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Sample records for oxo mo species

  1. Redox and oxo-abstraction reactions of silylamine with MoOCl4

    International Nuclear Information System (INIS)

    Vasisht, S.K.; Singh, G.

    1985-01-01

    Trimethylsilyldiethylamine Me 3 SiNEt 2 and MoOCl 4 (1:1) undergo a free radical redox reaction in CH 2 Cl 2 or Et 2 O to form MoCl 3 O(HNEt 2 ). Reduction occurs even in aprotic media like CCl 4 and CS 2 to give Mo(V) complexes Mo 2 Cl 6 O 2 (N 2 Et 4 ) and Mo 2 Cl 6 O 2 [(SCNEt 2 ) 2 S 2 ], respectively. A 2:1 reaction in nonionizing protic solvents undergoes redox cum cleavage to provide MoCl 2 O(NEt 2 )(HNEt 2 ) but a reaction at reflux temperature in 1,2-dichloroethane leads to diethylammonium salt, [Et 2 NH 2 ][MoCl 4 O(HNEt 2 )]. Higher molar reactions (3:1, 4:1) in CH 2 Cl 2 or Et 2 O are associated with redox reaction as well as oxygen atom abstraction to form de-oxo Mo(IV) complex MoCl 3 (NEt 2 )(HNEt 2 ) 2 , whereas, a 3:1 reaction in CS 2 forms Mo 2 Cl 4 O(S 2 CNEt 2 ) 4 . Compounds have been characterized by elemental analyses, redox titration, magnetic moment, conductance, infrared, electronic absorption and 1 H-NMR measurements. (author)

  2. Sulfur K-edge X-ray absorption spectroscopy and density functional theory calculations on monooxo Mo(IV) and bisoxo Mo(VI) bis-dithiolenes: insights into the mechanism of oxo transfer in sulfite oxidase and its relation to the mechanism of DMSO reductase.

    Science.gov (United States)

    Ha, Yang; Tenderholt, Adam L; Holm, Richard H; Hedman, Britt; Hodgson, Keith O; Solomon, Edward I

    2014-06-25

    Sulfur K-edge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations have been used to determine the electronic structures of two complexes [Mo(IV)O(bdt)2](2-) and [Mo(VI)O2(bdt)2](2-) (bdt = benzene-1,2-dithiolate(2-)) that relate to the reduced and oxidized forms of sulfite oxidase (SO). These are compared with those of previously studied dimethyl sulfoxide reductase (DMSOr) models. DFT calculations supported by the data are extended to evaluate the reaction coordinate for oxo transfer to a phosphite ester substrate. Three possible transition states are found with the one at lowest energy, stabilized by a P-S interaction, in good agreement with experimental kinetics data. Comparison of both oxo transfer reactions shows that in DMSOr, where the oxo is transferred from the substrate to the metal ion, the oxo transfer induces electron transfer, while in SO, where the oxo transfer is from the metal site to the substrate, the electron transfer initiates oxo transfer. This difference in reactivity is related to the difference in frontier molecular orbitals (FMO) of the metal-oxo and substrate-oxo bonds. Finally, these experimentally related calculations are extended to oxo transfer by sulfite oxidase. The presence of only one dithiolene at the enzyme active site selectively activates the equatorial oxo for transfer, and allows facile structural reorganization during turnover.

  3. Bis(μ-oxo) dicopper(III) species of the simplest peralkylated diamine: enhanced reactivity toward exogenous substrates.

    Science.gov (United States)

    Kang, Peng; Bobyr, Elena; Dustman, John; Hodgson, Keith O; Hedman, Britt; Solomon, Edward I; Stack, T Daniel P

    2010-12-06

    N,N,N',N'-tetramethylethylenediamine (TMED), the simplest and most extensively used peralkylated diamine ligand, is conspicuously absent from those known to form a bis(μ-oxo)dicopper(III) (O) species, [(TMED)(2)Cu(III)(2)(μ(2)-O)(2)](2+), upon oxygenation of its Cu(I) complex. Presented here is the characterization of this O species and its reactivity toward exogenous substrates. Its formation is complicated both by the instability of the [(TMED)Cu(I)](1+) precursor and by competitive formation of a presumed mixed-valent trinuclear [(TMED)(3)Cu(III)Cu(II)(2)(μ(3)-O)(2)](3+) (T) species. Under most reaction conditions, the T species dominates, yet, the O species can be formed preferentially (>80%) upon oxygenation of acetone solutions, if the copper concentration is low (theory (DFT) computational methods for geometry optimization and spectroscopic predictions. The enhanced thermal stability of [(TMED)(2)Cu(III)(2)(μ(2)-O)(2)](2+) and its limited steric demands compared to other O species allows more efficient oxidation of exogenous substrates, including benzyl alcohol to benzaldehyde (80% yield), highlighting the importance of ligand structure to not only enhance the oxidant stability but also maintain accessibility to the nascent metal/O(2) oxidant.

  4. DFT studies of the substituent effects of dimethylamino on non-heme active oxidizing species: iron(V)-oxo species or iron(IV)-oxo acetate aminopyridine cation radical species?

    Science.gov (United States)

    Wang, Fang; Sun, Wei; Xia, Chungu; Wang, Yong

    2017-10-01

    Through the introduction of dimethylamino (Me 2 N) substituent at the pyridine ring of 2-((R)-2-[(R)-1-(pyridine-2-ylmethyl)pyrrolidin-2-yl]pyrrolidin-1-ylmethyl)pyridine (PDP) ligand, the non-heme Fe II ( Me2N PDP)/H 2 O 2 /AcOH catalyst system was found to exhibit significant higher catalytic activity and enantioselectivity than the non-substituent one in the asymmetric epoxidation experiments. The mechanistic origin of the remarkable substituent effects in these oxidation reactions has not been well established. To ascertain the potent oxidant and the related reaction mechanism, a detailed DFT calculation was performed. Interestingly, a novel Fe(IV)-oxo Me2N PDP cation radical species, [( Me2N PDP) + · Fe IV (O)(OAc)] 2+ ( Me2N 5), with about one spin spreading over the non-heme Me2N PDP ligand was formed via a carboxylic-acid-assisted O-O bond heterolysis, which is reminiscent of Compound I (an Fe(IV)(O)(porphyrin cation radical) species) in cytochrome P450 chemistry. Me2N 5 is energetically comparable with the cyclic ferric peracetate species Me2N 6, while in the pristine Fe(PDP) catalyst system, H 6 is more stable than H 5. Comparison of the activation energy for the ethylene epoxidation promoted by Me2N 5 and Me2N 6, Me2N 5 is supposed as the true oxidant triggering the epoxidation of olefins. In addition, a systematic research on the substituent effects varied from the electron-donating substituent (dMM, the substituents at sites 3, 4, and 5 of the pyridine ring: methyl, methoxyl, and methyl) to the electron-withdrawing one (CF 3 , 2,6-bis(trifluoromethyl)phenyl) on the electronic structure of the reaction intermediates has also been investigated. An alternative cyclic ferric peracetate complex is obtained, indicating that the substituents at the pyridine ring of PDP ligands have significant impacts on the electronic structure of the oxidants.

  5. The crystal chemistry of novel thorium and uranium compounds with oxo-anions from group VI of periodic table (S, Se, Te, Cr, Mo and W)

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Bin

    2016-01-26

    used as the flux for the high-temperature synthesis method to decrease the crystal growth temperature. This also gives an opportunity to allow Te{sup 4+} anion to interact with anion of Mo{sup 6+} or W{sup 6+}, leading to a more complex mixed oxo-anion system, which is reported in Chapter 7 from page 122. Last, some attractive features of structural chemistry of actinides, such as cation-cation interaction of uranyl groups(Chapter 8.1 from page 136), and the first thorium compounds containing alkaline-earth or rare earth metals (Chapter 8.2 from page 145) are discussed in Chapter 8.

  6. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

    KAUST Repository

    Merle, Nicolas; Le Qué mé ner, Fré dé ric; Bouhoute, Yassine; Szeto, Kai C.; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja; Delevoye, Laurent; Gauvin, Ré gis M.; Taoufik, Mostafa; Basset, Jean-Marie

    2016-01-01

    The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  7. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

    KAUST Repository

    Merle, Nicolas

    2016-12-05

    The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  8. Study on Mo(V) species, location and adsorbates interactions in MoH-SAPO-34 by employing ESR and electron spin-echo modulation spectroscopies

    International Nuclear Information System (INIS)

    Back, Gern Ho; Jang, Chang Ki; Ru, Chang Kuk; Cho, Young Hwan; So, Hyun Soo; Larry, Keven

    2002-01-01

    A solid-state reaction of MoO 3 with as-synthesized H-SAPO-34 generated paramagnetic Mo(V) species. The dehydration resulted in weak Mo(V) species, and subsequent activation resulted in the formation of Mo(V) species such as Mo(V) 5c and Mo(V) 6c that are characterized by ESR. The data of ESR and ESEM show the oxomolybdenum species, to be (MoO 2 ) + or (MoO) 3+ . The (MoO 2 ) + species seems to be more probable. Since H-SAPO-34 has a low framework negative charge, (MoO) 3+ with a high positive charge can not be easily stabilized. A solution reaction between the solution of silico-molybdic acid and calcined H-SAPO-34 resulted in only MoO + 2 species. A rhombic ESR signal is observed on adsorption of D 2 O, CD 3 OH, CH 3 CH 2 OD and ND 3 . The Location and coordination structure of Mo(V) species has been determined by three-pulse electron spin-echo modulation data and their simulations. After the adsorption of methanol, ethylene, ammonia, and water for MoH-SAPO-34, three molecules, one and one molecule, respectively, are directly coordinated to (MoO 2 ) +

  9. Bioinspired catalytic generation of high-valent cobalt-oxo species by the axially coordinated CoPc on pyridine-functionalized MWCNTs for the elimination of organic contaminants

    Science.gov (United States)

    Li, Nan; Wang, Ying; Wu, Chenren; Lu, Wangyang; Pei, Kemei; Chen, Wenxing

    2018-03-01

    Enzymes have always been a source of inspiration for the design and improvement of catalysts. Many examples are occurring in heme/non-heme metalloenzymes with the generation of active high-valent metal-oxo intermediates that are controlled by the surrounding amino acids/protein and axial residue ligands, facilitating the efficient oxidation of substrates in biochemical processes. Here, the high-valent cobalt-oxo species have been formed during the heterolysis of H2O2 activated by the bioinspired catalyst, axially coordinated cobalt phthalocyanine (CoPc) on pyridine-functionalized multi-walled carbon nanotubes (MWCNTs-Py), characterized by ultraviolet-visible and X-ray photoelectron spectroscopy. Formation process of the active cobalt-oxo species has been further confirmed by electrospray ionization mass spectrometry analysis and the results from the density functional theory (B3LYP/6-311G) calculations. Such high-valent cobalt-oxo species exhibit high reactivity and enough persistence for the oxidation of the target substrate, C.I. Acid Red 1. The oxidation products are nearly biodegradable small molecules identified by ultra-performance liquid chromatography/high-definition mass spectrometry. This strategy provides a foundation on developing efficient and persistent catalytic system, in particular oxidation processes based on the complex catalysts with N4 macrocycle structures.

  10. Species dependent studies of no-carrier-added 93mMo: A green method

    International Nuclear Information System (INIS)

    Mandal, Swadesh; Nayak, Dalia

    2010-01-01

    The present paper reports a combination of radioanalytical and green methodology for the ultra-trace scale speciation of molybdenum. The differential attitude of iron-doped calcium alginate (Fe-CA) and chitosan biopolymers towards no-carrier-added 93m Mo radionuclide was studied to develop environmentally sustainable speciation methodology in ultra-trace scale. The affinity of 93m Mo towards the Fe-CA beads is greater than that of chitosan. Species information was obtained by comparing the adsorption profile of 93m Mo on Fe-CA and chitosan biopolymer with the software code CHEAQS PRO program. From the experimental results it is concluded that no-carrier-added 93m Mo radionuclide form mononuclear species instead of polynuclear species in aqueous solution. Use of biodegradable, non-toxic biopolymer makes this method a step forward towards green chemistry.

  11. Thermal spreading of MoO3 in H-ZY

    International Nuclear Information System (INIS)

    Mosqueira, L.; Angeles-Chavez, C.; Torres-Garcia, E.

    2011-01-01

    Research highlights: → Molybdenum oxo-species were formed during thermally driven migration on H-ZY. → Oxo-species were identified according to the edge energy (E g ) values of bulk molybdenum oxide reference compounds. → The migration occurred via MoO 2 (OH) 2 species leading first to (MoO 4 ) 2- and (Mo 2 O 7 ) 2- formation, and finally of (Mo 7 O 24 ) 6- . - Abstract: This work provides a structural, optical and kinetics approach to the molybdenum oxo-species formed during thermally driven migration on H-ZY starting from mechanical mixtures with MoO 3 . The samples were characterized as a function of time of treatment by UV-vis diffuse reflectance, X-ray diffraction, N 2 adsorption and scanning transmission electron microscopy (STEM). Local analysis of elemental compositions obtained from linear scan of characteristic X-ray signal show a direct evidence of molybdenum presence into the zeolite crystals. Ultraviolet absorption spectra were used to determine both the kinetics of the spreading and the speciation of MoO x in the H-ZY. Besides MoO 3 , three surface molybdenum oxo-species were identified according to the edge energy (E g ) values of bulk molybdenum oxide reference compounds. This study shows that the tetrahedral species prevailed on H-ZY. This is consistent with limitations in the migration and growth of MoO x in the channel structure of the zeolite. Kinetic study suggest that migration of MoO x in the H-ZY at low temperature (ca. 723 K) occurs across the formation and diffusion of hydrated species such as MoO 2 (OH) 2 , which interact with the zeolite and form monomeric and dimeric structures (like (MoO 4 ) 2- and (Mo 2 O 7 ) 2- ). Migration of MoO x species in the H-ZY studied is significant even at 723 K and after very short periods of treatment (<5 min).

  12. Thermal spreading of MoO{sub 3} in H-ZY

    Energy Technology Data Exchange (ETDEWEB)

    Mosqueira, L., E-mail: mmosquei@imp.mx [Instituto Mexicano del Petroleo, Eje Central Norte, Lazaro Cardenas 152, San Bartolo Atepehuacan, 07730 Mexico, D.F. (Mexico); Angeles-Chavez, C. [Instituto Mexicano del Petroleo, Eje Central Norte, Lazaro Cardenas 152, San Bartolo Atepehuacan, 07730 Mexico, D.F. (Mexico); Torres-Garcia, E., E-mail: etorresg@imp.mx [Instituto Mexicano del Petroleo, Eje Central Norte, Lazaro Cardenas 152, San Bartolo Atepehuacan, 07730 Mexico, D.F. (Mexico)

    2011-04-15

    Research highlights: {yields} Molybdenum oxo-species were formed during thermally driven migration on H-ZY. {yields} Oxo-species were identified according to the edge energy (E{sub g}) values of bulk molybdenum oxide reference compounds. {yields} The migration occurred via MoO{sub 2}(OH){sub 2} species leading first to (MoO{sub 4}){sup 2-} and (Mo{sub 2}O{sub 7}){sup 2-} formation, and finally of (Mo{sub 7}O{sub 24}){sup 6-}. - Abstract: This work provides a structural, optical and kinetics approach to the molybdenum oxo-species formed during thermally driven migration on H-ZY starting from mechanical mixtures with MoO{sub 3}. The samples were characterized as a function of time of treatment by UV-vis diffuse reflectance, X-ray diffraction, N{sub 2} adsorption and scanning transmission electron microscopy (STEM). Local analysis of elemental compositions obtained from linear scan of characteristic X-ray signal show a direct evidence of molybdenum presence into the zeolite crystals. Ultraviolet absorption spectra were used to determine both the kinetics of the spreading and the speciation of MoO{sub x} in the H-ZY. Besides MoO{sub 3}, three surface molybdenum oxo-species were identified according to the edge energy (E{sub g}) values of bulk molybdenum oxide reference compounds. This study shows that the tetrahedral species prevailed on H-ZY. This is consistent with limitations in the migration and growth of MoO{sub x} in the channel structure of the zeolite. Kinetic study suggest that migration of MoO{sub x} in the H-ZY at low temperature (ca. 723 K) occurs across the formation and diffusion of hydrated species such as MoO{sub 2}(OH){sub 2}, which interact with the zeolite and form monomeric and dimeric structures (like (MoO{sub 4}){sup 2-} and (Mo{sub 2}O{sub 7}){sup 2-}). Migration of MoO{sub x} species in the H-ZY studied is significant even at 723 K and after very short periods of treatment (<5 min).

  13. Analysis and removal of heteroatom containing species in coal liquid distillate over NiMo catalysts

    Energy Technology Data Exchange (ETDEWEB)

    S.D. Sumbogo Murtia; Ki-Hyouk Choi; Kinya Sakanishi; Osamu Okuma; Yozo Korai; Isao Mochida [Kyushu University, Fukuoka (Japan). Institute for Materials Chemistry and Engineering

    2005-02-01

    Heteroatom containing molecules in South Banko coal liquid (SBCL) distillate were identified with a gas chromatograph equipped with an atomic emission detector (GC-AED). Thiophenes and benzothiophenes were found to be the major sulfur compounds. Pyridines, anilines, and phenols were the major nitrogen and oxygen compounds, respectively. Reactivities of heteroatom containing species in hydrotreatment over conventional NiMoS/Al{sub 2}O{sub 3}, NiMoS/Al{sub 2}O{sub 3}-SiO{sub 2} catalysts were very different according to their cyclic structure as well as the kind of heteroatom in the species. The sulfur species were completely desulfurized over the catalysts examined in the present study by 60 min at 360{degree}C under initial hydrogen pressure of 5 MPa. However, hydrodenitrogenation was more difficult than hydrodesulfurization even at 450{degree}C. Anilines were found the most refractory ones among the nitrogen species. Hydrodeoxygenation of SBCL was also difficult in the hydrotreatment conditions examined in the present study. Dibenzofuran was the most refractory molecule among the oxygen species. A two-stage reaction configuration at 340 and 360{degree}C improved HDN and HDO reactivities, although the conversions were still insufficient. Increasing the acidity of the support as well as the loading of the metals on the NiMoS/Al{sub 2}O{sub 3} catalysts improved very much the heteroatom reduction to achieve complete removal of nitrogen by two-stage reaction configuration at 340-360{degree}C and oxygen at 360{degree}C, respectively. The addition of H{sub 2}S in the reaction atmosphere inhibited the HDN reaction but increased markedly the HDO conversion. The acidic support increased the activity in hydrotreatment through enhancing the hydrogenation activity, while H{sub 2}S maintained the catalyst in a sufficiently sulfided state. 19 refs., 4 figs., 8 tabs.

  14. Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

    KAUST Repository

    Merle, Nicolas

    2017-09-25

    A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

  15. Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

    KAUST Repository

    Merle, Nicolas; Le Qué mé ner, Fré dé ric; Barman, Samir; Samantaray, Manoja; Szeto, Kai C.; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

    2017-01-01

    A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

  16. Uranyl oxo activation and functionalization by metal cation coordination

    International Nuclear Information System (INIS)

    Arnold Polly, L.; Pecharman, A. F.; Hollis, E.; Parsons, S.; Love, J. B.; Yahia, A.; Maron, L.; Yahia, A.; Maron, L.

