as bone marrow-derived macrophages. These phagocytic cell types also demonstrated features of pyroptosis and increased IL-1β production. Collectively, these findings demonstrate important mechanistic considerations that can be used for safety evaluation of metal oxides, including commercial products that are developed from these materials.

  16. Polymer-pyrolysis assisted synthesis of vanadium trioxide and carbon nanocomposites as high performance anode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Dong, Yucheng; Ma, Ruguang; Hu, Mingjun; Cheng, Hua; Lee, Jong-Min; Li, Yang Yang; Zapien, Juan Antonio

    2014-09-01

    We present a simple polymer-pyrolysis assisted method to prepare vanadium trioxide and carbon nanocomposites as an advanced anode material for lithium-ion batteries. The as-prepared material deliver a superior battery performance with highly retained capacity of ∼780 mAh g-1 over 100 cycles at a current density of 200 mA g-1, showing excellent cyclic stability, and good rate capability. The improved electrochemical performance of vanadium trioxide and carbon nanocomposites electrode makes it promising as a suitable anode material for practical battery applications.

  17. Acute promyelocytic leukaemia: novel insights into the mechanisms of cure.

    PubMed

    de Thé, Hugues; Chen, Zhu

    2010-11-01

    The fusion oncogene, promyelocytic leukaemia (PML)-retinoic acid receptor-α (RARA), initiates acute promyelocytic leukaemia (APL) through both a block to differentiation and increased self-renewal of leukaemic progenitor cells. The current standard of care is retinoic acid (RA) and chemotherapy, but arsenic trioxide also cures many patients with APL, and an RA plus arsenic trioxide combination cures most patients. This Review discusses the recent evidence that reveals surprising new insights into how RA and arsenic trioxide cure this leukaemia, by targeting PML-RARα for degradation. Drug-triggered oncoprotein degradation may be a strategy that is applicable to many cancers.

  18. Re-Os systematics of komatiites and komatiitic basalts at Dundonald Beach, Ontario, Canada: Evidence for a complex alteration history and implications of a late-Archean chondritic mantle source

    NASA Astrophysics Data System (ADS)

    Gangopadhyay, Amitava; Sproule, Rebecca A.; Walker, Richard J.; Lesher, C. Michael

    2005-11-01

    Osmium isotopic compositions, and Re and Os concentrations have been examined in one komatiite unit and two komatiitic basalt units at Dundonald Beach, part of the 2.7 Ga Kidd-Munro volcanic assemblage in the Abitibi greenstone belt, Ontario, Canada. The komatiitic rocks in this locality record at least three episodes of alteration of Re-Os elemental and isotope systematics. First, an average of 40% and as much as 75% Re may have been lost due to shallow degassing during eruption and/or hydrothermal leaching during or immediately after emplacement. Second, the Re-Os isotope systematics of whole rock samples with 187Re/ 188Os ratios >1 were reset at ˜2.5 Ga, possibly due to a regional metamorphic event. Third, there is evidence for relatively recent gain and loss of Re in some rocks. Despite the open-system behavior, some aspects of the Re-Os systematics of these rocks can be deciphered. The bulk distribution coefficient for Os (D Ossolid/liquid) for the Dundonald rocks is ˜3 ± 1 and is well within the estimated D values obtained for komatiites from the nearby Alexo area and stratigraphically-equivalent komatiites from Munro Township. This suggests that Os was moderately compatible during crystal-liquid fractionation of the magmas parental to the Kidd-Munro komatiitic rocks. Whole-rock samples and chromite separates with low 187Re/ 188Os ratios (<1) yield a precise chondritic average initial 187Os/ 188Os ratio of 0.1083 ± 0.0006 (γ Os = 0.0 ± 0.6) for their well-constrained ˜2715 Ma crystallization age. The chondritic initial Os isotopic composition of the mantle source for the Dundonald rocks is consistent with that determined for komatiites in the Alexo area and in Munro Township, suggesting that the mantle source region for the Kidd-Munro volcanic assemblage had evolved with a long-term chondritic Re/Os before eruption. The chondritic initial Os isotopic composition of the Kidd-Munro komatiites is indistinguishable from that of the projected contemporaneous convective upper mantle. The uniform chondritic Os isotopic composition of the Kidd-Munro komatiites contrasts with the typical large-scale Os isotopic heterogeneity in the mantle sources for ca. 89 Ma komatiites from the Gorgona Island, arc-related rocks and present-day ocean island basalts. This suggests that the Kidd-Munro komatiites sampled a late-Archean mantle source region that was significantly more homogeneous with respect to Re/Os relative to most modern mantle-derived rocks.

  19. 24 CFR 291.200 - Future REO acquisition method.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...), which shall provide for the right and obligation of the transferor(s) to acquire a future quantity of... Development (Continued) OFFICE OF ASSISTANT SECRETARY FOR HOUSING-FEDERAL HOUSING COMMISSIONER, DEPARTMENT OF... Sales Procedures § 291.200 Future REO acquisition method. (a) Under this method of property disposition...

  20. 24 CFR 291.200 - Future REO acquisition method.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...), which shall provide for the right and obligation of the transferor(s) to acquire a future quantity of... Development (Continued) OFFICE OF ASSISTANT SECRETARY FOR HOUSING-FEDERAL HOUSING COMMISSIONER, DEPARTMENT OF... Sales Procedures § 291.200 Future REO acquisition method. (a) Under this method of property disposition...

  1. 24 CFR 291.200 - Future REO acquisition method.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...), which shall provide for the right and obligation of the transferor(s) to acquire a future quantity of... Development (Continued) OFFICE OF ASSISTANT SECRETARY FOR HOUSING-FEDERAL HOUSING COMMISSIONER, DEPARTMENT OF... Sales Procedures § 291.200 Future REO acquisition method. (a) Under this method of property disposition...

  2. Novel paint design based on nanopowder to protection against X and gamma rays

    PubMed Central

    Movahedi, Mohammad Mehdi; Abdi, Adibe; Mehdizadeh, Alireza; Dehghan, Naser; Heidari, Emad; Masumi, Yusef; Abbaszadeh, Mojtaba

    2014-01-01

    Background: Lead-based shields are the standard method of intraoperative radiation protection in the radiology and nuclear medicine department. Human lead toxicity is well documented. The lead used is heavy, lacks durability, is difficult to launder, and its disposal is associated with environmental hazards. The aim of this study was to design a lead free paint for protection against X and gamma rays. Materials and Methods: In this pilot st we evaluated several types of nano metal powder that seemed to have good absorption. The Monte Carlo code, MCNP4C, was used to model the attenuation of X-ray photons in paints with different designs. Experimental measurements were carried out to assess the attenuation properties of each paint design. Results: Among the different nano metal powder, nano tungsten trioxide and nano tin dioxide were the two most appropriate candidates for making paint in diagnostic photon energy range. Nano tungsten trioxide (15%) and nano tin dioxide (85%) provided the best protection in both simulation and experiments. After this step, attempts were made to produce appropriate nano tungsten trioxide-nano tin dioxide paints. The density of this nano tungsten trioxide-nano tin dioxide paint was 4.2 g/cm3. The MCNP simulation and experimental measurements for HVL (Half-Value Layer) values of this shield at 100 kVp were 0.25 and 0.23 mm, respectively. Conclusions: The results showed the cost-effective lead-free paint can be a great power in absorbing the X-rays and gamma rays and it can be used instead of lead. PMID:24591777

  3. Tungsten-rhenium thin film thermocouples for SiC-based ceramic matrix composites

    NASA Astrophysics Data System (ADS)

    Tian, Bian; Zhang, Zhongkai; Shi, Peng; Zheng, Chen; Yu, Qiuyue; Jing, Weixuan; Jiang, Zhuangde

    2017-01-01

    A tungsten-rhenium thin film thermocouple is designed and fabricated, depending on the principle of thermal-electric effect caused by the high temperature. The characteristics of thin film thermocouples in different temperatures are investigated via numerical analysis and analog simulation. The working mechanism and thermo-electric features of the thermocouples are analyzed depending on the simulation results. Then the thin film thermocouples are fabricated and calibrated. The calibration results show that the thin film thermocouples based on the tungsten-rhenium material achieve ideal static characteristics and work well in the practical applications.

  4. Transient episodes of mild environmental oxygenation and oxidative continental weathering during the late Archean

    PubMed Central

    Kendall, Brian; Creaser, Robert A.; Reinhard, Christopher T.; Lyons, Timothy W.; Anbar, Ariel D.

    2015-01-01

    It is not known whether environmental O2 levels increased in a linear fashion or fluctuated dynamically between the evolution of oxygenic photosynthesis and the later Great Oxidation Event. New rhenium-osmium isotope data from the late Archean Mount McRae Shale, Western Australia, reveal a transient episode of oxidative continental weathering more than 50 million years before the onset of the Great Oxidation Event. A depositional age of 2495 ± 14 million years and an initial 187Os/188Os of 0.34 ± 0.19 were obtained for rhenium- and molybdenum-rich black shales. The initial 187Os/188Os is higher than the mantle/extraterrestrial value of 0.11, pointing to mild environmental oxygenation and oxidative mobilization of rhenium, molybdenum, and radiogenic osmium from the upper continental crust and to contemporaneous transport of these metals to seawater. By contrast, stratigraphically overlying black shales are rhenium- and molybdenum-poor and have a mantle-like initial 187Os/188Os of 0.06 ± 0.09, indicating a reduced continental flux of rhenium, molybdenum, and osmium to seawater because of a drop in environmental O2 levels. Transient oxygenation events, like the one captured by the Mount McRae Shale, probably separated intervals of less oxygenated conditions during the late Archean. PMID:26702438

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

    PubMed

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

    2012-11-20

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

  6. Re-Os Geochronology Pins Age and Os Isotope Composition of Middle Triassic Black Shales and Seawater, Barents Sea and Spitsbergen (Svalbard)

    NASA Astrophysics Data System (ADS)

    Xu, G.; Hannah, J. L.; Bingen, B.; Stein, H. J.; Yang, G.; Zimmerman, A.; Weitschat, W.; Weiss, H. M.

    2008-12-01

    Absolute age control throughout the Triassic is extraordinarily sparse. Two "golden spikes" have been added recently (http://www.stratigraphy.org/cheu.pdf) within the otherwise unconstrained Triassic, but ages of stage boundaries remain controversial. Here we report two Re-Os isochrons for Anisian (Middle Triassic) black shales from outcrop in western Svalbard and drill core from the Svalis Dome about 600 km to the SE in the Barents Sea. Black shales of the Blanknuten Member, Botneheia Formation, from the type section at Botneheia, western Spitsbergen (Svalbard), have total organic carbon (TOC) contents of 2.6 to 6.0 wt%. Rock-Eval data suggest moderately mature (Tmax = 440-450° C) Type II-III kerogens (Hydrogen Index (HI) = 232-311 mg HC/g TOC). Re-Os data yield a well-constrained Model 3 age of 241 Ma and initial 187Os/188Os (Osi) of 0.83 (MSWD = 16, n = 6). Samples of the possibly correlative Steinkobbe Formation from IKU core hole 7323/07-U-04 into the Svalis Dome in the Barents Sea (at about 73°30'N, 23°15'E) have TOC contents of 1.4 to 2.4%. Rock-Eval data suggest immature (Tmax = 410-430°) Type II-III kerogens (HI = 246-294 mg HC/g TOC). Re-Os data yield a precise Model 1 age of 239 Ma and Osi of 0.776 (MSWD = 0.2, n = 5). The sampled section of Blanknuten shale underlies a distinctive Frechitas (formerly Ptychites) layer, and is therefore assumed to be middle Anisian. The Steinkobbe core was sampled at 99-100 m, just above the Olenekian-Anisian transition. It is therefore assumed to be lower Anisian. The two isochron ages overlap within uncertainty, and fall within constraints provided by biozones and the current ICS-approved stage boundary ages. The Re-Os ages support the correlation of the Botneheia and Steinkobbe formations. The nearly identical Osi ratios suggest regional homogeneity of seawater and provide new information for the Os seawater curve, marking a relatively high 187Os/188Os ratio during profound ocean anoxia in the Middle Triassic.

  7. 40 CFR 61.183 - Emission monitoring.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS National Emission Standard for Inorganic Arsenic Emissions From Arsenic Trioxide and Metallic Arsenic Production Facilities § 61.183 Emission monitoring. (a... arsenic trioxide and metallic arsenic process emission stream that exits from a control device. (b) The...

  8. 40 CFR 61.183 - Emission monitoring.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS National Emission Standard for Inorganic Arsenic Emissions From Arsenic Trioxide and Metallic Arsenic Production Facilities § 61.183 Emission monitoring. (a... arsenic trioxide and metallic arsenic process emission stream that exits from a control device. (b) The...

  9. Nuclear Planetology: Constraining the Driving Force in Wegener's Continental Drift Theory

    NASA Astrophysics Data System (ADS)

    Roller, G.

    2015-12-01

    Nuclear planetology [1] is a new research field, which aims at deciphering the nuclear physics processes responsible for the evolution of ultra-substellar objects and the driving force in Wegener's continental drift theory by means of Re-Os nuclear geochronometry [2]. Terrestrial Re/Os ratios observed within diamond sulphide inclusions [3], compatible with lunar r-process production ratios of Th/U≈1≈Au/Ir [4], drop from ≈0.8 to 0.2-0.05 for nucleogeochronometric ages between 2.3 Ga and 1.4 Ga [5]. It has therefore been argued [5,6] that the Re/Os fractionation is related to a change in oxygen fugacity due to the physics/chemistry of Earth's core after a possibly Fermi-pressure controlled core collapse [4]. Here, Pd/Ru, Pd/Pt, Pd/Ir, Pd/Os, Ru/Ir, Ru/Os, Pt/Ir or Pt/Os ratios from 24 published H chondrite components [7] are connected to their respective nucleogeochronometric ages to constrain an extended fossil fractionation record over 800 Ma. The following ranges are obtained: 0.06-1.04 (Pd/Ru), 0.06-0.79 (Pd/Pt), 0.06-1.76 (Pd/Os), 0.07-1.94 (Pd/Ir), 1.08-1.99 (Ru/Ir), 0.83-2.41 (Pt/Os), 0.82-2.64 (Pt/Ir). Comparing the Re/Os fractionation pattern of the diamond sulphide inclusions with these results and considering that Re is readily oxidized even at ultra-low oxygen fugacity, it may be concluded that (i) extremely reducing conditions within Earth's core basically preserve any unfractionated r-process element ratio until today; and (ii) nuclear/quantum physics processes leading to the observed ratios and fractionation pattern are ultimately the driving force in Wegener's continental drift theory. [1] Roller (2015), Abstract T34B-0407, AGU Spring Meeting. [2] Roller (2015), Geophys. Res. Abstr. 17, EGU2015-17. [3] Smit et al. (2010), GCA 74, 3292. [4] Roller (2015), Abstract #5041, 78th Ann. Met. Soc. Meeting. [5] Roller (2015), Geophys. Res. Abstr. 17, EGU2015-2399. [6] Roller (2015), Abstract PG34A-0283, AGU Spring Meeting. [7] Horan et al. (2009), GCA 73, 6984.

  10. 24 CFR 291.90 - Sales methods.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 24 Housing and Urban Development 2 2010-04-01 2010-04-01 false Sales methods. 291.90 Section 291....90 Sales methods. HUD will prescribe the terms and conditions for all methods of sale. HUD may, in... following methods of sale: (a) Future REO acquisition method. The Future Real Estate-Owned (REO) acquisition...

  11. 24 CFR 291.90 - Sales methods.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 24 Housing and Urban Development 2 2014-04-01 2014-04-01 false Sales methods. 291.90 Section 291....90 Sales methods. HUD will prescribe the terms and conditions for all methods of sale. HUD may, in... following methods of sale: (a) Future REO acquisition method. The Future Real Estate-Owned (REO) acquisition...

  12. 24 CFR 291.90 - Sales methods.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 24 Housing and Urban Development 2 2013-04-01 2013-04-01 false Sales methods. 291.90 Section 291....90 Sales methods. HUD will prescribe the terms and conditions for all methods of sale. HUD may, in... following methods of sale: (a) Future REO acquisition method. The Future Real Estate-Owned (REO) acquisition...

  13. 24 CFR 291.90 - Sales methods.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 24 Housing and Urban Development 2 2012-04-01 2012-04-01 false Sales methods. 291.90 Section 291....90 Sales methods. HUD will prescribe the terms and conditions for all methods of sale. HUD may, in... following methods of sale: (a) Future REO acquisition method. The Future Real Estate-Owned (REO) acquisition...

  14. 24 CFR 291.90 - Sales methods.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 24 Housing and Urban Development 2 2011-04-01 2011-04-01 false Sales methods. 291.90 Section 291....90 Sales methods. HUD will prescribe the terms and conditions for all methods of sale. HUD may, in... following methods of sale: (a) Future REO acquisition method. The Future Real Estate-Owned (REO) acquisition...

  15. Re-Os evidence used to link regional mineralization process to the Chesapeake Bag Bolig's impact in the northeastern United States.

    DOT National Transportation Integrated Search

    2010-10-01

    Re-Os isotope measurements of sulfide minerals from 10 occurrences that span a radial distance of over 200 Km : serve to geochemically link epithermal mineralization in Pennsylvania to an Eocene event. The most likely geologic : event that could have...

  16. Iridium-Coated Rhenium Combustion Chamber

    NASA Technical Reports Server (NTRS)

    Schneider, Steven J.; Tuffias, Robert H.; Rosenberg, Sanders D.

    1994-01-01

    Iridium-coated rhenium combustion chamber withstands operating temperatures up to 2,200 degrees C. Chamber designed to replace older silicide-coated combustion chamber in small rocket engine. Modified versions of newer chamber could be designed for use on Earth in gas turbines, ramjets, and scramjets.

  17. Highly Siderophile Elements as Tracers for the Subcontinental Mantle Evolution Beneath the Southwestern USA: The San Carlos and Kilbourne Hole Peridotite Xenoliths Revisited

    NASA Technical Reports Server (NTRS)

    vanAcken, D.; Brandon, A. D.; Peslier, A. H.; Lee, C.-T. A.

    2010-01-01

    Peridotite xenoliths from San Carlos, Arizona, and Kilbourne Hole, New Mexico, have been studied since the 1970 s to give insights into melting and metasomatism in the subcontinental mantle beneath the southwestern USA. More recently, the highly siderophile elements (HSE; Os, Ir, Ru, Rh, Pt, Pd, and Re) and the included Re-Os isotope system have been established as powerful tools for the study of mantle processes because of their range in compatibility during mantle melting and their siderophile and chalcophile geochemical behavior. Model aluminachron Re-Os ages for San Carlos and Kilbourne Hole, as well as for the nearby Dish Hill and Vulcan's Throne sites, give consistent depletion ages of around 2.2 Ga. This age can be interpreted as a single large scale mantle melting event linked to crustal formation and continental growth under the southwestern USA. Highly siderophile elements, however, may be added to depleted peridotites via melt-rock interaction, especially the more incompatible and hence mobile Pt, Pd, and Re. This may result in overprinting of the signature of melt extraction, thus abating the usefulness of Re-Os mantle extraction model ages. A comprehensive characterization of the suite of mantle xenoliths from the SW USA in terms of HSE concentrations is thus necessary to re-assess the Re-Os system for dating purposes. San Carlos peridotites are depleted to moderately fertile, as indicated by their bulk Al2O3 contents between 0.66 wt% and 3.13 wt%. Bulk Os-187/Os-188 in San Carlos peridotites range from 0.1206 to 0.1357. In contrast, Kilbourne Hole peridotites tend to be more fertile with Al2O3 between 2.11 and 3.78 wt%, excluding one extremely depleted sample with 0.30 wt% Al2O3, and have Os-187/Os-188 between 0.1156 and 0.1272, typical for mantle peridotites. No large fractionation between the more compatible HSE Os, Ir, and Ru are observed. The more incompatible HSE Re, Pd, and to a minor extent, Pt, however, are depleted in a number of samples by factors of up to 4 for Pt, 6 for Pd, and 20 for Re, compared to primitive mantle estimates. This is in agreement with previous studies from the same locales, which demonstrated the presence of different populations of mantle xenoliths having undergone various degrees of melt extraction. The depletion of the more incompatible elements (Re, Pd, and Pt) also suggests that the HSE budgets of the SW USA peridotites were primarily established by extraction of basaltic melt, and reflect only minor influence from later episodes of metasomatism. Model Re-Os ages obtained from San Carlos and Kilbourne Hole xenoliths may thus reflect ages of crustal formation and mantle depletion in the SW USA region.

  18. A systems evaluation on the effectiveness of a catalyst retrofit program in China.

    PubMed

    Jones, M; Wilson, R; Norbeck, J M; Han, W; Hurley, R; Schuetzle, D

    2001-09-01

    A low-cost, rare-earth oxide (REO) catalyst has been recommended as part of China's retrofit program for Chinese carbureted vehicles. This study evaluated: (1) the emission reduction efficiency of the REO catalyst during chassis dynamometer testing on the FTP cycle; (2) the effect that fuel properties had on tailpipe emissions and catalyst efficiency; (3) the importance of vehicle premaintenance as part of a retrofit protocol; and (4) the emission reductions obtained following implementation of the program. Results also show that current in-use Chinese noncatalyst, carbureted vehicles operate excessively rich, resulting in extremely high emissions of CO, gaseous toxic compounds, and other non-methane hydrocarbon species (NMHC). Preretrofit maintenance alone has the potential to reduce these emissions by approximately 50%. Dynamometer emission tests showed emissions reductions of >95% for hydrocarbons, CO, and gaseous toxics after retrofit of the REO catalyst. In particular, the relative unit health risk associated with the decrease in emissions of airborne toxic compounds using unleaded Chinese fuel was reduced from 6.33 to 0.30. (Use of low-sulfur California Phase II gasoline rather than current in-use Chinese fuel reduced emissions further.) Following implementation of the program, a follow-up study showed that in-use emissions benefits were considerably less than anticipated, primarily because of poor quality control at the retrofit service centers, a less aggressive preretrofit maintenance procedure, and unauthorized modification to the recommended retrofit control system. Overall results indicate that a carefully controlled retrofit program using REO catalyst technology can reduce emissions significantly. However, well-defined implementation guidelines, and strict adherence to these guidelines are needed to achieve maximum benefits.

  19. Characterization of rhenium compounds obtained by electrochemical synthesis after aging process

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

    Vargas-Uscategui, Alejandro, E-mail: avargasuscat@ing.uchile.cl; Mosquera, Edgar; López-Encarnación, Juan M.

    2014-12-15

    The proper identification of the molecular nature of the aged rhenium compound obtained by means of electrodeposition from an alkaline aqueous electrolyte was determined. Chemical, structural and vibrational experimental characterization of the aged Re compound showed agreement with quantum-computations, thereby allowing the unambiguous identification of the Re compound as H(ReO{sub 4})H{sub 2}O. - Graphical abstract: Rhenium oxides were electrodeposited on a copper surface and after environmental aging was formed the H(ReO{sub 4})H{sub 2}O compound. The characterization of the synthesized material was made through the comparison of experimental evidence with quantum mechanical computations carried out by means of density functional theorymore » (DFT). - Highlights: • Aged rhenium compound obtained by means of electrodeposition was studied. • The study was made by combining experimental and DFT-computational information. • The aged electrodeposited material is consistent with the H(ReO{sub 4})H{sub 2}O compound.« less

  20. The unexpected mechanism underlying the high-valent mono-oxo-rhenium(V) hydride catalyzed hydrosilylation of C=N functionalities: insights from a DFT study.

    PubMed

    Wang, Jiandi; Wang, Wenmin; Huang, Liangfang; Yang, Xiaodi; Wei, Haiyan

    2015-04-07

    In this study, we theoretically investigated the mechanism underlying the high-valent mono-oxo-rhenium(V) hydride Re(O)HCl2(PPh3)2 (1) catalyzed hydrosilylation of C=N functionalities. Our results suggest that an ionic S(N)2-Si outer-sphere pathway involving the heterolytic cleavage of the Si-H bond competes with the hydride pathway involving the C=N bond inserted into the Re-H bond for the rhenium hydride (1) catalyzed hydrosilylation of the less steric C=N functionalities (phenylmethanimine, PhCH=NH, and N-phenylbenzylideneimine, PhCH=NPh). The rate-determining free-energy barriers for the ionic outer-sphere pathway are calculated to be ∼28.1 and 27.6 kcal mol(-1), respectively. These values are slightly more favorable than those obtained for the hydride pathway (by ∼1-3 kcal mol(-1)), whereas for the large steric C=N functionality of N,1,1-tri(phenyl)methanimine (PhCPh=NPh), the ionic outer-sphere pathway (33.1 kcal mol(-1)) is more favorable than the hydride pathway by as much as 11.5 kcal mol(-1). Along the ionic outer-sphere pathway, neither the multiply bonded oxo ligand nor the inherent hydride moiety participate in the activation of the Si-H bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Rhenium tetrazolato complexes coordinated to thioalkyl-functionalised phenanthroline ligands: synthesis, photophysical characterisation, and incubation in live HeLa cells.