    2010-01-01

    The oxo groups in the uranyl ion [UO 2 ] 2+ - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

  17. Uranyl oxo activation and functionalization by metal cation coordination

    Energy Technology Data Exchange (ETDEWEB)

    Arnold Polly, L; Pecharman, A F; Hollis, E; Parsons, S; Love, J B [Univ Edinburgh, EaStCHEM Sch Chem, Edinburgh EH9 3JJ, Midlothian (United Kingdom); Yahia, A; Maron, L [Univ Toulouse 3, LPCNO, UMR 5215, INSA, CNRS, F-31077 Toulouse 4 (France); Yahia, A; Maron, L [Univ Montpellier 2, ENSCM, CNRS, ICSM, UMR 5257, CEA, Ctr Marcoule, F-30207 Bagnols Sur Ceze (France)

    2010-07-01

    The oxo groups in the uranyl ion [UO{sub 2}]{sup 2+} - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

  18. Selective adsorption of refractory sulfur species on active carbons and carbon based CoMo catalyst.

    Science.gov (United States)

    Farag, Hamdy

    2007-03-01

    Adsorption technique could be a reliable alternative in removing to a certain remarkable extent the sulfur species from the feedstock of petroleum oil. The performance of various carbons on adsorption of model sulfur compounds in a simulated feed solution and the sulfur containing compounds in the real gas oil was evaluated. The adsorption experiments have been carried out in a batch scale at ambient temperature and under the atmospheric pressure. In general, the most refractory sulfur compounds in the hydrotreatment reactions were selectively removed and adsorbed. It was found that the adsorbents affinities to dibenzothiophene and 4,6-dimethyldibenzothiophene were much more favored and pronounced than the aromatic matrices like fluorene, 1-methylnaphthalene and 9-methylanthracene. Among the sulfur species, 4,6-dimethyldibenzothiophene was the highest to be removed in terms of both selectivity and capacity over all the present adsorbents. The studied adsorbents showed significant capacities for the polyaromatic thiophenes. The electronic characteristics seem to play a certain role in such behavior. Regeneration of the used adsorbent was successfully attained either by washing it with toluene or by the release of the adsorbates through heat treatment. A suggested adsorptive removal process of sulfur compounds from petroleum distillate over carbon supported CoMo catalyst was discussed.

  19. Relevance of the Mo-precursor state in H-ZSM-5 for methane dehydroaromatization

    KAUST Repository

    Vollmer, Ina

    2018-01-04

    Although the local geometry of Mo in Mo/HZSM-5 has been characterized before, we present a systematic way to manipulate the configuration of Mo and link it to its catalytic properties. The location and geometry of cationic Mo-complexes, the precursor of the active metal site for methane dehydroaromatization, are altered by directing the way they anchor to the framework of the zeolite. The feature used to direct the anchoring of Mo is the location of Al in the zeolite framework. According to DFT calculations, the local geometry of Mo should change, while UV-vis and pyridine FTIR spectroscopy indicated differences in the dispersion of Mo. Both aspects, however, did not influence the catalytic behavior of Mo/HZSM-5, indicating that as long as enough isolated Mo species are present inside the pores of the zeolite, the catalytic behavior is unaffected. This paves the way to better understand how the Mo oxo precursor transforms into the active phase under the reaction conditions.

  20. Relevance of the Mo-precursor state in H-ZSM-5 for methane dehydroaromatization

    KAUST Repository

    Vollmer, Ina; Li, Guanna; Yarulina, Irina; Kosinov, Nikolay; Hensen, Emiel J.; Houben, Klaartje; Mance, Deni; Baldus, Marc; Gascon, Jorge; Kapteijn, Freek

    2018-01-01

    Although the local geometry of Mo in Mo/HZSM-5 has been characterized before, we present a systematic way to manipulate the configuration of Mo and link it to its catalytic properties. The location and geometry of cationic Mo-complexes, the precursor of the active metal site for methane dehydroaromatization, are altered by directing the way they anchor to the framework of the zeolite. The feature used to direct the anchoring of Mo is the location of Al in the zeolite framework. According to DFT calculations, the local geometry of Mo should change, while UV-vis and pyridine FTIR spectroscopy indicated differences in the dispersion of Mo. Both aspects, however, did not influence the catalytic behavior of Mo/HZSM-5, indicating that as long as enough isolated Mo species are present inside the pores of the zeolite, the catalytic behavior is unaffected. This paves the way to better understand how the Mo oxo precursor transforms into the active phase under the reaction conditions.

  1. Diastereoselective reduction of 1-(4-fluorophenyl)-3(R)-[3-oxo-3-(4-fluorophenyl) -propyl]-4 (S)-(4-hydroxyphenyl)azetidin-2-one to Ezetimibe by the whole cell catalyst Rhodococcus fascians MO22

    Czech Academy of Sciences Publication Activity Database

    Kyslíková, Eva; Babiak, P.; Marešová, Helena; Palyzová, Andrea; Hajíček, J.; Kyslík, Pavel

    2010-01-01

    Roč. 67, 3-4 (2010), s. 266-270 ISSN 1381-1177 R&D Projects: GA MŠk 2B08064 Institutional research plan: CEZ:AV0Z50200510 Keywords : Biotransformation * Rhodococcus fascians MO22 * Ezetimibe Subject RIV: CE - Biochemistry Impact factor: 2.330, year: 2010

  2. A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Junying; Lee, Yong-Min; Davis, Katherine M.; Wu, Xiujuan; Seo, Mi Sook; Cho, Kyung-Bin; Yoon, Heejung; Park, Young Jun; Fukuzumi, Shunichi; Pushkar, Yulia N.; Nam, Wonwoo [Ewha; (Purdue); (Osaka)

    2013-05-29

    Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal–oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)–oxo complex bearing a pentadentate N5 ligand has been synthesized and used in the synthesis of a Mn(IV)–oxo complex binding scandium ions. The Mn(IV)–oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)–oxo complex are markedly influenced by binding of Sc3+ ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C–H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)–oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal–oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.

  3. Structure–acidity correlation of supported tungsten(VI)-oxo-species: FT-IR and TPD studies of adsorbed pyridine and catalytic decomposition of 2-propanol

    Energy Technology Data Exchange (ETDEWEB)

    Zaki, M.I., E-mail: mizaki@mu.edu.eg; Mekhemer, G.A.H.; Fouad, N.E.; Rabee, A.I.M.

    2014-07-01

    The amount of 10 wt%-WO{sub 3} was supported on alumina, titania or silica by impregnation with aqueous solution of ammonium paratungstate and subsequent calcination at 500 °C for 10 h. Tungstate-related chemical and physical changes in the calcination products were resolved by ex-situ infrared (IR) spectroscopy. Nature of exposed surface acid sites were probed by in-situ IR spectroscopy of adsorbed pyridine (Py) molecules at room temperature (RT). The relative strength of the acid sites thus probed was gauged by combining results of temperature-programmed desorption (TPD) measurements of the RT-adsorbed Py with those communicated by in-situ IR spectra of residual Py on the surface after a brief thermoevacuation at high temperatures (100–300 °C). Reactivity of the surface acid sites was tested toward 2-propanal catalytic decomposition, and observed by in-situ IR gas phase spectra. Results obtained were correlated with predominant structures assumed by the supported tungstate species. Accordingly, polymerization of the supported tungstate into 2-/3-dimensional structures, was found to be relatively most advanced on favorable locations of titania surfaces as compared to the case on alumina or silica surfaces. Consequently, the Lewis acidity was strengthened, and strong Bronsted acidity was evolved, leading to a 2-propanol dehydration catalyst (tungstate/titania) of optimal activity and selectivity. Strong tungstate/support interfacial interactions were found to hamper the formation of the strongly acidic and catalytically active polymeric structures of the supported tungstate (i.e., the case on alumina or silica).

  4. Structure–acidity correlation of supported tungsten(VI)-oxo-species: FT-IR and TPD studies of adsorbed pyridine and catalytic decomposition of 2-propanol

    International Nuclear Information System (INIS)

    Zaki, M.I.; Mekhemer, G.A.H.; Fouad, N.E.; Rabee, A.I.M.

    2014-01-01

    The amount of 10 wt%-WO 3 was supported on alumina, titania or silica by impregnation with aqueous solution of ammonium paratungstate and subsequent calcination at 500 °C for 10 h. Tungstate-related chemical and physical changes in the calcination products were resolved by ex-situ infrared (IR) spectroscopy. Nature of exposed surface acid sites were probed by in-situ IR spectroscopy of adsorbed pyridine (Py) molecules at room temperature (RT). The relative strength of the acid sites thus probed was gauged by combining results of temperature-programmed desorption (TPD) measurements of the RT-adsorbed Py with those communicated by in-situ IR spectra of residual Py on the surface after a brief thermoevacuation at high temperatures (100–300 °C). Reactivity of the surface acid sites was tested toward 2-propanal catalytic decomposition, and observed by in-situ IR gas phase spectra. Results obtained were correlated with predominant structures assumed by the supported tungstate species. Accordingly, polymerization of the supported tungstate into 2-/3-dimensional structures, was found to be relatively most advanced on favorable locations of titania surfaces as compared to the case on alumina or silica surfaces. Consequently, the Lewis acidity was strengthened, and strong Bronsted acidity was evolved, leading to a 2-propanol dehydration catalyst (tungstate/titania) of optimal activity and selectivity. Strong tungstate/support interfacial interactions were found to hamper the formation of the strongly acidic and catalytically active polymeric structures of the supported tungstate (i.e., the case on alumina or silica).

  5. Terminal Gold-Oxo Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Cao, R.; Anderson, T.M.; Piccoli, P.M.B.; Schultz, A.J.; Koetzle, T.F.; Geletii, Y.V.; Slonkina, E.; Hedman, B.; Hodgson, K.O.; Hardcastle, K.I.; Fang, X.; Kirk, M.L.; Knottenbelt, S.; Kogerler, P.; Musaev, D.G.; Morokuma, K.; Takahashi, M.; Hill, C.L.; /Emory U. /Argonne /SLAC, SSRL /New Mexico U. /Iowa State U. /Toho U.

    2007-10-19

    In contradiction to current bonding paradigms, two terminal Au-oxo molecular complexes have been synthesized by reaction of AuCl{sub 3} with metal oxide-cluster ligands that model redox-active metal oxide surfaces. Use of K{sub 10}[{alpha}{sub 2}-P{sub 2}W{sub 17}O{sub 61}] x 20H{sub 2}O and K{sub 2}WO{sub 4} (forming the [A-PW{sub 9}O{sub 34}]{sup 9-} ligand in situ) produces K{sub 15}H{sub 2}[Au(O)(OH{sub 2})P{sub 2}W{sub 18}O{sub 68}] x 25H{sub 2}O (1); use of K{sub 10}[P{sub 2}W{sub 20}O{sub 70}(OH{sub 2}){sub 2}] x 22H{sub 2}O (3) produces K{sub 7}H{sub 2}[Au(O)(OH{sub 2})P{sub 2}W{sub 20}O{sub 70}(OH{sub 2}){sub 2}] x 27H{sub 2}O (2). Complex 1 crystallizes in orthorhombic Fddd, with a = 28.594(4) Angstroms, b = 31.866(4) Angstroms, c = 38.241(5) Angstroms, V = 34844(7) Angstroms{sup 3}, Z = 16 (final R = 0.0540), and complex 2 crystallizes in hexagonal P6(3)/mmc, with a = 16.1730(9) Angstroms, b = 16.1730(9) Angstroms, c = 19.7659(15) Angstroms, V = 4477.4(5) Angstroms{sup 3}, Z = 2 (final R = 0.0634). The polyanion unit in 1 is disorder-free. Very short ({approx}1.76 Angstroms) Au-oxo distances are established by both X-ray and 30 K neutron diffraction studies, and the latter confirms oxo and trans aqua (H2O) ligands on Au. Seven findings clarify that Au and not W is present in the Au-oxo position in 1 and 2. Five lines of evidence are consistent with the presence of d8 Au(III) centers that are stabilized by the flanking polytungstate ligands in both 1 and 2: redox titrations, electrochemical measurements, 17 K optical spectra, Au L2 edge X-ray absorption spectroscopy, and Au-oxo bond distances. Variable-temperature magnetic susceptibility data for crystalline 1 and 2 establish that both solids are diamagnetic, and {sup 31}P and {sup 17}O NMR spectroscopy confirm that both remain diamagnetic in solution. Both complexes have been further characterized by FT-IR, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and other techniques.

  6. Reaction of BH4- with [Mo2Cp2(mu-SMe)n] species to give tetrahydroborato, hydrido or dimetallaborane compounds: control of product by ancillary ligands.

    Science.gov (United States)

    Cabon, Nolwenn; Petillon, Francois Y; Schollhammer, Philippe; Talarmin, Jean; Muir, Kenneth W

    2004-09-07

    The reaction of mono- or dichloro-dimolybdenum(III) complexes [Mo2Cp2(mu-SMe)2(mu-Cl)(mu-Y)] (Cp=eta5-C5H5; 1, Y=SMe; 2, Y=PPh2; 3, Y=Cl) with NaBH4 at room temperature gave in high yields tetrahydroborato (8), hydrido (9) or metallaborane (12) complexes depending on the ancillary ligands. The correct formulation of derivatives and has been unambigously determined by X-ray diffraction methods. That of the hydrido compound 9 has been established in solution by NMR analysis and confirmed by an X-ray study of the mu-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-PPh2)(mu-N=CHMe)] (10) obtained from the insertion of acetonitrile into the Mo-H bond of 9. Reaction of NaBH4 with nitrile derivatives, [Mo2Cp2(mu-SMe)4-n(CH3CN)2n]n+(5, n=1; 6 n=2), afforded the tetrahydroborato compound 8, together with a mu-azavinylidene species [Mo2Cp2(mu-SMe)3(mu-N=CHMe)](14), when n=1, and the metallaborane complex 12, together with a mixed borohydrato-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-BH4)(mu-N=CHMe)] (13), when n=2. The molecular structures of these complexes have been confirmed by X-ray analysis. Preparations of some of the starting complexes (3 and 4) are also described, as are the molecular structures of the precursors [Mo2Cp2(mu-SMe)2(mu-X)(mu-Y)] (1, X/Y=Cl/SMe; 2, X/Y=Cl/PPh2; 4, X/Y=SMe/PPh2).

  7. Distinct energetics and closing pathways for DNA polymerase β with 8-oxoG template and different incoming nucleotides

    Directory of Open Access Journals (Sweden)

    Wang Yanli

    2007-02-01

    Full Text Available Abstract Background 8-Oxoguanine (8-oxoG is a common oxidative lesion frequently encountered by DNA polymerases such as the repair enzyme DNA polymerase β (pol β. To interpret in atomic and energetic detail how pol β processes 8-oxoG, we apply transition path sampling to delineate closing pathways of pol β 8-oxoG complexes with dCTP and dATP incoming nucleotides and compare the results to those of the nonlesioned G:dCTP and G:dATPanalogues. Results Our analyses show that the closing pathways of the 8-oxoG complexes are different from one another and from the nonlesioned analogues in terms of the individual transition states along each pathway, associated energies, and the stability of each pathway's closed state relative to the corresponding open state. In particular, the closed-to-open state stability difference in each system establishes a hierarchy of stability (from high to low as G:C > 8-oxoG:C > 8-oxoG:A > G:A, corresponding to -3, -2, 2, 9 kBT, respectively. This hierarchy of closed state stability parallels the experimentally observed processing efficiencies for the four pairs. Network models based on the calculated rate constants in each pathway indicate that the closed species are more populated than the open species for 8-oxoG:dCTP, whereas the opposite is true for 8-oxoG:dATP. Conclusion These results suggest that the lower insertion efficiency (larger Km for dATP compared to dCTP opposite 8-oxoG is caused by a less stable closed-form of pol β, destabilized by unfavorable interactions between Tyr271 and the mispair. This stability of the closed vs. open form can also explain the higher insertion efficiency for 8-oxoG:dATP compared to the nonlesioned G:dATP pair, which also has a higher overall conformational barrier. Our study offers atomic details of the complexes at different states, in addition to helping interpret the different insertion efficiencies of dATP and dCTP opposite 8-oxoG and G.

  8. N-terminal sequence of human leukocyte glycoprotein Mo1: conservation across species and homology to platelet IIb/IIIa.

    Science.gov (United States)

    Pierce, M W; Remold-O'Donnell, E; Todd, R F; Arnaout, M A

    1986-12-12

    Mo1 and gp160-gp93 are two surface membrane glycoprotein heterodimers present on granulocytes and monocytes derived from humans and guinea pigs, respectively. We purified both antigens and found that their alpha subunits had identical N-termini which were significantly homologous to the alpha subunit of the human adhesion platelet glycoprotein IIb/IIIa.

  9. Development of the first well-defined tungsten oxo alkyl derivatives supported on silica by SOMC: towards a model of WO3/SiO2 olefin metathesis catalyst

    KAUST Repository

    Mazoyer, Etienne; Merle, Nicolas; Mallmann, Aimery De; Basset, Jean-Marie; Berrier, Elise; Delevoye, Laurent; Paul, Jean Franois; Nicholas, Christopher P.; Gauvin, Ré gis M.; Taoufik, Mostafa

    2010-01-01

    A well-defined, silica-supported tungsten oxo alkyl species prepared by the surface organometallic chemistry approach displays high and sustained activity in propene metathesis. Remarkably, its catalytic performances outpace those of the parent imido derivative, underlining the importance of the oxo ligand in the design of robust catalysts. © 2010 The Royal Society of Chemistry.

  10. Ligand assisted cleavage of uranium oxo-clusters

    Energy Technology Data Exchange (ETDEWEB)

    Nocton, Gregory; Pecaut, Jacques; Mazzanti, Marinella [Laboratoire de Reconnaissance Ionique et Chimie de Coordination, Service de Chimie Inorganique et Biologique, UMR-E 3 CEA-UJF, CEA/DSM/INAC, CEA-Grenoble, 38054 Grenoble, Cedex 09 (France); Filinchuk, Yaroslav [Swiss Norwegian Beam Lines (SNBL) at the European Synchrotron Radiation Facility (ESRF), rue Jules Horowitz, 38043 Grenoble (France)

    2010-07-01

    Dibenzoylmethanate replaces the bridging triflate ligands in uranium triflate poly-oxo-clusters and cleaves the U{sub 12}O{sub 20} core yielding the new [U{sub 6}O{sub 4}(OH){sub 4}({eta}-dbm){sub 12}] dibenzoylmethanate (dbm{sup -}) cluster which slowly dissociates into a monomeric complex. This reactivity demonstrates the importance of bridging ligands in stabilizing uranium poly-oxo-clusters. (authors)

  11. Theoretical investigation on the mechanism and dynamics of oxo exchange of neptunyl(VI) hydroxide in aqueous solution.

    Science.gov (United States)

    Yang, Xia; Chai, Zhifang; Wang, Dongqi

    2015-03-21

    Four types of reaction mechanisms for the oxo ligand exchange of monomeric and dimeric neptunyl(VI) hydroxide in aqueous solution were explored computationally using density functional theory (DFT) and ab initio classical molecular dynamics. The obtained results were compared with previous studies on the oxo exchange of uranyl hydroxide, as well as with experiments. It is found that the stable T-shaped [NpO3(OH)3](3-) intermediate is a key species for oxo exchange in the proton transfer in mononuclear Path I and binuclear Path IV, similar to the case of uranyl(VI) hydroxide. Path I is thought to be the preferred oxo exchange mechanism for neptunyl(VI) hydroxide in our calculations, due to the lower activation energy (22.7 and 13.1 kcal mol(-1) for ΔG(‡) and ΔH(‡), respectively) of the overall reaction. Path II via a cis-neptunyl structure assisted by a water molecule might be a competitive channel against Path I with a mononuclear mechanism, owing to a rapid dynamical process occurring in Path II. In Path IV with the binuclear mechanism, oxo exchange is accomplished via the interaction between [NpO2(OH)4](2-) and T-shaped [NpO3(OH)3](3-) with a low activation energy for the rate-determining step, however, the overall energy required to fulfill the reaction is slightly higher than that in mononuclear Path I, suggesting a possible binuclear process in the higher energy region. The chemical bonding evolution along the reaction pathways was discussed by using topological methodologies of the electron localization function (ELF).

  12. Detection of the electronic structure of iron-(iii)-oxo oligomers forming in aqueous solutions.

    Science.gov (United States)

    Seidel, Robert; Kraffert, Katrin; Kabelitz, Anke; Pohl, Marvin N; Kraehnert, Ralph; Emmerling, Franziska; Winter, Bernd

    2017-12-13

    The nature of the small iron-oxo oligomers in iron-(iii) aqueous solutions has a determining effect on the chemical processes that govern the formation of nanoparticles in aqueous phase. Here we report on a liquid-jet photoelectron-spectroscopy experiment for the investigation of the electronic structure of the occurring iron-oxo oligomers in FeCl 3 aqueous solutions. The only iron species in the as-prepared 0.75 M solution are Fe 3+ monomers. Addition of NaOH initiates Fe 3+ hydrolysis which is followed by the formation of iron-oxo oligomers. At small enough NaOH concentrations, corresponding to approximately [OH]/[Fe] = 0.2-0.25 ratio, the iron oligomers can be stabilized for several hours without engaging in further aggregation. Here, we apply a combination of non-resonant as well as iron 2p and oxygen 1s resonant photoelectron spectroscopy from a liquid microjet to detect the electronic structure of the occurring species. Specifically, the oxygen 1s partial electron yield X-ray absorption (PEY-XA) spectra are found to exhibit a peak well below the onset of liquid water and OH - (aq) absorption. The iron 2p absorption gives rise to signal centered between the main absorption bands typical for aqueous Fe 3+ . Absorption bands in both PEY-XA spectra are found to correlate with an enhanced photoelectron peak near 20 eV binding energy, which demonstrates the sensitivity of resonant photoelectron (RPE) spectroscopy to mixing between iron and ligand orbitals. These various signals from the iron-oxo oligomers exhibit maximum intensity at [OH]/[Fe] = 0.25 ratio. For the same ratio, we observe changes in the pH as well as in complementary Raman spectra, which can be assigned to the transition from monomeric to oligomeric species. At approximately [OH]/[Fe] = 0.3 we begin to observe particles larger than 1 nm in radius, detected by small-angle X-ray scattering.