    PubMed

    Werrett, Melissa V; Wright, Phillip J; Simpson, Peter V; Raiteri, Paolo; Skelton, Brian W; Stagni, Stefano; Buckley, Alysia G; Rigby, Paul J; Massi, Massimiliano

    2015-12-21

    Three new complexes of formulation fac-[Re(CO)3(diim)L], where diim is either 1,10-phenanthroline or 1,10-phenanthroline functionalised at position 5 by a thioalkyl chain, and L is either a chloro or aryltetrazolato ancillary ligand, were synthesised and photophysically characterised. The complexes exhibit phosphorescent emission with maxima around 600 nm, originating from triplet metal-to-ligand charge transfer states with partially mixed ligand-to-ligand charge transfer character. The emission is relatively long-lived, within the 200-400 ns range, and with quantum yields of 2-4%. The complexes were trialed as cellular markers in live HeLa cells, along with two previously reported rhenium tetrazolato complexes bound to unsubstituted 1,10-phenanthroline. All five complexes exhibit good cellular uptake and non-specific perinuclear localisation. Upon excitation at 405 nm, the emission from the rhenium complexes could be clearly distinguished from autofluorescence, as demonstrated by spectral detection within the live cells. Four of the complexes did not appear to be toxic, however prolonged excitation could result in membrane blebbing. No major sign of photobleaching was detected upon multiple imaging on the same cell sample.

  2. A whiff of oxygen before the great oxidation event?

    PubMed

    Anbar, Ariel D; Duan, Yun; Lyons, Timothy W; Arnold, Gail L; Kendall, Brian; Creaser, Robert A; Kaufman, Alan J; Gordon, Gwyneth W; Scott, Clinton; Garvin, Jessica; Buick, Roger

    2007-09-28

    High-resolution chemostratigraphy reveals an episode of enrichment of the redox-sensitive transition metals molybdenum and rhenium in the late Archean Mount McRae Shale in Western Australia. Correlations with organic carbon indicate that these metals were derived from contemporaneous seawater. Rhenium/osmium geochronology demonstrates that the enrichment is a primary sedimentary feature dating to 2501 +/- 8 million years ago (Ma). Molybdenum and rhenium were probably supplied to Archean oceans by oxidative weathering of crustal sulfide minerals. These findings point to the presence of small amounts of O2 in the environment more than 50 million years before the start of the Great Oxidation Event.

  3. Thermal shock and erosion resistant tantalum carbide ceramic material

    NASA Technical Reports Server (NTRS)

    Honeycutt, L., III; Manning, C. R. (Inventor)

    1978-01-01

    Ceramic tantalum carbide artifacts with high thermal shock and mechanical erosion resistance are provided by incorporating tungsten-rhenium and carbon particles in a tantalum carbide matrix. The mix is sintered by hot pressing to form the ceramic article which has a high fracture strength relative to its elastic modulus and thus has an improved thermal shock and mechanical erosion resistance. The tantalum carbide is preferable less than minus 100 mesh, the carbon particles are preferable less than minus 100 mesh, and the tungsten-rhenium particles are preferable elongate, having a length to thickness ratio of at least 2/1. Tungsten-rhenium wire pieces are suitable as well as graphite particles.

  4. Asymmetric rhenium tricarbonyl complexes show superior luminescence properties in live cell imaging.

    PubMed

    Raszeja, Lukasz J; Siegmund, Daniel; Cordes, Anna L; Güldenhaupt, Jörn; Gerwert, Klaus; Hahn, Stephan; Metzler-Nolte, Nils

    2017-01-16

    The synthesis and photophysical properties of a novel series of rhenium tricarbonyl complexes based on tridentate phenanthridinyl-containing ligands are described. Photophysical data reveal beneficial luminescence behaviour especially for compounds with an asymmetric ligand set. These advantageous properties are not limited to organic solvents, but indeed also improved in aqueous solutions. The suitability of our new rhenium complexes as potent imaging agents has been confirmed by fluorescence microscopy on living cancer cells, which also confirms superior long-time stability under fluorescence microscopy conditions. Colocalisation studies with commercial organelle stains reveal an accumulation of the complexes in the endoplasmic reticulum for all tested cell lines.

  5. Characterization of rhenium nitride films produced by reactive pulsed laser deposition

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

    Soto, G.; Rosas, A.; Farias, M.H.

    2007-06-15

    Rhenium nitride (ReN {sub x}) films were grown on (100)-Si substrates by the reactive pulsed laser deposition (PLD) method using a high purity Re rod in an environment of molecular nitrogen. The resulting films are characterized by several techniques, which include in situ Auger electron spectroscopy, X-ray photoelectron spectroscopy and ex situ X-ray diffraction, scanning electron and atomic force microscopy. Additionally, the four-probe method is used to determine the sheet resistance of deposited layers. Results show that films with N/Re ratios (x) lower than 1.3 are very good conductors. In fact, the resistivity of ReN films for 0.2 < xmore » < 1.3 is of the order of 5% of that of Re films, while at x = 1.3 there is an abrupt increment in resistivity, resulting in dielectric films for 1.3 < x < 1.35. These results differ from the prior understanding that in transition metals, resistivity should increase with nitrogen incorporation.« less

  6. Low-rhenium molybdenite by metamorphism in northern Sweden: Recognition, genesis, and global implications

    NASA Astrophysics Data System (ADS)

    Stein, Holly J.

    2006-04-01

    Re-Os dating of molybdenite is an accurate means to date intrusions and intrusion-related ore deposits using the model age or isochron approach. But, molybdenite has a new niche in the greenschist- to granulite-facies metamorphic environment. Re-Os ages for metamorphic molybdenite may be used to construct regional metamorphic histories. Age significance and accuracy are established by analyzing multiple molybdenite separates extracted from single, petrographically-characterized molybdenite occurrences. In this study, twelve geologically distinct molybdenite-bearing samples from two small Mo districts in northern Sweden trace a 150 m.y. Paleoproterozoic Svecofennian metamorphic history from ˜1900 to 1750 Ma. These data reveal a little-known, widespread and protracted, Late Svecofennian anatexis in northern Sweden. The Kåtaberget Mo-(Cu, F) deposit is located in the Moskosel granite batholith north of the economically-renown Skellefte district. Four different molybdenite samples from outcrop at Kåtaberget indicate an intrusion age of 1895 ± 6 Ma with the formation of later pegmatite-aplite at 1875 ± 6 Ma. The Allebuoda (Björntjärn) and Munka Mo-(W) deposits in the Rappen district are represented by three outcrop and five drill core samples of molybdenite-bearing aplite-pegmatite-granite. These two deposits were previously described as intrusion-related Climax-type Mo mineralization. Re-Os ages for molybdenites from these deposits range from 1865 to 1750 Ma and, significantly, Re concentrations are markedly low, extending to the sub-ppm level. Age agreement within the deposits is conspicuously lacking, whereas, with one exception, age agreement within any single sample (geologic occurrence), as established by analysis of additional molybdenite separates, is very good. These data, together with fundamental geologic observations discussed in this paper, suggest that Mo-(W) mineralization in northern Sweden is not intrusion-related, but the local product of episodic melting of Archean-Paleoproterozoic supracrustal gneisses related to the Svecofennian orogeny. Petrographic traverses across the boundary between widespread, foliation-parallel units of aplitic to pegmatitic pink granite and hosting biotite gneiss directly capture the process of ore formation. Dehydration breakdown of zircon-rich biotite aligned with the foliation in the gneiss is accompanied by formation of new pristine, post-deformational biotite plus sulfides, oxides, hydrothermal zircon and fluorite, all associated with microcline-dominant leucosomes. This process has profound implication for the traditional leucogranite, intrusion-related genesis attributed to the broad classification of Mo-W-Sn-base and precious metal mineralization (e.g., South Mountain Batholith, Nova Scotia; Okiep, Namaqualand, South Africa; Mactung, Yukon; Pogo-Liese, Tintina, Alaska; Carajás and Goiás-Rio Tocantins, Brazil; New England Batholith, NSW, Australia; Bergslagen, Sweden; Nevoria, Western Australia; Alpeinerscharte, Austria; Erzgebirge, Germany; Sardinia-Corsica Batholith). In addition to biotite, metallogenic contributions (e.g., Mo, W, Sn, U, Bi, Cu, Pb, Zn, Fe, Ni, Co, Au, Ag, Te, As, Sb, REE) in various combinations may also be controlled by breakdown of amphibole. In effect, the trace element composition of dehydrating or recrystallizing components in a gneissic rock essentially defines the local and district metallogenic suite. In the absence of focusing structures (e.g., shear zones, sheeted vein development), this process will generally form small and disconnected subeconomic deposits with erratic and unpredictable grades. Low Re content in associated molybdenite is a key indicator for a subeconomic origin by local melting of biotite gneiss (Mo-W) or muscovite schist (Sn-W).

  7. 187Os-enriched domain in an Archean mantle plume: evidence from 2.8 Ga komatiites of the Kostomuksha greenstone belt, NW Baltic Shield

    NASA Astrophysics Data System (ADS)

    Puchtel, Igor S.; Brügmann, Gerhard E.; Hofmann, Albrecht W.

    2001-04-01

    The Re-Os data on Archean komatiites from the Kostomuksha greenstone belt in the Baltic Shield are presented. This greenstone belt has been previously interpreted to represent a former oceanic plateau formed by the emplacement of an ancient plume head [Puchtel et al., Earth Planet. Sci. Lett. 155 (1998) 57-74]. Samples of flowtop breccia, spinifex-textured and cumulate komatiites and a chromite separate, all collected from the core of a 300 m deep diamond drill hole, yielded a Re-Os isochron with an age of 2795±40 Ma and an initial 187Os/188Os of 0.1117±0.0011 (γ187Os=+3.6±1.0). The high positive γ187Os(T) implies that the komatiites were derived from a mantle source with a time-integrated suprachondritic Re/Os ratio. Recycling of oceanic lithosphere to produce the enriched 187Os isotope signature is considered unlikely, as 15-25% crustal component is required to be incorporated into the plume source as early as 3.5-4.3 Ga. Such a substantial proportion of mafic material in the source would likely destroy the major and trace element characteristics of the komatiites. Our tentative interpretation is that the 187Os-enrichment in the Kostomuksha plume represents an outer core signature. If confirmed by the ongoing Pt-Os isotope studies, the results would provide evidence for the existence of whole-mantle convection in the late Archean, and might place constraints on the timing of core differentiation in the early Earth.

  8. Characteristics and geological significance of Re-Os isotopic system of evaporites in Mboukoumassi deposit, the Republic of Congo

    NASA Astrophysics Data System (ADS)

    Zhao, Xianfu; Wang, Zongqi; Liu, Chenglin; Li, Chao; Jiao, Pengcheng; Zhao, Yanjun; Zhang, Fan

    2018-02-01

    Evaporite dating has been an open problem. The study investigates the Re-Os isotopic system in the organic-rich sedimentary rocks to constrain the infilling of sedimentary basin and related geological events. In the Mboukoumassi potash deposit in the Republic of Congo (Congo-Brazzaville) in West Africa, several layers of organic-rich dark shale were found in the evaporite series. Through drilling core, the dark shale in the evaporite is found to satisfy the requirements of Re-Os isotope test. The result shows that the Re-Os isochron age of the dark shale in the study area ranges from 78.7 ± 1.1 to 96 ± 7 Ma, which is the first precise age of the Mboukoumassi potash deposit in the Republic of Congo (Congo-Brazzaville), West Africa. Therefore, the age of deposition of this set of evaporite may be Cenomanian-Turonian, which is younger than the age previously thought (around 113-125Ma, Aptian). The Re-Os isotopic dating technique used for the pioneering study on the precise dating of the Mboukoumassi potash deposit provides a new approach to the study of the sedimentary age of ancient evaporite deposits. The initial 187Os/188Os value decreasing from 2.02 ± 0.21 to 0.982 ± 0.03 for the core sample reflects the source rock chang along the core, and this is consistent with the geological evolution of the basin.

  9. Synthesis, reactivity, and properties of N-fused porphyrin rhenium(I) tricarbonyl complexes.

    PubMed

    Toganoh, Motoki; Ikeda, Shinya; Furuta, Hiroyuki

    2007-11-12

    The thermal reactions of N-fused tetraarylporphyrins or N-confused tetraarylporphyrins with Re2(CO)10 gave the rhenium(I) tricarbonyl complexes bearing N-fused porphyrinato ligands (4) in moderate to good yields. The rhenium complexes 4 are characterized by mass, IR, 1H, and 13C NMR spectroscopy, and the structures of tetraphenylporphynato complex 4a and its nitro derivative 15 are determined by X-ray single crystal analysis. The rhenium complexes 4 show excellent stability against heat, light, acids, bases, and oxidants. The aromatic substitution reactions of 4 proceed without a loss of the center metal to give the nitro (15), formyl (16), benzoyl (17), and cyano derivatives (19), regioselectively. In the electrochemical measurements for 4, one reversible oxidation wave and two reversible reduction waves are observed. Their redox potentials imply narrow HOMO-LUMO band gaps of 4 and are consistent with their electronic absorption spectra, in which the absorption edges exceed 1000 nm. Theoretical study reveals that the HOMO and LUMO of the rhenium complexes are exclusively composed of the N-fused porphyrin skeleton. Protonation of 4 takes place at the 21-position regioselectively, reflecting the high coefficient of the C21 atom in the HOMO orbital. The skeletal rearrangement reaction from N-confused porphyrin Re(I) complex (8) to N-fused porphyrin Re(I) complex (4) is suggested from the mechanistic study as well as DFT calculations.

  10. Reactions of rhenium(V) and molybdenum(V) oxypentahalides with 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane

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

    Ashurova, N.Kh.; Yakubov, K.G.

    1993-11-01

    The author studied complexation reactions of rhenium(V) and molybdenum(V) with a macrocyclic ligand 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (Tet a). The authors found that in hydrohalic acid medium, the onium complexes [H{sub 2}(Tet a)][EOX{sub 5}] are formed, with E = Re, Mo; X = Cl, Br. Reactions of [EOX{sub 5}]{sup 2{minus}} with (Tet a) in nitrometane yield complexes of molecular and cation types [EO(Tet a)Cl{sub 3}] and [EO(Tet a)Br]Br{sub 2}. Composition and structure of the obtained compounds are established by elemental analysis, conductometry, and mid- and far-IR spectroscopy.

  11. Nondestructive method for chemically machining crucibles or molds from their enclosed ingots and castings

    DOEpatents

    Stout, Norman D.; Newkirk, Herbert W.

    1991-01-01

    An inventive method is described for chemically machining rhenium, rhenium and tungsten alloy, and group 5b and 6b crucibles or molds from included ingots and castings comprised of oxide crystals including YAG and YAG based crystals, garnets, corundum crystals, and ceramic oxides. A mixture of potassium hydroxide and 15 to 90 weight percent of potassium nitrate is prepared and maintained at a temperature above melting and below the lower of 500 degrees centigrade or the temperature of decomposition of the mixture. The enveloping metal container together with its included oxide crystal object is rotated within the heated KOH-KNO.sub.3 mixture, until the container is safely chemically machined away from the included oxide crystal object.

  12. Facile Formation of Acetic Sulfuric Anhydride in a Supersonic Jet: Characterization by Microwave Spectroscopy and Computational Chemistry

    NASA Astrophysics Data System (ADS)

    Huff, Anna; Smith, CJ; Mackenzie, Becca; Leopold, Ken

    2017-06-01

    Sulfur trioxide and acetic acid are shown to react under supersonic jet conditions to form acetic sulfuric anhydride, CH_{3}COOSO_{2}OH. Rotational spectra of the parent, ^{34}S, methyl ^{13}C, and fully deuterated isotopologues have been observed by chirped-pulse and conventional cavity microwave spectroscopy. A and E internal rotation states have been observed for each isotopologue studied and the methyl group internal rotation barriers have been determined (241.043(65) \\wn for the parent species). The reaction is analogous to that of our previous report on the reaction of sulfur trioxide and formic acid. DFT and CCSD calculations are also presented which indicate that the reaction proceeds via a π_{2} + π_{2} + σ_{2} cycloaddition reaction. These results support our previous conjecture that the reaction of SO_{3} with carboxylic acids is both facile and general. Possible implications for atmospheric aerosol formation are discussed.

  13. [Spectrophotometric study of the interaction between rhenium complexes and phosphatidylcholine during liposome formation].

    PubMed

    Shtemenko, O V; Zeleniuk, M A; Shtemenko, N I; Verbyts'ka, Ia S

    2002-01-01

    The electron absorption spectra of halogenides and halogencarboxylate complex compounds of rhenium (III) having cluster structure with phosphatydilcholine and their lyposome forms were investigated. Some results which evidence for the interaction of these compounds with phosphatydilcholine were obtained. The possible mechanism of this interaction is discussed.

  14. Studies of magnetism in rhenium and manganese based perovskite oxides

    NASA Astrophysics Data System (ADS)

    Wiebe, Christopher Ryan

    The bulk of this thesis consists of studies of geometric frustration in S = ½ FCC perovskites based upon the chemical formula A2BReO 6. The magnetism of these materials is expected to exhibit geometric frustration, a situation in which the ideal spin arrangements cannot be achieved for antiferromagnetic interactions between adjacent spins. It is proposed that subtle quantum effects are driving these systems to unique ground states in the absence of chemical disorder. Both compounds Sr2CaReO 6 and Sr2MgReO6 exhibit spin glass behaviour at low temperatures (TG ˜ 14 K and TG ˜ 50 K respectively), in which the magnetic moments freeze out in random orientations instead of an ordered array. This work shows that these materials possess several unconventional properties, which suggest that interesting spin dynamics may be present. Other perovskite and perovskite-related materials studied in this thesis include the magnetoresistive CaMnO3-delta and the "pillared" material La5Re3MnO16. Neutron diffraction studies have shown that both CaMnO2.94 and CaMnO2.89 order at TN ˜ 125 K, but possess unique yet related magnetic structures. CaMnO2.94 orders into a simple G-type magnetic structure, as observed in the compound CaMnO3. The slightly more doped sample CaMnO2.89, on the other hand, orders into a magnetic structure related to the G-type, and involves a Mn3+/Mn 4+ charge ordering over every four lattice spacings. The new material La5Re3MnO16 consists of layers of corner shared ReO6 and MnO6 octahedra that are separated by layers of Re2O10 dimer units. Metal-metal bonding involving Re atoms have been postulated for these dimers which separate the Re/Mn layers by approximately 10 A. The magnetic behaviour exhibited by this new class of materials is rich and complex. Despite the large distances separating the perovskite layers, the Re and Mn magnetic moments order into a ferrimagnetic Q = (0, 0, ½) structure below a relatively high T N of 161 K. There may be an additional spin rearrangement at lower temperatures as evidenced by weak magnetic Bragg peaks below ˜50 K.

  15. Synthesis of the first radiolabeled 188Re N-heterocyclic carbene complex and initial studies on its potential use in radiopharmaceutical applications

    PubMed Central

    Wagner, Thomas; Zeglis, Brian M.; Groveman, Sam; Hille, Claudia; Pöthig, Alexander; Francesconi, Lynn C.; Herrmann, Wolfgang A.; Kühn, Fritz E.; Reiner, Thomas

    2015-01-01

    A novel approach towards the synthesis of radiolabeled organometallic rhenium complexes is presented. We successfully synthesized and analyzed the first 188Re-labeled N-heterocyclic biscarbene complex, trans-dioxobis(1,1′-methylene-bis(3,3′-diisopropylimidazolium-2-ylidene))188rhenium(V) hexafluorophosphate (188Re-4) via transmetalation using an air-stable and moisture-stable silver(I) biscarbene complex. In order to assess the viability of this complex as a potential lead structure for in vivo applications, the stability of the 188Re-NHC complex was tested in physiologically relevant media. Ultimately, our studies illustrate that the complex we synthesized dissociates rapidly and is therefore unsuitable for use in radiopharmaceuticals. However, it is clear that the transmetalation approach we have developed is a rapid, robust, and mild method for the synthesis of new 188Re-labeled carbene complexes. PMID:24889257

  16. 187Os/188Os in Spinel Peridotites from Borée, Massif Central, France: Seeing through the Effects of Melt Infiltration in the Sub-continental Lithospheric Mantle

    NASA Astrophysics Data System (ADS)

    Barnett, C. J.; Harvey, J.

    2015-12-01

    The Re-Os isotope system can be used to model the timing of melt extraction in peridotites, although secondary metasomatic processes can obscure primary melt depletion signatures, implying that bulk-rock Os model ages should be treated with caution.1Spinel peridotites from the volcanic Maar de Borée (French Massif Central) have equigranular to protogranular and occasionally poikilitic textures. Their bulk-rock chemistry are consistent with moderate degrees of partial melting, but elevated incompatible trace element ratios (e.g. La/YbN) are indicative of subsequent secondary processes. Petrographic observation reveals no infiltration of host basalt, but melt infiltration unrelated to the host basalt has occurred, most likely within the sub-continental lithospheric mantle prior to entrainment as xenoliths. The peridotites have a mean [Os] concentration of 2.35 ng g-1 and 187Os/188Os values from 0.12081 ± 16 to 0.12639 ± 14 (cf. PUM = 0.1296 ± 00082), with rhenium depletion model ages (TRD) ranging from 0.48 to 1.30 Ga. Silicate melt contains up to 2 orders of magnitude less Os than peridotites3 but the 187Os/188Os of melt infiltrated peridotite can be skewed by the precipitation of immiscible sulfide when an infiltrating melt reaches S-saturation4. The Borée peridotites retain an unradiogenic Os-isotope signature despite silicate melt infiltration; this may be due to primary base metal sulfides enclosed in silicate minerals and therefore protected from interaction with infiltrating melts. TRD of enclosed sulphides should therefore be able to 'see through' any secondary metasomatic events and reveal melt depletion ages significantly older than those obtained from bulk-rock analyses (cf. 4). 1. Rudnick & Walker (2009) Lithos 112S, 1083-1095. 2. Meisel et al. (2001) Geochim Cosmochim Ac 65, 1311-1323. 3. Day, J.M.D. (2013) Chem Geol 341, 50-74. 4. Harvey et al. (2010) Geochim Cosmochim Acta 74, 293-320.

  17. Re-Os geochronology and coupled Os-Sr isotope constraints on the Sturtian snowball Earth.

    PubMed

    Rooney, Alan D; Macdonald, Francis A; Strauss, Justin V; Dudás, Francis Ö; Hallmann, Christian; Selby, David

    2014-01-07

    After nearly a billion years with no evidence for glaciation, ice advanced to equatorial latitudes at least twice between 717 and 635 Mya. Although the initiation mechanism of these Neoproterozoic Snowball Earth events has remained a mystery, the broad synchronicity of rifting of the supercontinent Rodinia, the emplacement of large igneous provinces at low latitude, and the onset of the Sturtian glaciation has suggested a tectonic forcing. We present unique Re-Os geochronology and high-resolution Os and Sr isotope profiles bracketing Sturtian-age glacial deposits of the Rapitan Group in northwest Canada. Coupled with existing U-Pb dates, the postglacial Re-Os date of 662.4 ± 3.9 Mya represents direct geochronological constraints for both the onset and demise of a Cryogenian glaciation from the same continental margin and suggests a 55-My duration of the Sturtian glacial epoch. The Os and Sr isotope data allow us to assess the relative weathering input of old radiogenic crust and more juvenile, mantle-derived substrate. The preglacial isotopic signals are consistent with an enhanced contribution of juvenile material to the oceans and glacial initiation through enhanced global weatherability. In contrast, postglacial strata feature radiogenic Os and Sr isotope compositions indicative of extensive glacial scouring of the continents and intense silicate weathering in a post-Snowball Earth hothouse.

  18. Te Reo Maori: Indigenous Language Acquisition in the Context of New Zealand English

    ERIC Educational Resources Information Center

    Reese, Elaine; Keegan, Peter; McNaughton, Stuart; Kingi, Te Kani; Carr, Polly Atatoa; Schmidt, Johanna; Mohal, Jatender; Grant, Cameron; Morton, Susan

    2018-01-01

    This study assessed the status of te reo Maori, the indigenous language of New Zealand, in the context of New Zealand English. From a broadly representative sample of 6327 two-year-olds ("Growing Up in New Zealand"), 6090 mothers (96%) reported their children understood English, and 763 mothers (12%) reported their children understood…

  19. Os isotopes in SNC meteorites and their implications to the early evolution of Mars and Earth

    NASA Technical Reports Server (NTRS)

    Jagoutz, E.; Luck, J. M.; Othman, D. Ben; Wanke, H.

    1993-01-01

    A new development on the measurement of the Os isotopic composition by mass spectrometry using negative ions opened a new field of applications. The Re-Os systematic provides time information on the differentiation of the nobel metals. The nobel metals are strongly partitioned into metal and sulphide phases, but also the generation of silicate melts might fractionate the Re-Os system. Compared to the other isotopic systems which are mainly dating the fractionation of the alkalis and alkali-earth elements, the Re-Os system is expected to disclose entirely new information about the geochemistry. Especially the differentiation and early evolution of the planets such as the formation of the core will be elucidated with this method.

  20. Structural and chemical characterization of terbia thin films grown on hexagonally close packed metal substrates

    NASA Astrophysics Data System (ADS)

    Cartas, William

    Rare earth oxides (REOs) exhibit favorable catalytic performance for a diverse set of chemical transformations, including both partial and complete oxidation reactions. I will discuss our efforts to develop thin film systems of terbia for model surface science investigations of a REO that is effectively reducible, and which is thus expected to promote complete oxidation chemistry of adsorbed species. The growth of terbia on Cu(111) is shown to produce a complex surface that exhibits multiple phases of the oxide as well as exposed substrate. Growing the film on Pt(111) results in more uniform, single phase, and closed film. We used low energy electron diffraction (LEED) and scanning tunneling microscopy (STM) to characterize the structural properties of terbia thin films grown on Pt(111) in ultrahigh vacuum (UHV) using physical vapor deposition. We find that the REO grows as a high quality Tb2O 3(111) film, and adopts oxygen-deficient fluorite structures wherein the metal cations form a hexagonal lattice in registry with the Pt(111) substrate, while oxygen vacancies are randomly distributed within the film. The Tb 2O3(111) films are thermally stable when heated to 1000 K in UHV. LEED and STM show that a fraction of the Tb2O3 forms hexagonal islands when first deposited, and further depositions typically result in three dimensional growth of the film. The Tb2O3 (111) / Pt(111) system produces a coincidence structure, seen very clearly in LEED images. We have also found that Tb2O3(111) films can be oxidized in UHV by exposure to plasma-generated atomic oxygen beams. The oxidized films have an estimated TbO2 stoichiometry and decompose to Tb2O3 during heating, with O2 desorption starting at about 500 K. Terbia films oxidized at 90 K show a weakly bound state of oxygen that is likely chemisorbed. Temperature programmed reaction spectroscopy (TPRS) studies using methanol show that increased oxygen in the film does not modify the chemical selectivity of the film; however, the increased oxygen content does increase the activity of the film toward methanol dehydrogenation. We have found that when methanol is adsorbed onto the terbia-Pt(111) system, it reacts to form formaldehyde and water and reduces the surface. The development of high-quality terbia thin films on Pt(111) provides new opportunities to investigate oxidation chemistry on an REO that has distinct reduction and oxidation properties.

  1. Synthesis of tripeptide derivatized cyclopentadienyl complexes of technetium and rhenium as radiopharmaceutical probes.

    PubMed

    Nadeem, Qaisar; Can, Daniel; Shen, Yunjun; Felber, Michael; Mahmood, Zaid; Alberto, Roger

    2014-03-28

    We describe the syntheses of half-sandwich complexes of the type [(η(5)-Cp(CONH-R))M(CO)3] with M = Re or (99m)Tc. The R group represents different tri-peptides (tpe) which display high binding affinities for oligopeptide transporters PEPT2. The (99m)Tc complexes were prepared directly from [(99m)Tc(OH2)3(CO)3](+) and Diels-Alder dimerized, cyclopentadienyl derivatized peptides in water. This approach corroborates the feasibility of metal-mediated retro Diels-Alder reactions for the preparation of not only small molecules but also peptides carrying a [(η(5)-Cp)(99m)Tc(CO)3] tag. We synthesized the Diels-Alder product [(HCpCONH-tpe)2] from Thiele's acid [(η(5)-HCpCOOH)2] via double peptide coupling. The Re-complexes [(η(5)-CpCONH-tpe)Re(CO)3] were obtained by attaching [(Cp-COOH)Re(CO)3] directly to the N-terminus of peptides as received from SPPS. The authenticity of the (99m)Tc-complexes is confirmed by chromatographic comparison with the corresponding rhenium complexes, fully characterized by spectroscopic techniques.

  2. Arsenic trioxide-induced osteo-necrosis treatment in a child: mini-review and case report.

    PubMed

    Marty, M; Noirrit-Esclassan, E; Diemer, F

    2016-10-01

    Arsenic oxide compounds were traditionally used as devitalizing agents. Due to its toxicity, leakage of such compounds into the periodontium can cause gingival and osteo-necrosis. Their use is forbidden in Europe and the USA for decades, however, some dentists seem to still use it. We report the case of a 14-year-old girl referred to the paediatric dentistry department of Toulouse University hospital, France, presenting a bone necrosis following the use of an arsenic trioxide product to accelerate pulp necrosis. The treatment included surgical removal of necrosis bone sequestrum, complete pulpectomy and an intermediate restoration of the tooth 27. After 1 week, the clinical conditions greatly improved. A restoration using a ceramic crown was performed after 2 months, and complete healing was observed after 1 year follow-up. Although arsenic trioxide is neither appropriate nor permitted for use in modern dentistry, especially in paediatric dentistry, some rare cases of arsenic-induced osteo-necrosis can still be encountered. A clearer message must be given to all dental practitioners against the use of arsenic trioxide in modern endodontic treatment.

  3. Template-free fabrication of hierarchically flower-like tungsten trioxide assemblies with enhanced visible-light-driven photocatalytic activity.

    PubMed

    Yu, Jiaguo; Qi, Lifang

    2009-09-30

    Hierarchically flower-like tungsten trioxide assemblies were fabricated on a large scale by a simple hydrothermal treatment of sodium tungstate in aqueous solution of nitric acid. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy and N(2) adsorption-desorption measurements. The photocatalytic activity was evaluated by photocatalytic decolorization of rhodamine B aqueous solution under visible-light irradiation. It was found that the three-dimensional tungsten trioxide assemblies were constructed from two-dimensional layers, which were further composed of a large number of interconnected lathy nanoplates with different sizes. Such flower-like assemblies exhibited hierarchically porous structure and higher visible-light photocatalytic activity than the samples without such hierarchical structures due to their specific hierarchical pores that served as the transport paths for light and reactants. After five recycles for the photodegradation of RhB, the catalyst did not exhibit any great loss in activity, confirming hierarchically flower-like tungsten trioxide was stability and not photocorroded. This study may provide new insight into environmentally benign preparation and design of novel photocatalytic materials and enhancement of photocatalytic activity.

  4. Robust, heat-resistant and multifunctional superhydrophobic coating of carbon microflowers with molybdenum trioxide nanoparticles.

    PubMed

    Wu, Yang; Zhao, Meiyun; Guo, Zhiguang

    2017-11-15

    Superhydrophobic materials have triggered large interest due to their widespread applications, such as self-cleaning, corrosion resistance, anti-icing, and oil/water separation. However, suffering from weak mechanical strength, plenty of superhydrophobic materials are limited in practical application. Herein, we prepared hierarchical carbon microflowers (CMF) dispersed with molybdenum trioxide (MoO 3 ) nanoparticles (MoO 3 /CMF) via a two-step preparation method. Taking advantage of high-adhesion epoxy resin and the modification with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PDES), the modified MoO 3 /CMF (PDES-MoO 3 /CMF) coating on various substrates shows great waterproof ability, excellent chemical stability, good mechanical durability, and self-cleaning property. More significantly, the prepared PDES-MoO 3 /CMF powder with high thermal stability (250°C) can be used for oil/water separation due to its special flower-like structure and superhydrophobicity/superoleophilicity. All of these advantages endow the superhydrophobic powders with huge potential in the practical applications. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Space Storable Rocket Technology program (SSRT). Option 1 program

    NASA Astrophysics Data System (ADS)

    Chazen, Melvin L.; Mueller, Thomas; Rust, Thomas

    1993-08-01

    The Space Storable Rocket Technology (SSRT) Option 1 Program was initiated in October 1991 after completion of the Basic Program. The program was restructured in mid-July 1992 to incorporate a Rhenium Technology Task and reduce the scope of the LO2-N2H4 engine development. The program was also extended to late February 1993 to allow for the Rhenium Technology Task completion. The Option 1 Program was devoted to evaluation of two new injector elements, evaluation of two different methods of thermal protection of the injector, evaluation of high temperature material properties of rhenium and evaluation of methods of joining the rhenium thrust chamber to the columbium injector and nozzle extension. In addition, critical experiments were conducted (Funded by Option 2) to evaluate mechanisms to understand the effects of GO2 injection into the chamber, helium injection into the main LO2, effect of the splash plate and effect of decreasing the aspect ratio of the 120-slot (-13a) element. The performance and thermal models were used to further correlate the test results with analyses. The results of the work accomplished are summarized.

  6. Rhenium-osmium evidence for regional mineralization in southwestern north america.

    PubMed

    McCandless, T E; Ruiz, J

    1993-09-03

    More than 40 base metal porphyry ore deposits in southwestern North America are associated with the Laramide orogeny (about 90 million to 50 million years ago). Rhenium-osmium dates on molybdenite, a rhenium-enriched sulfide common in many of the deposits, reveal that in individual deposits mineralization occurs near the final stages of magmatic activity irrespective of the time of inception, magnitude, or duration of magmatism. Deposits that differ widely in location and in the extent and timing of magmatism have nearly identical ages for mineralization. Rhenium-osmium-ages suggest that mineralization occurred during two distinct intervals from about 74 million to 70 million years ago and from 60 million to 55 million years ago. Most deposits that formed in the oldest interval are within the older Precambrian basement of northwestern Arizona, whereas the younger deposits are restricted to the younger Precambrian basement in southern Arizona and northern Mexico. Synchronous, widespread mineralization indicates that similar crust-mantle interaction occurred on a regional scale for ore deposits once thought to be the product of localized processes.

  7. Space Storable Rocket Technology program (SSRT). Option 1 program

    NASA Technical Reports Server (NTRS)

    Chazen, Melvin L.; Mueller, Thomas; Rust, Thomas

    1993-01-01

    The Space Storable Rocket Technology (SSRT) Option 1 Program was initiated in October 1991 after completion of the Basic Program. The program was restructured in mid-July 1992 to incorporate a Rhenium Technology Task and reduce the scope of the LO2-N2H4 engine development. The program was also extended to late February 1993 to allow for the Rhenium Technology Task completion. The Option 1 Program was devoted to evaluation of two new injector elements, evaluation of two different methods of thermal protection of the injector, evaluation of high temperature material properties of rhenium and evaluation of methods of joining the rhenium thrust chamber to the columbium injector and nozzle extension. In addition, critical experiments were conducted (Funded by Option 2) to evaluate mechanisms to understand the effects of GO2 injection into the chamber, helium injection into the main LO2, effect of the splash plate and effect of decreasing the aspect ratio of the 120-slot (-13a) element. The performance and thermal models were used to further correlate the test results with analyses. The results of the work accomplished are summarized.

  8. 21 CFR 186.1093 - Sulfamic acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sulfamic acid. 186.1093 Section 186.1093 Food and... Substances Affirmed as GRAS § 186.1093 Sulfamic acid. (a) Sulfamic acid (H3NO3S, CAS Reg. No. 5329-14-6) is a white crystalline solid manufactured from urea, sulfur trioxide, and sulfuric acid. It is soluble and...

  9. The Role of Rhenium on the Temporal Evolution of the Nanostructure of a Model Ni-Al-Cr-Re Superalloy

    NASA Technical Reports Server (NTRS)

    Yoon, Kevin E.; Noebe, Ronald D.; Seidman, David N.

    2004-01-01

    Rhenium (2 at.%) additions to a model Ni-8.5 at.% Cr-10 at.% Al alloy are studied with respect to its effects on the temporal evolution of the nanostructure and the partitioning behavior of the four elements between the gamma (fcc) and gamma' (L1(sub 2)) phases. Chemical evolution of this quaternary alloy aged at 1073 K from 0.25 to 264 h, is investigated by three-dimensional atom-probe (3DAP) microscopy. The morphology of gamma'-precipitates remains spheroidal, even at an aging time of 264 h. The results demonstrate that Re slows the coarsening of gamma'-precipitates, in comparison to the ternary Ni-10 at.% A1-8.5 at.% Cr alloy at 1073 K.

  10. Modification of 1,2,4,5-tetrazine with cationic rhenium(I) polypyridine units to afford phosphorogenic bioorthogonal probes with enhanced reaction kinetics.

    PubMed

    Choi, Alex Wing-Tat; Tso, Karson Ka-Shun; Yim, Vicki Man-Wai; Liu, Hua-Wei; Lo, Kenneth Kam-Wing

    2015-02-25

    New phosphorogenic bioorthogonal probes derived from mononuclear and binuclear rhenium(I) polypyridine complexes containing a 1,2,4,5-tetrazine moiety were designed; these complexes displayed substantial dienophile-induced emission enhancement, and accelerated reaction kinetics and could target a protein conjugate in living cells.

  11. Electrotransport and diffusivity of molybdenum, rhenium, tungsten, and zirconium in beta-thorium

    NASA Technical Reports Server (NTRS)

    Schmidt, F. A.; Beck, M. S.; Rehbein, D. K.; Conzemius, R. J.; Carlson, O. N.

    1984-01-01

    The electric mobilities, diffusivities, and effective valences were determined for molybdenum, rhenium, tungsten, and zirconium in beta-thorium. All four solutes migrated in the same direction as the electron flow. Rhenium and molybdenum were found to be very mobile, with tungsten somewhat slower. Zirconium was found to move at a rate near that of the self-diffusion of beta-thorium, viz., about 10 to the -11th sq m/s at 1500 C. The electromigration velocities showed a similar trend. A comparison was made between experimental data obtained by scanning laser mass spectrometry and theoretical transport equations for two purification experiments. Good agreement was obtained with both the concentration profile predicted by DeGroot and the purification ratio predicted by Verhoeven.

  12. Rhenium-catalyzed deoxydehydration of diols and polyols.

    PubMed

    Dethlefsen, Johannes R; Fristrup, Peter

    2015-03-01

    The substitution of platform chemicals of fossil origin by biomass-derived analogues requires the development of chemical transformations capable of reducing the very high oxygen content of biomass. One such reaction, which has received increasing attention within the past five years, is the rhenium-catalyzed deoxydehydration (DODH) of a vicinal diol into an alkene; this is a model system for abundant polyols like glycerol and sugar alcohols. The present contribution includes a review of early investigations of stoichiometric reactions involving rhenium, diols, and alkenes followed by a discussion of the various catalytic systems that have been developed with emphasis on the nature of the reductant, the substrate scope, and mechanistic investigations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Investigation on the photophysical properties of tungsten trioxide and tungstate based nanocomposites

    NASA Astrophysics Data System (ADS)

    Palanisamy, G.; Pazhanivel, T.

    2018-04-01

    Tungsten trioxide (WO3), Metal tungstates (SrWO4, Cr2WO6), WO3/SrWO4 and WO3/Cr2WO6 nanocomposites were successfully prepared by microwave irradiation method at relatively low temperature (500 °C). The synthesized samples were subjected to different investigation techniques, to know the materials physical and chemical properties. The structural and phase change formation of nanoparticles were investigated through XRD analysis. It shows that, the nanoparticles have highly crystalline nature. The shape and composition of the prepared nanoparticles were investigated through SEM and EDAX analysis. The optical properties of the synthesized samples were verified by Ultraviolet-diffuse reflectance spectroscopy and photoluminescence spectrometer. The emission intensity maximum of WO3 nanoparticle was red shifted when compared to composites. It may be due to the effect of delocalized electrons in the parent material. Simultaneously, the emission intensity was decreased because of trap states occurred on the surface of the composite nanoparticles. The photoluminescence spectra of the synthesized samples exhibit different emission (violet and blue) behavior. Hence, it may be useful for light emitting diode (LED) applications.

  14. Photoresist removal using gaseous sulfur trioxide cleaning technology

    NASA Astrophysics Data System (ADS)

    Del Puppo, Helene; Bocian, Paul B.; Waleh, Ahmad

    1999-06-01

    A novel cleaning method for removing photoresists and organic polymers from semiconductor wafers is described. This non-plasma method uses anhydrous sulfur trioxide gas in a two-step process, during which, the substrate is first exposed to SO3 vapor at relatively low temperatures and then is rinsed with de-ionized water. The process is radically different from conventional plasma-ashing methods in that the photoresist is not etched or removed during the exposure to SO3. Rather, the removal of the modified photoresist takes place during the subsequent DI-water rinse step. The SO3 process completely removes photoresist and polymer residues in many post-etch applications. Additional advantages of the process are absence of halogen gases and elimination of the need for other solvents and wet chemicals. The process also enjoys a very low cost of ownership and has minimal environmental impact. The SEM and SIMS surface analysis results are presented to show the effectiveness of gaseous SO3 process after polysilicon, metal an oxide etch applications. The effects of both chlorine- and fluorine-based plasma chemistries on resist removal are described.

  15. Maori Children's Biliteracy Experiences Moving from a Kohanga Reo Setting to a Kura Kaupapa Maori, Bilingual, and Mainstream Education Setting: An Exploratory Study

    ERIC Educational Resources Information Center

    Rona, Sarika; McLachlan, Claire J.

    2018-01-01

    This research explored the biliteracy experiences of three kohanga reo children as they started school in one of three school settings: a bilingual unit, a mainstream classroom, and kura kaupapa Maori. A Kaupapa Maori approach underpinned this research and guided the case study methodology employed. The children's literacy experiences were…

  16. Surface study and sensing activity of nanotubular indium trioxide to NH3, H2S, NO2 and CO environmental pollutants

    NASA Astrophysics Data System (ADS)

    Zamani, Mehdi

    2016-02-01

    Molecular and electronic structures of nanotubular indium trioxide were studied using B3LYP and CAM-B3LYP density functional methods. Three nanotube models including nanotubes with closed ends (CENT), one opened end (OOENT) and two opened ends (TOENT) were considered. The highest occupied molecular orbital (HOMO) of CENT is distributed over the entire nanotube; while it is distributed on the end cap of OOENT. In both CENT and OOENT, the distribution of the lowest unoccupied molecular orbital (LUMO) is on the end caps. HOMO and LUMO of TOENT are distributed on the center of nanotube. The sensing activity of OOENT to environmental pollutants was evaluated regarding the interaction of nanotube with NH3, H2S, NO2 and CO molecules. Adsorptions over different positions of OOENT are exothermic and the NH3 adsorption is thermodynamically more favorable. The selectivity of OOENT toward gaseous pollutants is investigated as NH3 > H2S > CO > NO2. Interaction of NO2 and CO over the closed end (end cap) of nanotube is preferred; while adsorption of NH3 and H2S on the opened end is more favorable.

  17. The Hadean upper mantle conundrum: evidence for source depletion and enrichment from Sm-Nd, Re-Os, and Pb isotopic compositions in 3.71 Gy boninite-like metabasalts from the Isua Supracrustal Belt, Greenland

    NASA Astrophysics Data System (ADS)

    Frei, Robert; Polat, Ali; Meibom, Anders

    2004-04-01

    Here we present Sm-Nd, Re-Os, and Pb isotopic data of carefully screened, least altered samples of boninite-like metabasalts from the Isua Supracrustal Belt (ISB, W Greenland)that characterize their mantle source at the time of their formation. The principal observations of this study are that by 3.7-3.8 Ga melt source regions existed in the upper mantle with complicated enrichment/depletion histories. Sm-Nd isotopic data define a correlation line with a slope corresponding to an age of 3.69 ± 0.18 Gy and an initial εNd value of +2.0 ± 4.7. This Sm-Nd age is consistent with indirect (but more precise) U-Pb geochronological estimates for their formation between 3.69-3.71 Ga. Relying on the maximum formation age of 3.71 Gy defined by the external age constraints, we calculate an average εNd [T = 3.71 Ga] value of +2.2 ± 0.9 (n = 18, 1σ) for these samples, which is indicative of a strongly depleted mantle source. This is consistent with the high Os concentrations, falling in the range between 1.9-3.4 ppb, which is similar to the estimated Os concentration for the primitive upper mantle. Re-Os isotopic data (excluding three outliers) yield an isochron defining an age of 3.76 ± 0.09 Gy (with an initial γOs value of 3.9 ± 1.2), within error consistent with the Sm-Nd age and the indirect U-Pb age estimates. An average initial γOs [T = 3.71 Ga] value of + 4.4 ± 1.2 (n = 8; 2σ) is indicative of enrichment of their source region during, or prior to, its melting. Thus, this study provides the first observation of an early Archean upper mantle domain with a distinctly radiogenic Os isotopic signature. This requires a mixing component characterized by time-integrated suprachondritic Re/Os evolution and a Os concentration high enough to strongly affect the Os budget of the mantle source; modern sediments, recycled basaltic crust, or the outer core do not constitute suitable candidates. At this point, the nature of the mantle or crustal component responsible for the radiogenic Os isotopic signature is not known. Compared with the Sm-Nd and Re-Os isotope systems, the Pb isotope systematics show evidence for substantial perturbation by postformational hydrothermal-metasomatic alteration processes accompanying an early Archean metamorphic event at 3510 ± 65 Ma and indicate that the U-Th-Pb system was partially opened to Pb-loss on a whole rock scale. Single stage mantle evolution models fail to provide a solution to the Pb isotopic data, which requires that a high-μ component was mixed with the depleted mantle component before or during the extrusion of the basalts. Relatively high 207Pb/204Pb ratios (compared to contemporaneous mantle), support the hypothesis that erosion products of the ancient terrestrial protocrust existed for several hundred My before recycling into the mantle before ∼3.7 Ga. Our results are broadly consistent with models favoring a time-integrated Hadean history of mantle depletion and with the existence of an early Hadean protocrust, the complement to the Hadean depleted mantle, which after establishment of subduction-like processes was, at least locally, recycled into the upper mantle before 3.7 Ga. Thus, already in the Hadean, the upper mantle seems to be characterized by geochemical heterogeneity on a range of length scales; one property that is shared with the modern upper mantle. However, a simple two component mixing scenario between depleted mantle and an enriched-, crustal component with a modern analogue can not account for the complicated and contradictory geochemical properties of this particular Hadean upper mantle source.

  18. Removal of Radioactive Materials from Groundwater Using Porous Iron Composite Media

    NASA Astrophysics Data System (ADS)

    Dorward, E.; Thomas, R.; Cochran, J. P.; Chang, H. S.; Tandukar, M.; Coutelot, F.; Seaman, J. C.

    2017-12-01

    Uranium (U) is a concern in aqueous environments because of its toxicity. Reducing the mobile U(VI) to the relatively immobile U(IV) can decrease soluble U concentrations. Zero valent iron (ZVI) has been demonstrated as an effective reducing agent for U(VI) as well as other frequently occurring co-contaminants, such as nitrate (NO3-). However, the ability of ZVI to chemically reduce and immobilize U and other associated contaminants in more complex systems containing many alternate electron acceptors and non-ideal chemical conditions remains a concern. Porous iron composite (PIC) materials were evaluated for their ability to address these concerns in both batch and column experiments. We created an artificial groundwater surrogate containing ≈ 100 mg L-1 NO3-, 200 mg L-1 alkalinity, 100 µg L-1 U(VI) as uranyl (UO2+2), 100 µg L-1 rhenium (Re) as perrhenate (ReO4-), and 50 µg L-1 arsenic (As). In batch, we reacted 5 grams of PIC material with 200 mL groundwater surrogate under two different atmospheric conditions to evaluate the impact of O2. At specific time intervals, 5 mL aliquots from each batch treatment were removed for chemical analysis (i.e., U, Re, As, Fe, NO3, etc.) and the pH and ORP of the remaining suspension was measured. The PIC was effective at fully reducing NO3- levels over the extended reaction time despite rapid pH increase (> 8) during equilibration. Soluble levels of U and Re, a chemical surrogate for 99Tc, decreased in a similar fashion to NO3- in both the presence and absence of O2. Soluble As levels decreased more rapidly than other contaminants, but remained at ≈ 1 µg L-1. Very little nitrite (NO2-) was detected in the batch tests, with NH4+ levels consistent with the amount of NO3- reduced. Similar rates of immobilization for U, Re, and As were observed in the presence and absence of NO3-. Subsequent leaching tests corresponding to residence times ranging from 120 to 7.5 minutes demonstrated the ability of the PIC to reduce NO3- to NH4+, with no persistence of NO2-. Uranium and As were readily immobilized regardless of flow velocity. A strong kinetic component was observed for Re leaching behavior in the column tests. These results indicate the strong ability of PIC material to reduce U, NO3-, and other species under conditions that frequently inhibit conventional ZVI effectiveness.

  19. Re-Os isotope and platinum group elements of a FOcal ZOne mantle source, Louisville Seamounts Chain, Pacific ocean

    NASA Astrophysics Data System (ADS)

    Tejada, Maria Luisa G.; Hanyu, Takeshi; Ishikawa, Akira; Senda, Ryoko; Suzuki, Katsuhiko; Fitton, Godfrey; Williams, Rebecca

    2015-02-01

    The Louisville Seamount Chain (LSC) is, besides the Hawaiian-Emperor Chain, one of the longest-lived hotspot traces. We report here the first Re-Os isotope and platinum group element (PGE) data for Canopus, Rigil, and Burton Guyots along the chain, which were drilled during IODP Expedition 330. The LSC basalts possess (187Os/188Os)i = 0.1245-0.1314 that are remarkably homogeneous and do not vary with age. A Re-Os isochron age of 64.9 ± 3.2 Ma was obtained for Burton seamount (the youngest of the three seamounts drilled), consistent with 40Ar-39Ar data. Isochron-derived initial 187Os/188Os ratio of 0.1272 ± 0.0008, together with data for olivines (0.1271-0.1275), are within the estimated primitive mantle values. This (187Os/188Os)i range is similar to those of Rarotonga (0.124-0.139) and Samoan shield (0.1276-0.1313) basalts and lower than those of Cook-Austral (0.136-0.155) and Hawaiian shield (0.1283-0.1578) basalts, suggesting little or no recycled component in the LSC mantle source. The PGE data of LSC basalts are distinct from those of oceanic lower crust. Variation in PGE patterns can be largely explained by different low degrees of melting under sulfide-saturated conditions of the same relatively fertile mantle source, consistent with their primitive mantle-like Os and primordial Ne isotope signatures. The PGE patterns and the low 187Os/188Os composition of LSC basalts contrast with those of Ontong Java Plateau (OJP) tholeiites. We conclude that the Re-Os isotope and PGE composition of LSC basalts reflect a relatively pure deep-sourced common mantle sampled by some ocean island basalts but is not discernible in the composition of OJP tholeiites.