  13. Bowl adamanzanes-bicyclic tetraamines: syntheses and crystal structures of complexes with cobalt(III) and chelating coordinated oxo-anions

    DEFF Research Database (Denmark)

    Broge, Louise; Søtofte, Inger; Jensen, Kristian

    2007-01-01

    complex is provided. Four of the seven complexes contain a chelate coordinating oxo-anion ( sulfate, formiate, nitrate, carbonate). Equilibration of these species with the corresponding diaqua complex is generally slow. The rates of equilibration in 5 mol dm(-3) perchloric acid at 25 degrees C have been...

  14. Degradation of oxo-biodegradable plastic by Pleurotus ostreatus.

    Science.gov (United States)

    da Luz, José Maria Rodrigues; Paes, Sirlaine Albino; Nunes, Mateus Dias; da Silva, Marliane de Cássia Soares; Kasuya, Maria Catarina Megumi

    2013-01-01

    Growing concerns regarding the impact of the accumulation of plastic waste over several decades on the environmental have led to the development of biodegradable plastic. These plastics can be degraded by microorganisms and absorbed by the environment and are therefore gaining public support as a possible alternative to petroleum-derived plastics. Among the developed biodegradable plastics, oxo-biodegradable polymers have been used to produce plastic bags. Exposure of this waste plastic to ultraviolet light (UV) or heat can lead to breakage of the polymer chains in the plastic, and the resulting compounds are easily degraded by microorganisms. However, few studies have characterized the microbial degradation of oxo-biodegradable plastics. In this study, we tested the capability of Pleurotus ostreatus to degrade oxo-biodegradable (D2W) plastic without prior physical treatment, such as exposure to UV or thermal heating. After 45 d of incubation in substrate-containing plastic bags, the oxo-biodegradable plastic, which is commonly used in supermarkets, developed cracks and small holes in the plastic surface as a result of the formation of hydroxyl groups and carbon-oxygen bonds. These alterations may be due to laccase activity. Furthermore, we observed the degradation of the dye found in these bags as well as mushroom formation. Thus, P. ostreatus degrades oxo-biodegradable plastics and produces mushrooms using this plastic as substrate.

  15. Degradation of oxo-biodegradable plastic by Pleurotus ostreatus.

    Directory of Open Access Journals (Sweden)

    José Maria Rodrigues da Luz

    Full Text Available Growing concerns regarding the impact of the accumulation of plastic waste over several decades on the environmental have led to the development of biodegradable plastic. These plastics can be degraded by microorganisms and absorbed by the environment and are therefore gaining public support as a possible alternative to petroleum-derived plastics. Among the developed biodegradable plastics, oxo-biodegradable polymers have been used to produce plastic bags. Exposure of this waste plastic to ultraviolet light (UV or heat can lead to breakage of the polymer chains in the plastic, and the resulting compounds are easily degraded by microorganisms. However, few studies have characterized the microbial degradation of oxo-biodegradable plastics. In this study, we tested the capability of Pleurotus ostreatus to degrade oxo-biodegradable (D2W plastic without prior physical treatment, such as exposure to UV or thermal heating. After 45 d of incubation in substrate-containing plastic bags, the oxo-biodegradable plastic, which is commonly used in supermarkets, developed cracks and small holes in the plastic surface as a result of the formation of hydroxyl groups and carbon-oxygen bonds. These alterations may be due to laccase activity. Furthermore, we observed the degradation of the dye found in these bags as well as mushroom formation. Thus, P. ostreatus degrades oxo-biodegradable plastics and produces mushrooms using this plastic as substrate.

  16. Degradation of Oxo-Biodegradable Plastic by Pleurotus ostreatus

    Science.gov (United States)

    da Luz, José Maria Rodrigues; Paes, Sirlaine Albino; Nunes, Mateus Dias; da Silva, Marliane de Cássia Soares; Kasuya, Maria Catarina Megumi

    2013-01-01

    Growing concerns regarding the impact of the accumulation of plastic waste over several decades on the environmental have led to the development of biodegradable plastic. These plastics can be degraded by microorganisms and absorbed by the environment and are therefore gaining public support as a possible alternative to petroleum-derived plastics. Among the developed biodegradable plastics, oxo-biodegradable polymers have been used to produce plastic bags. Exposure of this waste plastic to ultraviolet light (UV) or heat can lead to breakage of the polymer chains in the plastic, and the resulting compounds are easily degraded by microorganisms. However, few studies have characterized the microbial degradation of oxo-biodegradable plastics. In this study, we tested the capability of Pleurotus ostreatus to degrade oxo-biodegradable (D2W) plastic without prior physical treatment, such as exposure to UV or thermal heating. After 45 d of incubation in substrate-containing plastic bags, the oxo-biodegradable plastic, which is commonly used in supermarkets, developed cracks and small holes in the plastic surface as a result of the formation of hydroxyl groups and carbon-oxygen bonds. These alterations may be due to laccase activity. Furthermore, we observed the degradation of the dye found in these bags as well as mushroom formation. Thus, P. ostreatus degrades oxo-biodegradable plastics and produces mushrooms using this plastic as substrate. PMID:23967057

  17. Spectrophotometric and potentiometric studies of oxidation of Mo(III) by Mo(VI) in phosphoric acid medium

    International Nuclear Information System (INIS)

    Kumar, Arvind; Verma, G.S.P.

    1975-01-01

    Oxidation of Mo(III) (green) by Mo(VI) in an inert atmosphere and in orthophosphoric acid medium at various acid concentrations is reported. Potentiometric and spectrophotometric data suggest that oxidation of Mo(III) proceeds to Mo(V) through a binuclear species Mo(III) Mo(IV) absorbing at 400 nm. The formation of this species is facilitated at high acid concentrations. It is further found that quantitative conversion of Mo(III) into Mo(V) takes place at fairly high acid concentrations. In high phosphoric acid concentrations, solution of Mo(III) has been found to be oxidized to Mo(VI) by air and hence this can be used as a good oxygen absorber. (author)

  18. Spectrophotometric and potentiometric studies of oxidation of Mo(III) by Mo(VI) in phosphoric acid medium

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, A; Verma, G S.P. [Ranchi Coll. (India). Dept. of Chemistry

    1975-12-01

    Oxidation of Mo(III) (green) by Mo(VI) in an inert atmosphere and in orthophosphoric acid medium at various acid concentrations is reported. Potentiometric and spectrophotometric data suggest that oxidation of Mo(III) proceeds to Mo(V) through a binuclear species Mo(III) Mo(IV) absorbing at 400 nm. The formation of this species is facilitated at high acid concentrations. It is further found that quantitative conversion of Mo(III) into Mo(V) takes place at fairly high acid concentrations. In high phosphoric acid concentrations, solution of Mo(III) has been found to be oxidized to Mo(VI) by air and hence this can be used as a good oxygen absorber.

  19. Investigation of an eco-friendly aerogel as a substrate for the immobilization of MoS2 nanoflowers for removal of mercury species from aqueous solutions.

    Science.gov (United States)

    Ma, Chong-Bo; Du, Yan; Du, Baoji; Wang, Hao; Wang, Erkang

    2018-04-21

    An adsorbent that exhibits high affinity for inorganic mercury (Hg 2+ ) with a high removal efficiency of methylmercury (MeHg + ) has been developed. The adsorbent demonstrates a symbiotic relationship between its two components, molybdenum disulphide nanoflowers (MoS 2 NFs) and a poly (vinyl alcohol) (PVA) aerogel. Furthermore, we modified the distribution and loading of the MoS 2 NFs, which was possible due to the stable porous support, and investigated the biocompatibility of the aerogel-support adsorbent. The performance of the optimized material exhibited a distribution coefficient of 9.71 × 10 7  mL g -1 . In addition, the adsorbent was effective over a wide pH range and could efficiently purify both contaminated lake and sea water. The key motivation for using an aerogel support was to stabilise the MoS 2 NFs during purification of the water (resulting in improved performance compared to using freestanding MoS 2 NFs) and the ability to regenerate the used adsorbent. In addition, animal tests confirmed an extremely low toxicity of the adsorbent to fish, along with the excellent purification results. Copyright © 2018 Elsevier Inc. All rights reserved.

  20. Formation of nitridotechnetium(VI) μ-oxo dimer complexes with EDTA and EDDA

    International Nuclear Information System (INIS)

    Takayama, T.; Kani, Y.; Sekine, T.; Kudo, H.; Yoshihara, K.

    1995-01-01

    Reactions of [ 99 TcNCl 4 ] - with ethylenediaminetetraacetic acid 4 (ETDA) and ethylenediamine-N,N'-diacetic acid (EDDA) in a mixture of water and acetone gave Tc VI N-EDTA and Tc VI N-EDTA complexes. The infrared spectra of both reaction products showed the existence of the Tc≡N and C=O groups. The elemental analysis indicated the 1:1 TcN-ligand ratio in the EDTA and EDDA complexes. Electrophoresis showed that the Tc VI -EDTA complex was an anionic species in a perchlorate solution. For the Tc VI N-EDDA complex, neutral and anionic species were formed, depending on the pH of the solution. Formation of the μ-oxo dimer complexes was suggested from the UV-Vis absorption spectra. (author) 11 refs.; 4 figs.; 1 tab

  1. Inter-laboratory validation of procedures for measuring 8-oxo-7,8-dihydrooxoguanine/8-oxo-7,8-dihydro-2`-deoxyguanosine in DNA

    DEFF Research Database (Denmark)

    Collins, A.R.; Gedik, C.M.; Wood, S.

    2002-01-01

    The aim of ESCODD, a European Commission funded Concerted Action, is to improve the precision and accuracy of methods for measuring 8-oxo-7,8-dihydroguanine (8-oxoGua) or the nucleoside (8-oxodG). On two occasions, participating laboratories received samples of different concentrations of 8-oxodG...

  2. Solution chemistry of Mo(III) and Mo(IV): Thermodynamic foundation for modeling localized corrosion

    International Nuclear Information System (INIS)

    Wang Peiming; Wilson, Leslie L.; Wesolowski, David J.; Rosenqvist, Joergen; Anderko, Andrzej

    2010-01-01

    To investigate the behavior of molybdenum dissolution products in systems that approximate localized corrosion environments, solubility of Mo(III) in equilibrium with solid MoO 2 has been determined at 80 deg. C as a function of solution acidity, chloride concentration and partial pressure of hydrogen. The measurements indicate a strong increase in solubility with acidity and chloride concentration and a weak effect of hydrogen partial pressure. The obtained results have been combined with literature data for systems containing Mo(III), Mo(IV), and Mo(VI) in solutions to develop a comprehensive thermodynamic model of aqueous molybdenum chemistry. The model is based on a previously developed framework for simulating the properties of electrolyte systems ranging from infinite dilution to solid saturation or fused salt limit. To reproduce the measurements, the model assumes the presence of a chloride complex of Mo(III) (i.e., MoCl 2+ ) and hydrolyzed species (MoOH 2+ , Mo(OH) 2 + , and Mo(OH) 3 0 ) in addition to the Mo 3+ ion. The model generally reproduces the experimental data within experimental scattering and provides a tool for predicting the phase behavior and speciation in complex, concentrated aqueous solutions. Thus, it provides a foundation for simulating the behavior of molybdenum species in localized corrosion environments.

  3. Menadione-induced DNA fragmentation without 8-oxo-2'-deoxyguanosine formation in isolated rat hepatocytes

    DEFF Research Database (Denmark)

    Fischer-Nielsen, A; Corcoran, G B; Poulsen, H E

    1995-01-01

    Menadione (2-methyl-1,4-naphthoquinone) induces oxidative stress in cells causing perturbations in the cytoplasm as well as nicking of DNA. The mechanisms by which DNA damage occurs are still unclear, but a widely discussed issue is whether menadione-generated reactive oxygen species (ROS) directly...... damage DNA. In the present study, we measured the effect of menadione on formation of 7,8-dihydro-8-oxo-2'-deoxyguanosine (8-oxodG), an index of oxidative DNA base modifications, and on DNA fragmentation. Isolated hepatocytes from phenobarbital-pretreated rats were exposed to menadione, 25-400 micro......M, for 15, 90 or 180 min with or without prior depletion of reduced glutathione (GSH) by diethyl maleate. Menadione caused profound GSH depletion and internucleosomal DNA fragmentation, which was demonstrated by a prominent fragmentation ladder on agarose gel electrophoresis. We found no oxidative...

  4. Abiotic and Biotic Degradation of Oxo-Biodegradable Plastic Bags by Pleurotus ostreatus

    OpenAIRE

    da Luz, José Maria Rodrigues; Paes, Sirlaine Albino; Bazzolli, Denise Mara Soares; Tótola, Marcos Rogério; Demuner, Antônio Jacinto; Kasuya, Maria Catarina Megumi

    2014-01-01

    In this study, we evaluated the growth of Pleurotus ostreatus PLO6 using oxo-biodegradable plastics as a carbon and energy source. Oxo-biodegradable polymers contain pro-oxidants that accelerate their physical and biological degradation. These polymers were developed to decrease the accumulation of plastic waste in landfills. To study the degradation of the plastic polymers, oxo-biodegradable plastic bags were exposed to sunlight for up to 120 days, and fragments of these bags were used as su...

  5. Oxo-group-14-element bond formation in binuclear uranium(V) pacman complexes

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2013-01-01

    Simple and versatile routes to the functionalization of uranyl-derived U"V-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)_3LiOUO}_2(L)] and [{(py)_3LiOUO}(OUOSiMe_3)(L)] were prepared by the direct combination of the uranyl(VI) silylamide ''ate'' complex [Li(py)_2][(OUO)(N'')_3](N''=N(SiMe_3)_2) with the polypyrrolic macrocycle H_4L or the mononuclear uranyl (VI) Pacman complex [UO_2(py)(H_2L)], respectively. These oxo-metalated complexes display distinct U-O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R_3Sn)OUO}_2(L)] (R=nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr)_3] to form U-O-C bonds [{(py)_3LiOUO}(OUOiPr)(L)] and [(iPrOUO)_2(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. α-Oxo-Ketenimines from Isocyanides and α-Haloketones: Synthesis and Divergent Reactivity.

    Science.gov (United States)

    Mamboury, Mathias; Wang, Qian; Zhu, Jieping

    2017-09-18

    The palladium-catalyzed reaction of α-haloketones with isocyanides afforded α-oxo-ketenimines through β-hydride elimination of the β-oxo-imidoyl palladium intermediates. Reaction of these relatively stable α-oxo-ketenimines with nucleophiles such as hydrazines, hydrazoic acid, amines, and Grignard reagent afforded pyrazoles, tetrazole, β-keto amidines, and enaminone, respectively, with high chemoselectivity. Whereas amines attack exclusively on the ketenimine functions, the formal [3+2] cycloaddition between N-monosubstituted hydrazines and α-oxo-ketenimines was initiated by nucleophilic addition to the carbonyl group. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)-Oxo Sites in Magnesium-Diluted Fe2(dobdc).

    Science.gov (United States)

    Verma, Pragya; Vogiatzis, Konstantinos D; Planas, Nora; Borycz, Joshua; Xiao, Dianne J; Long, Jeffrey R; Gagliardi, Laura; Truhlar, Donald G

    2015-05-06

    The catalytic properties of the metal-organic framework Fe2(dobdc), containing open Fe(II) sites, include hydroxylation of phenol by pure Fe2(dobdc) and hydroxylation of ethane by its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc). In earlier work, the latter reaction was proposed to occur through a redox mechanism involving the generation of an iron(IV)-oxo species, which is an intermediate that is also observed or postulated (depending on the case) in some heme and nonheme enzymes and their model complexes. In the present work, we present a detailed mechanism by which the catalytic material, Fe0.1Mg1.9(dobdc), activates the strong C-H bonds of ethane. Kohn-Sham density functional and multireference wave function calculations have been performed to characterize the electronic structure of key species. We show that the catalytic nonheme-Fe hydroxylation of the strong C-H bond of ethane proceeds by a quintet single-state σ-attack pathway after the formation of highly reactive iron-oxo intermediate. The mechanistic pathway involves three key transition states, with the highest activation barrier for the transfer of oxygen from N2O to the Fe(II) center. The uncatalyzed reaction, where nitrous oxide directly oxidizes ethane to ethanol is found to have an activation barrier of 280 kJ/mol, in contrast to 82 kJ/mol for the slowest step in the iron(IV)-oxo catalytic mechanism. The energetics of the C-H bond activation steps of ethane and methane are also compared. Dehydrogenation and dissociation pathways that can compete with the formation of ethanol were shown to involve higher barriers than the hydroxylation pathway.

  8. New insights into thorium and uranium oxo-arsenic (III/V) and oxo-phosphates (V) crystal chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Na

    2015-12-11

    The fundamental chemistry of actinides is of great interest owing to the diverse number of valence states and complex coordination chemistry of the actinides. The phases based on actinides and oxo-salt fragments have been under thorough investigation in the last decades. These compounds can be widely found in nature and they affect the migration process of actinides in nature. A better understanding of the fundamental coordination chemistry of actinide compounds with oxo-salts of group V elements is not only important for understanding the actinides behavior within the migration process but can also be used to understand actinide properties in phosphate ceramics. Concerning the radioactive issues, the less radioactive early actinides (i.e. U, Th) can be taken as modeling elements to study the crystal chemistry of the transuranic elements (Np, Pu) without the major handling problems. This can be done as Th(IV) has a very similar coordination chemistry with An(IV) and U(VI) can be chosen as a modeling element for transuranic elements in higher valence states. Therefore, a systematic research on the actinides (U, Th) bearing phases with tetrahedral oxo-anions such as phosphates and arsenates have been performed in this work. High temperature (HT) solid state reaction, High pressure high temperature (HP-HT) solid state reaction and the hydrothermal method were the methods of choice for synthesizing actinide bearing oxo-arsenic(III/V) and oxo- phosphorus(V) phases in the past three years. As a result, numerous novel compounds containing actinides were obtained. The structures of all compounds were determined using single crystal X-ray diffraction data. Raman spectroscopy, EDS, DSC and high temperature powder X-ray diffraction (HT-PXRD) measurements were implemented to characterize the chemical and physical properties of the obtained compounds. The core of this dissertation is a fundamental study of the crystal chemistry of actinides (Th, U) oxo-arsenic (III/V) and oxo

  9. New insights into thorium and uranium oxo-arsenic (III/V) and oxo-phosphates (V) crystal chemistry

    International Nuclear Information System (INIS)

    Yu, Na

    2015-01-01

    The fundamental chemistry of actinides is of great interest owing to the diverse number of valence states and complex coordination chemistry of the actinides. The phases based on actinides and oxo-salt fragments have been under thorough investigation in the last decades. These compounds can be widely found in nature and they affect the migration process of actinides in nature. A better understanding of the fundamental coordination chemistry of actinide compounds with oxo-salts of group V elements is not only important for understanding the actinides behavior within the migration process but can also be used to understand actinide properties in phosphate ceramics. Concerning the radioactive issues, the less radioactive early actinides (i.e. U, Th) can be taken as modeling elements to study the crystal chemistry of the transuranic elements (Np, Pu) without the major handling problems. This can be done as Th(IV) has a very similar coordination chemistry with An(IV) and U(VI) can be chosen as a modeling element for transuranic elements in higher valence states. Therefore, a systematic research on the actinides (U, Th) bearing phases with tetrahedral oxo-anions such as phosphates and arsenates have been performed in this work. High temperature (HT) solid state reaction, High pressure high temperature (HP-HT) solid state reaction and the hydrothermal method were the methods of choice for synthesizing actinide bearing oxo-arsenic(III/V) and oxo- phosphorus(V) phases in the past three years. As a result, numerous novel compounds containing actinides were obtained. The structures of all compounds were determined using single crystal X-ray diffraction data. Raman spectroscopy, EDS, DSC and high temperature powder X-ray diffraction (HT-PXRD) measurements were implemented to characterize the chemical and physical properties of the obtained compounds. The core of this dissertation is a fundamental study of the crystal chemistry of actinides (Th, U) oxo-arsenic (III/V) and oxo

  10. Urinary excretion of 8-oxo-7,8-dihydroguanine as biomarker of oxidative damage to DNA

    DEFF Research Database (Denmark)

    Loft, Steffen; Danielsen, Pernille Høgh; Løhr, Mille

    2012-01-01

    to air pollution, toxic metals, tobacco smoke and low plasma antioxidant levels, whereas fruit and vegetable intake or dietary interventions showed no association. In rodent studies some types of feed may be source of 8-oxoGua in collected urine. Of cancer therapies, cisplatin increased 8-oxo...

  11. A concise synthesis of the potent inflammatory mediator 5-oxo-ETE

    DEFF Research Database (Denmark)

    Tyagi, Rahul; Shimpukade, Bharat; Blättermann, Stefanie

    2012-01-01

    A concise and practical method for synthesis of the potent inflammatory mediator 5-oxo-6E,8Z,11Z,14Z-eicosatetraenoic acid (5-oxo-ETE, 1) from arachidonic acid in four steps and 70% overall yield is reported. Stability studies indicate that 1 can be safely handled without rigorous precautions...

  12. Oxidations of Organic and Inorganic Substrates by Superoxo-, hydroperoxo-, and oxo-compounds of the transition metals

    International Nuclear Information System (INIS)

    Michael John Vasbinder

    2006-01-01

    Chapters 1 and 2 dealt with the chemistry of superoxo-, hydroperoxo-, and oxo- complexes of chromium, rhodium and cobalt. Chapter 3 dealt with the mechanism of oxygen-atom transfer catalyzed by an oxo-complex of rhenium. In Chapter 1, it was shown that hydroperoxometal complexes of cobalt and rhodium react with superoxochromium and chromyl ions, generating reduced chromium species while oxidizing the hydroperoxometal ions to their corresponding superoxometal ions. It was shown that the chromyl and superoxochromium ions are the more powerful oxidants. Evidence supports hydrogen atom transfer from the hydroperoxometal ion to the oxidizing superoxochromium or chromyl ion as the reaction mechanism. There is a significant H/D kinetic isotope effect. Comparisons to the rate constants of other known hydrogen atom transfer reactions show the expected correlation with bond dissociation energies. In Chapter 2, it was found that the superoxometal complexes Cr aq OO 2+ and Rh(NH 3 ) 4 (H 2 O)OO 2+ oxidize stable nitroxyl radicals of the TEMPO series with rate constants that correlate with the redox potentials of both the oxidant and reductant. These reactions fit the Marcus equation for electron transfer near the theoretical value. Acid catalysis is important to the reaction, especially the thermodynamically limited cases involving Rh(NH 3 ) 4 (H 2 O)OO 2+ as the oxidant. The rate constants are notably less than those measured in the reaction between the same nitroxyl radicals and other strong free-radical oxidants, an illustration of the delocalized and stabilized nature of the superoxometal ions. Chapter 3 showed that oxo-rhenium catalysts needed a nucleophile to complete the catalytic oxygen-atom transfer from substituted pyridine-N-oxides to triphenylphosphine. The reaction was studied by introducing various pyridine-derived nucleophiles and monitoring their effect on the rate, then fitting the observed rate constants to the Hammett correlation. It was found that the

  13. A non-diazo approach to α-oxo gold carbenes via gold-catalyzed alkyne oxidation.

    Science.gov (United States)

    Zhang, Liming

    2014-03-18

    For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, α-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C-H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile α-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of α-oxo gold carbene intermediates. The

  14. A Non-Diazo Approach to α-Oxo Gold Carbenes via Gold-Catalyzed Alkyne Oxidation

    Science.gov (United States)

    2015-01-01

    For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, α-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C–H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile α-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of α-oxo gold carbene intermediates. The

  15. Hydrothermal Synthesis of MoO2 and Supported MoO2 Cata-lysts for Oxidative Desulfurization of Dibenzothiophene

    Institute of Scientific and Technical Information of China (English)

    Wang Danhong; Zhang Jianyong; Liu Ni; Zhao Xin; Zhang Minghui

    2014-01-01

    A novel method for obtaining spherical MoO2 nanoparticles and SiO2-Al2O3 supported MoO2 by hydrothermal reduction of Mo (VI) species was studied. The obtained MoO2 catalysts show very high catalytic activity in the oxidative desulfurization (ODS) process. The effect of hydrothermal temperature and crystallization temperature on ODS activity was investigated. The ODS activity of supported MoO2 catalysts with various MoO2 contents were also investigated. The mecha-nism for formation of MoO2 involving oxalic acid was proposed.

  16. Moessbauer spectroscopy and nuclear inelastic scattering studies on polynuclear oxo-bridged iron catalyst-first results

    International Nuclear Information System (INIS)

    Rajagopalan, S.; Asthalter, T.; Rabe, V.; Buerck, U. van; Wagner, F. E.; Laschat, S.

    2008-01-01

    Polynuclear iron catalysts are interesting materials because of their novel properties. In the future they may help to replace high cost and hazardous heavy metal catalysts by efficient, non toxic and economic iron compounds. In this work, we present some preliminary results on a novel polynuclear oxo-bridged iron catalyst. The chemical environment of the metal species (Fe) was studied under Gif-type conditions (Fe catalyst/Zn/O 2 in pyridine/acetic acid) with cyclohexene as substrate. Such Gif-type catalysts are able to catalyse the selective oxidation of alkanes and alkenes. The characterization was done by Moessbauer spectroscopy and nuclear inelastic scattering. In order to identify the intermediate species during the reaction (selective oxidation using molecular O 2 ), a freeze-quench technique was used. This also helps to understand the kinetics of the chemical reaction.

  17. Oxo-group-14-element bond formation in binuclear uranium(V) pacman complexes

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom)

    2013-07-29

    Simple and versatile routes to the functionalization of uranyl-derived U{sup V}-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)_3LiOUO}{sub 2}(L)] and [{(py)_3LiOUO}(OUOSiMe{sub 3})(L)] were prepared by the direct combination of the uranyl(VI) silylamide ''ate'' complex [Li(py){sub 2}][(OUO)(N''){sub 3}](N''=N(SiMe{sub 3}){sub 2}) with the polypyrrolic macrocycle H{sub 4}L or the mononuclear uranyl (VI) Pacman complex [UO{sub 2}(py)(H{sub 2}L)], respectively. These oxo-metalated complexes display distinct U-O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R_3Sn)OUO}{sub 2}(L)] (R=nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr){sub 3}] to form U-O-C bonds [{(py)_3LiOUO}(OUOiPr)(L)] and [(iPrOUO){sub 2}(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Titanium oxo-clusters: precursors for a Lego-like construction of nanostructured hybrid materials.

    Science.gov (United States)

    Rozes, Laurence; Sanchez, Clément

    2011-02-01

    Titanium oxo-clusters, well-defined monodispersed nano-objects, are appropriate nano-building blocks for the preparation of organic-inorganic materials by a bottom up approach. This critical review proposes to present the different structures of titanium oxo-clusters referenced in the literature and the different strategies followed to build up hybrid materials with these versatile building units. In particular, this critical review cites and reports on the most important papers in the literature, concentrating on recent developments in the field of synthesis, characterization, and the use of titanium oxo-clusters for the construction of advanced hybrid materials (137 references).

  19. Study of the radiation effect of "9"9Mo/"9"9"mTc generator on Bacillus subtilis and Bacillus pumilus species

    International Nuclear Information System (INIS)

    Fukumori, Neuza T.O.; Endo, Erica M.M.; Felgueiras, Carlos F.; Matsuda, Margareth M.N.; Osso Junior, João A.

    2016-01-01

    In this work, molybdenum-99 loaded columns were challenged with Bacillus subtilis vegetative cells and Bacillus pumilus spores inside and outside the alumina column, and microbial recovery and radiation effect were assessed. Alumina was a barrier for the passage of microorganisms regardless the species, whilst spores were more retained than vegetative cells with a lower microbial recovery, without significant differences between 9.25 and 74 GBq generators. Bacillus pumilus biological indicator showed lower recoveries, suggesting a radiation inactivating effect on microorganisms. - Highlights: • Microorganisms in radionuclide generator may impair the quality of the product. • Killing of Bacillus pumilus was not complete even after 20 days of exposition. • Alumina column was a physical barrier for the microbial recovery. • An alternative biological indicator based on B. pumilus spores is proposed.

  20. Holey Reduced Graphene Oxide Coupled with an Mo2 N-Mo2 C Heterojunction for Efficient Hydrogen Evolution.

    Science.gov (United States)

    Yan, Haijing; Xie, Ying; Jiao, Yanqing; Wu, Aiping; Tian, Chungui; Zhang, Xiaomeng; Wang, Lei; Fu, Honggang

    2018-01-01

    An in situ catalytic etching strategy is developed to fabricate holey reduced graphene oxide along with simultaneous coupling with a small-sized Mo 2 N-Mo 2 C heterojunction (Mo 2 N-Mo 2 C/HGr). The method includes the first immobilization of H 3 PMo 12 O 40 (PMo 12 ) clusters on graphite oxide (GO), followed by calcination in air and NH 3 to form Mo 2 N-Mo 2 C/HGr. PMo 12 not only acts as the Mo heterojunction source, but also provides the Mo species that can in situ catalyze the decomposition of adjacent reduced GO to form HGr, while the released gas (CO) and introduced NH 3 simultaneously react with the Mo species to form an Mo 2 N-Mo 2 C heterojunction on HGr. The hybrid exhibits superior activity towards the hydrogen evolution reaction with low onset potentials of 11 mV (0.5 m H 2 SO 4 ) and 18 mV (1 m KOH) as well as remarkable stability. The activity in alkaline media is also superior to Pt/C at large current densities (>88 mA cm -2 ). The good activity of Mo 2 N-Mo 2 C/HGr is ascribed to its small size, the heterojunction of Mo 2 N-Mo 2 C, and the good charge/mass-transfer ability of HGr, as supported by a series of experiments and theoretical calculations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Influence of substituents in meso-aryl groups of iron l-oxo porphyrins\

    Czech Academy of Sciences Publication Activity Database

    Tabor, Edyta; Poltowicz, J.; Pamin, K.; Basag, S.; Kubiak, W.

    2016-01-01

    Roč. 119, NOV 2016 (2016), s. 342-349 ISSN 0277-5387 Institutional support: RVO:61388955 Keywords : iron porphyrins * μ-Oxo porphyrins * oxidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.926, year: 2016

  2. Cobalt(III)-oxo cubane clusters as catalysts for oxidation of organic ...

    Indian Academy of Sciences (India)

    been prepared by a general method and these have been characterized by analytical, spectroscopic, electro- chemical and ... alkylaromatics, alkenes and alcohols.1 Several indus- .... us to obtain the cobalt(III)-oxo clusters in good to very.

  3. Extreme ultraviolet patterning of tin-oxo cages

    Science.gov (United States)

    Haitjema, Jarich; Zhang, Yu; Vockenhuber, Michaela; Kazazis, Dimitrios; Ekinci, Yasin; Brouwer, Albert M.

    2017-07-01

    We report on the extreme ultraviolet (EUV) patterning performance of tin-oxo cages. These cage molecules were already known to function as a negative tone photoresist for EUV radiation, but in this work, we significantly optimized their performance. Our results show that sensitivity and resolution are only meaningful photoresist parameters if the process conditions are optimized. We focus on contrast curves of the materials using large area EUV exposures and patterning of the cages using EUV interference lithography. It is shown that baking steps, such as postexposure baking, can significantly affect both the sensitivity and contrast in the open-frame experiments as well as the patterning experiments. A layer thickness increase reduced the necessary dose to induce a solubility change but decreased the patterning quality. The patterning experiments were affected by minor changes in processing conditions such as an increased rinsing time. In addition, we show that the anions of the cage can influence the sensitivity and quality of the patterning, probably through their effect on physical properties of the materials.

  4. High performance Mo adsorbent PZC

    Energy Technology Data Exchange (ETDEWEB)

    Anon,

    1998-10-01

    We have developed Mo adsorbents for natural Mo(n, {gamma}){sup 99}Mo-{sup 99m}Tc generator. Among them, we called the highest performance adsorbent PZC that could adsorb about 250 mg-Mo/g. In this report, we will show the structure, adsorption mechanism of Mo, and the other useful properties of PZC when you carry out the examination of Mo adsorption and elution of {sup 99m}Tc. (author)

  5. How do two Lupinus species respond to temperature along an altitudinal gradient in the Venezuelan Andes? ¿Cómo responden dos especies de Lupinus a la temperatura en un gradiente altitudinal en los Andes venezolanos?

    Directory of Open Access Journals (Sweden)

    FERMÍN RADA

    2008-09-01

    Full Text Available Temperature determines plant formations and species distribution along altitudinal gradients. Plants in the tropical high Andes, through different physiological and morphological characteristics, respond to freezing night temperatures and high daytime energy inputs which occur anytime of the year. The main objective of this study was to characterize day and night temperature related responses of two Lupinus species with different altitudinal ranges (L. meridanus, 1,800-3,600 and L. eromonomos, 3,700-4,300 m of altitude. Are there differences in night low temperature resistance mechanisms between the species along the gradient? How do these species respond, in terms of optimum temperature for photosynthesis, to increasing altitude? Lupinus meridanus shows frost avoidance, in contrast to L. eromonomos, which tolerates freezing at higher altitudes. Optimum temperature for photosynthesis decreases along the gradient for both species. Maximum C0(2 assimilation rates were higher in L. meridanus, while L. eromonomos showed decreasing C0(2 assimilation rates at the higher altitude. In most cases, measured daily leaf temperature is always within the 80 % of optimum for photosynthesis. L. meridanus7 upper distribution limit seems to be restricted by cold resistance mechanisms, while L. eromonomos7 to a combination of both cold resistance and to C0(2 assimilation responses at higher altitudes.La temperatura determina las formaciones vegetales y la distribución de especies a lo largo de gradientes altitudinales. Las plantas en los altos Andes tropicales, a través de diferentes características morfológicas y fisiológicas, responden a temperaturas congelantes nocturnas y altas entradas energéticas durante el día en cualquier momento del año. El objetivo principal de este estudio fue caracterizar las respuestas relacionadas con temperaturas diurnas y nocturnas en dos especies de Lupinus con diferente distribución altitudinal (L. meridanus, 1

  6. Potent PPARα activator derived from tomato juice, 13-oxo-9,11-octadecadienoic acid, decreases plasma and hepatic triglyceride in obese diabetic mice.

    Directory of Open Access Journals (Sweden)

    Young-il Kim

    Full Text Available Dyslipidemia is a major risk factor for development of several obesity-related diseases. The peroxisome proliferator-activated receptor α (PPARα is a ligand-activated transcription factor that regulates energy metabolism. Previously, we reported that 9-oxo-10,12-octadecadienoic acid (9-oxo-ODA is presented in fresh tomato fruits and acts as a PPARα agonist. In addition to 9-oxo-ODA, we developed that 13-oxo-9,11-octadecadienoic acid (13-oxo-ODA, which is an isomer of 9-oxo-ODA, is present only in tomato juice. In this study, we explored the possibility that 13-oxo-ODA acts as a PPARα agonist in vitro and whether its effect ameliorates dyslipidemia and hepatic steatosis in vivo. In vitro luciferase assay experiments revealed that 13-oxo-ODA significantly induced PPARα activation; moreover, the luciferase activity of 13-oxo-ODA was stronger than that of 9-oxo-ODA and conjugated linoleic acid (CLA, which is a precursor of 13-oxo-ODA and is well-known as a potent PPARα activator. In addition to in vitro experiment, treatment with 13-oxo-ODA decreased the levels of plasma and hepatic triglycerides in obese KK-Ay mice fed a high-fat diet. In conclusion, our findings indicate that 13-oxo-ODA act as a potent PPARα agonist, suggesting a possibility to improve obesity-induced dyslipidemia and hepatic steatosis.

  7. Decay of 99Mo

    International Nuclear Information System (INIS)

    Dickens, J.K.; Love, T.A.

    1976-01-01

    Relative intensities for K x-rays and gamma rays emanating from 99 Mo in equilibrium with its 99 Tc* daughter have been measured using several Ge photon detectors. Combining these intensities with an evaluated set of electron-conversion coefficients has provided a set of absolute intensities for the observed gamma rays. The absolute intensity for the dominant 140.5-keV gamma ray in 99 Tc was determined to be 90.7 +- 0.6/100 99 Mo disintegrations for 99 Mo decay in equilibrium with decay of the 99 Tc* daughter

  8. Disposition of 14C-LY195115 (1,3-dihydro-3,3-dimethyl-5-[1,4,5,6-tetrahydro-6-oxo-3-pyridazinyl-6-14C]-2H-indol-2-one), a potent cardiotonic drug, in several animal species

    International Nuclear Information System (INIS)

    Bernstein, J.R.; Miller, B.J.; Franklin, R.B.

    1986-01-01

    Following the oral administration of 14 C-LY195115 to rats, mice, dogs, and monkeys (25,15,5, and 5 mg/kg, respectively), between 40 and 60% of the radioactivity was excreted into the urine within 24 hr. The elimination half-time of radioactivity from plasma was approximately 5 hr for rats and mice, 8 hr for monkeys, and 14 hr in dogs. Analysis of the 24 hr urine by thin-layer chromatography (tlc) revealed that the predominant radioactive moiety from all species was parent drug (> 30% of the dose). The urinary metabolite profile in the monkey showed parent drug and 2 polar, minor metabolites. The pattern was similar in rats, mice and dogs. Additionally in monkeys there was a very polar metabolite which was not conjugated with β-glucuronic acid. The major metabolite in the urine was isolated and shown to have a molecular weight of 255 (LY195115=257). Synthesis of the dehydro derivative of LY195115 indicated that the metabolite was identical to this material. A tissue distribution study in rats, following an oral dose of 14 C-LY195115 resulted in no apparent accumulation of radioactivity in any particular organ

  9. 3-oxo-rhazinilam: a new indole alkaloid from Rauvolfia serpentina x Rhazya stricta hybrid plant cell cultures.

    Science.gov (United States)

    Gerasimenko, I; Sheludko, Y; Stöckigt, J

    2001-01-01

    A new monoterpenoid indole alkaloid, 3-oxo-rhazinilam (1), was isolated from intergeneric somatic hybrid cell cultures of Rauvolfia serpentina and Rhazya stricta, and the structure was determined by detailed 1D and 2D NMR analysis. It was also proved that 3-oxo-rhazinilam (1) is a natural constituent of the hybrid cells.

  10. Solution structures of lipoyl domains of the 2-oxo acid dehydrogenase complexes from Azotobacter vinelandii : implications for molecular recognition

    NARCIS (Netherlands)

    Berg, A.

    1997-01-01

    The 2-oxo acid dehydrogenase complexes are large multienzyme complexes that catalyse the irreversible oxidative decarboxylation of a specific 2-oxo acid to the corresponding acyl-CoA derivative. The pyruvate dehydrogenase complex (PDHC) converts the product of the glycolysis, pyruvate, to

  11. Abiotic and biotic degradation of oxo-biodegradable plastic bags by Pleurotus ostreatus.

    Directory of Open Access Journals (Sweden)

    José Maria Rodrigues da Luz

    Full Text Available In this study, we evaluated the growth of Pleurotus ostreatus PLO6 using oxo-biodegradable plastics as a carbon and energy source. Oxo-biodegradable polymers contain pro-oxidants that accelerate their physical and biological degradation. These polymers were developed to decrease the accumulation of plastic waste in landfills. To study the degradation of the plastic polymers, oxo-biodegradable plastic bags were exposed to sunlight for up to 120 days, and fragments of these bags were used as substrates for P. ostreatus. We observed that physical treatment alone was not sufficient to initiate degradation. Instead, mechanical modifications and reduced titanium oxide (TiO2 concentrations caused by sunlight exposure triggered microbial degradation. The low specificity of lignocellulolytic enzymes and presence of endomycotic nitrogen-fixing microorganisms were also contributing factors in this process.