  20. Synthesis and characterization of 5-bis(benzyl thio)-1, 3, 4-thiadiazole complexes with fac-ReBr3(CO) 32-

    USDA-ARS?s Scientific Manuscript database

    Reactions of 2,5-bis(benzylthio)-1,3,4-thiadiazole (Compound 1) with a common organometallic rhenium starting material [NEt4]2[fac-[Re(I)Br3(CO)3] yielded two distinct types of complexes. Both complexes coordinate only through the nitrogen of the thiadiazole ring. Reaction of Compound 1 with the rhe...

  1. High activity Rhenium-186 HEDP with autologous peripheral blood stem cell rescue: a phase I study in progressive hormone refractory prostate cancer metastatic to bone

    PubMed Central

    O'Sullivan, J M; McCready, V R; Flux, G; Norman, A R; Buffa, F M; Chittenden, S; Guy, M; Pomeroy, K; Cook, G; Gadd, J; Treleaven, J; Al-Deen, A; Horwich, A; Huddart, R A; Dearnaley, D P

    2002-01-01

    We tested the feasibility and toxicity of high activities Rhenium-186 hydroxyethylidene diphosphonate, with peripheral blood stem cell rescue in patients with progressive hormone refractory prostate cancer metastatic to bone. Twenty-five patients received between 2500 and 5000 MBq of Rhenium-186 hydroxyethylidene diphosphonate followed 14 days later by the return of peripheral blood peripheral blood stem cells. Activity limiting toxicity was defined as grade III haematological toxicity, lasting at least 7 days, or grade IV haematological toxicity of any duration or any serious unexpected toxicity. Activity limiting toxicity occurred in two of six who received activities of 5000 MBq and maximum tolerated activity was defined at this activity level. Prostate specific antigen reductions of 50% or more lasting at least 4 weeks were seen in five of the 25 patients (20%) all of whom received more than 3500 MBq of Rhenium-186 hydroxyethylidene diphosphonate. The actuarial survival at 1 year is 54%. Administered activities of 5000 MBq of Rhenium-186 hydroxyethylidene diphosphonate are feasible using autologous peripheral blood peripheral blood stem cell rescue in patients with progressive hormone refractory prostate cancer metastatic to bone. The main toxicity is thrombocytopaenia, which is short lasting. A statistically significant activity/prostate specific antigen response was seen. We have now commenced a Phase II trial to further evaluate response rates. British Journal of Cancer (2002) 86, 1715–1720. doi:10.1038/sj.bjc.6600348 www.bjcancer.com © 2002 Cancer Research UK PMID:12087455

  2. Rhenium Solubility in Borosilicate Nuclear Waste Glass: Implications for the Processing and Immobilization of Technetium-99

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

    McCloy, John S.; Riley, Brian J.; Goel, Ashutosh

    2012-10-26

    The immobilization of 99Tc in a suitable host matrix has proved to be an arduous task for the researchers in nuclear waste community around the world. At the Hanford site in Washington State, the total amount of 99Tc in low-activity waste (LAW) is ~1300 kg and the current strategy is to immobilize the 99Tc in borosilicate glass with vitrification. In this context, the present article reports on the solubility/retention of rhenium, a nonradioactive surrogate for 99Tc, in a LAW borosilicate glass. Due to the radioactive nature of technetium, rhenium was chosen as a simulant because of the similarity between theirmore » ionic radii and other chemical aspects. The glasses containing Re (0 – 10,000 ppm by mass) were synthesized in vacuum-sealed quartz ampoules in order to minimize the loss of Re by volatilization during melting at 1000 °C. The rhenium was found to predominantly exist as Re (VII) in all the glasses as observed by X-ray absorption near-edge structure (XANES). The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) with inductively coupled plasma-optical emission spectroscopy (ICP-OES). At higher rhenium concentrations, some additional material was retained in the glasses in the form of crystalline inclusions that were detected by X-ray diffraction (XRD) and laser ablation-ICP mass spectrometry (LA-ICP-MS). The implications of these results on the immobilization of 99Tc from radioactive wastes in borosilicate glasses have been discussed.« less

  3. Radiosynovectomy in haemophilic synovitis of elbows and ankles: Is the effectiveness of yttrium-90 and rhenium-186 different?

    PubMed

    Rodriguez-Merchan, E C; De La Corte-Rodriguez, H

    2016-04-01

    Radiosynovectomy (RS) reduces the number of haemarthroses and the synovial size in chronic haemophilic synovitis. The purpose of this study was to quantitatively compare the effectiveness of two types of RS (yttrium-90 vs. rhenium-186) in terms of the objective improvement of haemarthroses and synovial size. Seventy RSs were performed in 70 joints (44 elbows, 26 ankles) of 70 haemophiliacs diagnosed with chronic synovitis. Yttrium-90 was used in 21 joints and rhenium-186 was used in 49 joints. The mean patient age was 20.61 years. RS resulted in significant improvement in the three variables studied (six months before RS vs. six months after RS), namely in the number of episodes of haemarthrosis (67.8% improvement); the size of the synovium as measured by means of a clinical scale (43.8% improvement) and imaging techniques in millimetres (26.7% improvement). We did not find significant statistical differences between yttrium-90 and rhenium-186 regarding their efficacy. No correlation was found between the results and other variables: age, joint (ankle or elbow), presence or absence of radiological involvement, type of haemophilia (A or B), grade of haemophilia (mild, moderate or severe), previous haematological treatment (on demand or prophylaxis), and the presence or absence of inhibitor Yttrium-90 RS and rhenium-186 RS were equally effective in reducing the number of haemarthroses and the size of the synovium in ankles and elbows in the short-term (6 months). No correlation was found between the results and other patients' characteristics. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Rhenium(I) polypyridine dibenzocyclooctyne complexes as phosphorescent bioorthogonal probes: Synthesis, characterization, emissive behavior, and biolabeling properties.

    PubMed

    Choi, Alex Wing-Tat; Liu, Hua-Wei; Lo, Kenneth Kam-Wing

    2015-07-01

    We report the development of rhenium(I) polypyridine complexes appended with a dibenzocyclooctyne (DIBO) moiety as bioorthogonal probes for azide-modified biomolecules. Three phosphorescent rhenium(I) polypyridine DIBO complexes [Re(N^N)(CO)3(py-C6-DIBO)][CF3SO3] (py-C6-DIBO=3-(N-(6-(3,4:7,8-dibenzocyclooctyne-5-oxycarbonylamino)hexyl)aminocarbonyl)pyridine; N^N=1,10-phenanthroline (phen) (1a), 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4-phen) (2a), 4,7-diphenyl-1,10-phenanthroline (Ph2-phen) (3a)) and their DIBO-free counterparts [Re(N^N)(CO)3(py-C6-BOC)][CF3SO3] (py-C6-BOC=3-(N-(6-(tert-butoxycarbonylamino)hexyl)aminocarbonyl)pyridine; N^N=phen (1b), Me4-phen (2b), Ph2-phen (3b)) were synthesized and characterized. Upon photoexcitation, all the complexes displayed intense and long-lived yellow triplet metal-to-ligand charge-transfer ((3)MLCT) (dπ(Re)→π*(N^N)) emission. The DIBO complexes underwent facile reactions with benzyl azide in methanol at 298 K with second-order rate constants (k2) in the range of 0.077 to 0.091 M(-1) s(-1). As revealed from SDS-PAGE analysis, the DIBO complexes can selectively label azide-modified proteins and the resulting bioconjugates displayed strong phosphorescence upon photoexcitation. Results of inductively coupled plasma mass spectrometry (ICP-MS) and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assays indicated that the DIBO complexes accumulated in Chinese Hamster Ovary (CHO) cells with considerable cytotoxic activity. Upon incubation of CHO cells with these complexes, relatively weak intracellular emission was observed. In contrast, upon pretreatment of the cells with 1,3,4,6-tetra-O-acetyl-N-azidoacetyl-D-mannosamine (Ac4ManNAz), intense emission was observed from the cell membrane and some internal compartments. The results suggest that the DIBO complexes are promising candidates for imaging azide-labeled biomolecules. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Rhenium(V)-oxo complexes of neutral and monoanionic tetraazamacrocycles. X-ray structures of trans-oxohydroxo(1,4,8,11-tetraazacyclotetradecane)rhenium(V) bis(perchlorate)

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

    Tsang, B.W.; Reibenspies, J.; Martell, A.E.

    1993-03-17

    The complexes of ReO[sub 2][sup +] and ReO(OH)[sup 2+] with 1,4,8,11-tetraazacyclotetradecane (cyclam) and 1,4,8,11-tetraazacyclotetradecan-2-one (O[sub 1]cyclam) have been synthesized and characterized. The complexes were prepared by ligand exchange reactions of the macrocycles with a variety of starting compounds including ReOCl[sub 3](PPh[sub 3])[sub 2] and ReO[sub 2](en)[sub 2]Cl. The ReO(OH)[sup 2+] complexes have been structurally characterized. ReO(OH)(H[sub [minus]1]O[sub 1]cyclam)ReO[sub 4] crystallizes in the monoclinic P2[sub 1]/n space group with a = 10.308(3) [Angstrom], b = 9.527(2) [Angstrom], c = 17.808(3) [Angstrom], and [beta] = 106.57(2)[degrees]. ReO(OH)(cyclam)(ClO[sub 4])[sub 2] crystallizes in the monoclinic C2/c space group with a = 9.734(4) [Angstrom], bmore » = 16.999(5) [Angstrom], c = 12.187(5) [Angstrom], and [beta] = 106.36[degrees]. The complex ReO(OH)(H[sub [minus]1]O[sub 1]cyclam)ReO[sub 4] has a distorted octahedral structure with one short ReO(oxo) bond and one long ReO(hydroxo) bond (1.685(8) vs 1.970(8) [Angstrom]). The deprotonated amide ReN(sp[sup 2]) bond is shorter than the other three ReN(sp[sup 3]) bond lengths (1.98(1) vs 2.13(3) [Angstrom] (average)). The structure of the ReO(OH)(cyclam)(ClO[sub 4])[sub 2] complex shows no distinction between the lengths of the two ReO(oxo and hydroxo) bonds (1.766(5) [Angstrom]) due to disorder of the oxo and hydroxo groups. Spectroscopic evidence is reported to confirm the presence of both oxo and hydroxo groups coordinated to rhenium. 38 refs., 7 figs., 6 tabs.« less

  6. A Preliminary Report on the Strength and Metallography of a Bimetallic Friction Stir Weld Joint Between AA6061 and MIL-DTL-46100E High Hardness Steel Armor

    DTIC Science & Technology

    2012-11-26

    alloy and High Hardness steel armor (MIL- STD-46100) were successfully joined by the friction stir welding (FSW) process using a tungsten- rhenium ...tungsten- rhenium stir tool. Process parameter variation experiments, which included inductive pre-heating, tool design geometry, plunge and traverse

  7. Low-Cost, High-Performance Combustion Chamber

    NASA Technical Reports Server (NTRS)

    Fortini, Arthur J.

    2015-01-01

    Ultramet designed and fabricated a lightweight, high-temperature combustion chamber for use with cryogenic LOX/CH4 propellants that can deliver a specific impulse of approx.355 seconds. This increase over the current 320-second baseline of nitrogen tetroxide/monomethylhydrazine (NTO/MMH) will result in a propellant mass decrease of 55 lb for a typical lunar mission. The material system was based on Ultramet's proven oxide-iridium/rhenium architecture, which has been hot-fire tested with stoichiometric oxygen/hydrogen for hours. Instead of rhenium, however, the structural material was a niobium or tantalum alloy that has excellent yield strength at both ambient and elevated temperatures. Phase I demonstrated alloys with yield strength-to-weight ratios more than three times that of rhenium, which will significantly reduce chamber weight. The starting materials were also two orders of magnitude less expensive than rhenium and were less expensive than the C103 niobium alloy commonly used in low-performance engines. Phase II focused on the design, fabrication, and hot-fire testing of a 12-lbf thrust class chamber with LOX/CH4, and a 100-lbf chamber for LOX/CH4. A 5-lbf chamber for NTO/MMH also was designed and fabricated.

  8. CVD Rhenium Engines for Solar-Thermal Propulsion Systems

    NASA Technical Reports Server (NTRS)

    Williams, Brian E.; Fortini, Arthur J.; Tuffias, Robert H.; Duffy, Andrew J.; Tucker, Stephen P.

    1999-01-01

    Solar-thermal upper-stage propulsion systems have the potential to provide specific impulse approaching 900 seconds, with 760 seconds already demonstrated in ground testing. Such performance levels offer a 100% increase in payload capability compared to state-of-the-art chemical upper-stage systems, at lower cost. Although alternatives such as electric propulsion offer even greater performance, the 6- to 18- month orbital transfer time is a far greater deviation from the state of the art than the one to two months required for solar propulsion. Rhenium metal is the only material that is capable of withstanding the predicted thermal, mechanical, and chemical environment of a solar-thermal propulsion device. Chemical vapor deposition (CVD) is the most well-established and cost-effective process for the fabrication of complex rhenium structures. CVD rhenium engines have been successfully constructed for the Air Force ISUS program (bimodal thrust/electricity) and the NASA Shooting Star program (thrust only), as well as under an Air Force SBIR project (thrust only). The bimodal engine represents a more long-term and versatile approach to solar-thermal propulsion, while the thrust-only engines provide a potentially lower weight/lower cost and more near-term replacement for current upper-stage propulsion systems.

  9. Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage.

    PubMed

    Wang, Xianfu; Xie, Yiming; Tang, Kai; Wang, Chao; Yan, Chenglin

    2018-05-11

    Hydrogen ions are ideal charge carriers for rechargeable batteries due to their small ionic radius and wide availability. However, little attention has been paid to hydrogen-ion storage devices because they generally deliver relatively low Coulombic efficiency as a result of the hydrogen evolution reaction that occurs in an aqueous electrolyte. Herein, we successfully demonstrate that hydrogen ions can be electrochemically stored in an inorganic molybdenum trioxide (MoO 3 ) electrode with high Coulombic efficiency and stability. The as-obtained electrode exhibits ultrafast hydrogen-ion storage properties with a specific capacity of 88 mA hg -1 at an ultrahigh rate of 100 C. The redox reaction mechanism of the MoO 3 electrode in the hydrogen-ion cell was investigated in detail. The results reveal a conversion reaction of the MoO 3 electrode into H 0.88 MoO 3 during the first hydrogen-ion insertion process and reversible intercalation/deintercalation of hydrogen ions between H 0.88 MoO 3 and H 0.12 MoO 3 during the following cycles. This study reveals new opportunities for the development of high-power energy storage devices with lightweight elements. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. A Study of Tungsten-Technetium Alloys

    NASA Technical Reports Server (NTRS)

    Maltz, J. W.

    1965-01-01

    Technetium is a sister element to rhenium and has many properties that are similar to rhenium. It is predicted that technetium will have about the same effects on tungsten as rhenium in regard to increase in workability, lowered ductile to brittle transition temperature, and improved ductility. The objectives of the current work are to recover technetium from fission product wastes at Hanford Atomic Products Operation and reduce to purified metal; prepare W-Tc alloys containing up to 50 atomic% Tc; fabricate the alloy ingots to sheet stock, assessing the effect of technetium on workability; and perform metallurgical and mechanical properties evaluation of the fabricated alloys. Previous reports have described the separation and purification of 800 g of technetium metal powder, melting of technetium and W-Tc alloys, and some initial observation of the alloy material.

  11. Rhenium ion beam for implantation into semiconductors

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

    Kulevoy, T. V.; Seleznev, D. N.; Alyoshin, M. E.

    2012-02-15

    At the ion source test bench in Institute for Theoretical and Experimental Physics the program of ion source development for semiconductor industry is in progress. In framework of the program the Metal Vapor Vacuum Arc ion source for germanium and rhenium ion beam generation was developed and investigated. It was shown that at special conditions of ion beam implantation it is possible to fabricate not only homogenous layers of rhenium silicides solid solutions but also clusters of this compound with properties of quantum dots. At the present moment the compound is very interesting for semiconductor industry, especially for nanoelectronics andmore » nanophotonics, but there is no very developed technology for production of nanostructures (for example quantum sized structures) with required parameters. The results of materials synthesis and exploration are presented.« less

  12. Alkoxy bridged binuclear rhenium (I) complexes as a potential sensor for β-amyloid aggregation.

    PubMed

    Sathish, Veerasamy; Babu, Eththilu; Ramdass, Arumugam; Lu, Zong-Zhan; Velayudham, Murugesan; Thanasekaran, Pounraj; Lu, Kuang-Lieh; Rajagopal, Seenivasan

    2014-12-01

    Alkoxy bridged binuclear rhenium(I) complexes are used as a probe for the selective and sensitive detection of aggregation of β-amyloid fibrils that are consorted with Alzheimer's disease (AD). The strong binding of the complexes is affirmed by the fluorescence enhancement and calculated binding constant value in the order of 10(5)M(-1) is obtained from the Scatchard plots. The binding of β-amyloid can be attributed to π-π stacking interaction of naphthalene moiety present in rhenium(I) complexes, and it is supported by docking studies. The selectivity is quite high towards other proteins and the formation of fibrils can be observed in the range of 30-40 nm through the AFM and TEM techniques. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Re-Os systematics and geochemistry of cobaltite (CoAsS) in the Idaho cobalt belt, Belt-Purcell Basin, USA: Evidence for middle Mesoproterozoic sediment-hosted Co-Cu sulfide mineralization with Grenvillian and Cretaceous remobilization

    USGS Publications Warehouse

    Saintilan, N.J.; Creaser, R.A.; Bookstrom, Arthur A.

    2017-01-01

    We report the first study of the Re-Os systematics of cobaltite (CoAsS) using disseminated grains and massive sulfides from samples of two breccia-type and two stratabound deposits in the Co-Cu-Au Idaho cobalt belt (ICB), Lemhi subbasin to the Belt-Purcell Basin, Idaho, USA. Using a 185Re + 190Os spike solution, magnetic and non-magnetic fractions of cobaltite mineral separates give reproducible Re-Os analytical data for aliquot sizes of 150 to 200 mg. Cobaltite from the ICB has highly radiogenic 187Os/188Os ratios (17–45) and high 187Re/188Os ratios (600–1800) but low Re and total Os contents (ca. 0.4–4 ppb and 14–64 ppt, respectively). Containing 30 to 74% radiogenic 187Os, cobaltite from the ICB is amenable to Re-Os age determination using the isochron regression approach.Re-Os data for disseminated cobaltite mineralization in a quartz-tourmaline breccia from the Haynes-Stellite deposit yield a Model 1 isochron age of 1349 ± 76 Ma (2σ, n = 4, mean squared weighted deviation MSWD = 2.1, initial 187Os/188Os ratio = 4.7 ± 2.2). This middle Mesoproterozoic age is preserved despite a possible metamorphic overprint or a pulse of metamorphic-hydrothermal remobilization of pre-existing cobaltite that formed along fold cleavages during the ca. 1190–1006 Ma Grenvillian orogeny. This phase of remobilization is tentatively identified by a Model 3 isochron age of 1132 ± 240 Ma (2σ, n = 7, MSWD = 9.3, initial 187Os/188Os ratio of 9.0 ± 2.9) for cobaltite in the quartz-tourmaline breccia from the Idaho zone in the Blackbird mine.All Mesoproterozoic cobaltite mineralization in the district was affected by greenschist- to lower amphibolite-facies (garnet zone) metamorphism during the Late Jurassic to Late Cretaceous Cordilleran orogeny. However, the fine- to coarse-grained massive cobaltite mineralization from the shear zone-hosted Chicago zone, Blackbird mine, is the only studied deposit that has severely disturbed Re-Os systematics with evidence for a linear trend of mixing with (metamorphic?) fluids.The new Re-Os ages and extremely high initial 187Os/188Os ratios of cobaltite reported here favor a magmatic-hydrothermal genetic model for a multi-stage REE-Y-Co-Cu-Au mineralization occurring at ca. 1370 to 1349 Ma, and related to the emplacement of the Big Deer Creek granite pluton at ca. 1377 Ma. In our model, deposition of paragenetically early xenotime and gadolinite was followed by an influx of Mesoproterozoic evaporitic brines and magmatic-hydrothermal fluids containing metals and reduced sulfur derived from mafic and oceanic island-arc Archean to Paleoproterozoic rocks in the Laurentian basement. Cobaltite mineralization occurred upon cooling of these fluids at an inferred temperature of 300 °C or below.

  14. Tretinoin, Cytarabine, and Daunorubicin Hydrochloride With or Without Arsenic Trioxide Followed by Tretinoin With or Without Mercaptopurine and Methotrexate in Treating Patients With Acute Promyelocytic Leukemia

    ClinicalTrials.gov

    2013-06-04

    Adult Acute Myeloid Leukemia With t(15;17)(q22;q12); Adult Acute Promyelocytic Leukemia (M3); Childhood Acute Promyelocytic Leukemia (M3); Untreated Adult Acute Myeloid Leukemia; Untreated Childhood Acute Myeloid Leukemia and Other Myeloid Malignancies

  15. M/V Santa Clara I - Board of Inquiry Report Concerning The Loss of Hazardous Materials Near the New Jersey Coast on 3 January 1992

    DOT National Transportation Integrated Search

    1992-05-18

    This report examines the circumstances surrounding the loss of 4 containers of arsenic trioxide, a hazardous substance, overboard from the Panamanian M/V SANTA CLARA I during heavy weather approximately 40 miles off the New Jersey coast on January 3,...

  16. Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

    DOE PAGES

    Balasekaran, Samundeeswari Mariappan; Sattelberger, Alfred P.; Hagenbach, Adelheid; ...

    2017-12-08

    Quadruply bonded rhenium(III) dimers with the stoichiometry Re 2L 4F 2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp –); 2, L = diphenyl formamidinate (dpf –)) were prepared from the solid-state melt reactions (SSMRs) between (NH 4) 2[Re 2F 8]·2H 2O and HL. Then those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV–visible spectroscopy and cyclic voltammetry. The compound [Re 2(hpp) 4F 2]PF 6 (3) was prepared from the one-electron oxidation of Re 2(hpp) 4F 2 with [Cp 2Fe]PF 6. Compounds 1–3 are isostructural with the corresponding chloro derivatives. In summation, compound 1 undergoesmore » two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re 2(hpp) 4F 2 (1) is more easily oxidized than its chloro and bromo analogues.« less

  17. Comparative study of the anchorage and the catalytic properties of nanoporous TiO2 films modified with ruthenium (II) and rhenium (I) carbonyl complexes

    NASA Astrophysics Data System (ADS)

    Oyarzún, Diego P.; Chardon-Noblat, Sylvie; Linarez Pérez, Omar E.; López Teijelo, Manuel; Zúñiga, César; Zarate, Ximena; Shott, Eduardo; Carreño, Alexander; Arratia-Perez, Ramiro

    2018-02-01

    In this article we study the anchoring of cis-[Ru(bpyC4pyr)(CO)2(CH3CN)2]2+, cis-[Ru(bpy)2(CO)2]2+ and cis-[Ru(bpyac)(CO)2Cl2], onto nanoporous TiO2 employing electropolymerization, electrostatic interaction and chemical bonding. Also, the [Re(bpyac)(CO)3Cl] rhenium(I) complex for chemical anchorage was analyzed. The characterization of TiO2/Ru(II) and TiO2/Re(I) nanocomposite films was performed by field emission scanning electron microscopy (FESEM), electron dispersive X-ray spectroscopy (EDS) and Raman spectroscopy. In addition, for the more stable nanocomposites obtained, the catalytic properties (solar energy conversion and CO2 reduction) were evaluated. The efficiency improvement in redox process derived from the (photo)electrochemical evidence indicates that modified nanoporous TiO2 structures enhance the rate of charge transfer reactions.