  12. Abiotic and biotic degradation of oxo-biodegradable plastic bags by Pleurotus ostreatus.

    Science.gov (United States)

    da Luz, José Maria Rodrigues; Paes, Sirlaine Albino; Bazzolli, Denise Mara Soares; Tótola, Marcos Rogério; Demuner, Antônio Jacinto; Kasuya, Maria Catarina Megumi

    2014-01-01

    In this study, we evaluated the growth of Pleurotus ostreatus PLO6 using oxo-biodegradable plastics as a carbon and energy source. Oxo-biodegradable polymers contain pro-oxidants that accelerate their physical and biological degradation. These polymers were developed to decrease the accumulation of plastic waste in landfills. To study the degradation of the plastic polymers, oxo-biodegradable plastic bags were exposed to sunlight for up to 120 days, and fragments of these bags were used as substrates for P. ostreatus. We observed that physical treatment alone was not sufficient to initiate degradation. Instead, mechanical modifications and reduced titanium oxide (TiO2) concentrations caused by sunlight exposure triggered microbial degradation. The low specificity of lignocellulolytic enzymes and presence of endomycotic nitrogen-fixing microorganisms were also contributing factors in this process.

  13. Abiotic and Biotic Degradation of Oxo-Biodegradable Plastic Bags by Pleurotus ostreatus

    Science.gov (United States)

    da Luz, José Maria Rodrigues; Paes, Sirlaine Albino; Bazzolli, Denise Mara Soares; Tótola, Marcos Rogério; Demuner, Antônio Jacinto; Kasuya, Maria Catarina Megumi

    2014-01-01

    In this study, we evaluated the growth of Pleurotus ostreatus PLO6 using oxo-biodegradable plastics as a carbon and energy source. Oxo-biodegradable polymers contain pro-oxidants that accelerate their physical and biological degradation. These polymers were developed to decrease the accumulation of plastic waste in landfills. To study the degradation of the plastic polymers, oxo-biodegradable plastic bags were exposed to sunlight for up to 120 days, and fragments of these bags were used as substrates for P. ostreatus. We observed that physical treatment alone was not sufficient to initiate degradation. Instead, mechanical modifications and reduced titanium oxide (TiO2) concentrations caused by sunlight exposure triggered microbial degradation. The low specificity of lignocellulolytic enzymes and presence of endomycotic nitrogen-fixing microorganisms were also contributing factors in this process. PMID:25419675

  14. Synthesis of Substituted Oxo-Azepines by Regio- and Diastereoselective Hydroxylation

    Directory of Open Access Journals (Sweden)

    Harold Spedding

    2017-10-01

    Full Text Available Substituted seven-membered N-heterocycles are prevalent bioactive epitopes and useful synthons for preparing enzyme inhibitors or molecular recognition systems. To fully exploit the chemical properties of this flexible N-heterocycle scaffold, efficient methods for its diverse functionalization are required. Here we utilize the late-stage oxidation of tetrahydroazepines as an approach to access densely functionalized oxo-azepines in a total of 8 steps and ~30% overall yield from commercially available starting materials. Hydroboration of tetrahydroazepines proceeded with diastereoselectivity in a substrate-dependent manner to yield regioisomeric azepanols before their oxidation to the corresponding oxo-azepines. Regioselectivity of the hydroboration step may be improved moderately by a rhodium catalyst, albeit with loss of conversion to a competing hydrogenation pathway. Overall our method allows efficient access to azepanols and oxo-azepines as versatile epitopes and synthons with a high degree of diastereoselectivity and moderate regioselectivity.

  15. Optical properties of CaWO4 and CaMoO4 crystals in the 4-25 eV region

    International Nuclear Information System (INIS)

    Grasser, R.; Pitt, E.; Scharmann, A.; Zimmerer, G.

    1975-04-01

    The reflection spectra of CaWO 4 and CaMoO 4 single crystals were measured in the region between 4 and 25 eV. The measurements were performed using the electron synchrotron DESY as a light source. Both crystals show very similar spectral features. A relatively sharp, well separated low energy peak is accompanied on the high energy side by two groups of maxima, each group containing three broad main reflection bands which strongly overlap. Besides this, a less pronounced structure is observed over the whole spectral region. The experimental results are discussed in terms of semiempirical MO calculations of the anionic transition metal oxo complexes. (orig.) [de

  16. MoEDAL expands

    CERN Multimedia

    Anaïs Schaeffer

    2011-01-01

    The MoEDAL collaboration deployed a test array of 18 plastic Nuclear Track Etch Detector (NTD) stacks – covering an area of 1 m2 – in the MoEDAL/VELO cavern at Point 8 of the LHC ring in November 2009. This small array was supplemented by a further 110 stacks this past January. The MoEDAL test array, which now covers an area of 8 m2, will reveal its secrets early in 2013. The full MoEDAL detector will be installed in the next long shutdown of the LHC in 2013.   View of the MoEDAL detectors installed at Point 8 of the LHC ring in January 2011. MoEDAL (Monopole and Exotics Detector At the LHC), the seventh LHC experiment, was approved by the CERN Research Board at the end of 2009. Its goal is to search for very specific exotics such as highly ionising massive stable (or pseudo-stable) particles with conventional electrical charge and magnetic monopoles. “The main LHC experiments are designed to detect conventionally charged particles, with conventional ionisation patte...

  17. Photochemical studies of alkylammonium molybdates. Part 12. O→Mo charge-transfer triplet-states-initiated self-assembly to {Mo154} ring- and tube-molybdenum-blues

    Science.gov (United States)

    Yamase, T.; Prokop, P.; Arai, Y.

    2003-08-01

    The chemically induced dynamic electron-spin-polarization technique is employed in order to investigate the primary steps of the photoredox reaction between polyoxomolybdates and alkylammonium cations as both proton and electron-donors in solutions. An observation of emissive electron-spin-polarization signals of alkylamino radical cations for the photoredox reaction between polyoxomolybdates and alkylammonium cations in solutions reveals that the O→Mo ligand-to-metal charge-transfer triplet states are involved in the transfers of both proton and electron from alkylammonium cation to polyoxomolybdate anions. Prolonged photolysis of aqueous solutions containing [Mo36O112(H2O)16]8-, [iPrNH3]+, and LaCl3 at pH 1.0 leads to formation of two kinds of {Mo154} molybdenum-blues, [Mo28VMo126VIO462H28(H2O)70]·156.5H2O (1) and [iPrNH3]8 [Mo28VMo126VIO458H12(H2O)66]·127H2O (2), which were X-ray crystallographically characterized. The former exhibits the intact car-tire-shaped {Mo154} ring structure (with thickness of about 1.1 nm and with outer- and inner-rings of approximately 3.5- and 2.3-nm diameters, respectively) derived formally from the dehydrated cyclic heptamerization of four-electron reduced building blocks of {Mo22} (≡[Mo4VMo18VIO70H12(H2O)10]) with overall symmetry of D7d. The anion for the latter, [Mo28VMo126VIO458H12(H2O)66]8- (2a), exhibits a nanotube structure of {Mo154} rings, each inner ring of which contains a bis(μ-oxo)-linkaged [MoO2(μ-O)(μ-H2O)MoO2]2+ unit replacing one of seven [Mo(H2O)O2(μ-O)Mo(H2O)O2]2+linker units. The neighboring {Mo154} rings are connected by six Mo-O-Mo bridge between inner-rings consisting of 7 head- and 14 linkers-MoO6 octahedra for each.

  18. Preparation and properties of a monomeric Mn(IV)-oxo complex.

    Science.gov (United States)

    Parsell, Trenton H; Behan, Rachel K; Green, Michael T; Hendrich, Michael P; Borovik, A S

    2006-07-12

    Manganese-oxo complexes have long been investigated because of their proposed roles in biological and chemical catalysis. However, there are few examples of monomeric complexes with terminal oxo ligands, especially those with oxomanganese(IV) units. A oxomanganese(IV) complex has been prepared from [MnIIIH3buea(O)]2- ([H3buea]3-, tris[(N'-tert-butylureaylato)-N-ethylene]aminato), a monomeric MnIII-O complex in which the oxo ligand arises from cleavage of dioxygen. Treating [MnIIIH3buea(O)]2- with [Cp2Fe]BF4 in either DMF at -45 degrees C or DMSO at room temperature produces [MnIVH3buea(O)]-: lambdamax = 635 nm; nu(Mn-16O) = 737 cm-1; nu(Mn-18O) = 709 cm-1; g = 5.15, 2.44, 1.63, D = 3.0 cm-1, E/D = 0.26, aMn = 66 G (A = 190 MHz). These spectroscopic properties support the assignment of a mononuclear MnIV-oxo complex with an S = 3/2 ground state. Density functional theory supports this assignment and the Jahn-Teller distortion around the high-spin MnIV center that would alter the molecular structure of [MnIVH3buea(O)]- from trigonal symmetry (as indicated by the highly rhombic EPR signal). [MnIVH3buea(O)]- is relatively unstable in DMSO, converting to [MnIIIH3buea(OH)]- via a proposed X-H bond cleavage. [MnIVH3buea(O)]- reacts with 1,2-diphenylhydrazine to from azobenzene (95% yield) and [MnIIIH3buea(OH)]-. The MnIV-oxo does not react with triphenyl- or tricyclohexylphosphine. However, O-atom transfer is observed with methyldiphenylphosphine and dimethylphenylphosphine, producing the corresponding phosphine oxides. These results illustrate the diverse reactivity of the MnIV-oxo unit.

  19. Synthesis and IR spectral study of MoO2Cl2 molecular complex with acetoacetanilides. Crystal structure of MoO2Cl2 complex with acetoacet-2-toluidine

    International Nuclear Information System (INIS)

    Abramenko, V.L.; Sergienko, V.S.; Churakov, A.V.

    2000-01-01

    Certain MoO 2 Cl 2 complexes with acetoacetanilide derivatives were synthesized, two IR spectral study being performed. Crystal and molecular structure of MoO 2 Cl 2 complex with acetoacet-2-toluidine (HL) was determined using X-ray diffraction analysis. The crystals are monoclinic, a = 7.621 (7), b = 9.498 (3), c = 19.980 (9) A, β = 95.16 (7), Z = 4, sp.gr. P2 1 /n. Coordination polyhedron of Mo atom is a distorted octahedron with two O oxoatoms in cis-position, two Cl atom in mutual trans-position and two O(HL) atoms in trans-positions in reference to O(oxo) [ru

  20. The activity state of the branched-chain 2-oxo acid dehydrogenase complex in rat tissues.

    OpenAIRE

    Wagenmakers, A J; Schepens, J T; Veldhuizen, J A; Veerkamp, J H

    1984-01-01

    An assay is described to define the proportion of the branched-chain 2-oxo acid dehydrogenase complex that is present in the active state in rat tissues. Activities are measured in homogenates in two ways: actual activities, present in tissues, by blocking both the kinase and phosphatase of the enzyme complex during homogenization, preincubation, and incubation with 1-14C-labelled branched-chain 2-oxo acid, and total activities by blocking only the kinase during the 5 min preincubation (neces...

  1. Developmental changes in rat liver branched-chain 2-oxo acid dehydrogenase.

    OpenAIRE

    May, E E; May, M E; Aftring, R P; Buse, M G

    1982-01-01

    Branched-chain 2-oxo acid dehydrogenase catalyses the first irreversible step in the degradation of the branched-chain amino acids leucine, isoleucine and valine. With specifically labelled 4-methyl-2-oxo[1-14C]pentanoate as substrate, the enzyme's activity was measured in rat liver homogenates. Activity (per g wet wL of liver or per mg of protein) increased most rapidly during the perinatal period (2 days before to 1 day after birth), reaching approximately adult values by the time of weanin...

  2. Oxygen Atom Transfer Using an Iron(IV)-Oxo Embedded in a Tetracyclic N-Heterocyclic Carbene System: How Does the Reactivity Compare to Cytochrome P450 Compound I?

    Science.gov (United States)

    Cantú Reinhard, Fabián G; de Visser, Sam P

    2017-02-24

    N-Heterocyclic carbenes (NHC) are commonly featured as ligands in transition metal catalysis. Recently, a cyclic system containing four NHC groups with a central iron atom was synthesized and its iron(IV)-oxo species, [Fe IV (O)(cNHC 4 )] 2+ , was characterized. This tetracyclic NHC ligand system may give the iron(IV)-oxo species unique catalytic properties as compared to traditional non-heme and heme iron ligand systems. Therefore, we performed a computational study on the structure and reactivity of the [Fe IV (O)(cNHC 4 )] 2+ complex in substrate hydroxylation and epoxidation reactions. The reactivity patterns are compared with cytochrome P450 Compound I and non-heme iron(IV)-oxo models and it is shown that the [Fe IV (O)(cNHC 4 )] 2+ system is an effective oxidant with oxidative power analogous to P450 Compound I. Unfortunately, in polar solvents, a solvent molecule will bind to the sixth ligand position and decrease the catalytic activity of the oxidant. A molecular orbital and valence bond analysis provides insight into the origin of the reactivity differences and makes predictions of how to further exploit these systems in chemical catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. 99Mo production by 100Mo(n,2n)99Mo using accelerator neutrons

    International Nuclear Information System (INIS)

    Sato, Nozomi; Kawabata, Masako; Nagai, Yasuki; Hashimoto, Kazuyuki; Hatsukawa, Yuichi; Saeki, Hideya; Motoishi, Shoji; Kin, Tadahiro; Konno, Chikara; Ochiai, Kentaro; Takakura, Kosuke; Minato, Futoshi; Iwamoto, Osamu; Iwamoto, Nobuyuki; Hashimoto, Shintaro

    2013-01-01

    We proposed a new route to produce a medical radioisotope 99 Mo by the 100 Mo(n,2n) 99 Mo reaction using accelerator neutrons. A high-quality 99 Mo with a minimum level of radioactive waste can be obtained by the proposed reaction. The decay product of 99 Mo, 99m Tc, is separated from 99 Mo by the sublimation method. The proposed route could bring a major breakthrough in the solution of ensuring a constant and reliable supply of 99 Mo. (author)

  4. Organo-gallium and indium complexes with dithiolate and oxo ligands

    Indian Academy of Sciences (India)

    Page 1 ... of several of these com- plexes have been established by single crystal X-ray diffraction analyses. Complexes derived from oxo ligands ... diode) applications.8. Organometallic complexes derived from chelating ligands, such as substituted. 8-hydroxyqunoline and azomethine linkages, are emerging as potential ...

  5. Synthesis, screening and QSAR studies of 3-benzoyl-2-oxo/thioxo-1 ...

    African Journals Online (AJOL)

    5-Acyl-6-methyl-4-substituted-2-oxo/thioxo-1,2,3,4-tetrahydropyrimidines (A) were synthesized by cyclocondensation reaction between appropriate aldehyde, acetoacetate and urea/thiourea in presence of aluminium chloride and hydrochloric acid which upon treatment with benzoyl chloride in presence of pyridine in ...

  6. Neutron activation analysis for chemical characterization of Brazilian oxo-biodegradable plastics

    International Nuclear Information System (INIS)

    Mateus Eugenio Boscaro; De Nadai Fernandes, E.A.; Marcio Arruda Bacchi; Luis Gustavo Cofani dos Santos; Cofani dos Santos, S.N.S.; Sandra Mara Martins-Franchetti

    2015-01-01

    The chemical characterization of oxo-biodegradable plastic bags was performed by neutron activation analysis. The presence of several chemical elements (As, Br, Ca, Co, Cr, Fe, Hf, K, La, Na, Sb, Sc, Ta and Zn) with large variability of mass fractions amongst samples indicates that these plastics receive additives and may have been contaminated during manufacturing process thereby becoming potential environmental pollutants. (author)

  7. One step synthesis of 6-oxo-cholestan-3β,5α-diol

    International Nuclear Information System (INIS)

    Voisin, Maud; Silvente-Poirot, Sandrine; Poirot, Marc

    2014-01-01

    Highlights: • Cholesterol-5,6-epoxides are metabolized into cholestane-3β,5α,6β-triol (CT) in cancer cells. • 6-Oxo-cholestan-3β,5α-diol (OCDO) is a putative metabolite of CT. • The one step syntheses of CT and OCDO from cholesterol are reported. • The one step syntheses of labelled CT and OCDO are reported. - Abstract: Cholesterol metabolism has been recently linked to cancer, highlighting the importance of the characterization of new metabolic pathways in the sterol series. One of these pathways is centered on cholesterol-5,6-epoxides (5,6-ECs). 5,6-ECs can either generate dendrogenin A, a tumor suppressor present in healthy mammalian tissues, or the carcinogenic cholestane-3β,5α,6β-triol (CT) and its putative metabolite 6-oxo-cholestan-3β,5α-diol (OCDO) in tumor cells. We are currently investigating the identification of the enzyme involved in OCDO biosynthesis, which would be highly facilitated by the use of commercially unavailable [ 14 C]-cholestane-3β,5α,6β-triol and [ 14 C]-6-oxo-cholestan-3β,5α-diol. In the present study we report the one-step synthesis of [ 14 C]-cholestane-3β,5α,6β-triol and [ 14 C]-6-oxo-cholestan-3β,5α-diol by oxidation of [ 14 C]-cholesterol with iodide metaperiodate (HIO 4 )

  8. Formation process of the poly-oxo cluster U{sub 38}

    Energy Technology Data Exchange (ETDEWEB)

    Henning, Christoph [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Molecular Structures; Falaise, C.; Volkringer, Christoph; Loiseau, T. [Lille Univ., Villeneuve d' Ascq (France). Unite de Catalyse et Chimie du Solide

    2016-07-01

    Recently, a new poly-oxo cluster with 38 uranium atoms, U{sub 38}O{sub 56}Cl{sub 18}(THF){sub 8}(bz){sub 24}.8THF, (U{sub 38}), has been synthesized [1]. We studied ex situ the reaction kinetics of this complex [2].

  9. Synthesis of an oxo trialkyl tungsten fluoride complex and its dual reactivity with silica dehydroxylated at high temperature

    KAUST Repository

    Merle, Nicolas

    2018-05-22

    The novel complex W (=O)Np3F has been prepared by fluorination of the corresponding chloride counterpart with AgBF4. The reactivity of this complex with silica dehydroxylated at 700 °C afforded a well-defined silica supported monopodal tungsten oxo trialkyl surface species (≡SiO)W (=O)Np3. The reaction proceeds both through silanolysis of the W-F bond and opening of a siloxane bridge, with formation of a Si-F fragment, thanks to the affinity of silicon for fluoride. The resulting surface species was characterized by elemental analysis, DRIFT, solid state NMR and EXAFS spectroscopy. This material presenting fluorine on its surface shows an enhanced catalytic activity in propylene self-metathesis compared to its monopodal counterpart (≡SiO)W (=O)Np3 (prepared from W (=O)Np3Cl) suggesting that the Si-F in a close vicinity to the W decreases the electron density of the W and thus increases its reactivity towards the olefinic substrate.

  10. Synthesis of an oxo trialkyl tungsten fluoride complex and its dual reactivity with silica dehydroxylated at high temperature

    KAUST Repository

    Merle, Nicolas; Mazoyer, Etienne; Szeto, Kai C.; Rouge, Pascal; de Mallmann, Aimery; Berrier, Elise; Delevoye, Laurent; Gauvin, Ré gis M.; Nicholas, Christopher P.; Basset, Jean-Marie; Taoufik, Mostafa

    2018-01-01

    The novel complex W (=O)Np3F has been prepared by fluorination of the corresponding chloride counterpart with AgBF4. The reactivity of this complex with silica dehydroxylated at 700 °C afforded a well-defined silica supported monopodal tungsten oxo trialkyl surface species (≡SiO)W (=O)Np3. The reaction proceeds both through silanolysis of the W-F bond and opening of a siloxane bridge, with formation of a Si-F fragment, thanks to the affinity of silicon for fluoride. The resulting surface species was characterized by elemental analysis, DRIFT, solid state NMR and EXAFS spectroscopy. This material presenting fluorine on its surface shows an enhanced catalytic activity in propylene self-metathesis compared to its monopodal counterpart (≡SiO)W (=O)Np3 (prepared from W (=O)Np3Cl) suggesting that the Si-F in a close vicinity to the W decreases the electron density of the W and thus increases its reactivity towards the olefinic substrate.

  11. Metabolism of leukotriene B4 to dihydro and dihydro-oxo products by porcine leukocytes

    International Nuclear Information System (INIS)

    Powell, W.S.; Gravelle, F.

    1989-01-01

    Porcine leukocytes contain a novel pathway for the metabolism of leukotriene B4 (LTB4) which results in reduction of the conjugated triene chromophore to a conjugated diene. These cells converted LTB4 to two major metabolites, both of which exhibited maximal absorbance at 230 nm in their UV spectra. These products were purified by high pressure liquid chromatography and identified as 10, 11-dihydro-LTB4 and 10,11-dihydro-12-oxo-LTB4 on the basis of the mass spectra of various derivatives. The position of the double bond of LTB4 which had been reduced was established by cleaving the remaining double bonds of 10, 11-dihydro-LTB4 with ozone followed by oxidation or reduction of the resulting ozonide and analysis of the products by mass spectrometry. Experiments with deuterium-labeled substrate indicated that LTB4 could be directly converted to 10, 11-dihydro-LTB4 without the prior oxidation of either of its hydroxyl groups, as is required for the formation of dihydro metabolites of prostaglandins. Incubation of porcine leukocytes with 10, 11-dihydro-LTB4 and 10, 11-dihydro-12-oxo-LTB4 indicated that these two products can be interconverted and are in equilibrium with one another. The dihydro-oxo metabolite can therefore be formed from 10, 11-dihydro-LTB4, although we have not ruled out the possibility that it is also produced via 12-oxo-LTB4, which could be a transitory intermediate. These results indicate that porcine leukocytes contain a novel reductase/dehydrogenase pathway distinct from the pathway responsible for the metabolism of prostaglandins. This pathway is also different from the pathway in human polymorphonuclear leukocytes which converts 6-trans-isomers of LTB4 to dihydro products, since the latter pathway involves 5-oxo intermediates and results in a shift in the positions of the remaining double bonds

  12. Photochemical organic oxidations and dechlorinations with a mu-oxo bridged heme/non-heme diiron complex.

    Science.gov (United States)

    Wasser, Ian M; Fry, H Christopher; Hoertz, Paul G; Meyer, Gerald J; Karlin, Kenneth D

    2004-12-27

    Steady state and laser flash photolysis studies of the heme/non-heme mu-oxo diiron complex [((6)L)Fe(III)-O-Fe(III)-Cl](+) (1) have been undertaken. The anaerobic photolysis of benzene solutions of 1 did not result in the buildup of any photoproduct. However, the addition of excess triphenylphosphine resulted in the quantitative photoreduction of 1 to [((6)L)Fe(II)...Fe(II)-Cl](+) (2), with concomitant production by oxo-transfer of 1 equiv of triphenylphosphine oxide. Under aerobic conditions and excess triphenylphosphine, the reaction produces multiple turnovers (approximately 28) before the diiron complex is degraded. The anaerobic photolysis of tetrahydrofuran (THF) or toluene solutions of 1 likewise results in the buildup of 2. The oxidation products from these reactions included gamma-butyrolactone (approximately 15%) for the reaction in THF and benzaldehyde (approximately 23%) from the reaction in toluene. In either case, the O-atom which is incorporated into the carbonyl product is derived from dioxygen present under workup or under aerobic photolysis conditions. Transient absorption measurements of low-temperature THF solutions of 1 revealed the presence of an (P)Fe(II)-like [P = tetraaryl porphyrinate dianion] species suggesting that the reactive species is a formal (heme)Fe(II)/Fe(IV)=O(non-heme) pair. The non-heme Fe(IV)=O is thus most likely responsible for C-H bond cleavage and subsequent radical chemistry. The photolysis of 1 in chlorobenzene or 1,2-dichlorobenzene resulted in C-Cl cleavage reactions and the formation of [[((6)L)Fe(III)-Cl...Fe(III)-Cl](2)O](2+) (3), with chloride ligands that are derived from solvent dehalogenation chemistry. The resulting organic products are biphenyl trichlorides or biphenyl monochlorides, derived from dichlorobenzene and chlorobenzene, respectively. Similarly, product 3 is obtained by the photolysis of benzene-benzyl chloride solutions of 1; the organic product is benzaldehyde (approximately 70%). A brief

  13. Molecular metal-Oxo catalysts for generating hydrogen from water

    Science.gov (United States)

    Long, Jeffrey R; Chang, Christopher J; Karunadasa, Hemamala I

    2015-02-24

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W.sub.2)MO].sup.2+, wherein PY5W.sub.2 is (NC.sub.5XYZ)(NC.sub.5H.sub.4).sub.4C.sub.2W.sub.2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF.sub.3, or SiR.sub.3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl.sup.-, I.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H.sub.2/mol catalyst per h.

  14. RoMo

    DEFF Research Database (Denmark)

    Pedersen, Esben Warming; Hornbæk, Kasper

    2011-01-01

    In TUIs, physical/digital conflicts can occur when the digital model does not match the model implied by the spatial lay- out of tangibles. We show how tangible tabletop interfaces (TTI) can be modified to allow robot movement of tangi- bles, thereby avoiding conflicts. We present RoMo, an open...... source Java library that allow existing TTI applications to perform robot movement, and demonstrate its functionality with three applications....

  15. Effect of degrading yellow oxo-biodegradable low-density polyethylene films to water quality

    Science.gov (United States)

    Requejo, B. A.; Pajarito, B. B.

    2017-05-01

    Polyethylene (PE) contributes largely to plastic wastes that are disposed in aquatic environment as a consequence of its widespread use. In this study, yellow oxo-biodegradable low-density PE films were immersed in deionized water at 50°C for 49 days. Indicators of water quality: pH, oxidation-reduction potential, turbidity, and total dissolved solids (TDS), were monitored at regular intervals. It was observed that pH initially rises and then slowly decreases with time, oxidation-reduction potential decreases then slowly increases with time, turbidity rises above the control at varied rates, and TDS increases abruptly and rises at a hindered rate. Moreover, the films potentially leach out lead chromate. The results imply that degrading oxo-biodegradable LDPE films results to significant reduction of water quality.

  16. Health status of cows fed maize silage covered with oxo-biodegradable foil

    OpenAIRE

    Piotr SZTERK; Piotr DORSZEWSKI; Małgorzata GRABOWICZ; Lucyna PODKÓWKA

    2017-01-01

    In agricultural practice, silage production uses pure, low density polyethylene foil. This foil, after use, becomes farm waste, having a negative impact on the environment. Instead of conventional foil, an environmentally safe biodegradable foil can be used, made from naturally occurring polymers or from synthetic multiparticulates, easily degradable by microorganisms. Silage covered with this type of foil should be safe for animal health. The purpose of the study was to determine whether oxo...

  17. Purification of 2-oxo acid dehydrogenase multienzyme complexes from ox heart by a new method.

    OpenAIRE

    Stanley, C J; Perham, R N

    1980-01-01

    A new method is described that allows the parallel purification of the pyruvate dehydrogenase and 2-oxoglutarate dehydrogenase multienzyme complexes from ox heart without the need for prior isolation of mitochondria. All the assayable activity of the 2-oxo acid dehydrogenase complexes in the disrupted tissue is made soluble by the inclusion of non-ionic detergents such as Triton X-100 or Tween-80 in the buffer used for the initial extraction of the enzyme complexes. The yields of the pyruvate...

  18. Multinary lithium (oxo)nitridosilicates. Syntheses, structures and their materials properties

    International Nuclear Information System (INIS)

    Horky, Katrin

    2017-01-01

    The objective of this thesis was the synthesis, identification and characterization of novel lithium(oxo)nitridosilicates in order to investigate as well as to expand the materials properties of this compound class. Therefore, different synthesis strategies were carried out. Crystal structure elucidation with single-crystal X-ray diffraction was carried out on new compounds. Moreover, investigations of physical properties like luminescence and lithium ion conductivity were performed.

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

    Science.gov (United States)

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

    2017-11-02

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

  20. One step synthesis of 6-oxo-cholestan-3β,5α-diol

    Energy Technology Data Exchange (ETDEWEB)

    Voisin, Maud; Silvente-Poirot, Sandrine; Poirot, Marc, E-mail: marc.poirot@inserm.fr

    2014-04-11

    Highlights: • Cholesterol-5,6-epoxides are metabolized into cholestane-3β,5α,6β-triol (CT) in cancer cells. • 6-Oxo-cholestan-3β,5α-diol (OCDO) is a putative metabolite of CT. • The one step syntheses of CT and OCDO from cholesterol are reported. • The one step syntheses of labelled CT and OCDO are reported. - Abstract: Cholesterol metabolism has been recently linked to cancer, highlighting the importance of the characterization of new metabolic pathways in the sterol series. One of these pathways is centered on cholesterol-5,6-epoxides (5,6-ECs). 5,6-ECs can either generate dendrogenin A, a tumor suppressor present in healthy mammalian tissues, or the carcinogenic cholestane-3β,5α,6β-triol (CT) and its putative metabolite 6-oxo-cholestan-3β,5α-diol (OCDO) in tumor cells. We are currently investigating the identification of the enzyme involved in OCDO biosynthesis, which would be highly facilitated by the use of commercially unavailable [{sup 14}C]-cholestane-3β,5α,6β-triol and [{sup 14}C]-6-oxo-cholestan-3β,5α-diol. In the present study we report the one-step synthesis of [{sup 14}C]-cholestane-3β,5α,6β-triol and [{sup 14}C]-6-oxo-cholestan-3β,5α-diol by oxidation of [{sup 14}C]-cholesterol with iodide metaperiodate (HIO{sub 4})

  1. Polynuclear Iron-Oxo/Hydroxy Complexes of Ketoacidoximate Ligands: Synthesis, Structures and Conversion to Ferric Oxide

    KAUST Repository

    Davaasuren, Bambar; Khanderi, Jayaprakash; Rothenberger, Alexander

    2017-01-01

    The polynuclear iron-oxo/hydroxy complexes containing ketoacidoximate ligands described in this report are [Fe3(μ3-O){O2C-C(C6H5)=NOCH3}6(py)3] (1) (py=pyridine), [Fe2(μ3-O){O2C-C(CH2-C6H5)=NO}2(H2O)(CH3OH)]2 (2) and [{Fe(μ2-OH)(O2C-C(CH3)=NO

  2. Multinary lithium (oxo)nitridosilicates. Syntheses, structures and their materials properties

    Energy Technology Data Exchange (ETDEWEB)

    Horky, Katrin

    2017-11-06

    The objective of this thesis was the synthesis, identification and characterization of novel lithium(oxo)nitridosilicates in order to investigate as well as to expand the materials properties of this compound class. Therefore, different synthesis strategies were carried out. Crystal structure elucidation with single-crystal X-ray diffraction was carried out on new compounds. Moreover, investigations of physical properties like luminescence and lithium ion conductivity were performed.

  3. Bowl adamanzanes--bicyclic tetraamines: syntheses and crystal structures of complexes with cobalt(III) and chelating coordinated oxo-anions.

    Science.gov (United States)

    Broge, Louise; Søtofte, Inger; Jensen, Kristian; Jensen, Nicolai; Pretzmann, Ulla; Springborg, Johan

    2007-09-14

    Seven cobalt(III) complexes of the macrobicyclic tetraamine ligand [2(4).3(1)]adamanzane ([2(4).3(1)]adz) are reported along with the crystal structure of six of these complexes. The solid state and solution structures are discussed, and a detailed assignment of the NMR spectra of the sulfato complex is provided. Four of the seven complexes contain a chelate coordinating oxo-anion (sulfate, formiate, nitrate, carbonate). Equilibration of these species with the corresponding diaqua complex is generally slow. The rates of equilibration in 5 mol dm(-3) perchloric acid at 25 degrees C have been measured, yielding half lives of 20 min, 10 min and 3 h for the sulfato, formiato and carbonato species respectively. The corresponding reaction for the nitrato complex occurs with a half life of less than 3 min. The concentration acid dissociation constant for the Co([2(4).3(1)]adz)(HCO(3))(2+) ion has been measured to K(a) = 0.33 mol dm(-3) [25 degrees C, I = 2 mol dm(-3)] and K(a) = 0.15 mol dm(-3) [25 degrees C, I = 5 mol dm(-3)]. The propensity for coordination of sulfate was found to be large enough for a quantitative conversion of the carbonato complex to the sulfato complex to occur in 3 mol dm(-3) triflic acid containing a small sulfate contamination. On this basis the decarboxylation in 5 mol dm(-3) triflic acid of the corresponding cobalt(III) carbonato complex of the larger macrobicyclic tetraamine ligand [3(5)]adz was reinvestigated and found to lead to the sulfato complex as well. The difference in exchange rate of the oxo-anion ligands for the cobalt(III) complexes of the two adamanzane ligands is discussed and attributed to fundamental differences in the molecular structure where an inverted configuration of the secondary non-bridged amine groups is seen for the complexes of the larger [3(5)]adz ligand. The high affinity for chelating coordination of oxo-anions for these two cobalt(iii)-adamanzane-moieties is rationalised on basis of the N-Co-N angles. N

  4. Diffusion barrier performances of thin Mo, Mo-N and Mo/Mo-N films between Cu and Si

    International Nuclear Information System (INIS)

    Song Shuangxi; Liu Yuzhang; Mao Dali; Ling Huiqin; Li Ming

    2005-01-01

    In this work, we have studied the diffusion barrier performances of Mo, Mo-N and Mo/Mo-N metallization layers deposited by sputtering Mo in Ar/N 2 atmospheres, respectively. Samples were subsequently annealed at different temperatures ranging from 400 to 800 deg C in vacuum condition. The film properties and their suitability as diffusion barriers and protective coatings in silicon devices were characterized using four-point probe measurement, X-ray diffractometry, scanning electron microscopy, Auger electron spectroscopy and transmission electron microscopy analyses. Experimental results revealed that the Mo (20 nm)/Mo-N (30 nm) layer was able to prevent the diffusion reaction between Cu and Si substrate after being annealed at 600 deg C for 30 min. The adhesion between layers and the content of N atoms are the key parameters to improve the properties of Mo-based barrier materials. The Mo layer interposed between Cu and Mo-N diluted the high nitrogen concentration of the barrier and so enhanced the barrier performances

  5. Oxo-exchange of gas-phase uranyl, neptunyl, and plutonyl with water and methanol.

    Science.gov (United States)

    Lucena, Ana F; Odoh, Samuel O; Zhao, Jing; Marçalo, Joaquim; Schreckenbach, Georg; Gibson, John K

    2014-02-17

    A challenge in actinide chemistry is activation of the strong bonds in the actinyl ions, AnO2(+) and AnO2(2+), where An = U, Np, or Pu. Actinyl activation in oxo-exchange with water in solution is well established, but the exchange mechanisms are unknown. Gas-phase actinyl oxo-exchange is a means to probe these processes in detail for simple systems, which are amenable to computational modeling. Gas-phase exchange reactions of UO2(+), NpO2(+), PuO2(+), and UO2(2+) with water and methanol were studied by experiment and density functional theory (DFT); reported for the first time are experimental results for UO2(2+) and for methanol exchange, as well as exchange rate constants. Key findings are faster exchange of UO2(2+) versus UO2(+) and faster exchange with methanol versus water; faster exchange of UO2(+) versus PuO2(+) was quantified. Computed potential energy profiles (PEPs) are in accord with the observed kinetics, validating the utility of DFT to model these exchange processes. The seemingly enigmatic result of faster exchange for uranyl, which has the strongest oxo-bonds, may reflect reduced covalency in uranyl as compared with plutonyl.

  6. Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [Nottingham Univ. (United Kingdom). School of Chemistry; Tuna, Floriana; McInnes, Eric J.L. [Manchester Univ. (United Kingdom). School of Chemistry and Photon Science Inst.

    2014-06-23

    We report the uranium(VI) carbene imido oxo complex [U(BIPM{sup TMS})(NMes)(O)(DMAP){sub 2}] (5, BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; Mes=2,4,6-Me{sub 3}C{sub 6}H{sub 2}; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM{sup TMS})(O){sub 2}(DMAP){sub 2}] (6).

  7. Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [School of Chemistry, University of Nottingham (United Kingdom); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, University of Manchester (United Kingdom)

    2014-06-23

    We report the uranium(VI) carbene imido oxo complex [U(BIPM{sup TMS})(NMes)(O)(DMAP){sub 2}] (5, BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; Mes=2,4,6-Me{sub 3}C{sub 6}H{sub 2}; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM{sup TMS})(O){sub 2}(DMAP){sub 2}] (6). (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Thermodynamic properties and cloud droplet activation of a series of oxo-acids

    Directory of Open Access Journals (Sweden)

    M. Frosch

    2010-07-01

    Full Text Available We have investigated the thermodynamic properties of four aliphatic oxo-dicarboyxlic acids identified or thought to be present in atmospheric particulate matter: oxosuccinic acid, 2-oxoglutaric acid, 3-oxoglutaric acid, and 4-oxopimelic acid. The compounds were characterized in terms of their cloud condensation nuclei (CCN activity, vapor pressure, density, and tendency to decarboxylate in aqueous solution. We deployed a variety of experimental techniques and instruments: a CCN counter, a Tandem Differential Mobililty Analyzer (TDMA coupled with a laminar flow-tube, and liquid chromatography/mass spectrometry (LC/MS. The presence of the oxo functional group in the α-position causes the vapor pressure of the compounds to diminish by an order of magnitude with respect to the parent dicarboxylic acid, while the CCN activity is similar or increased. Dicarboxylic acids with an oxo-group in the β-position decarboxylate in aqueous solution. We studied the effects of this process on our measurements and findings.

  9. Oxo Crater on (1) Ceres: Geological History and the Role of Water-ice

    Energy Technology Data Exchange (ETDEWEB)

    Nathues, A.; Platz, T.; Hoffmann, M.; Thangjam, G.; Le Corre, L.; Reddy, V. [Max Planck Institute for Solar System Research, Justus-von-Liebig-Weg 3, D-37077 Goettingen (Germany); Cloutis, E. A.; Applin, D. M. [University of Winnipeg, Winnipeg, MB R3B 2E9 (Canada); Mengel, K. [IELF, TU Clausthal, Adolph-Roemer-Straße 2A, D-38678 Clausthal-Zellerfeld (Germany); Protopapa, S. [University of Maryland, Department of Astronomy, College Park, MD 20742 (United States); Takir, D. [SETI Institute, Mountain View, CA 94043 (United States); Preusker, F. [German Aerospace Center (DLR), Institute of Planetary Research, D-12489 Berlin (Germany); Schmidt, B. E. [Georgia Institute of Technology, Atlanta, GA (United States); Russell, C. T., E-mail: nathues@mps.mpg.de [Institute of Geophysics and Planetary Physics, Dept. of Earth, Planetary and Space Sciences, University of California Los Angeles, Los Angeles, CA (United States)

    2017-09-01

    Dwarf planet Ceres (∅ ∼ 940 km) is the largest object in the main asteroid belt. Investigations suggest that Ceres is a thermally evolved, volatile-rich body with potential geological activity, a body that was never completely molten, but one that possibly partially differentiated into a rocky core and an ice-rich mantle, and may contain remnant internal liquid water. Thermal alteration and the infall of exogenic material contribute to producing a (dark) carbonaceous chondritic-like surface containing ammoniated phyllosilicates. Here we report imaging and spectroscopic analyses of data on the bright Oxo crater derived from the Framing Camera and the Visible and Infrared Spectrometer on board the Dawn spacecraft. We confirm that the transitional complex crater Oxo (∅ ∼ 9 km) exhibits exposed surface water-ice. We show that this water-ice-rich material is associated exclusively with two lobate deposits at pole-facing scarps, deposits that also contain carbonates and admixed phyllosilicates. Due to Oxo’s location at −4802 m below the cerean reference ellipsoid and its very young age of only 190 ka (1 σ : +100 ka, −70 ka), Oxo is predestined for ongoing water-ice sublimation.