  18. Forbidden unique beta-decays and neutrino mass

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

    Dvornický, Rastislav; Šimkovic, Fedor

    2013-12-30

    The measurement of the electron spectrum in beta-decays provides a robust direct determination of the values of neutrino masses. The planned rhenium beta-decay experiment, called the “Microcalorimeter Arrays for a Rhenium Experiment” (MARE), might probe the absolute mass scale of neutrinos with the same sensitivity as the Karlsruhe tritium neutrino mass (KATRIN) experiment, which is expected to collect data in a near future. In this contribution we discuss the spectrum of emitted electrons close to the end point in the case of the first unique forbidden beta-decay of {sup 79}Se, {sup 107}Pd and {sup 187}Re. It is found that themore » p{sub 3/2}-wave emission dominates over the s{sub 1/2}-wave. It is shown that the Kurie plot near the end point is within a good accuracy linear in the limit of massless neutrinos like the Kurie plot of the superallowed beta-decay of {sup 3}H.« less

  19. Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

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

    Balasekaran, Samundeeswari Mariappan; Sattelberger, Alfred P.; Hagenbach, Adelheid

    Quadruply bonded rhenium(III) dimers with the stoichiometry Re 2L 4F 2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp –); 2, L = diphenyl formamidinate (dpf –)) were prepared from the solid-state melt reactions (SSMRs) between (NH 4) 2[Re 2F 8]·2H 2O and HL. Then those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV–visible spectroscopy and cyclic voltammetry. The compound [Re 2(hpp) 4F 2]PF 6 (3) was prepared from the one-electron oxidation of Re 2(hpp) 4F 2 with [Cp 2Fe]PF 6. Compounds 1–3 are isostructural with the corresponding chloro derivatives. In summation, compound 1 undergoesmore » two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re 2(hpp) 4F 2 (1) is more easily oxidized than its chloro and bromo analogues.« less

  20. Thiourea derivatives as chelating agents for bioconjugation of rhenium and technetium.

    PubMed

    Gomez, J D Castillo; Hagenbach, A; Gerling-Driessen, U I M; Koksch, B; Beindorff, N; Brenner, W; Abram, U

    2017-10-31

    Potential tetradentate thiocarbamoylbenzamidine derivatives H 4 L have been synthesized from the corresponding benzimidoyl chlorides and triglycine. They are suitable chelating agents for the oxidotechnetium(v) and oxidorhenium(v) cores and form stable, neutral [MO(HL)] complexes with an equatorial SN 3 coordination sphere and an additional, uncoordinated carboxylic group, which can be used for bioconjugation. Representatives of the rhenium and 99 Tc products have been isolated and analyzed with spectroscopic methods and X-ray diffraction. Bioconjugates of these complexes with angiotensin-II have been synthesized and structurally characterized. Analogous 99m Tc complexes have been produced and tested in vitro and in vivo. The experiments confirm a considerable stability for the [ 99m Tc(HL)] product as well as for its bioconjugate and recommend this class of compounds for further bioconjugation studies towards clinical applications.

  1. Arsenic trioxide controls the fate of the PML-RARalpha oncoprotein by directly binding PML.

    PubMed

    Zhang, Xiao-Wei; Yan, Xiao-Jing; Zhou, Zi-Ren; Yang, Fei-Fei; Wu, Zi-Yu; Sun, Hong-Bin; Liang, Wen-Xue; Song, Ai-Xin; Lallemand-Breitenbach, Valérie; Jeanne, Marion; Zhang, Qun-Ye; Yang, Huai-Yu; Huang, Qiu-Hua; Zhou, Guang-Biao; Tong, Jian-Hua; Zhang, Yan; Wu, Ji-Hui; Hu, Hong-Yu; de Thé, Hugues; Chen, Sai-Juan; Chen, Zhu

    2010-04-09

    Arsenic, an ancient drug used in traditional Chinese medicine, has attracted worldwide interest because it shows substantial anticancer activity in patients with acute promyelocytic leukemia (APL). Arsenic trioxide (As2O3) exerts its therapeutic effect by promoting degradation of an oncogenic protein that drives the growth of APL cells, PML-RARalpha (a fusion protein containing sequences from the PML zinc finger protein and retinoic acid receptor alpha). PML and PML-RARalpha degradation is triggered by their SUMOylation, but the mechanism by which As2O3 induces this posttranslational modification is unclear. Here we show that arsenic binds directly to cysteine residues in zinc fingers located within the RBCC domain of PML-RARalpha and PML. Arsenic binding induces PML oligomerization, which increases its interaction with the small ubiquitin-like protein modifier (SUMO)-conjugating enzyme UBC9, resulting in enhanced SUMOylation and degradation. The identification of PML as a direct target of As2O3 provides new insights into the drug's mechanism of action and its specificity for APL.

  2. IMMEDIATE AND DELAYED SOLUBILITY OF MINERAL TRIOXIDE AGGREGATE AND PORTLAND CEMENT

    PubMed Central

    Bodanezi, Augusto; Carvalho, Nara; Silva, Daniela; Bernardineli, Norberti; Bramante, Clovis Monteiro; Garcia, Roberto Brandão; de Moraes, Ivaldo Gomes

    2008-01-01

    This study investigated the solubility of mineral trioxide aggregate (MTA) and Portland cement since its mixture until 672 hours, by means of two complimentary methods. Metal ring molds filled with the cements were covered with distilled water and, at each experimental time (3, 24, 72, 168, 336 and 672 hours), were weighed as soon as the plates in which the samples have been placed. Empty rings served as the control group (n=8). Mean weight gain and loss was determined and analyzed statistically by two-way ANOVA and Tukey's test for all pairwise comparisons. Only Portland cement showed less than 3% weight loss through 24 hours. Detached MTA residues were heavier than those of Portland cement over the 3 to 168 hours. The weight of MTA rings increased more than that of Portland rings within 672 hours (p=0.05). The findings of the present study indicate that, in an aqueous environment MTA is more soluble than Portland cement and exceeds the maximum weight loss considered acceptable by ISO 6876 standard (2001). PMID:19089204

  3. Early Childhood Services in New Zealand.

    ERIC Educational Resources Information Center

    Oborn, Glennie

    2002-01-01

    Describes the types and characteristics of New Zealand early childhood education services. Specific areas addressed include: (1) Te Whaariki, the New Zealand early childhood curriculum; (2) great outdoors as a feature of early education; (3) education and care centers; (4) kindergartens and playcenters; and (5) Te Kohanga Reo, Maori language and…

  4. Rhenium, Molybdenum, Tungsten - Prospects for Production and Industrial Applications

    DTIC Science & Technology

    1998-06-18

    concentrates from unique complex copper -containing porphyry deposit of the Almalyk region. The ore containing over 10 associated valuable constituents is...L.I.Ruzin, M .F.Sherem etyev ............................................... 71 Recovery of rhenium as by-product of treatment of molybdenite and copper ...for processing copper -molybdenum ores from "Erdenet- Ovoo" deposit S.Davaanyam, I.Sh.Sataev, Zh.Baatarkhuu, A.M.Desyatov, M.I.Khersonsky

  5. Unprecedented staining of polar lipids by a luminescent rhenium complex revealed by FTIR microspectroscopy in adipocytes.

    PubMed

    Bader, C A; Carter, E A; Safitri, A; Simpson, P V; Wright, P; Stagni, S; Massi, M; Lay, P A; Brooks, D A; Plush, S E

    2016-06-21

    Fourier transform infrared (FTIR) microspectroscopy and confocal imaging have been used to demonstrate that the neutral rhenium(i) tricarbonyl 1,10-phenanthroline complex bound to 4-cyanophenyltetrazolate as the ancillary ligand is able to localise in regions with high concentrations of polar lipids such as phosphatidylethanolamine (PE), sphingomyelin, sphingosphine and lysophosphatidic acid (LPA) in mammalian adipocytes.

  6. The effect of novel rhenium compounds on lymphosarcoma, PC-3 prostate and myeloid leukemia cancer cell lines and an investigation on the DNA binding properties of one of these compounds through electronic spectroscopy

    PubMed Central

    Parson, Carl; Smith, Valerie; Krauss, Christopher; Banerjee, Hirendra N.; Reilly, Christopher; Krause, Jeanette A.; Wachira, James M.; Giri, Dipak; Winstead, Angela; Mandal, Santosh K.

    2014-01-01

    Despite the tremendous success of cisplatin and other platinum-based anticancer drugs, severe toxicity and resistance to tumors limit their applications. It is believed that the coordination (formation of covalent bond) of the metal (platinum) to the nitrogen bases of DNA cause the ruptures of the cancer as well as normal cells. A search for anticancer drugs with different modes of action resulted in the synthesis of variety of novel compounds. Many of them are in clinical trials now. Recently we synthesized a series of novel rhenium pentylcarbonato compounds (PC1–PC6). The rhenium atom in each compound is coordinated (bonded) to a planar polypyridyl aromatic ligand, thereby forcing each compound to intercalate between the DNA bases. We have investigated the DNA binding properties of one of the PC-series of compounds (PC6) using electronic spectroscopy. The UV absorption titration of PC6 with DNA shows hypochromic effect with concomitant bathochromic shift of the charge transfer band at 290 nm. These results suggest that the compound PC6 binds to DNA through intercalation. It is therefore likely that the other PC-series of compounds will behave in a similar manner. Thus it is expected that these compounds will exhibit negligible or no side effect. We have observed that the PC-series of compounds are strong cytotoxic agents against lymphosarcoma (average GI50 ≈ 2±2.6 µM), PC-3 prostate (average GI50 ≈ 3±2.8 µM) and myeloid leukemia (average GI50 ≈ 3±2.8 µM) cancer cell lines. The average GI50 values of the PC-series of compounds are 2–3 less than the corresponding GI50 values of cisplatin. Also each of the PC-series of compounds exhibits less toxicity than cisplatin in the glomerular mesangial cells. PMID:25221731

  7. Identification of rhenium donors and sulfur vacancy acceptors in layered MoS{sub 2} bulk samples

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

    Brandão, F. D., E-mail: fdbrand@fisica.ufmg.br; Ribeiro, G. M.; Vaz, P. H.

    2016-06-21

    MoS{sub 2} monolayers, a two-dimensional (2D) direct semiconductor material with an energy gap of 1.9 eV, offer many opportunities to be explored in different electronic devices. Defects often play dominant roles in the electronic and optical properties of semiconductor devices. However, little experimental information about intrinsic and extrinsic defects or impurities is available for this 2D system, and even for macroscopic 3D samples for which MoS{sub 2} shows an indirect bandgap of 1.3 eV. In this work, we evaluate the nature of impurities with unpaired spins using electron paramagnetic resonance (EPR) in different geological macroscopic samples. Regarding the fact that monolayers aremore » mostly obtained from natural crystals, we expect that the majority of impurities found in macroscopic samples are also randomly present in MoS{sub 2} monolayers. By EPR at low temperatures, rhenium donors and sulfur vacancy acceptors are identified as the main impurities in bulk MoS{sub 2} with a corresponding donor concentration of about 10{sup 8–12} defects/cm{sup 2} for MoS{sub 2} monolayer. Electrical transport experiments as a function of temperature are in good agreement with the EPR results, revealing a shallow donor state with an ionization energy of 89 meV and a concentration of 7 × 10{sup 15 }cm{sup −3}, which we attribute to rhenium, as well as a second deeper donor state with ionization energy of 241 meV with high concentration of 2 × 10{sup 19 }cm{sup −3} and net acceptor concentration of 5 × 10{sup 18 }cm{sup −3} related to sulfur vacancies.« less

  8. 21 CFR 82.3 - Definitions.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...) The term mixed oxides means the sum of the quantities of aluminum, iron, calcium, and magnesium (in whatever combination they may exist in a coal-tar color) calculated as aluminum trioxide, ferric oxide, calcium oxide, and magnesium oxide. (k)-(m) [Reserved] (n) The term externally applied drugs and cosmetics...

  9. 21 CFR 82.3 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...) The term mixed oxides means the sum of the quantities of aluminum, iron, calcium, and magnesium (in whatever combination they may exist in a coal-tar color) calculated as aluminum trioxide, ferric oxide, calcium oxide, and magnesium oxide. (k)-(m) [Reserved] (n) The term externally applied drugs and cosmetics...

  10. Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction

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

    Oh, Seokjoon; Gallagher, James R.; Miller, Jeffrey T.

    2016-02-17

    Condensation of fac-Re(5,6-diamino-1,10-phenanthroline)(CO)(3)Cl to o-quinone edge defects on graphitic carbon surfaces generates graphite-conjugated rhenium (GCC-Re) catalysts that are highly active for CO2 reduction to CO in acetonitrile electrolyte. X-ray photo-electron and X-ray absorption spectroscopies establish the formation of surface-bound Re centers with well-defined coordination environments. GCC-Re species on glassy carbon surfaces display catalytic currents greater than 50 mA cm(-2) with 96 +/- 3% Faradaic efficiency for CO production. Normalized for the number of Re active sites, GCC-Re catalysts exhibit higher turnover frequencies than that of a soluble molecular analogue, fac-Re(1,10-phenanthroline)(CO)(3)Cl, and turnover numbers greater than 12,000. In contrast to themore » molecular analogue, GCC-Re surfaces display a Tafel slope of 150 mV/decade, indicative of a catalytic mechanism involving rate-limiting one-electron transfer. This work establishes graphite conjugation as a powerful strategy for generating well-defined, tunable, heterogeneous electrocatalysts on ubiquitous graphitic carbon surfaces.« less

  11. Flexible neutron shielding composite material of EPDM rubber with boron trioxide: Mechanical, thermal investigations and neutron shielding tests

    NASA Astrophysics Data System (ADS)

    Özdemir, T.; Güngör, A.; Reyhancan, İ. A.

    2017-02-01

    In this study, EPDM and boron trioxide composite was produced and mechanical, thermal and neutron shielding tests were performed. EPDM rubber (Ethylene Propylene Diene Monomer) having a considerably high hydrogen content is an effective neutron shielding material. On the other hand, the materials containing boron components have effective thermal neutron absorption crossection. The composite of EPDM and boron trioxide would be an effective solution for both respects of flexibility and effectiveness for developing a neutron shielding material. Flexible nature of EPDM would be a great asset for the shielding purpose in case of intervention action to a radiation accident. The theoretical calculations and experimental neutron absorption tests have shown that the results were in parallel and an effective neutron shielding has been achieved with the use of the developed composite material.

  12. Preparation and evaluation of APTES-PEG coated iron oxide nanoparticles conjugated to rhenium-188 labeled rituximab.

    PubMed

    Azadbakht, Bakhtiar; Afarideh, Hossein; Ghannadi-Maragheh, Mohammad; Bahrami-Samani, Ali; Asgari, Mehdi

    2017-05-01

    Radioimmuno-conjugated (Rhenium-188 labeled Rituximab), 3-aminopropyltriethoxysilane (APTES)-polyethylene glycol (PEG) coated iron oxide nanoparticles were synthesized and then characterized. Therapeutic effect and targeting efficacy of complex were evaluated in CD20 express B cell lines and tumor bearing Balb/c mice respectively. To reach these purposes, superparamagnetic iron oxide nanoparticles (SPIONs) were synthesized using coprecipitation method and then their surface was treated with APTES for increasing retention time of SPIONs in blood circulation and amine group creation. In the next step, N-hydroxysuccinimide (NHS) ester of polyethylene glycol maleimide (NHS-PEG-Mal) was conjugated to the APTES-treated SPIONs. After radiolabeling of Rituximab antibody with Rhenium-188 (T 1/2 =16.9h) using synthesized N 2 S 4 chelator, it was attached to the APTES-PEG-MAL-SPIONs surface through thiol-maleimide coupling reaction. In vitro evaluation of the 188 ReN 2 S 4 -Rituximab-SPION-complex thus obtained revealed that at 24 and 48h post-treatment effective cancer cell killing had been achieved. Bio-distribution study in tumor bearing mice showed capability of this complex for targeted cancer therapy. Active and passive tumor targeting strategies were applied through incorporated anti-CD20 (Rituximab) antibody and also enhanced permeability and retention (EPR) effect of solid tumors for nanoparticles respectively. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. Characterization of Rhenium Oxides Using ESCA

    NASA Technical Reports Server (NTRS)

    Panda, Binayak; Gentz, Steven J. (Technical Monitor)

    2001-01-01

    High melting point and inherent ductility (toughness) over a wide range of temperature has made Rhenium an engineering material of choice for several thrust chambers in propulsion systems. Although the material remains tough at high temperatures, it still can readily transform to several oxides. As many as eight different oxides have been reported in literature. When characterized using ESCA (Electron Spectroscopy for Chemical Analyses) these oxides show large shifts in the Re 4f line positions. While this unique property could be used as a tool for oxide characterization, literature indicates that only a few of these oxides have been characterized. Current work focuses on characterizing oxides of Rhenium using ESCA. Spectral line Re 4f have been measured for various oxides and the results have been compared with the Re 4f line positions of real-time oxidation products from space hardware.

  14. Rhenium Mechanical Properties and Joining Technology

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.; Biaglow, James A.

    1996-01-01

    Iridium-coated rhenium (Ir/Re) provides thermal margin for high performance and long life radiation cooled rockets. Two issues that have arisen in the development of flight Ir/Re engines are the sparsity of rhenium (Re) mechanical property data (particularly at high temperatures) required for engineering design, and the inability to directly electron beam weld Re chambers to C103 nozzle skirts. To address these issues, a Re mechanical property database is being established and techniques for creating Re/C103 transition joints are being investigated. This paper discusses the tensile testing results of powder metallurgy Re samples at temperatures from 1370 to 2090 C. Also discussed is the evaluation of Re/C103 transition pieces joined by both, explosive and diffusion bonding. Finally, the evaluation of full size Re transition pieces, joined by inertia welding, as well as explosive and diffusion bonding, is detailed.

  15. AB INITIO EQUATIONS OF STATE FOR HYDROGEN (H-REOS.3) AND HELIUM (He-REOS.3) AND THEIR IMPLICATIONS FOR THE INTERIOR OF BROWN DWARFS

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

    Becker, Andreas; Lorenzen, Winfried; Schöttler, Manuel

    2015-01-01

    We present new equations of state (EOSs) for hydrogen and helium covering a wide range of temperatures from 60 K to 10{sup 7} K and densities from 10{sup –10} g cm{sup –3} to 10{sup 3} g cm{sup –3}. They include an extended set of ab initio EOS data for the strongly correlated quantum regime with an accurate connection to data derived from other approaches for the neighboring regions. We compare linear mixing isotherms based on our EOS tables with available real mixture data. A first important astrophysical application of this new EOS data is the calculation of interior models formore » Jupiter and comparison with recent results. Second, mass-radius relations are calculated for Brown Dwarfs (BDs) which we compare with predictions derived from the widely used EOS of Saumon, Chabrier, and van Horn. Furthermore, we calculate interior models for typical BDs with different masses, namely, Corot-3b, Gliese-229b, and Corot-15b, and the giant planet KOI-889b. The predictions for the central pressures and densities differ by up to 10% dependent on the EOS used. Our EOS tables are made available in the supplemental material of this paper.« less

  16. HIGH TEMPERATURE THERMOCOUPLE

    DOEpatents

    Eshayu, A.M.

    1963-02-12

    This invention contemplates a high temperature thermocouple for use in an inert or a reducing atmosphere. The thermocouple limbs are made of rhenium and graphite and these limbs are connected at their hot ends in compressed removable contact. The rhenium and graphite are of high purity and are substantially stable and free from diffusion into each other even without shielding. Also, the graphite may be thick enough to support the thermocouple in a gas stream. (AEC)

  17. Quantification of the Intracellular Life Time of Water Molecules to Measure Transport Rates of Human Aquaglyceroporins.

    PubMed

    Palmgren, Madelene; Hernebring, Malin; Eriksson, Stefanie; Elbing, Karin; Geijer, Cecilia; Lasič, Samo; Dahl, Peter; Hansen, Jesper S; Topgaard, Daniel; Lindkvist-Petersson, Karin

    2017-12-01

    Orthodox aquaporins are transmembrane channel proteins that facilitate rapid diffusion of water, while aquaglyceroporins facilitate the diffusion of small uncharged molecules such as glycerol and arsenic trioxide. Aquaglyceroporins play important roles in human physiology, in particular for glycerol metabolism and arsenic detoxification. We have developed a unique system applying the strain of the yeast Pichia pastoris, where the endogenous aquaporins/aquaglyceroporins have been removed and human aquaglyceroporins AQP3, AQP7, and AQP9 are recombinantly expressed enabling comparative permeability measurements between the expressed proteins. Using a newly established Nuclear Magnetic Resonance approach based on measurement of the intracellular life time of water, we propose that human aquaglyceroporins are poor facilitators of water and that the water transport efficiency is similar to that of passive diffusion across native cell membranes. This is distinctly different from glycerol and arsenic trioxide, where high glycerol transport efficiency was recorded.

  18. Optical and Chemical Properties of Mixed-valent Rhenium Oxide Films Synthesized by Reactive DC Magnetron Sputtering

    DTIC Science & Technology

    2015-04-03

    films were deposited within a stainless steel high vacuum chamber evacuated to a pressure of 5.3 105 Pa (4 107 Torr). A 3 mm thick, 50 mm diameter...G.E. Jellison, Thin Solid Films 234 (1993) 416 –422. [34] J.I. Pankove, Absorption, in: Optical Processes in Semiconductors, Dover Publications, New

  19. Fast dynamic electron transfer along infinite anion-cation chains in technetium and rhenium acido clusters

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

    Antipov, B.G.; Kryuchkov, S.V.; Grigor`ev, M.S.

    1995-09-01

    New technetium and rhenium compounds with ferricenium cations - [Fe(C{sub 5}H{sub 5}){sub 2}]{sub 3}[Tc{sub 6}I{sub 14}], [Fe(C{sub 5}H{sub 5}){sub 2}]{sub 3}[Tc{sub 6}Cl{sub 14}], [Fe(C{sub 5}H{sub 5}){sub 2}]{sub 2}[Tc{sub 8}Br{sub 14}], and [Fe(C{sub 5}H{sub 5}){sub 2}]{sub 2}[Re{sub 2}Br{sub 8}] - are synthesized and identified. The compounds are characterized by the methods of static magnetic susceptibility and differential scanning calorimetry; solid-state conductivity measurements; and IR, EPR, {sup 57}Fe Moessbauer, and X-ray photoelectron spectroscopic data. These data are compared with the physicochemical characteristics of ferricenium pertechnetate and hexachlorotechnetate, as well as of a number of reference technetium and rhenium compounds containing the samemore » anions but different cations. The structure of [Fe(C{sub 5}H{sub 5}){sub 2}]{sub 3}[Tc{sub 6}I{sub 14}] is determined by X-ray diffraction analysis of a single crystal [space group P6/m, a = 15.34(2), c = 12.70(1) {angstrom}]. The structures of the remaining compounds were confirmed by comparing their spectroscopic properties with corresponding properties of compounds with known composition and structure. None of the compounds with ferricenium cations exhibit covalent or other localized bonds between anions and cations. However, the physicochemical properties of these compounds indicate the occurrence of a fast dynamic electron transfer along infinite anion-cation chains. Compounds [Fe(C{sub 5}H{sub 5}){sub 2}]{sub 3}[Tc{sub 6}Cl{sub 14}] and [Fe(C{sub 5}H{sub 5}){sub 2}]{sub 2}[Tc{sub 8}Br{sub 14}] were found to exhibit a new phenomenon of X-ray-induced low-temper ature high-energy electron emission.« less

  20. Alloy formation and metal oxide segregation on Pt-Re/. gamma. -Al/sub 2/O/sub 3/ catalysts as investigated by temperature-programmed reduction

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

    Wagstaff, N.; Prins, R.

    1979-10-15

    Catalysts resembling reforming catalysts were prepared to contain finely dispersed 0.75% Pt, 0.7% Re, or 0.35% Pt plus 0.1-2% Re on chlorided ..gamma..-alumina. The catalysts were dried in an oxidizing atmosphere and studied by temperature-programed reduction. Up to a Re/Pt ratio of 0.6:1 the metals were completely reduced in hydrogen below 255/sup 0/C, i.e., the platinum catalyzed rhenium reduction. A small amount of added water (< 50 ppm) also promoted rhenium reduction. Segregation of the metals occurred in oxygen above 200/sup 0/C, but at 100/sup 0/C, the rate of segregation was slow. These results suggested that under reforming conditions, Pt-Remore » catalysts are completely reduced bimetallic clusters. The mechanisms of reduction, cluster formation, and oxidative segregation are discussed.« less

  1. Catalytic transformation of functionalized carboxylic acids using multifunctional rhenium complexes.

    PubMed

    Naruto, Masayuki; Agrawal, Santosh; Toda, Katsuaki; Saito, Susumu

    2017-06-13

    Carboxylic acids (CAs) are one of the most ubiquitous and important chemical feedstocks available from biorenewable resources, CO 2 , and the petrochemical industry. Unfortunately, chemoselective catalytic transformations of CH n CO 2 H (n = 1-3) groups into other functionalities remain a significant challenge. Herein, we report rhenium V complexes as extremely effective precatalysts for this purpose. Compared to previously reported heterogeneous and homogeneous catalysts derived from high- or low-valent metals, the present method involves a α-C-H bond functionalization, a hydrogenation, and a hydrogenolysis, which affords functionalized alcohols with a wide substrate scope and high chemoselectivity under relatively mild reaction conditions. The results represent an important step toward a paradigm shift from 'low-valent' to 'high-valent' metal complexes by exploring a new portfolio of selective functional group transformations of highly oxygenated organic substrates, as well as toward the exploitation of CAs as a valuable biorenewable feedstock.