  10. The activity state of the branched-chain 2-oxo acid dehydrogenase complex in rat tissues.

    Science.gov (United States)

    Wagenmakers, A J; Schepens, J T; Veldhuizen, J A; Veerkamp, J H

    1984-05-15

    An assay is described to define the proportion of the branched-chain 2-oxo acid dehydrogenase complex that is present in the active state in rat tissues. Activities are measured in homogenates in two ways: actual activities, present in tissues, by blocking both the kinase and phosphatase of the enzyme complex during homogenization, preincubation, and incubation with 1-14C-labelled branched-chain 2-oxo acid, and total activities by blocking only the kinase during the 5 min preincubation (necessary for activation). The kinase is blocked by 5 mM-ADP and absence of Mg2+ and the phosphatase by the simultaneous presence of 50 mM-NaF. About 6% of the enzyme is active in skeletal muscle of fed rats, 7% in heart, 20% in diaphragm, 47% in kidney, 60% in brain and 98% in liver. An entirely different assay, which measures activities in crude tissue extracts before and after treatment with a broad-specificity protein phosphatase, gave similar results for heart, liver and kidney. Advantages of our assay with homogenates are the presence of intact mitochondria, the simplicity, the short duration and the high sensitivity. The actual activities measured indicate that the degradation of branched-chain 2-oxo acids predominantly occurs in liver and kidney and is limited in skeletal muscle in the fed state.

  11. Malondialdehyde and 8-oxo-7.8-dihydro-2'deoxyguanosine in the urine of residents from Balkan endemic nephropathy area in Croatia--a pilot study

    DEFF Research Database (Denmark)

    Domijan, Ana-Marija; Miletić-Medved, Marica; Peraica, Maja

    2013-01-01

    Balkan endemic nephropathy (BEN) is a human chronic tubulointerstitial renal disease that occurs in rural areas of some Balkan countries. The disease is insidious and fatal, and mostly affects persons in their sixties or seventies. BEN areas have unusually high rates of otherwise rare upper urinary...... tract tumors (UTT). Since extensive production of reactive oxygen species leading to oxidative stress has been implicated in tumor development, the aim of this study was to see whether oxidative stress is involved in the development of BEN and UTT. Urine samples were collected from a BEN village (N = 22......) and a control village (N = 16) residents and analyzed for malondialdehyde (MDA) and 8-oxo-7,8-dihydro-2'deoxyguanosine (8-oxodG). The levels of both oxidative stress parameters were significantly higher in the BEN village residents than controls. However, there was no correlation between MDA and 8-oxodG results...

  12. Synthesis and investigation of uranyl molybdate UO2MoO4

    International Nuclear Information System (INIS)

    Nagai, Takayuki; Sato, Nobuaki; Kitawaki, Shin-ichi; Uehara, Akihiro; Fujii, Toshiyuki; Yamana, Hajimu; Myochin, Munetaka

    2013-01-01

    In order to examine easily synthetic conditions of uranyl molybdate, UO 2 MoO 4 , used for the reprocessing process study of spent nuclear oxide fuels in alkaline molybdate melts, the uranium molybdate compounds were produced from U 3 O 8 powder and anhydrous MoO 3 reagent. The results of having investigated them in solid state by using X-ray diffractometry and Raman spectrometry, it was confirmed that UO 2 MoO 4 could be synthesized by heating mixed powder of U 3 O 8 and MoO 3 with stoichiometric mole ratio at 770 °C for 4 h under air atmosphere. Moreover, adding this UO 2 MoO 4 into Li 2 MoO 4 -Na 2 MoO 4 eutectic melt, most of the dissolved uranium species in the melt were observed as hexa–valent uranyl ions by absorption spectrophotometry

  13. Label-free colorimetric detection of mercury via Hg2+ ions-accelerated structural transformation of nanoscale metal-oxo clusters

    Science.gov (United States)

    Chen, Kun; She, Shan; Zhang, Jiangwei; Bayaguud, Aruuhan; Wei, Yongge

    2015-11-01

    Mercury and its compounds are known to be extremely toxic but widely distributed in environment. Although many works have been reported to efficiently detect mercury, development of simple and convenient sensors is still longed for quick analyzing mercury in water. In this work, a nanoscale metal-oxo cluster, (n-Bu4N)2[Mo5NaO13(OCH3)4(NO)], (MLPOM), organically-derivatized from monolacunary Lindqvist-type polyoxomolybdate, is found to specifically react with Hg2+ in methanol/water via structural transformation. The MLPOM methanol solution displays a color change from purple to brown within seconds after being mixed with an aqueous solution containing Hg2+. By comparing the structure of polyoxomolybdate before and after reaction, the color change is revealed to be the essentially structural transformation of MLPOM accelerated by Hg2+. Based on this discovery, MLPOM could be utilized as a colorimetric sensor to sense the existence of Hg2+, and a simple and label-free method is developed to selectively detect aqueous Hg2+. Furthermore, the colorimetric sensor has been applied to indicating mercury contamination in industrial sewage.

  14. Aloe vera extract reduces 8-oxo-2'-deoxyguanosine levels and improves total antioxidants in streptozotocin-induced diabetic rats

    Directory of Open Access Journals (Sweden)

    Wulan Christijanti

    2017-04-01

    Full Text Available Background Diabetes mellitus is a chronic disease caused by lack of insulin production in the pancreas or by insulin resistance, the disease being characterized by elevated blood glucose levels. Hyperglycemia in diabetes could lead to oxidative stress due to the rise in 8-oxo-2'-deoxyguanosine (8-oxo-dG levels and the decrease in levels of total antioxidant status (TAS. The purpose of this study was to assess the effect Aloe vera extract on 8-oxo-dG level and total antioxidant status in diabetic rat testis.   Methods This was an experimental laboratory study with 20 rat samples which were divided into 4 groups (1 control group and 3 treatment groups. Diabetes was induced in the rats by streptozotocin (STZ at 65 mg/kgBW. The diabetic rats were then treated for 28 days with Aloe vera extract at 0 mg (P0, 200 mg rind (P1, 200 mg pulp (P2, respectively. The level of 8 -oxo-dG was measured by ELISA and total antioxidant status with 2,2' -azino-bis (3-ethylbenzothiazoline-6-sulfonic acid (ABTS. Data were analyzed with ANOVA and Least Significant Difference Advanced Test at P<0.05.   Results 8-Oxo-dG levels were significantly different between the control group and both P0 and P2, but not between the control group and P1. Among the treatment groups the 8-oxo-dG levels were significantly different. Mean total antioxidant status was significantly different between control and treatment groups, and also between treatment groups (p<0.05.   Conclusions Aloe vera extract reduced free radicals (level of 8-oxo-dG and increased the total antioxidant status in diabetic rat testis.

  15. Water Splitting by Thin Film Metal-Oxo Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Nocera, Daniel [Harvard Univ., Cambridge, MA (United States)

    2013-03-15

    OER with differential electrochemical mass spectrometry (DEMS) of Co-OEC. The OER mechanism of M-OECs was examined with complementary studies of model dicobalt compounds that captured the critical steps of the OER reaction. Additionally, the role of activating M-OECS with metal ion dopants was defined by developing structure–function relationships, guided by the principles of inorganic chemistry. We found that the M(IV) oxidation state in oxidic OER frameworks was correlated to the presence of the dopant metal, as assessed by coulometric titration and ICP-MS analysis. To investigate why greater M(IV) valence is beneficial to greater catalytic OER activity, we probed the influence of formal M valence on the electronic structure of oxygen ions in M-OECs by undertaking O and Ni K-edge spectroscopy, which revealed greater M-O covalency and hence M-oxyl radical character with M(IV) formation. Such oxyl radical character is consistent with increasing evidence for the role of oxygen radicals in O–O bond formation by a proton-coupled electron transfer mechanism involving water, to generate a hydroperoxide intermediate from which oxygen is generate. In accomplishing this science, the DOE program leveraged its expertise in spectroscopy and structural methods, inorganic and materials synthesis, and electrochemical characterization. The knowledge garnered from this proposed program enables the design of next generation catalysts with improved OER kinetics that operate over a wide range of conditions and environments.

  16. EXAFS study on structure of sulfide K-Co-Mo catalysts

    International Nuclear Information System (INIS)

    Bao Jun; Bian Guozhu; Fu Yilu; Liu Tao; Xie Yaning; Hu Tiandou

    2002-01-01

    Recently, authors prepared a kind of K-Co-Mo ultrafine particles by sol-gel method and it shoes much small particle size but higher activity and selectivity toward alcohol formation than the one prepared by conventional method. The aim of the present work is to research the microstructures of the Mo and Co species in the K-Co-Mo samples prepared by different method

  17. Measurement of 8-oxo-7,8-dihydro-2'-deoxyguanosine and 8-oxo-7,8-dihydro-guanosine in cerebrospinal fluid by ultra performance liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Weimann, Allan; Simonsen, Anja Hviid; Poulsen, Henrik E

    2018-01-15

    Increased levels of nucleosides modified by oxidation in human cerebrospinal fluid (CSF) have several times been reported in Alzheimer patients and patients suffering from Parkinson's disease. The focus has especially been on nucleosides containing the 8-hydroxylation of guanine. Only few reports on quantification of the ribonucleoside 8-oxo-7,8-dihydro-guanosine (8oxoGuo) in CSF have been published, whereas more have been published on the quantification of the deoxy-ribonucleoside 8-oxo-7,8-dihydro-2'-deoxyguanosine (8oxodGuo). The reports on the quantification of 8oxodGuo concentrations in CSF report absolute concentrations varying by a factor >10 5 in healthy humans. This could indicate that there is a serious specificity problem in some of the methods. In this paper an isotope-dilution UPLC-MS/MS method with high specificity and sensitivity for the quantification of 8oxoGuo and 8oxodGuo in CSF is presented. LLOQ for the two analytes is determined to 4pM and 2pM, respectively. The calibration curves has been tested to be linear in the range from 4 to 3,000pM for 8oxoGuo and between 2 and 3,000pM for 8oxodGuo. Using a weighting factor of 1/x the correlation coefficient "r" for both analytes is >0.999. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Rhenium(V) oxo complexes relevant to technetium renal imaging agents derived from mercaptoacetylglycylglycylaminobenzoic acid isomers. Structural and molecular mechanics studies

    International Nuclear Information System (INIS)

    Hansen, L.; Taylor, A. Jr; Marzilli, L.G.; Cini, R.

    1992-01-01

    The synthesis and characterization of three rhenium(V) oxo complexes derived from isomers of mercaptoacetylglycylglycylaminobenzoic acid (MAG 2 -ABAH 5 ) are reported. The isomers were synthesized from o-, m- and p-aminobenzoic acid and differed in the position of the terminal carboxyl group. The anions of 8-10, [ReO(MAG 2 -*ABAH)] - (* = para (8), meta (9), ortho (10)), contained the tetraanionic form of the ligands with the carboxyl group protonated. Compounds 8,9, and 10 were synthesized by exchange reactions of ReOCl 3 (Me 2 SO)(Ph 3 P) under moderate conditions and were isolated as [Ph 4 P] + , [Bu 4 N] + , and [Ph 4 P] + salts, respectively. The structures of 8 and 10 were determined by X-ray diffraction methods; except for the location of the carboxyl group, the structures are similar. The coordination geometry is pseudo square pyramidal, with nitrogen and sulfur donor atoms forming a square base and the oxo ligand at the apex. The orientation of the carboxyl group in 10 is anti to the Re double-bond O group. Since the carboxyl groups are protonated in 8 and 10 and in other relevant structures from this class of radiopharmaceuticals including [Ph 4 As][TcO(MAG 3 H)] (MAG 3 H = tetraanionic form of mercaptoacetyltriglycine), the authors developed molecular mechanics parameters that allowed them to calculate the structures of 8, 10, and [TcO(MAG 3 H)] - . They then extended the calculations to all three isomeric complexes in their deprotonated forms and to [TcO(MAG 3 )] 2- in order to approximate their solution phase structures. They conclude that the [TcO(MAG 3 )] 2- species is conformationally flexible, and they have made an initial assessment of structures vs renal clearance

  19. Synthesis of cobalt stearate as oxidant additive for oxo-biodegradable polyethylene

    Energy Technology Data Exchange (ETDEWEB)

    Asriza, Ristika O.; Arcana, I Made, E-mail: arcana@chem.itb.ac.id [Division of Inorganic and Physical Chemistry, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung, 40132 (Indonesia)

    2015-09-30

    Cobalt stearate is an oxidant additives that can initiate a process of degradation in high density polyethylene (HDPE). To determine the effect of cobalt stearate in HDPE, oxo-biodegradable polyethylene film was given an irradiation with UV light or heating at various temperature. After given a heating, the FTIR spectra showed a new absorption peak at wave number 1712 cm{sup −1} indicating the presence of carbonyl groups in polymers, whereas after irradiation with UV light is not visible the presence of this absorption peak. The increase concentration of cobalt stearate added in HDPE and the higher heating temperature, the intensity of the absorption peak of the carbonyl group increased. The increasing intensity of the carbonyl group absorption is caused the presence of damage in the film surface after heating, and this result is supported by analysis the surface properties of the film with using SEM. Biodegradation tests were performed on oxo-biodegradable polyethylene film which has been given heating or UV light with using activated sludge under optimal conditions the growth of microorganisms. After biodegradation, the maximum weight decreased by 23% in the oxo-biodegradable polyethylene film with a cobalt stearate concentration of 0.2% and after heating at a temperature of 75 °C for 10 days, and only 0.69% in the same film after irradiation UV light for 10 days. Based on the results above, cobalt stearate additive is more effective to initiate the oxidative degradation of HDPE when it is initiated by heating compared to irradiation with UV light.

  20. Synthesis of cobalt stearate as oxidant additive for oxo-biodegradable polyethylene

    Science.gov (United States)

    Asriza, Ristika O.; Arcana, I. Made

    2015-09-01

    Cobalt stearate is an oxidant additives that can initiate a process of degradation in high density polyethylene (HDPE). To determine the effect of cobalt stearate in HDPE, oxo-biodegradable polyethylene film was given an irradiation with UV light or heating at various temperature. After given a heating, the FTIR spectra showed a new absorption peak at wave number 1712 cm-1 indicating the presence of carbonyl groups in polymers, whereas after irradiation with UV light is not visible the presence of this absorption peak. The increase concentration of cobalt stearate added in HDPE and the higher heating temperature, the intensity of the absorption peak of the carbonyl group increased. The increasing intensity of the carbonyl group absorption is caused the presence of damage in the film surface after heating, and this result is supported by analysis the surface properties of the film with using SEM. Biodegradation tests were performed on oxo-biodegradable polyethylene film which has been given heating or UV light with using activated sludge under optimal conditions the growth of microorganisms. After biodegradation, the maximum weight decreased by 23% in the oxo-biodegradable polyethylene film with a cobalt stearate concentration of 0.2% and after heating at a temperature of 75 °C for 10 days, and only 0.69% in the same film after irradiation UV light for 10 days. Based on the results above, cobalt stearate additive is more effective to initiate the oxidative degradation of HDPE when it is initiated by heating compared to irradiation with UV light.

  1. Reversible formation of high-valent-iron-oxo-porphyrin intermediate in heme-based catalysis: revisiting the kinetic model for horseradish peroxidase.

    NARCIS (Netherlands)

    Haandel, van M.J.H.; Primus, J.L.; Teunis, C.; Boersma, M.G.; Osman, A.M.; Veeger, C.; Rietjens, I.M.C.M.

    1998-01-01

    Many heme-containing biocatalysts exert their catalytic action through the initial formation of so-called high-valent-iron-oxo porphyrin intermediates. For horseradish peroxidase the initial intermediate formed has been identified as a high-valent-iron-oxo porphyrin π-radical cation, called compound

  2. The Effect of the Equatorial Environment on Oxo-Group Silylation of the Uranyl Dication: A Computational Study

    International Nuclear Information System (INIS)

    Yahia, A.; Maron, L.; Yahia, A.; Arnold, P.L.; Love, J.B.

    2010-01-01

    A theoretical investigation of the reductive oxo-group silylation reaction of the uranyl dication held in a Pacman macrocyclic environment has been carried out. The effect of the modeling of the Pacman ligand on the reaction profiles is found to be important, with the dipotassiation of a single oxo group identified as a key component in promoting the reaction between the Si-X and uranium-oxo bonds. This reductive silylation reaction is also proposed to occur in an aqueous environment but was found not to operate on bare ions; in this latter case, substitution of a ligand in the equatorial plane was the most likely reaction. These results demonstrate the importance of the presence but not the identity of the equatorial ligands upon the silylation of the uranyl U-O bond. (authors)

  3. Red-excitation resonance Raman analysis of the nu(Fe=O) mode of ferryl-oxo hemoproteins.

    Science.gov (United States)

    Ikemura, Kenichiro; Mukai, Masahiro; Shimada, Hideo; Tsukihara, Tomitake; Yamaguchi, Satoru; Shinzawa-Itoh, Kyoko; Yoshikawa, Shinya; Ogura, Takashi

    2008-11-05

    The Raman excitation profile of the nuFe O mode of horseradish peroxidase compound II exhibits a maximum at 580 nm. This maximum is located within an absorption band with a shoulder assignable to an oxygen-to-iron charge transfer band on the longer wavelength side of the alpha-band. Resonance Raman bands of the nuFe O mode of various ferryl-oxo type hemoproteins measured at 590 nm excitation indicate that many hemoproteins in the ferryl-oxo state have an oxygen-to-iron charge transfer band in the visible region. Since this red-excited resonance Raman technique causes much less photochemical damage in the proteins relative to blue-excited resonance Raman spectroscopy, it produces a higher signal-to-noise ratio and thus represents a powerful tool for investigations of ferryl-oxo intermediates of hemoproteins.

  4. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2012-01-01

    Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me_3SiOUO)_2(L)_2] (A) is inert to oxidation, but after two-electron reduction to [(Me_3SiOUO)_2(L)]"2"- (1), it can be desilylated to form [OU(μ-O)_2UO(L)_2]"2"- (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U"V"I"/"V couple in dioxygen reduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2012-01-01

    The silylated uranium(V) dioxo complex [(Me_3SiOUO)_2(L)_2] is inert to oxidation, but after two-electron reduction to [(Me_3SiOUO)_2(L)]"2"-, it can be desilylated to form [OU(μ-O)_2UO(L)_2]"2"- with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U"V"I"/"V couple in dioxygen reduction. [de

  6. Molecular and crystal structure of 3,4-dihydroxy-2-oxo-1-methyl-4-phenylpiperidine

    International Nuclear Information System (INIS)

    Kuleshova, L.N.; Khrustalev, V.N.; Struchkov, Yu.T.; Soldatenkov, A.T.; Bekro, I.A.; Mamyrbekova, Zh.A.; Soldatova, S.A.

    1996-01-01

    The molecular and crystal structure of 3,4-dihydroxy-2-oxo-1-methyl-4-phenylpiperidine was determined. The crystal is orthorhombic: sp. gr. Pca21; a=15.764, b=5.635, and c=25.536 A; and Z=8. The structure was solved by direct methods; R1=0.051, for 2643 unique refections. Symmetry-independent molecules are related by a pseudocenter of symmetry. The piperidine cycle has an asymmetric half-chair conformation. The orientation of substituents is determined. In the crystal, intermolecular OH...O hydrogen bonds link the molecules into chains parallel to the Y-axis

  7. Phase I study of 6-diazo-5-oxo-L-norleucine (DON).

    Science.gov (United States)

    Sklaroff, R B; Casper, E S; Magill, G B; Young, C W

    1980-01-01

    We conducted a phase I study of 6-diazo-5-oxo-L-norleucine given iv on a twice weekly schedule. Twenty-six evaluable patients received 31 courses of the drug. Doses ranged from 100 to 500 mg/m2. Nausea with vomiting was the dose-limiting toxic effect, transient thrombocytopenia was seen frequently, and mucositis occurred in 39% of the patients. No definite therapeutic responses were observed in 18 patients with measurable lesions. The recommended dose for phase II studies is 200-300 mg/m2 iv twice weekly.

  8. Urinary albumin and 8-oxo-7,8-dihydroguanosine as markers of mortality and cardiovascular disease during 19 years after diagnosis of type 2 diabetes

    DEFF Research Database (Denmark)

    Broedbaek, Kasper; Køster-Rasmussen, Rasmus; Siersma, Volkert

    2017-01-01

    ,8-dihydroguanosine (8-oxoGuo) that represents intracellular oxidative stress. We investigated the ability of microalbuminuria (MA) and urinary 8-oxoGuo, alone and in combination, to predict mortality and cardiovascular disease (CVD) in patients with type 2 diabetes. We used data from 1381 newly diagnosed diabetes...... patients, and urinary albumin and 8-oxoGuo were assessed in morning urine collected at the time of diabetes diagnosis and at a follow-up visit 6 years later. Associations between the urinary markers and mortality and CVD were assessed in Cox proportional hazards regression models. Test performance......-up. At diagnosis only urinary albumin was associated with CVD. In contrast, only 8-oxoGuo was associated with CVD at 6-year follow-up. When investigating test performance, we found that by combining information from MA and 8-oxoGuo the ability to correctly identify patients at risk could be improved. The findings...