  2. Vacuum Plasma Spray (VPS) Forming of Solar Thermal Propulsion Components Using Refractory Metals

    NASA Technical Reports Server (NTRS)

    Zimmerman, Frank; Gerish, Harold; Davis, William; Hissam, D. Andy

    1998-01-01

    The Thermal Spray Laboratory at NASA's Marshall Space Flight Center has developed and demonstrated a fabrication technique using Vacuum Plasma Spray (VPS) to form structural components from a tungsten/rhenium alloy. The components were assembled into an absorption cavity for a fully-functioning, ground test unit of a solar thermal propulsion engine. The VPS process deposits refractory metal onto a graphite mandrel of the desired shape. The mandrel acts as a male mold, forming the required contour and dimensions of the inside surface of the deposit. Tungsten and tungsten/25% rhenium were used in the development and production of several absorber cavity components. These materials were selected for their high temperature (less than 2500 C) strength. Each absorber cavity comprises 3 coaxial shells with two, double-helical flow passages through which the propellant gas flows. This paper describes the processing techniques, design considerations, and process development associated with forming these engine components.

  3. Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(I) chromophore and a fullerene electron acceptor unit.

    PubMed

    Nastasi, Francesco; Puntoriero, Fausto; Natali, Mirco; Mba, Miriam; Maggini, Michele; Mussini, Patrizia; Panigati, Monica; Campagna, Sebastiano

    2015-05-01

    A novel molecular dyad, 1, made of a dinuclear {[Re2(μ-X)2(CO)6(μ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties - including pump-probe transient absorption spectroscopy in the visible and near-infrared region - have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer ((3)MLLCT) state of the dinuclear rhenium(I) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.

  4. [Molecular remission induced by gemtuzumab ozogamicin in an elderly patient with relapsed acute promyelocytic leukemia].

    PubMed

    Yago, Kazuhiro; Aono, Maki; Shimada, Hideto

    2010-04-01

    A 79-year-old female with acute promyelocytic leukemia (APL) presented with second hematological relapse. She had been treated previously with modified AIDA protocol as the front-line therapy and had achieved complete remission. During ATRA maintenance therapy, the first hematological relapse occurred and she was treated with arsenic trioxide (ATO), achieving the second complete remission. After four courses of consolidation therapy of ATO, the second hematological relapse occurred. At this time, except for a transient effect of tamibarotene, neither arsenic trioxide nor combination chemotherapy was effective. The patient was then treated with two courses of gemtuzumab ozogamicin (GO) and achieved the third complete remission. At present, she is maintaining molecular remission more than one year after GO treatment. GO is considered to be a promising agent for elderly patients with relapsed acute promyelocytic leukemia resistant to arsenic trioxide.

  5. Re-Os isotope evidence from Mesozoic and Cenozoic basalts for secular evolution of the mantle beneath the North China Craton

    NASA Astrophysics Data System (ADS)

    Huang, Feng; Xu, Ji-Feng; Liu, Yong-Sheng; Li, Jie; Chen, Jian-Lin; Li, Xi-Yao

    2017-05-01

    The mechanism and process of lithospheric thinning beneath the North China Craton (NCC) are still debated. A key criterion in distinguishing among the proposed mechanisms is whether associated continental basalts were derived from the thinning lithospheric mantle or upwelling asthenosphere. Herein, we investigate the possible mechanisms of lithospheric thinning based on a systematic Re-Os isotopic study of Mesozoic to Cenozoic basalts from the NCC. Our whole-rock Re-Os isotopic results indicate that the Mesozoic basalts generally have high Re and Os concentrations that vary widely from 97.2 to 839.4 ppt and 74.4 to 519.6 ppt, respectively. They have high initial 187Os/188Os ratios ranging from 0.1513 to 0.3805, with corresponding variable γOs(t) values (+20 to +202). In contrast, the Re-Os concentrations and radiogenic Os isotope compositions of the Cenozoic basalts are typically lower than those of the Mesozoic basalts. The lowest initial 187Os/188Os ratios of the Cenozoic basalts are 0.1465 and 0.1479, with corresponding γOs(t) values of +15 and +16, which are within the range of ocean island basalts. These new Re-Os isotopic results, combined with the findings of previous studies, indicate that the Mesozoic basalts were a hybrid product of the melting of pyroxenite and peridotite in ancient lithospheric mantle beneath the NCC. The Cenozoic basalts were derived mainly from upwelling asthenosphere mixed with small amounts of lithospheric materials. The marked differences in geochemistry between the Mesozoic and Cenozoic basalts suggest a greatly reduced involvement of lithospheric mantle as the magma source from the Mesozoic to the Cenozoic. The subsequent lithospheric thinning of the NCC and replacement by upwelling asthenospheric mantle resulted in a change to asthenosphere-derived Cenozoic basalts.

  6. Ling-Zhi polysaccharides potentiate cytotoxic effects of anticancer drugs against drug-resistant urothelial carcinoma cells.

    PubMed

    Huang, Chao-Yuan; Chen, Jeff Yi-Fu; Wu, Jia-En; Pu, Yeong-Shiau; Liu, Guang-Yaw; Pan, Min-Hsiung; Huang, Ying-Tang; Huang, A-Mei; Hwang, Chi-Ching; Chung, Shu-Ju; Hour, Tzyh-Chyuan

    2010-08-11

    The combined effects of ling-zhi polysaccharide fraction 3 (LZP-F3) and anticancer drugs (cisplatin and arsenic trioxide) were examined in three human urothelial carcinoma (UC) cells (parental, NTUB1; cisplatin-resistant, N/P(14); and arsenic-resistant, N/As(0.5)). MTT assay and median-effect analysis revealed that LZP-F3 could profoundly reverse the chemosensitivity of N/P(14) and N/As(0.5) to cisplatin and arsenic, respectively, in a dose-dependent manner, which involved activation of p38 and down-regulation of Akt and XPA. A dose of 10 mug/mL of LZP-F3 induced significant G1 arrest in N/P(14) and N/As(0.5) cells by flow cytometry, which may be mediated by the induction of p21(WAF1/CIP1). The combination of LZP-F3 and arsenic trioxide produced a significant synergistic growth inhibition of NTUB1 and N/As(0.5) cells. Similar results were also found in N/P(14) cells. These molecular events of combined effects involved significant and earlier induction of Fas, caspase 3 and 8 activation, Bax and Bad up-regulation, Bcl-2 and Bcl-x(L) down-regulatuion, and cytochrome c release.

  7. Powder Injection Molding (PIM) for Low Cost Manufacturing of Intricate Parts to Net-Shape

    DTIC Science & Technology

    2006-05-01

    tungsten - or molybdenum-pseudoalloys, which can be net-shape manufactured only by PIM because of the tight dimension tolerances needed for the final...materials. Rhenium metal, for instance, which costs about US$ 800 /lb, offers the advantage of a high melting point. It can maintain reasonable...tubes, valves and thrusters of solid fluid propeller systems. Production of these components is however both expensive and difficult, as rhenium cannot

  8. Probing C-O bond activation on gas-phase transition metal clusters: Infrared multiple photon dissociation spectroscopy of Fe, Ru, Re, and W cluster CO complexes

    NASA Astrophysics Data System (ADS)

    Lyon, Jonathan T.; Gruene, Philipp; Fielicke, André; Meijer, Gerard; Rayner, David M.

    2009-11-01

    The binding of carbon monoxide to iron, ruthenium, rhenium, and tungsten clusters is studied by means of infrared multiple photon dissociation spectroscopy. The CO stretching mode is used to probe the interaction of the CO molecule with the metal clusters and thereby the activation of the C-O bond. CO is found to adsorb molecularly to atop positions on iron clusters. On ruthenium and rhenium clusters it also binds molecularly. In the case of ruthenium, binding is predominantly to atop sites, however higher coordinated CO binding is also observed for both metals and becomes prevalent for rhenium clusters containing more than nine atoms. Tungsten clusters exhibit a clear size dependence for molecular versus dissociative CO binding. This behavior denotes the crossover to the purely dissociative CO binding on the earlier transition metals such as tantalum.

  9. Large enhancement of superconducting transition temperature in single-element superconducting rhenium by shear strain

    PubMed Central

    Mito, Masaki; Matsui, Hideaki; Tsuruta, Kazuki; Yamaguchi, Tomiko; Nakamura, Kazuma; Deguchi, Hiroyuki; Shirakawa, Naoki; Adachi, Hiroki; Yamasaki, Tohru; Iwaoka, Hideaki; Ikoma, Yoshifumi; Horita, Zenji

    2016-01-01

    Finding a physical approach for increasing the superconducting transition temperature (Tc) is a challenge in the field of material science. Shear strain effects on the superconductivity of rhenium were investigated using magnetic measurements, X-ray diffraction, transmission electron microscopy, and first-principles calculations. A large shear strain reduces the grain size and simultaneously expands the unit cells, resulting in an increase in Tc. Here we show that this shear strain approach is a new method for enhancing Tc and differs from that using hydrostatic strain. The enhancement of Tc is explained by an increase in net electron–electron coupling rather than a change in the density of states near the Fermi level. The shear strain effect in rhenium could be a successful example of manipulating Bardeen–Cooper–Schrieffer-type Cooper pairing, in which the unit cell volumes are indeed a key parameter. PMID:27811983

  10. Rhenium-osmium-isotope constraints on the age of iron meteorites

    NASA Technical Reports Server (NTRS)

    Horan, M. F.; Morgan, J. W.; Walker, R. J.; Grossman, J. N.

    1992-01-01

    Rhenium and osmium concentrations and the osmium isotopic compositions of iron meteorites were determined by negative thermal ionization mass spectrometry. Data for the IIA iron meteorites define an isochron with an uncertainty of approximately +/-31 million years for meteorites about 4500 million years old. Although an absolute rhenium-osmium closure age for this iron group cannot be as precisely constrained because of uncertainty in the decay constant of Re-187, an age of 4460 million years ago is the minimum permitted by combined uncertainties. These age constraints imply that the parent body of the IIAB magmatic irons melted and subsequently cooled within 100 million years after the formation of the oldest portions of chondrites. Other iron meteorites plot above the IIA isochron, indicating that the planetary bodies represented by these iron groups may have cooled significantly later than the parent body of the IIA irons.

  11. Iridium-coated rhenium thrusters by CVD

    NASA Technical Reports Server (NTRS)

    Harding, J. T.; Kazaroff, J. M.; Appel, M. A.

    1989-01-01

    Operation of spacecraft thrusters at increased temperature reduces propellant requirements. Inasmuch as propellant comprises the bulk of a satellite's mass, even a small percentage reduction makes possible a significant enhancement of the mission in terms of increased payload. Because of its excellent high temperature strength, rhenium is often the structural material of choice. It can be fabricated into free-standing shapes by chemical vapor deposition (CVD) onto an expendable mandrel. What rhenium lacks is oxidation resistance, but this can be provided by a coating of iridium, also by CVD. This paper describes the process used by Ultramet to fabricate 22-N (5-lbf) and, more recently, 445-N (100-lbf) Ir/Re thrusters; characterizes the CVD-deposited materials; and summarizes the materials effects of firing these thrusters. Optimal propellant mixture ratios can be employed because the materials withstand an oxidizing environment up to the melting temperature of iridium, 2400 C (4350 F).

  12. Rhenium-osmium isotope constraints on the age of iron meteorites

    USGS Publications Warehouse

    Horan, M.F.; Morgan, J.W.; Walker, R.J.; Grossman, J.N.

    1992-01-01

    Rhenium and osmium concentrations and the osmium isotopic compositions of iron meteorites were determined by negative thermal ionization mass spectrometry. Data for the IIA iron meteorites define an isochron with an uncertainty of approximately ??31 million years for meteorites ???4500 million years old. Although an absolute rhenium-osmium closure age for this iron group cannot be as precisely constrained because of uncertainty in the decay constant of 187Re, an age of 4460 million years ago is the minimum permitted by combined uncertainties. These age constraints imply that the parent body of the IIAB magmatic irons melted and subsequently cooled within 100 million years after the formation of the oldest portions of chondrites. Other iron meteorites plot above the IIA isochron, indicating that the planetary bodies represented by these iron groups may have cooled significantly later than the parent body of the IIA irons.

  13. Iridium-coated rhenium thrusters by CVD

    NASA Technical Reports Server (NTRS)

    Harding, John T.; Kazaroff, John M.; Appel, Marshall A.

    1988-01-01

    Operation of spacecraft thrusters at increased temperature reduces propellant requirements. Inasmuch as propellant comprises the bulk of a satellite's mass, even a small percentage reduction makes possible a significant enhancement of the mission in terms of increased payload. Because of its excellent high temperature strength, rhenium is often the structural material of choice. It can be fabricated into free-standing shapes by chemical vapor deposition (CVD) onto an expendable mandrel. What rhenium lacks is oxidation resistance, but this can be provided by a coating of iridium, also by CVD. This paper describes the process used by Ultramet to fabricate 22-N (5-lbf) and, more recently, 445-N (100-lbf) Ir/Re thrusters; characterizes the CVD-deposited materials; and summarizes the materials effects of firing these thrusters. Optimal propellant mixture ratios can be employed because the materials withstand an oxidizing environment up to the meltimg temperature of iridium, 2400 C (4350 F).

  14. Testing a High-Sensitivity ATR FTIR Water Monitor for Ionic CWA Breakdown Products

    DTIC Science & Technology

    2003-12-31

    for ClO4− (perchlorate) 37 The Limits of Detection for ClO3− (chlorate) 41 The Limits of Detection for PFOS− ( perfluorooctanesulfonate ) 44 The... perfluorooctanesulfonate (PFOS−), C8F17SO3−, perfluorobutanesulfonate (PFBS−), C4F9SO3−, trifluoromethanesulfonate, CF3SO3−, permanganate, MnO4−, perrhenate, ReO4...become a significant environmental concern in many western states.3 Perfluorooctanesulfonate was, for decades a key ingredient in aqueous film

  15. Behavior of Re and Os during contact between an aqueous solution and oil: Consequences for the application of the Re-Os geochronometer to petroleum

    NASA Astrophysics Data System (ADS)

    Mahdaoui, Fatima; Michels, Raymond; Reisberg, Laurie; Pujol, Magali; Poirier, Yannick

    2015-06-01

    Several recent studies have raised the exciting possibility that oils can be dated using the Re-Os radioisotope system. However the exact nature of the events dated by this technique often remains unclear. Geochronologic interpretation of Re-Os data for oils is hampered by our limited knowledge of how these metals behave in petroleum systems. In particular, it is difficult to understand how isotopic homogenization, an essential prerequisite for the development of an isochronal relationship, can be achieved at the scale of a petroleum basin. The mechanisms capable of fractionating the Re/Os ratio in a suite of oils are also poorly understood. For this reason, we have performed an experimental study aimed at investigating the behavior of Re and Os during a particularly widespread phenomenon in petroleum systems, the interaction of formation waters with oils during migration. Contact experiments between natural oils and aqueous solutions enriched in Re and/or Os were carried out for varying lengths of time (6 h to 5 months), at different temperatures (25-150 °C), over a wide range of metal concentrations in the enriched solution (0.001-100 μg/g for Re; 1 and 10 ng/g for Os). In addition, the effect of oil composition on Re-Os exchange at the water-oil interface was examined by testing two oils with very different properties. All of our results demonstrate that Re and Os are transferred massively and very rapidly from the aqueous solution to the organic phase. This is true regardless of temperature or oil composition. It is also true for a very wide range of metal concentrations in the aqueous solution, up to an apparent saturation level that exceeds natural concentrations in oils by several orders of magnitude. Given the efficiency of Re and Os transfer from water to oil demonstrated here, and assuming that our findings are applicable to natural conditions, water/oil ratios of only about 250 would be needed to explain the Re and Os contents of most oils, based on the measured concentrations of Re and Os in groundwaters. Thus transfer of Re and Os from formation waters could plausibly provide a source for these metals in oils. Waters from a given basin may have roughly homogeneous Os isotopic compositions, approximating the average value of the source rocks. On the other hand, variable Re/Os ratios might be expected to develop, as a result of interaction with various phases (e.g. Fe-Mn oxides or authigenic pyrite) encountered by the water as it flows through the reservoir. If homogeneous 187Os/188Os ratios coupled with variable Re/Os ratios are transferred to the oils with which the waters come in contact, the isotopic geochronometer could be reset.

  16. Comparison of clinical outcomes of patients with relapsed acute promyelocytic leukemia induced with arsenic trioxide and consolidated with either an autologous stem cell transplant or an arsenic trioxide-based regimen.

    PubMed

    Thirugnanam, Rajasekar; George, Biju; Chendamarai, Ezhil; Lakshmi, Kavitha M; Balasubramanian, Poonkuzhali; Viswabandya, Auro; Srivastava, Alok; Chandy, Mammen; Mathews, Vikram

    2009-11-01

    In patients with relapsed acute promyelocytic leukemia (APL), the best consolidation regimen following induction of remission with arsenic trioxide (ATO) remains to be defined. Since January 2000, 37 patients with relapsed APL were treated at our center. The median age was 34 years (range, 6-57 years), and there were 20 males (54.1%). The median duration of first remission was 20.3 months (range, 2.9-81.2 months). Relapse was treated with single-agent ATO in 22 patients (59.5%), ATO+ATRA in 5 patients (13.5%), and ATO+ATRA + anthracycline in 10 patients (27%). Thirty-three patients (89%) achieved molecular remission after induction and a consolidation course. Fourteen patients opted to undergo autologous stem cell transplantation (SCT), and the remaining 19 patients received monthly cycles of ATO as a single agent (n=13) or ATO+ATRA (n=6) for 6 months. At a median follow-up of 32 months, the 5-year Kaplan-Meier estimate of event-free survival (EFS) was 83.33% +/- 15.21% in those who underwent autologous SCT versus 34.45% +/- 11.24% in those who did not (P=.001; log-rank test). Following remission induction with ATO-based regimens in patients with relapsed APL, consolidation with autologous SCT is associated with a significantly superior clinical outcome compared with ATO- and ATO+ATRA-based maintenance regimens.

  17. 40 CFR 63.11412 - What definitions apply to this subpart?

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... ore from trivalent to hexavalent chromium. Sodium chromate means Na2CrO4. It is produced by roasting...: Chromium Compounds Other Requirements and Information § 63.11412 What definitions apply to this subpart... matter loadings. Chromic acid means chromium trioxide (CrO3). It is produced by the electrolytic reaction...

  18. 40 CFR 63.11412 - What definitions apply to this subpart?

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... ore from trivalent to hexavalent chromium. Sodium chromate means Na2CrO4. It is produced by roasting...: Chromium Compounds Other Requirements and Information § 63.11412 What definitions apply to this subpart... matter loadings. Chromic acid means chromium trioxide (CrO3). It is produced by the electrolytic reaction...

  19. 40 CFR 63.11412 - What definitions apply to this subpart?

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... ore from trivalent to hexavalent chromium. Sodium chromate means Na2CrO4. It is produced by roasting...: Chromium Compounds Other Requirements and Information § 63.11412 What definitions apply to this subpart... matter loadings. Chromic acid means chromium trioxide (CrO3). It is produced by the electrolytic reaction...

  20. FLY ASH CONDITIONING WITH SULFUR TRIOXIDE

    EPA Science Inventory

    The report describes an evaluation of an SO3 injection system for the George Neal Unit 2 boiler of the Iowa Public Service Co. in Sioux City, Iowa. Results of base line tests without conditioning indicate a dust resistivity of 6 x 10 to the 12th power ohm-cm at 118C: the precipit...

  1. Arsenic trioxide (ATO) influences the gene expression of metallothioneins in human glioblastoma cells.

    PubMed

    Falnoga, Ingrid; Zelenik Pevec, Andreja; Šlejkovec, Zdenka; Žnidarič, Magda Tušek; Zajc, Irena; Mlakar, Simona Jurković; Marc, Janja

    2012-12-01

    Arsenic trioxide (As(2)O(3); ATO, TRISENOX®) is used to treat patients with refractory or relapsed acute promyelocytic leukaemia while its application for treatment of solid cancers like glioblastoma is still under evaluation. In the present study, we investigated the interaction of arsenic trioxide with metallothionein (MT) isoforms as a possible (protective response) resistance of glioblastoma cells to arsenic-induced cytotoxicity. Special attention was focused on MT3, the isoform expressed mainly in the brain. MT3 has low metal inducibility, fast metal binding/releasing properties and outstanding neuronal inhibitory activity. The human astrocytoma (glioblastoma) cell line U87 MG was treated with 0.6, 2 and 6-7 μM arsenic (equivalent to 0.3, 1 and 3-3.5 μM As(2)O(3)) for 12, 24 or 48 h and gene expression for different MT isoforms, namely MT2A, MT1A, MT1F, MT1X, MT1E and MT3, was measured by real time qPCR using SYBR Green I and Taqman® gene expression assays. TfR, 18S rRNA, GAPDH and AB were tested as reference genes, and the last two evaluated to be appropriate in conditions of low (GAPDH) and high (AB) arsenic exposure. The gene expression of MT3 gene was additionally tested and confirmed by restriction enzyme analysis with PvuII. In the given conditions the mRNAs of six MT isoforms were identified in human glioblastoma cell line U87 MG. Depending on arsenic exposure conditions, an increase or decrease of MT gene expression was observed for each isoform, with the highest increase for isoforms MT1X, MT1F and MT2A mRNA (up to 13-fold) and more persistent decreases for MT1A, MT1E and MT3 mRNA. Despite the common assumption of the noninducibility of MT3, the evident MT3 mRNA increase was observed during high As exposure (up to 4-fold). In conclusion, our results clearly demonstrate the influence of As on MT isoform gene expression. The MT1X, MT1F and MT2A increase could represent brain tumour acquired resistance to As cytotoxicity while the MT3 increase is more enigmatic, with its possible involvement in arsenic-related induction of type II cell death.

  2. Sealing ability of white and gray mineral trioxide aggregate mixed with distilled water and 0.12% chlorhexidine gluconate when used as root-end filling materials.

    PubMed

    Shahi, Shahriar; Rahimi, Saeed; Yavari, Hamid Reza; Shakouie, Sahar; Nezafati, Saeed; Abdolrahimi, Majid

    2007-12-01

    This in vitro study used dye penetration to compare the sealing ability of white and gray mineral trioxide aggregate mixed with distilled water and 0.12% chlorhexidine gluconate when used as root-end filling materials. Ninety-six single-rooted human teeth were cleaned, shaped, and obturated with gutta-percha and AH26 root canal sealer. The apical 3 mm of each root was resected, and 3-mm deep root-end cavity preparations were made. The teeth were randomly divided into 4 experimental groups, each containing 20 teeth, and 2 negative and positive control groups, each containing 8 teeth. Root-end cavities in the experimental groups were filled with the experimental materials. After decoronation of the teeth and application of nail polish, the teeth were exposed to India ink for 72 hours and longitudinally sectioned, and the extent of dye penetration was measured with a stereomicroscope. Statistical analysis showed that there were no significant differences among the 4 experimental groups.

  3. Comparison of in vivo dental pulp responses to capping with iRoot BP Plus and mineral trioxide aggregate.

    PubMed

    Shi, S; Bao, Z F; Liu, Y; Zhang, D D; Chen, X; Jiang, L M; Zhong, M

    2016-02-01

    To compare dental pulp responses to capping with iRoot BP Plus and mineral trioxide aggregate (MTA) in dogs. Pulps in 36 incisors of three 8-month-old beagle dogs were mechanically exposed and assigned to two experimental groups (iRoot BP Plus group and MTA group, n = 15 per group) and one control group (n = 6). Direct pulp capping was performed using either iRoot BP Plus or MTA. The animals were sacrificed 3 months later. Histological sections were stained with haematoxylin and eosin and categorized using a histologic scoring system. Statistical analysis was performed using the Mann-Whitney U-test, with the significance set at 0.05. The majority of specimens in both experimental groups were associated with complete calcified bridge formation and the absence of pulpal inflammation. There was no significant difference in pulp response to iRoot BP Plus or MTA after 3 months (P > 0.05). iRoot BP Plus and MTA had similar favourable results when used as pulp-capping agents. © 2015 International Endodontic Journal. Published by John Wiley & Sons Ltd.

  4. Emissions of sulfur trioxide from coal-fired power plants.

    PubMed

    Srivastava, R K; Miller, C A; Erickson, C; Jambhekar, R

    2004-06-01

    Emissions of sulfur trioxide (SO3) are a key component of plume opacity and acid deposition. Consequently, these emissions need to be low enough to not cause opacity violations and acid deposition. Generally, a small fraction of sulfur (S) in coal is converted to SO3 in coal-fired combustion devices such as electric utility boilers. The emissions of SO3 from such a boiler depend on coal S content, combustion conditions, flue gas characteristics, and air pollution devices being used. It is well known that the catalyst used in the selective catalytic reduction (SCR) technology for nitrogen oxides control oxidizes a small fraction of sulfur dioxide in the flue gas to SO3. The extent of this oxidation depends on the catalyst formulation and SCR operating conditions. Gas-phase SO3 and sulfuric acid, on being quenched in plant equipment (e.g., air preheater and wet scrubber), result in fine acidic mist, which can cause increased plume opacity and undesirable emissions. Recently, such effects have been observed at plants firing high-S coal and equipped with SCR systems and wet scrubbers. This paper investigates the factors that affect acidic mist production in coal-fired electric utility boilers and discusses approaches for mitigating emission of this mist.

  5. Mechanism of Me–Re Bond Addition to Platinum(II) and Dioxygen Activation by the Resulting Pt–Re Bimetallic Center

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

    Pichaandi, Kothanda Rama; Kabalan, Lara; Amini, Hashem

    Unusual cis-oxidative addition of methyltrioxorhenium (MTO) to [PtMe 2(bpy)], (bpy = 2,2'-bipyridine) (1) is described. Addition of MTO to 1 first gives the Lewis acid–base adduct [(bpy)Me 2Pt–Re(Me)(O) 3] (2) and subsequently affords the oxidative addition product [(bpy)Me 3PtReO 3] (3). All complexes 1, MTO, 2, and 3 are in equilibrium in solution. The structure of 2 was confirmed by X-ray crystallography, and its dissociation constant in solution is 0.87 M. The structure of 3 was confirmed by extended X-ray absorption fine structure and X-ray absorption near-edge structure in tandem with one- and two-dimensional NMR spectroscopy augmented by deuterium andmore » 13C isotope-labeling studies. Kinetics of formation of compound 3 revealed saturation kinetics dependence on [MTO] and first-order in [Pt], complying with prior equilibrium formation of 2 with oxidative addition of Me–Re being the rate-determining step. Exposure of 3 to molecular oxygen or air resulted in the insertion of an oxygen atom into the platinum–rhenium bond forming [(bpy)Me 3PtOReO 3] (4) as final product. In conclusion, density functional theory analysis on oxygen insertion pathways leading to complex 4, merited on the basis of Russell oxidation pathway, revealed the involvement of rhenium peroxo species.'« less

  6. Iridium-Coated Rhenium Radiation-Cooled Rockets

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.; Biaglow, James A.; Schneider, Steven J.

    1997-01-01

    Radiation-cooled rockets are used for a range of low-thrust propulsion functions, including apogee insertion, attitude control, and repositioning of satellites, reaction control of launch vehicles, and primary propulsion for planetary space- craft. The key to high performance and long lifetimes for radiation-cooled rockets is the chamber temperature capability. The material system that is currently used for radiation-cooled rockets, a niobium alloy (C103) with a fused silica coating, has a maximum operating temperature of 1370 C. Temperature limitations of C103 rockets force the use of fuel film cooling, which degrades rocket performance and, in some cases, imposes a plume contamination issue from unburned fuel. A material system composed of a rhenium (Re) substrate and an iridium (Ir) coating has demonstrated operation at high temperatures (2200 C) and for long lifetimes (hours). The added thermal margin afforded by iridium-coated rhenium (Ir/Re) allows reduction or elimination of fuel film cooling. This, in turn, leads to higher performance and cleaner spacecraft environments. There are ongoing government- and industry-sponsored efforts to develop flight Ir/ Re engines, with the primary focus on 440-N, apogee insertion engines. Complementing these Ir/Re engine development efforts is a program to address specific concerns and fundamental characterization of the Ir/Re material system, including (1) development of Ir/Re rocket fabrication methods, (2) establishment of critical Re mechanical properly data, (3) development of reliable joining methods, and (4) characterization of Ir/Re life-limiting mechanisms.

  7. Platinum Group Coatings for Refractory Metals

    DTIC Science & Technology

    1984-06-01

    temperatures and deposition was very slow. We decided to try iridium hexaflouride, Siridium trichloride hydrate, iridiuw carbonyl and tris-acetyl acetonato...T:*ouu sue. CO. Rhenium Refractory Metals 03 1 d.pRsiý C rg Iridium Coatings 2i 8 bapo i 10. ASSTRACT Won#~.. on mov ofot~sfte.. iad k.dhItfV by b...b q Oxidation resistant coatings of iridium on rhenium substrates have been produced by chemical vapor deposition from an iridium acetyl acetonate

  8. Rhenium Radioisotopes for Therapeutic Radiopharmaceutical Development

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

    Beets, A.L.; Knapp, F.F., Jr.; Kropp, J.

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

  9. Negative Impact of Total Body Irradiation on the Antitumor Activity of Rhenium-(I)-diselenoether.

    PubMed

    Collery, Philippe; Santoni, Francois; Mohsen, Ahmed; Mignard, Caroline; Desmaele, Didier

    2016-11-01

    It has been shown that a rhenium-(I)-diselenoether complex had significant antitumor activity in MDA-MB231 tumor-bearing mice after repeated oral or intraperitoneal administrations for 4 weeks at safe doses of 10 mg/kg/day. It has also been suggested that lower doses could be as effective as this dose. We, thus, tested two doses (5 and 10 mg/kg). The drug was orally administered daily by gavage for 4 weeks and for a further 2 weeks with or without 15 mg/kg paclitaxel treatment (intravenously, once a week). This experiment was performed in MDA-MB 231 tumor-bearing mice, as a model of resistant breast tumor. However, in contrast to previous studies, the mice were pretreated with total body irradiation to increase the tumor growth. These two doses were safe, even in combination with paclitaxel. The expected tumor regression was not observed with the rhenium-(I)-diselenoether complex, and there was even a significant increase of the tumor volume in mice treated with 10 mg/kg versus controls. No synergism was observed with paclitaxel. We comment on the possible negative impact of radiotherapy on the antitumor activity of the drug. Plasma and tumor rhenium and selenium concentrations are also reported. Copyright© 2016 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

  10. Pharmacokinetic properties of new antitumor radiopharmaceutical on the basis of diamond nanoporous composites labeled with rhenium-188

    NASA Astrophysics Data System (ADS)

    Petriev, V. M.; Tishchenko, V. K.; Kuril'chik, A. A.; Skvortsov, V. G.

    2017-01-01

    Today the development of address therapeutic radionuclide delivery systems directly to tumor tissue is of current interest. It can be achieved by the design of drug containers of specific sizes and shapes from carbon-based composite materials. It will be allowed to enhance the efficacy of anticancer therapy and avoid serious side effects. In this work we studied the pharmacokinetic properties of nanodiamond nanoporous composite labeled with rhenium-188 in rats with hepatocholangioma PC-1 after intratumoral injection. It was established that substantial part of injected radioactivity remained in tumor tissue. Within three hours after 188Re-nanoporous composites injection activity in tumor constituted 79.1-91.3% of injected dose (ID). Then activity level declined to 45.9% ID at 120 hours. No more than 1.34% ID entered the bloodstream. In soft organs and tissues, except thyroid gland, the content of compound didn’t exceed 0.3% ID/g. The highest activity in thyroid gland was 6.95% ID/g. In conclusion, received results suggest 188Re-nanoporous composites can be promising radionuclide delivery systems for cancer treatment.

  11. Rhenium and technetium complexes that bind to amyloid-β plaques.

    PubMed

    Hayne, David J; North, Andrea J; Fodero-Tavoletti, Michelle; White, Jonathan M; Hung, Lin W; Rigopoulos, Angela; McLean, Catriona A; Adlard, Paul A; Ackermann, Uwe; Tochon-Danguy, Henri; Villemagne, Victor L; Barnham, Kevin J; Donnelly, Paul S

    2015-03-21

    Alzheimer's disease is associated with the presence of insoluble protein deposits in the brain called amyloid plaques. The major constituent of these deposits is aggregated amyloid-β peptide. Technetium-99m complexes that bind to amyloid-β plaques could provide important diagnostic information on amyloid-β plaque burden using Single Photon Emission Computed Tomography (SPECT). Tridentate ligands with a stilbene functional group were used to form complexes with the fac-[M(I)(CO)3](+) (M = Re or (99m)Tc) core. The rhenium carbonyl complexes with tridentate co-ligands that included a stilbene functional group and a dimethylamino substituent bound to amyloid-β present in human frontal cortex brain tissue from subjects with Alzheimer's disease. This chemistry was extended to make the analogous [(99m)Tc(I)(CO)3](+) complexes and the complexes were sufficiently stable in human serum. Whilst the lipophilicity (log D7.4) of the technetium complexes appeared ideally suited for penetration of the blood-brain barrier, preliminary biodistribution studies in an AD mouse model (APP/PS1) revealed relatively low brain uptake (0.24% ID g(-1) at 2 min post injection).

  12. New Pyrazolium Salts as a Support for Ionic Liquid Crystals and Ionic Conductors

    PubMed Central

    Pastor, María Jesús; Sánchez, Ignacio; Schmidt, Rainer; Cano, Mercedes

    2018-01-01

    Ionic liquid crystals (ILCs) are a class of materials that combine the properties of liquid crystals (LCs) and ionic liquids (ILs). This type of materials is directed towards properties such as conductivity in ordered systems at different temperatures. In this work, we synthesize five new families of ILCs containing symmetrical and unsymmetrical substituted pyrazolium cations, with different alkyl long-chains, and anions such as Cl−, BF4−, ReO4−, p-CH3-6H4SO3− (PTS) and CF3SO3− (OTf). We study their thermal behavior by polarized light optical microscopy (POM) and differential scanning calorimetry (DSC). All of them, except those with OTf as counteranion, show thermotropic mesomorphism. The observations by POM reveal textures of lamellar mesophases. Those agree with the arrangement observed in the X-ray crystal structure of [H2pzR(4),R(4)][ReO4]. The nature of the mesophases is also confirmed by variable temperature powder X-ray diffraction. On the other hand, the study of the dielectric properties at variable temperature in mesomorphic (Cl− and BF4−) and non-mesomorphic (OTf) salts indicates that the supramolecular arrangement of the mesophase favors a greater ionic mobility and therefore ionic conductivity. PMID:29614030

  13. Comparative investigations of sodium arsenite, arsenic trioxide and cadmium sulphate in combination with gamma-radiation on apoptosis, micronuclei induction and DNA damage in a human lymphoblastoid cell line.

    PubMed

    Hornhardt, Sabine; Gomolka, Maria; Walsh, Linda; Jung, Thomas

    2006-08-30

    In the field of radiation protection the combined exposure to radiation and other toxic agents is recognised as an important research area. To elucidate the basic mechanisms of simultaneous exposure, the interaction of the carcinogens and environmental toxicants cadmium and two arsenic compounds, arsenite and arsenic trioxide, in combination with gamma-radiation in human lymphoblastoid cells (TK6) were investigated. Gamma-radiation induced significant genotoxic effects such as micronuclei formation, DNA damage and apoptosis, whereas arsenic and cadmium had no significant effect on these indicators of cellular damage at non-toxic concentrations. However, in combination with gamma-radiation arsenic trioxide induced a more than additive apoptotic rate compared to the sum of the single effects. Here, the level of apoptotic cells was increased, in a dose-dependent way, up to two-fold compared to the irradiated control cells. Arsenite did not induce a significant additive effect at any of the concentrations or radiation doses tested. On the other hand, arsenic trioxide was less effective than arsenite in the induction of DNA protein cross-links. These data indicate that the two arsenic compounds interact through different pathways in the cell. Cadmium sulphate, like arsenite, had no significant effect on apoptosis in combination with gamma-radiation at low concentrations and, at high concentrations, even reduced the radiation-induced apoptosis. An additive effect on micronuclei induction was observed with 1muM cadmium sulphate with an increase of up to 80% compared to the irradiated control cells. Toxic concentrations of cadmium and arsenic trioxide seemed to reduce micronuclei induction. The results presented here indicate that relatively low concentrations of arsenic and cadmium, close to those occuring in nature, may interfere with radiation effects. Differences in action of the two arsenic compounds were identified.

  14. Robust transcriptional tumor signatures applicable to both formalin-fixed paraffin-embedded and fresh-frozen samples

    PubMed Central

    Cheng, Jun; He, Jun; Liu, Huaping; Cai, Hao; Hong, Guini; Zhang, Jiahui; Li, Na; Ao, Lu; Guo, Zheng

    2017-01-01

    Formalin-fixed paraffin-embedded (FFPE) samples represent a valuable resource for clinical researches. However, FFPE samples are usually considered an unreliable source for gene expression analysis due to the partial RNA degradation. In this study, through comparing gene expression profiles between FFPE samples and paired fresh-frozen (FF) samples for three cancer types, we firstly showed that expression measurements of thousands of genes had at least two-fold change in FFPE samples compared with paired FF samples. Therefore, for a transcriptional signature based on risk scores summarized from the expression levels of the signature genes, the risk score thresholds trained from FFPE (or FF) samples could not be applied to FF (or FFPE) samples. On the other hand, we found that more than 90% of the relative expression orderings (REOs) of gene pairs in the FF samples were maintained in their paired FFPE samples and largely unaffected by the storage time. The result suggested that the REOs of gene pairs were highly robust against partial RNA degradation in FFPE samples. Finally, as a case study, we developed a REOs-based signature to distinguish liver cirrhosis from hepatocellular carcinoma (HCC) using FFPE samples. The signature was validated in four datasets of FFPE samples and eight datasets of FF samples. In conclusion, the valuable FFPE samples can be fully exploited to identify REOs-based diagnostic and prognostic signatures which could be robustly applicable to both FF samples and FFPE samples with degraded RNA. PMID:28036264

  15. Long-term life testing of Geostationary Operational Environmental Satellite (GOES) encoder lamps

    NASA Technical Reports Server (NTRS)

    Powers, Charles E.

    1992-01-01

    The aging characteristics and lifetimes of tungsten filament encoder lamps were determined as a function of operating voltage and filament material. For pure tungsten and thoria doped (1 pct.) filament lamps, crystal grain growth over the center portion of the filament leads to the ultimate failure of the lamp. The development of notches associated with this grain growth is the cause of lamp burn out. Eventually, one of the notches will 'etch' through the filament, causing it to fail open. For rhenium doped (3 pct.) filament lamps, distortion of the filament leads to the ultimate failure of the lamp. The lifetime of these lamps is about 1 year at an operating voltage of 5.0 volts. The pure tungsten filament lamps have the longest average lifetime, and the thoria doped filament lamps have the shortest at 5.0 volts. The lifetimes of these lamps is about 7 years at an operating voltage of 3.5 volts. Data suggest that the rhenium doped lamps will have the longest average lifetime at 3.5 volts, and the thoria doped will have the shortest. These lifetimes are comparable to the desired lifetimes of 7 years.

  16. Liquid phase deposition synthesis of hexagonal molybdenum trioxide thin films

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

    Deki, Shigehito; Beleke, Alexis Bienvenu; Kotani, Yuki

    2009-09-15

    Hexagonal molybdenum trioxide thin films with good crystallinity and high purity have been fabricated by the liquid phase deposition (LPD) technique using molybdic acid (H{sub 2}MoO{sub 4}) dissolved in 2.82% hydrofluoric acid (HF) and H{sub 3}BO{sub 3} as precursors. The crystal was found to belong to a hexagonal hydrate system MoO{sub 3}.nH{sub 2}O (napprox0.56). The unit cell lattice parameters are a=10.651 A, c=3.725 A and V=365.997 A{sup 3}. Scanning electron microscope (SEM) images of the as-deposited samples showed well-shaped hexagonal rods nuclei that grew and where the amount increased with increase in reaction time. X-ray photon electron spectroscopy (XPS) spectramore » showed a Gaussian shape of the doublet of Mo 3d core level, indicating the presence of Mo{sup 6+} oxidation state in the deposited films. The deposited films exhibited an electrochromic behavior by lithium intercalation and deintercalation, which resulted in coloration and bleaching of the film. Upon dehydration at about 450 deg. C, the hexagonal MoO{sub 3}.nH{sub 2}O was transformed into the thermodynamically stable orthorhombic phase. - Abstract: SEM photograph of typical h-MoO{sub 3}.nH{sub 2}O thin film nuclei obtained after 36 h at 40 deg. C by the LPD method. Display Omitted« less

  17. Geochronology and geochemistry of the granitoids and ore - forming age in the Xiaoyao tungsten polymetallic skarn deposit in the Jiangnan Massif tungsten belt, China: Implications for their petrogenesis, geodynamic setting, and mineralization

    NASA Astrophysics Data System (ADS)

    Su, Qiangwei; Mao, Jingwen; Wu, Shenghua; Zhang, Zhaochong; Xu, Shengfa

    2018-01-01

    The Xiaoyao tungsten polymetallic skarn deposit in the eastern Jiangnan Massif of Yangtze Block is located at the contact between a granodiorite pluton and Sinian-Cambrian limestone. The intrusions in the tungsten-rich district comprise the Xiaoyao and other granodiorite plutons and granite porphyry dikes. The age determinations by LA-ICP-MS U-Pb dating of zircons indicate that the granodiorite formed at 149.4 ± 1.1 Ma, whereas the granite porphyry was emplaced at 133.2 ± 0.7 Ma. Re-Os dating of molybdenite from the skarn orebodies yielded a weighted average age of 148.7 ± 2.3 Ma (n = 5). These ages indicate that the tungsten mineralization is temporally related to the granodiorite. The granodiorites are metaluminous (A/CNK = 0.86-0.98) and in the high-K calc-alkaline series. They contain hornblende and have a negative correlation between P2O5 and SiO2, indicating that they are typical I-type intrusions. The granite porphyries exhibit high alkali contents (Na2O + K2O = 7.97-9.53%), elevated FeOT/(FeOT + MgO) ratios (0.83-0.94), high concentrations of Zr, Nb, Ce, and Y, and high Zr saturation temperatures (average of 812 °C); thus, they are geochemically similar to A-type intrusions. The initial 87Sr/86Sr and εNd(t) values range respectively from 0.7074 to 0.7083 and from - 7.9 to - 1.3 for the granodiorite, and from 0.7008 to 0.7083 and from - 6.3 to - 4.7 for the granite porphyry. In addition, two-stage Nd model ages (T2DM) of 1.0-1.6 Ga for the granodiorite and 1.3-1.4 Ga for the granite porphyry indicate that the Proterozoic crustal rocks of the Shangxi Group could have contributed to the Xiaoyao magmas. The rhenium contents of the molybdenite grains vary from 32 to 136 ppm, suggesting that the molybdenum was derived mainly from a mixture of mantle and crustal sources. Based on the new geochemical data and regional geological investigations, we propose that the Late Jurassic mineralization-related I-type granodiorite was derived from the Neoproterozoic Shangxi metamorphic rocks with some additional input of mantle material. The magmatism was triggered by asthenospheric upwelling induced by slab tearing during oblique subduction of the paleo-Pacific plate beneath the South China Block.

  18. Iridium/Rhenium Parts For Rocket Engines

    NASA Technical Reports Server (NTRS)

    Schneider, Steven J.; Harding, John T.; Wooten, John R.

    1991-01-01

    Oxidation/corrosion of metals at high temperatures primary life-limiting mechanism of parts in rocket engines. Combination of metals greatly increases operating temperature and longevity of these parts. Consists of two transition-element metals - iridium and rhenium - that melt at extremely high temperatures. Maximum operating temperature increased to 2,200 degrees C from 1,400 degrees C. Increases operating lifetimes of small rocket engines by more than factor of 10. Possible to make hotter-operating, longer-lasting components for turbines and other heat engines.

  19. Superconducting molybdenum-rhenium electrodes for single-molecule transport studies

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

    Gaudenzi, R.; Island, J. O.; Bruijckere, J. de

    2015-06-01

    We demonstrate that electronic transport through single molecules or molecular ensembles, commonly based on gold (Au) electrodes, can be extended to superconducting electrodes by combining gold with molybdenum-rhenium (MoRe). This combination induces proximity-effect superconductivity in the gold to temperatures of at least 4.6 K and magnetic fields of 6 T, improving on previously reported aluminum based superconducting nanojunctions. As a proof of concept, we show three-terminal superconductive transport measurements through an individual Fe{sub 4} single-molecule magnet.

  20. Molybdenite tricks with titanite give history of the Central Indian Tectonic Zone

    NASA Astrophysics Data System (ADS)

    Stein, Holly J.; Hannah, Judith L.; Pandit, Manoj K.; Mohanty, Saradaprasad; Corfu, Fernando; Zimmerman, Aaron

    2014-05-01

    The time that the cratonic blocks joined to form peninsular India creating the E-W-trending Central Indian Tectonic Zone (CITZ) is important for tectonic reconstructions and Paleoproterozoic glaciations, and fundamental to understanding how sutures behave through time. An abundance of recent literature highlights ~1.0 Ga as the time of suturing. This late 1.0 Ga meeting of the two cratons, however, is increasingly difficult to reconcile. One of the well-studied and well-mapped terranes in the southern part of the CITZ is the Sausar Belt [1]. The metasedimentary and metavolcanic rocks comprising the extensive Paleoproterozoic Sausar Group are multiply deformed. To examine the history of the Sausar Belt from a new vantage, we employed Re-Os dating of molybdenite, a sulfide that serves faithfully as a single-mineral radiometric clock in both magmatic and metamorphic environments [2]. Molybdenite is rare in the Sausar belt. Samples containing a 1-cm molybdenite patch and coarse-grained, euhedral, clear brown titanite were acquired from two different varieties of calc-silicate rocks near the village of Umri in central India. The molybdenite occurs in a calcite-quartz vein that clearly cross-cuts a strongly deformed calc-silicate host with quartz-biotite and quartz bands at the cm scale. This vein, metamorphic in character, is about 1-cm-wide and slightly deformed. The molybdenite was contained wholly within the vein. To check for possible Re-Os decoupling [2], we split the molybdenite patch into seven subsamples, analyzing each fraction separately; in sum, these seven fractions account for the entire molybdenite crystal. We obtained extremely disparate ages for the individual fractions, ranging from 1.4 to 3.1 Ga. These data were recombined on an atomic basis to calculate the Re-Os age for the entire crystal, a trick we employed after affirming there was no additional sulfide and no additional molybdenite that might compete for Re and Os in our hand-sample of 10 x 15 cm. This circumstance provided us the opportunity to turn Re-Os decoupling to our advantage. The whole-crystal Re-Os molybdenite age on combining data from individual separates is between 2.41 and 2.45 Ga, depending on estimates of very minor silicate dilution as the crystal was extracted piecemeal from the vein. The U-Pb age for euhedral titanite crystals in a dense massive calc-silicate host, not unexpectedly, is ~1.0 Ga. The molybdenite and titanite record two different episodes of metamorphism. These results suggest that the Sausar Group calc-silicate rocks we analyzed are earliest Paleoproterozoic, >2.41 Ga. Shortly after deposition these rocks were metamorphosed - the first event in a long history of metamorphism and deformation continually focused along an ancient suture. These results have implications for the CITZ, and are similar to ages found in terranes on either side of this continental scale collisional belt [3,4]. This study was funded by the U.S. National Science Foundation (EAR-1119655). References Cited [1] Mohanty, S. (2010) Journal of Asian Earth Sciences 39: 516-526. [2] Stein et al. (2003) Geochimica et Cosmochimica Acta 67: 3673-3686. [3] Stein et al. (2004) Precambrian Research 134: 189-226. [4] Radhakrishna et al. (2013) Precambrian Research 226: 91-104.

  1. Carbon nanotubes-bridged molybdenum trioxide nanosheets as high performance anode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sun, Haiyan; Hanlon, Damien; Dinh, Duc Anh; Boland, John B.; Esau Del Rio Castillo, Antonio; Di Giovanni, Carlo; Ansaldo, Alberto; Pellegrini, Vittorio; Coleman, Jonathan N.; Bonaccorso, Francesco

    2018-01-01

    The search for novel nanomaterials driving the development of high-performance electrodes in lithium ion batteries (LIBs) is at the cutting edge of research in the field of energy storage. Here, we report on the synthesis of single wall carbon nanotube (SWNT)-bridged molybdenum trioxide (MoO3) nanosheets as anode material for LIBs. We exploit liquid phase exfoliation of layered MoO3 crystallites to produce multilayer MoO3 nanosheets dispersed in isopropanol, which are then mixed with solution processed SWNTs in the same solvent. The addition of SWNTs to the MoO3 nanosheets provides the conductive framework for electron transport, as well as a bridge structure, which buffers the volume expansion upon lithiation/de-lithiation. We demonstrate that the hybrid SWNT-bridged MoO3 structure is beneficial for both the mechanical stability and the electrochemical characteristics of the anodes leading to a specific capacity of 865 mAh g-1 at 100 mA g-1 after 100 cycles, with a columbic efficiency approaching 100% and a capacity fading of 0.02% per cycle. The low-cost, non-toxic, binder-free hybrid MoO3/SWNT here developed represents a step forward for the applicability of exfoliated MoO3 in LIB anodes, delivering high energy and power densities as well as long lifetime.

  2. Contamination of tooth-colored mineral trioxide aggregate used as a root-end filling material: a bacterial leakage study.

    PubMed

    Montellano, Angela M; Schwartz, Scott A; Beeson, Thomas J

    2006-05-01

    This experiment investigated the ability of tooth-colored mineral trioxide aggregate (MTA) to maintain an apical seal in the presence of bacteria when contaminated with blood, saline or saliva. Ninety extracted human teeth with single canals were randomly placed into six groups of 15. Canals were prepared to size 50. The apical 3 mm of each root was removed and 3 mm root-end preparations were made with a #329 bur. Root-end preparations in groups 1 through 3 were filled with MTA after contamination with blood, saline, or saliva, respectively. In group 4, uncontaminated root-end preparations were filled with MTA. Groups 5 and 6 served as negative and positive controls. A tube/tooth assembly was utilized to suspend each root end in Trypticase Soy Broth (TSB). The access chambers were filled with Staphylococcus epidermidis. Positive growth over thirty days was demonstrated by turbidity of the TSB. Vitek analysis was used to confirm the presence of S. epidermidis in the positive samples. Data evaluation consisted of a chi(2) analysis (p < 0.05). Although all experimental groups demonstrated leakage, tooth-colored MTA contaminated with saliva (group 3) leaked significantly more than the uncontaminated tooth-colored MTA (group 4) (p = 0.028).

  3. Low Leakage Superconducting Tunnel Junctions with a Single Crystal Al2O3 Barrier

    DTIC Science & Technology

    2016-03-30

    have recently implemented Josephson junction superconducting devices into qubits [1-6]. Before a multi -qubit quantum computer is realized, however...Low-Leakage Superconducting Tunnel Junctions with a Single-Crystal Al2O3 Barrier* S Oh1,2, K Cicak1, R McDermott3, K B Cooper3, K D Osborn1, R W...growth scheme for single-crystal Al2O3 tunnel barriers. The barriers are epitaxially grown on single-crystal rhenium (Re) base electrodes that are

  4. Cage Compounds as Potential Energetic Oxidizers: A Theoretical Study of a Cage Isomer of N2O3

    DTIC Science & Technology

    2014-07-01

    Laboratory. References [1] P. W. M. Jacobs, H. M. Whitehead, Decomposition and Combustion of Ammonium Perchlorate, Chem. Rev., 1969, 69 551- 590 . [2...and Symmetric Dinitrogen Trioxide in Nitric-Oxide Matrices by Raman and Infrared- Spectroscopy, J. Phys. Chem. 1983, 87, 1113- 1120. [14] a) X. Wang

  5. Cyclic-RGD penta-peptides cRGDyK derivatized with cyclopentadienyl complexes of technetium and rhenium as radiopharmaceutical probes.

    PubMed

    Nadeem, Qaisar; Shen, Yunjun; Warsi, Muhammad Farooq; Nasar, Gulfam; Qadir, Muhammad Abdul; Alberto, Roger

    2017-07-01

    The present study reports the syntheses of half-sandwich complexes of the type [M(η 5 -C 5 H 4 CONH-R)(CO) 3 ] (M═Re, 99m Tc;R═cyclic RGD peptide (cRGDyK) for potential imaging of α v β 3 integrin expression. The 99m Tc complex was prepared directly from the reaction of [ 99m Tc(OH 2 ) 3 (CO) 3 ] + with cRGDyK, doubly conjugated to Thiele's acid [(C 5 H 5 COOH) 2 ] in water. This approach extends the viability of metal-mediated retro Diels-Alder reactions for the preparation of small molecules such as linear tripeptides to a more complex cyclic peptide carrying a [(η 5 -C 5 H 4 ) 99m Tc(CO) 3 ] tag. The Diels-Alder product [(C 5 H 5 CONH-cRGDyK) 2 ] was prepared from Thiele's acid via double peptide coupling. The Re-complex [Re(η 5 -C 5 H 4 CONH-cRGDyK)(CO) 3 ] was obtained by attaching [Re(η 5 -C 5 H 4 COOH)(CO) 3 ] directly to the N-terminus of cRGDyK. The identity of the 99m Tc-complex is confirmed by chromatographic comparison with the corresponding rhenium complex, fully characterized by spectroscopic techniques. Copyright © 2017 John Wiley & Sons, Ltd.

  6. Synthesis, spectroscopic, electrochemical and computational studies of rhenium(i) tricarbonyl complexes based on bidentate-coordinated 2,6-di(thiazol-2-yl)pyridine derivatives.

    PubMed

    Klemens, Tomasz; Czerwińska, Katarzyna; Szlapa-Kula, Agata; Kula, Slawomir; Switlicka, Anna; Kotowicz, Sonia; Siwy, Mariola; Bednarczyk, Katarzyna; Krompiec, Stanisław; Smolarek, Karolina; Maćkowski, Sebastian; Danikiewicz, Witold; Schab-Balcerzak, Ewa; Machura, Barbara

    2017-07-25

    Nine rhenium(i) complexes possessing three carbonyl groups together with a bidentate coordinated 2,6-di(thiazol-2-yl)pyridine derivative were synthesized to examine the impact of structure modification of the triimine ligand on the photophysical, thermal and electrochemical properties of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)]. The Re(i) complexes were fully characterized using IR, 1 H and 13 C, HRMS-ESI and single crystal X-ray analysis. Their thermal properties were evaluated using DSC and TGA measurements. Photoluminescence spectra of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)] were investigated in solution and in the solid state, at 298 and 77 K. Both emission wavelengths and quantum yields of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)] were found to be structure-related, demonstrating a crucial role of the substituent attached to the 2,6-di(thiazol-2-yl)pyridine skeleton. In order to fully understand the photophysical properties of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)], density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed. Furthermore, the complexes which showed appropriate solubility in chloroform were tested as an emissive active layer in OLED devices.

  7. Mineral trioxide aggregate enhances the odonto/osteogenic capacity of stem cells from inflammatory dental pulps via NF-κB pathway.

    PubMed

    Wang, Y; Yan, M; Fan, Z; Ma, L; Yu, Y; Yu, J

    2014-10-01

    This study was designed to investigate the effects of mineral trioxide aggregate (MTA) on the osteo/odontogenic differentiation of inflammatory dental pulp stem cells (iDPSCs). inflammatory DPSCs were isolated from the inflammatory pulps of rat incisors and cocultured with MTA-conditioned medium. MTT assay and flow cytometry were performed to evaluate the proliferation of iDPSCs. Alkaline phosphatase (ALP) activity, alizarin red staining, real-time RT-PCR, and Western blot assay were used to investigate the differentiation capacity as well as the involvement of NF-κB pathway in iDPSCs. Mineral trioxide aggregate-treated iDPSCs demonstrated the higher ALP activity and formed more mineralized nodules than the untreated group. The odonto/osteoblastic markers (Alp, Runx2/RUNX2, Osx/OSX, Ocn/OCN, and Dspp/DSP, respectively) in MTA-treated iDPSCs were significantly upregulated as compared with untreated iDPSCs. Mechanistically, cytoplastic phos-P65 and nuclear P65 in MTA-treated iDPSCs were significantly increased in a time-dependent manner. Moreover, the inhibition of NF-κB pathway suppressed the MTA-induced odonto/osteoblastic differentiation of iDPSCs, as indicated by decreased ALP levels, weakened mineralization capacity and downregulated levels of odonto/osteoblastic genes (Osx, Ocn, and Dspp). Mineral trioxide aggregate enhances the odonto/osteogenic capacity of DPSCs from inflammatory sites via activating the NF-κB pathway. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  8. The process development of laser surface modification of commercially pure titanium (Grade 2) with rhenium

    NASA Astrophysics Data System (ADS)

    Kobiela, K.; Smolina, I.; Dziedzic, R.; Szymczyk, P.; Kurzynowski, T.; Chlebus, E.

    2016-12-01

    The paper presents the results of the process development of laser surface modification of commercially pure titanium with rhenium. The criterion of the successful/optimal process is the repetitive geometry of the surface, characterized by predictable and repetitive chemical composition over its entire surface as well as special mechanical properties (hardness and wear resistance). The analysis of surface geometry concluded measurements of laser penetration depth and heat affected zone (HAZ), the width of a single track as well as width of a clad. The diode laser installed on the industrial robot carried out the laser treatment. This solution made possible the continuous supply of powder to the substrate during the process. The aim of an investigation is find out the possibility of improving the tribological characteristics of the surface due to the rhenium alloying. The verification of the surface properties (tribological) concluded geometry measurements, microstructure observation, hardness tests and evaluation of wear resistance.

  9. Glyco-functionalized dinuclear rhenium(i) complexes for cell imaging.

    PubMed

    Palmioli, Alessandro; Aliprandi, Alessandro; Septiadi, Dedy; Mauro, Matteo; Bernardi, Anna; De Cola, Luisa; Panigati, Monica

    2017-02-21

    The design, synthesis and photophysical characterization of four new luminescent glycosylated luminophores based on dinuclear rhenium complexes, namely Glyco-Re, are described. The derivatives have the general formula [Re 2 (μ-Cl) 2 (CO) 6 (μ-pydz-R)] (R-pydz = functionalized 1,2-pyridazine), where a sugar residue (R) is covalently bound to the pyridazine ligand in the β position. Different synthetic pathways have been investigated including the so-called neo-glycorandomization procedure, affording stereoselectively glyco-conjugates containing glucose and maltose in a β anomeric configuration. A multivalent dinuclear rhenium glycodendron bearing three glucose units is also synthesized. All the Glyco-Re conjugates are comprehensively characterized and their photophysical properties and cellular internalization experiments on human cervical adenocarcinoma (HeLa) cells are reported. The results show that such Glyco-Re complexes display interesting bio-imaging properties, i.e. high cell permeability, organelle selectivity, low cytotoxicity and fast internalization. These findings make the presented Glyco-Re derivatives efficient phosphorescent probes suitable for cell imaging application.

  10. Förster resonance energy transfer studies of luminescent gold nanoparticles functionalized with ruthenium(II) and rhenium(I) complexes: modulation via esterase hydrolysis.

    PubMed

    Leung, Frankie Chi-Ming; Tam, Anthony Yiu-Yan; Au, Vonika Ka-Man; Li, Mei-Jin; Yam, Vivian Wing-Wah

    2014-05-14

    A number of ruthenium(II) and rhenium(I) bipyridine complexes functionalized with lipoic acid moieties have been synthesized and characterized. Functionalization of gold nanoparticles with these chromophoric ruthenium(II) and rhenium(I) complexes has resulted in interesting supramolecular assemblies with Förster resonance energy transfer (FRET) properties that could be modulated via esterase hydrolysis. The luminescence of the metal complex chromophores was turned on upon cleavage of the ester bond linkage by esterase to reduce the efficiency of FRET quenching. The prepared nanoassembly conjugates have been characterized by transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), UV-visible spectroscopy, and emission spectroscopy. The quenching mechanism has also been studied by transient absorption and time-resolved emission decay measurements. The FRET efficiencies were found to vary with the nature of the chromophores and the length of the spacer between the donor (transition metal complexes) and the acceptor (gold nanoparticles).

  11. Dose Effect of Rhenium (I)-diselenoether as Anticancer Drug in Resistant Breast Tumor-bearing Mice After Repeated Administrations.

    PubMed

    Collery, Philippe; Santoni, François; Ciccolini, Joseph; Tran, Thi Ngoc Nga; Mohsen, Ahmed; Desmaele, Didier

    2016-11-01

    Rhenium (I)-diselenoether has shown promising antiproliferative efficacy in both in vitro and in vivo models. However, the maximal tolerated dose and dose-effect relationships have not been fully addressed for this compound. Here, we evaluated the tolerance and efficacy of three dose-levels (namely 10, 40 and 100 mg/kg) intraperitoneally administered daily over 28 days in mice bearing the resistant MDA-MB231 breast cancer cell line. The upper dose was found to be toxic and was reduced to 60 mg/kg. The 10 mg/kg dose well tolerated, whereas 40 mg/kg was associated with 10% mortality (LD 10 ). Both 10 and 40 mg/kg dosing achieved a significantly similar regression of tumor growth compared with untreated animals. This study suggests that 10 mg/kg daily is the recommended dose for rhenium (I) diselenoether. Copyright© 2016 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

  12. Tungsten trioxide nanoplate array supported platinum as a highly efficient counter electrode for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Song, Dandan; Cui, Peng; Zhao, Xing; Li, Meicheng; Chu, Lihua; Wang, Tianyue; Jiang, Bing

    2015-03-01

    A tungsten trioxide (WO3) nanoplate array is fabricated directly on the FTO/glass substrate and used as a platinum (Pt) nanoscale supporter for a highly efficient and low Pt-consumption counter electrode (CE) in dye-sensitized solar cells (DSCs). A Pt/WO3 composite structure, with Pt nanoparticles having a diameter of 2-3 nm, increases the electrochemical catalytic activity in catalyzing the reduction of triiodide. Accordingly, the power conversion efficiency is increased from less than 1% for WO3 CE and 8.1% for Pt CE, respectively, to 8.9% for Pt/WO3 CE. Moreover, the use of Pt/WO3 CE can dramatically reduce the consumption of scarce Pt material, with a relatively low Pt-loading of ~2 μg cm-2, while maintaining a much better performance. The excellent performance of Pt/WO3 CE is attributed to the efficient electron injection and transport via WO3 supporters, as well as the nanostructure array morphology of WO3 for deposition of fine Pt nanoparticles. This work provides an approach for developing highly catalytic and low-cost Pt based CEs, which also has implications for the development of Pt/WO3 nanoplate arrays for other applications.A tungsten trioxide (WO3) nanoplate array is fabricated directly on the FTO/glass substrate and used as a platinum (Pt) nanoscale supporter for a highly efficient and low Pt-consumption counter electrode (CE) in dye-sensitized solar cells (DSCs). A Pt/WO3 composite structure, with Pt nanoparticles having a diameter of 2-3 nm, increases the electrochemical catalytic activity in catalyzing the reduction of triiodide. Accordingly, the power conversion efficiency is increased from less than 1% for WO3 CE and 8.1% for Pt CE, respectively, to 8.9% for Pt/WO3 CE. Moreover, the use of Pt/WO3 CE can dramatically reduce the consumption of scarce Pt material, with a relatively low Pt-loading of ~2 μg cm-2, while maintaining a much better performance. The excellent performance of Pt/WO3 CE is attributed to the efficient electron injection and transport via WO3 supporters, as well as the nanostructure array morphology of WO3 for deposition of fine Pt nanoparticles. This work provides an approach for developing highly catalytic and low-cost Pt based CEs, which also has implications for the development of Pt/WO3 nanoplate arrays for other applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr06787h

  13. A gallery of oil components, their metals and Re-Os signatures

    NASA Astrophysics Data System (ADS)

    Stein, Holly J.; Hannah, Judith L.

    2016-04-01

    Most sediment-hosted metallic ore deposits are one degree of freedom from hydrocarbon. That is, sulfide fluid inclusions may contain vestiges of travel in tandem with hydrocarbon-bearing fluids. For metallic ore deposits of stated metamorphic and magmatic origin, the degrees of freedom are several times more or, in some cases, no relationship exists. Still, the fetish for stereotyping and classifying ore types into hardline ore deposit models (or hybrid models when the data are wildly uncooperative) impedes our ability to move toward a better understanding of source rock. Fluids in the deeper earth, fluids in the crust, and the extraterrestrial rain of metals provide the Re-Os template for oil. So, too, this combination ultimately drives the composition of many metallic ore deposits. The world of crude oil and its complex history of maturation, migration, mixing, metal-rich asphaltene precipitation, and subsequent mobility of lighter and metal-poor components, is an untapped resource for students of ore geology. In the same way that Mississippi Valley-type lead and zinc deposits are described as the outcome of two converging and mixing fluids (metal-bearing and sulfur-bearing fluids), asphaltene precipitation can be an outcome of a lighter oil meeting and mixing with a heavier one. In the petroleum industry, this can spell economic disaster if the pore-space becomes clogged with a non-producible heavy oil or solid bitumen. In ore geology, sulfide precipitation on loss of permeability may create a Pb-Zn deposit. Petroleum systems provide a gallery of successive time-integrated Re-Os results. Heavy or biodegraded oils, if intersected by lighter oil or gas, can generate asphaltite or tar mats, and release a reservoir of still lighter oil (or gas). During this process there are opportunities for separation of metal-enriched aqueous fluids that may retain an imprint of their earlier hydrocarbon history, ultimately trapped in fluid inclusions. Salinity, temperature and pH are part of the equation controlling composition of metal-bearing aqueous fluids siphoned from residual hydrocarbons. The Re-Os isotopic behavior of oil components is generally specific to location and may differ within a single oil field, or even within discrete fractions of a single sample of oil [1]. Different fractions in a crude oil, for example maltenes and asphaltenes, can preserve signatures of unique sources. This should not be surprising, since economic geologists have long called upon meeting and mixing of metal-bearing with sulfur-bearing fluids from different sources. A time-integrated geologic history can also be derived from bitumen veins, with the Re-Os age of the metal source cached in these veins. Preservation of early metal and hydrocarbon history, and intact Re-Os systematics preserved in younger-formed systems have enormous potential for the resource industry. Several examples will be presented. [1] Georgiev, S.V., Stein, H.J., Hannah, J.L., Galimberti, R., Nali, M., Yang, G., and Zimmerman, A. (returned post revision, 11 Jan 2016) Re-Os dating of maltenes and asphaltenes within single samples of crude oils: Geochimica et Comochimica Acta. Supported by a consortium of petroleum companies under the CHRONOS project.

  14. Effect of diboron trioxide on the crushing strength and smelting mechanism of high-chromium vanadium-titanium magnetite pellets

    NASA Astrophysics Data System (ADS)

    Cheng, Gong-jin; Gao, Zi-xian; Yang, He; Xue, Xiang-xin

    2017-11-01

    The effect of diboron trioxide (B2O3) on the crushing strength and smelting mechanism of high-chromium vanadium-titanium magnetite pellets was investigated in this work. The main characterization methods were X-ray fluorescence, inductively coupled plasma-atomic emission spectroscopy, mercury injection porosimetry, X-ray diffraction, metallographic microscopy, and scanning electron microscopy-energy-dispersive X-ray spectroscopy. The results showed that the crushing strength increased greatly with increasing B2O3 content and that the increase in crushing strength was strongly correlated with a decrease in porosity, the formation of liquid phases, and the growth and recrystallization consolidation of hematite crystalline grains. The smelting properties were measured under simulated blast furnace conditions; the results showed that the smelting properties within a certain B2O3 content range were improved and optimized except in the softening stage. The valuable element B was easily transformed to the slag, and this phenomenon became increasingly evident with increasing B2O3 content. The formation of Ti(C,N) was mostly avoided, and the slag and melted iron were separated well during smelting with the addition of B2O3. The size increase of the melted iron was consistent with the gradual optimization of the dripping characteristics with increasing B2O3 content.

  15. Anticancer Activity of Small Molecule and Nanoparticulate Arsenic(III) Complexes

    PubMed Central

    Swindell, Elden P.; Hankins, Patrick L.; Chen, Haimei; Miodragović, Ðenana U.; O'Halloran, Thomas V.

    2014-01-01

    Starting in ancient China and Greece, arsenic-containing compounds have been used in the treatment of disease for over 3000 years. They were used for a variety of diseases in the 20th century, including parasitic and sexually transmitted illnesses. A resurgence of interest in the therapeutic application of arsenicals has been driven by the discovery that low doses of a 1% aqueous solution of arsenic trioxide (i.e. arsenous acid) leads to complete remission of certain types of leukemia. Since FDA approval of arsenic trioxide (As2O3) for treatment of acute promyelocytic leukemia (APL) in 2000, it has become a front line therapy in this indication. There are currently over 100 active clinical trials involving inorganic arsenic or organoarsenic compounds registered with the FDA for the treatment of cancers. New generations of inorganic and organometallic arsenic compounds with enhanced activity or targeted cytotoxicity are being developed to overcome some of the shortcomings of arsenic therapeutics, namely short plasma half-lives and narrow therapeutic window. PMID:24147771

  16. Cytotoxicities and genotoxicities of cements based on calcium silicate and of dental formocresol.

    PubMed

    Ko, Hyunjung; Jeong, Youngdan; Kim, Miri

    2017-03-01

    Increasing interest is being paid to the toxicities of dental materials. The purpose of this study was to determine the cytotoxicities and genotoxicities of endodontic compounds to Chinese hamster ovary (CHO-K1) reproductive cells. Cultured CHO-K1 cells were treated with dental formocresol, two types of calcium hydroxide paste, and two types of mineral trioxide aggregate cement for 24h. A 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay was performed on each culture, and the micronucleus frequency was determined by performing a micronucleus assay. Alkaline comet assay and γ-H2AX immunofluorescence assay were used to detect DNA damage. Out of the five materials tested, only dental formocresol significantly increased DNA damage. The mineral trioxide aggregate cements based on calcium silicate were not found to be potentially genotoxic. The data suggest that dental formocresol should not be recommended for use in vital pulp therapy on young teeth. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Enhancement of the antimicrobial properties of orthorhombic molybdenum trioxide by thermal induced fracturing of the hydrates.

    PubMed

    Shafaei, Shahram; Van Opdenbosch, Daniel; Fey, Tobias; Koch, Marcus; Kraus, Tobias; Guggenbichler, Josef Peter; Zollfrank, Cordt

    2016-01-01

    The oxides of the transition metal molybdenum exhibit excellent antimicrobial properties. We present the preparation of molybdenum trioxide dihydrate (MoO3 × 2H2O) by an acidification method and demonstrate the thermal phase development and morphological evolution during and after calcination from 25 °C to 600 °C. The thermal dehydration of the material was found to proceed in two steps. Microbiological roll-on tests using Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa were performed and exceptional antimicrobial activities were determined for anhydrous samples with orthorhombic lattice symmetry and a large specific surface area. The increase in the specific surface area is due to crack formation and to the loss of the hydrate water after calcination at 300 °C. The results support the proposed antimicrobial mechanism for transition metal oxides, which based on a local acidity increase as a consequence of the augmented specific surface area. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Influence of glass-ionomer cement on the interface and setting reaction of mineral trioxide aggregate when used as a furcal repair material using laser Raman spectroscopic analysis.

    PubMed

    Nandini, Suresh; Ballal, Suma; Kandaswamy, Deivanayagam

    2007-02-01

    The prolonged setting time of mineral trioxide aggregate (MTA) is the main disadvantage of this material. This study analyzes the influence of glass-ionomer cement on the setting of MTA using laser Raman spectroscopy (LRS). Forty hollow glass molds were taken in which MTA was placed. In Group I specimens, MTA was layered with glass-ionomer cement after 45 minutes. Similar procedures were done for Groups II and III at 4 hours and 3 days, respectively. No glass ionomer was added in Group IV, which were then considered as control samples. Each sample was scanned at various time intervals. At each time interval, the interface between MTA and glass-ionomer cement was also scanned (excluding Group IV). The spectral analysis proved that placement of glass-ionomer cement over MTA after 45 minutes did not affect its setting reaction and calcium salts may be formed in the interface of these two materials.

  19. Comparative 187Re-187Os systematics of chondrites: Implications regarding early solar system processes

    USGS Publications Warehouse

    Walker, R.J.; Horan, M.F.; Morgan, J.W.; Becker, H.; Grossman, J.N.; Rubin, A.E.

    2002-01-01

    A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the 187Re/188Os and 187Os/188Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average 187Re/188Os for carbonaceous chondrites is 0.392 ?? 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ?? 0.025 and 0.421 ?? 0.013 for ordinary and enstatite chondrites (1?? standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ?? 0.0031, 0.0876 ?? 0.0052 and 0.0874 ?? 0.0027 respectively. Correspondingly, the 187Os/188Os ratios of carbonaceous chondrites average 0.1262 ?? 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ?? 0.0017 and 0.1281 ?? 0.0004, respectively (1?? standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history. A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga. The 187Os/188Os ratio of Earth's primitive upper mantle has been estimated to be 0.1296 ?? 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites. ?? 2002 Elsevier Science Ltd.

  20. Reply to the comment by Wu et al. (2016) on "Behavior of Re and Os during contact between an aqueous solution and oil: Consequences for the application of the Re-Os geochronometer to petroleum" [Geochim. Cosmochim. Acta 158 (2015) 1-21

    NASA Astrophysics Data System (ADS)

    Reisberg, Laurie; Michels, Raymond; Mahdaoui, Fatima

    2016-08-01

    We reply here to the questions raised by Wu et al. concerning the results published by Mahdaoui et al. (2015). This paper describes experiments in which aqueous solutions containing ReO4- and OsCl62- were brought in contact with natural oils at various ranges of concentration, time and temperature. The main observation is that the transfer of Re and Os to oils is very efficient under all experimental conditions. Wu et al. argue that thermodynamic equilibrium was not achieved in these experiments as apparent partition coefficients are inconsistent. They conclude that the experiments were flawed by possible leaking of reactors and that the conclusions by Mahdaoui et al. (2015) were not justified. In the following reply we explain that Mahdaoui et al. (2015) never claimed that thermodynamic equilibrium was achieved. Any calculations or considerations in this context are therefore meaningless. We recall the objectives of our publication, which were to experimentally test the behavior of ReO4- and OsCl6- (two plausible chemical forms of Re and Os in deep aquifers of petroleum systems) in aqueous solution-oil systems. To our knowledge these are the first experiments of their kind. The parameters that could influence the precision and reproducibility of our results were discussed in detail in Mahdaoui et al. (2015). The essential point is that all 60 of the experiments provide evidence of substantial transfer of Re and Os from water to oil. In contrast to what was mistakenly understood by Wu et al., the paper does not challenge the use of Re-Os to date geological events affecting petroleum. Instead, by providing a mechanism that might allow Os isotopic homogenization on a basin-wide scale, a critical step missing from most current models, it offers a possible explanation of how Re-Os geochronology in oils could potentially work. More generally, our study suggests that transfer of Re and Os from waters to oil may be an important phenomenon that should not be overlooked.

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