  9. Electrochemically Generated cis-Carboxylato-Coordinated Iron(IV) Oxo Acid-Base Congeners as Promiscuous Oxidants of Water Pollutants

    DEFF Research Database (Denmark)

    de Sousa, David P; Miller, Christopher J; Chang, Yingyue

    2017-01-01

    The nonheme iron(IV) oxo complex [FeIV(O)(tpenaH)]2+ and its conjugate base [FeIV(O)(tpena)]+ [tpena- = N,N,N'-tris(2-pyridylmethyl)ethylenediamine-N'-acetate] have been prepared electrochemically in water by bulk electrolysis of solutions prepared from [FeIII2(μ-O)(tpenaH)2](ClO4)4 at potentials...... of the electrochemically generated iron(IV) oxo complexes, in terms of the broad range of substrates examined, represents an important step toward the goal of cost-effective electrocatalytic water purification....

  10. Fission 99Mo production technology

    International Nuclear Information System (INIS)

    Miao Zengxing; Luo Zhifu; Ma Huimin; Liang Yufu; Yu Ningwen

    2003-01-01

    This paper describes a production technology of fission 99 Mo in the Department Isotope, CIAE. The irradiation target is tubular U-Al alloy containing highly enriched uranium. The target is irradiated in the swimming pool reactor core. The neutron flux is about 4x10 13 /cm 2 .sec. The production scale is 3.7-7.4 TBq (100-200Ci) of fission 99 Mo per batch. Total recovery of 99 Mo is more than 70%. The production practice proves that the process and equipment are safe and reliable. (author)

  11. Polarographic, spectrophotometric and coulometric studies of MoO=4 in H2SO4

    International Nuclear Information System (INIS)

    Tokoro, R.; Bertotti, M.

    1990-01-01

    This study characterizes the polarographic process of Mo O sup(=) sub(4) in H sub(2)SO sub(4) medium, determining which species is responsible by catalytic cycle. Spectrophotometric and coulometric studies are also described. (author)

  12. Health status of cows fed maize silage covered with oxo-biodegradable foil

    Directory of Open Access Journals (Sweden)

    Piotr SZTERK

    2017-11-01

    Full Text Available In agricultural practice, silage production uses pure, low density polyethylene foil. This foil, after use, becomes farm waste, having a negative impact on the environment. Instead of conventional foil, an environmentally safe biodegradable foil can be used, made from naturally occurring polymers or from synthetic multiparticulates, easily degradable by microorganisms. Silage covered with this type of foil should be safe for animal health. The purpose of the study was to determine whether oxo-biodegradable film could be used instead of conventional film in agricultural practice, to produce silage that is safe for the cows' health. Dairy cows were fed a partly mixed ratio (PMR, the component of which was silage made of whole maize plants, covered with oxo-biodegradable foil. The cow blood serum was marked for content of: glucose, total protein, cholesterol, triacylglycerols and enzyme activity: aspartic and alanine aminotransferase, γ-glutamyl transferase, alkaline phosphatase and amylase. The total protein concentration in the serum of cows analyzed at the end of the experiment was higher than the commonly accepted normal values. The content of glucose, cholesterol, triacylglycerols and the activity of aspartate and alanine aminotransferase, γ-glutamyl transferase, alkaline phosphatase and amylase was within reference limits. Feeding of silage from whole maize plants covered withoxo-biodegradable foil did not negatively affect the biochemical indicators of the cows' blood serum. The silage proved to be safe for the cows' health.

  13. Enhanced photocatalytic activity and synthesis of ZnO nanorods/MoS2 composites

    Science.gov (United States)

    Li, Hui; Shen, Hao; Duan, Libing; Liu, Ruidi; Li, Qiang; Zhang, Qian; Zhao, Xiaoru

    2018-05-01

    A stable and recyclable organic degradation catalyst based on MoS2 functionalized ZnO nanorods was introduced. ZnO nanorods were synthesized on the glass substrates (2 cm*2 cm) by sol-gel method and hydrothermal method and functionalized with MoS2 via an argon flow annealing method. The structure and morphology of the as-prepared samples were characterized by XRD, SEM and TEM. Results showed that a small amount of MoS2 was successfully wrapped on the surfaces of ZnO nanorods. XPS analyses showed the existence of Zn-S between ZnO and MoS2, indicating that the MoS2 was combined with ZnO through chemical bonds and formed the ZnO/MoS2 heterostructure. PL results revealed that ZnO/MoS2 had lower fluorescence spectra indicating an electron transport channel between ZnO and MoS2 which separated electrons and holes. Photocatalytic experiment showed that ZnO/MoS2 composites showed a better photodegradation performance of Rhodamine B (RhB) after functionalized with MoS2 under the UV light irradiation which could be attributed to the separation and transfer of photogenerated electrons and holes between ZnO and MoS2. Meanwhile, the high active adsorption sites on the edges of MoS2 also accelerated the degradation process. Furthermore, the scavengers were used to investigate the major active species and results indicated that h+ was the major reactive species for the degradation.

  14. The Recently Identified Isoleucine Conjugate of cis-12-Oxo-Phytodienoic Acid Is Partially Active in cis-12-Oxo-Phytodienoic Acid-Specific Gene Expression of Arabidopsis thaliana

    Czech Academy of Sciences Publication Activity Database

    Arnold, M.D.; Gruber, C.; Floková, Kristýna; Miersch, Otto; Strnad, Miroslav; Novák, Ondřej; Wasternack, Claus; Hause, B.

    2016-01-01

    Roč. 11, č. 9 (2016), e0162829 E-ISSN 1932-6203 R&D Projects: GA ČR GA14-34792S; GA MŠk(CZ) LO1204 Institutional support: RVO:61389030 Keywords : ALLENE-OXIDE-CYCLASE * 12-OXO-PHYTODIENOIC ACID * JASMONIC ACID Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.806, year: 2016

  15. Measurement of 8-oxo-7,8-dihydro-2'-deoxyguanosine and 8-oxo-7,8-dihydro-guanosine in cerebrospinal fluid by ultra performance liquid chromatography-tandem mass spectrometry

    DEFF Research Database (Denmark)

    Weimann, Allan; Simonsen, Anja Hviid; Poulsen, Henrik E

    2018-01-01

    absolute concentrations varying by a factor >105 in healthy humans. This could indicate that there is a serious specificity problem in some of the methods. In this paper an isotope-dilution UPLC-MS/MS method with high specificity and sensitivity for the quantification of 8oxoGuo and 8oxodGuo in CSF...

  16. 8-Oxo-7,8-dihydroadenine and 8-Oxo-7,8-dihydroadenosine-Chemistry, Structure, and Function in RNA and Their Presence in Natural Products and Potential Drug Derivatives.

    Science.gov (United States)

    Choi, Yu Jung; Chang, Stephanie J; Gibala, Krzysztof S; Resendiz, Marino J E

    2017-05-17

    A description and history of the role that 8-oxo-7,8-dihydroadenine (8-oxoAde) and 8-oxo-7,8-dihydroadenosine (8-oxoA) have in various fields has been compiled. This Review focusses on 1) the formation of this oxidatively generated modification in RNA, its interactions with other biopolymers, and its potential role in the development/progression of disease; 2) the independent synthesis and incorporation of this modified nucleoside into oligonucleotides of RNA to display the progress that has been made in establishing its behavior in biologically relevant systems; 3) reported synthetic routes, which date back to 1890, along with the progress that has been made in the total synthesis of the nucleobase, nucleoside, and their corresponding derivatives; and 4) the isolation, total synthesis, and biological activity of natural products containing these moieties as the backbone. The current state of research regarding this oxidatively generated lesion as well as its importance in the context of RNA, natural products, and potential as drug derivatives is illustrated using all available examples reported to date. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Preparation of MoB and MoB-MoSi2 composites by combustion synthesis in SHS mode

    International Nuclear Information System (INIS)

    Yeh, C.L.; Hsu, W.S.

    2007-01-01

    Combustion synthesis in the mode of self-propagating high-temperature synthesis (SHS) was carried out in the Mo-B and Mo-B-Si systems for the preparation of molybdenum boride MoB and the composite of MoB-MoSi 2 from elemental powder compacts. Under a preheating temperature above 150 deg. C , the reaction of Mo with boron in the sample compact of Mo:B = 1:1 is characterized by a planar combustion front propagating in a self-sustaining and steady manner. As the preheating temperature or sample compaction density increased, combustion temperature was found to increase and the propagation rate of the combustion front was correspondingly enhanced. Moreover, the XRD analysis provides evidence of yielding nearly single-phase α-MoB from the Mo-B sample at equiatomic stoichiometry. In the synthesis of MoB-MoSi 2 composites, the starting stoichiometry of the Mo-B-Si powder compact was varied so as to produce the final composites containing 20-80 mol% MoB. It was also found the increase of flame-front velocity and combustion temperature with increasing MoB content formed in the composite. The composition analysis by XRD shows excellent conversion from the Mo-B-Si powder compact to the MoB-MoSi 2 composite through the SHS reaction; that is, in addition to a small amount of Mo 5 Si 3 , the as-synthesized composite is composed entirely of MoB and MoSi 2

  18. Structural study of glasses in the binary system NaPO{sub 3}-MoO{sub 3} by X-ray absorption spectroscopy at the Mo K and L{sub 3} edges

    Energy Technology Data Exchange (ETDEWEB)

    Poirier, Gael, E-mail: gael@unifal-mg.edu.br [Department of Science and Technology, UNIFAL-MG, Rua Corumba 72, CEP 37701-100, Pocos de Caldas, MG (Brazil); Cassanjes, Fabia C. [Department of Science and Technology, UNIFAL-MG, Rua Corumba 72, CEP 37701-100, Pocos de Caldas, MG (Brazil)

    2010-04-15

    Glasses were prepared in the binary system (100 - x)NaPO{sub 3}-xMoO{sub 3} with x varying from 0 to 50 mol%. An increase in the MoO{sub 3} concentration promotes a strong absorption in the visible and near infrared attributed to Mo reduction during glass synthesis. X-ray absorption measurements were performed at the Mo K and L{sub 3} edges to investigate both the coordination number and oxidation state of Mo in these glasses. The evolution of the pre-peak observed at the K edge suggests that Mo atoms are six-fold coordinated in these glasses. This hypothesis was confirmed by data obtained at the Mo-L{sub 3}-absorption edge. Since the final electronic states at the L{sub 3}-absorption edge are mostly orbitals of d-character which are splitted by the ligand field, the amplitude of the d-orbital splitting could be estimated and the related coordination number of Mo obtained. Finally, the oxidation state of Mo could be related with a change of the white line intensity at the Mo-L{sub 3} edge. These results confirm that the optical absorption in the visible is due to Mo reduction and that transparent samples prepared by slow cooling contain less reduced Mo species.

  19. 5-Methyl-4-oxo-4,6-dihydro-3H-pyridazino[4,5-b]carbazole-1-carbonitrile

    Directory of Open Access Journals (Sweden)

    Norbert Haider

    2010-02-01

    Full Text Available The title compound was prepared in excellent yield from 5-methyl-4-oxo-4,6-dihydro-3H-pyridazino[4,5-b]carbazole-1-carbaldehyde by treatment with hydroxylamine hydrochloride in formic acid without isolation of the intermediate oxime.

  20. Syntheses and structures of technetium(V) and rhenium(V) oxo complexes of peptide having KYC-sequence

    International Nuclear Information System (INIS)

    Takayama, T.; Suzuki, K.; Sekine, T.; Kudo, H.

    2000-01-01

    Technetium(V) and rhenium(V) oxo complexes of a peptide having a KYC-sequence such as KYCAR (H 3 L 5 ) and KYCAREPPTRTNAYQGQG-NH 2 (H 3 L 18 ) were synthesized, and structures of the complexes were characterized by spectroscopic techniques. All of the complexes were synthesized by the ligand exchange reaction of [(n-C 4 H 9 ) 4 N][MOCl 4 ] (M = 99 Tc, Re) with peptide in methanol or dimethylformamide solution. These complexes have a square pyramidal structure with an oxo ligand at the apical position. The peptide is coordinated to a metal atom through N amine of lysine. S thiol of cysteine, and N amide of tyrosine and cysteine in the equatorial plane. A lysine (CH 2 ) 4 NH 2 group of the L 5 ligand has the syn conformation with respect to metal-oxo bonding in the complex. The syn isomer was selectively formed in the ligand exchange reaction. The conversion of the syn isomer to the anti isomer was observed only for syn-[ReO(L 5 )], in which the coordination of water to the trans position of the oxo ligand was involved. (orig.)

  1. Syntheses and structures of technetium(V) and rhenium(V) oxo complexes of peptide having KYC-sequence

    Energy Technology Data Exchange (ETDEWEB)

    Takayama, T.; Suzuki, K.; Sekine, T.; Kudo, H. [Dept. of Chemistry, Tohoku Univ., Sendai (Japan)

    2000-07-01

    Technetium(V) and rhenium(V) oxo complexes of a peptide having a KYC-sequence such as KYCAR (H{sub 3}L{sup 5}) and KYCAREPPTRTNAYQGQG-NH{sub 2} (H{sub 3}L{sup 18}) were synthesized, and structures of the complexes were characterized by spectroscopic techniques. All of the complexes were synthesized by the ligand exchange reaction of [(n-C{sub 4}H{sub 9}){sub 4}N][MOCl{sub 4}] (M = {sup 99}Tc, Re) with peptide in methanol or dimethylformamide solution. These complexes have a square pyramidal structure with an oxo ligand at the apical position. The peptide is coordinated to a metal atom through N{sub amine} of lysine. S{sub thiol} of cysteine, and N{sub amide} of tyrosine and cysteine in the equatorial plane. A lysine (CH{sub 2}){sub 4}NH{sub 2} group of the L{sup 5} ligand has the syn conformation with respect to metal-oxo bonding in the complex. The syn isomer was selectively formed in the ligand exchange reaction. The conversion of the syn isomer to the anti isomer was observed only for syn-[ReO(L{sup 5})], in which the coordination of water to the trans position of the oxo ligand was involved. (orig.)

  2. Design and synthesis of brain-targeted prodrugs of the glutamine antagonist 6-Diazo-5-oxo-L-norleucine

    Czech Academy of Sciences Publication Activity Database

    Tenora, Lukáš; Novotná, Kateřina; Monincová, Lenka; Jančařík, Andrej; Nedelcovych, M.; Alt, J.; Rais, R.; Slusher, B. S.; Majer, Pavel

    2017-01-01

    Roč. 284, Suppl 1 (2017), s. 344 ISSN 1742-464X. [FEBS Congress /42./ From Molecules to Cells and Back. 10.09.2017-14.09.2017, Jerusalem] Institutional support: RVO:61388963 Keywords : 6-Diazo-5-oxo-L-norleucine * prodrugs Subject RIV: CE - Biochemistry

  3. Design and synthesis of brain-targeted prodrugs of the glutamine antagonist 6-Diazo-5-oxo-L-norleucine

    Czech Academy of Sciences Publication Activity Database

    Tenora, Lukáš; Novotná, Kateřina; Monincová, Lenka; Jančařík, Andrej; Gadiano, A. J.; Dash, R.; Rais, R.; Alt, J.; Slusher, B. S.; Majer, Pavel

    2017-01-01

    Roč. 284, Suppl 1 (2017), s. 345 ISSN 1742-464X. [FEBS Congress /42./ From Molecules to Cells and Back. 10.09.2017-14.09.2017, Jerusalem] Institutional support: RVO:61388963 Keywords : 6-Diazo-5-oxo-L-norleucine * prodrugs Subject RIV: CE - Biochemistry

  4. Association between 8-oxo-7,8-dihydro-2'-deoxyguanosine excretion and risk of postmenopausal breast cancer

    DEFF Research Database (Denmark)

    Loft, Steffen; Olsen, Anja; Møller, Peter

    2013-01-01

    Oxidative stress may be important in carcinogenesis and a possible risk factor for breast cancer. The urinary excretion of oxidatively generated biomolecules, such as 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG), represents biomarkers of oxidative stress, reflecting the rate of global damage...

  5. Human and methodological sources of variability in the measurement of urinary 8-oxo-7,8-dihydro-2'-deoxyguanosine

    DEFF Research Database (Denmark)

    Barregard, Lars; Møller, Peter; Henriksen, Trine

    2013-01-01

    Urinary 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) is a widely used biomarker of oxidative stress. However, variability between chromatographic and ELISA methods hampers interpretation of data, and this variability may increase should urine composition differ between individuals, leading to as...

  6. Mo-Mo Quintuple Bond is Highly Reactive in H-H, C-H, and O-H σ-Bond Cleavages Because of the Polarized Electronic Structure in Transition State.

    Science.gov (United States)

    Chen, Yue; Sakaki, Shigeyoshi

    2017-04-03

    The recently reported high reactivity of the Mo-Mo quintuple bond of Mo 2 (N ∧ N) 2 (1) {N ∧ N = μ-κ 2 -CH[N(2,6-iPr 2 C 6 H 3 )] 2 } in the H-H σ-bond cleavage was investigated. DFT calculations disclosed that the H-H σ-bond cleavage by 1 occurs with nearly no barrier to afford the cis-dihydride species followed by cis-trans isomerization to form the trans-dihydride product, which is consistent with the experimental result. The O-H and C-H bond cleavages by 1 were computationally predicted to occur with moderate (ΔG° ⧧ = 9.0 kcal/mol) and acceptable activation energies (ΔG° ⧧ = 22.5 kcal/mol), respectively, suggesting that the Mo-Mo quintuple bond can be applied to various σ-bond cleavages. In these σ-bond cleavage reactions, the charge-transfer (CT Mo→XH ) from the Mo-Mo quintuple bond to the X-H (X = H, C, or O) bond and that (CT XH→Mo ) from the X-H bond to the Mo-Mo bond play crucial roles. Though the HOMO (dδ-MO) of 1 is at lower energy and the LUMO + 2 (dδ*-MO) of 1 is at higher energy than those of RhCl(PMe 3 ) 2 (LUMO and LUMO + 1 of 1 are not frontier MO), the H-H σ-bond cleavage by 1 more easily occurs than that by the Rh complex. Hence, the frontier MO energies are not the reason for the high reactivity of 1. The high reactivity of 1 arises from the polarization of dδ-type MOs of the Mo-Mo quintuple bond in the transition state. Such a polarized electronic structure enhances the bonding overlap between the dδ-MO of the Mo-Mo bond and the σ*-antibonding MO of the X-H bond to facilitate the CT Mo→XH and reduce the exchange repulsion between the Mo-Mo bond and the X-H bond. This polarized electronic structure of the transition state is similar to that of a frustrated Lewis pair. The easy polarization of the dδ-type MOs is one of the advantages of the metal-metal multiple bond, because such polarization is impossible in the mononuclear metal complex.

  7. Microstructures and room temperature fracture toughness of Nb/Nb5Si3 composites alloyed with W, Mo and W–Mo fabricated by spark plasma sintering

    International Nuclear Information System (INIS)

    Xiong, Bowen; Cai, Changchun; Wang, Zhenjun

    2014-01-01

    Highlights: • Microstructure of Nb/Nb 5 Si 3 composite alloyed with W and Mo is change obviously. • W and Mo elements can solid solution in Nb and Nb 5 Si 3 phase respectively. • Alloyed with W and Mo together, the solid solubility of Nb 5 Si 3 phases is undetected. • The Nb/Nb 5 Si 3 composite alloyed with W and Mo together has high fracture toughness. - Abstract: Microstructures and room temperature fracture toughness of Nb/Nb 5 Si 3 composites alloyed with W, Mo and W–Mo fabricated by spark plasma sintering were investigated. The microstructures were examined using scanning electron microscope (SEM). X-ray diffraction (XRD) was performed on the bulk specimens for identification of phases. The chemical species were analyzed using electron-probe micro-analysis (EPMA). Results indicated that the microstructures of Nb/Nb 5 Si 3 composites alloyed with W or Mo is unaltered, including primary Nb and eutectic mixtures of Nb and Nb 5 Si 3 , and the coarse and fine eutectic mixtures. The W and Mo elements solid solution in Nb and Nb 5 Si 3 phase are detected. But that alloyed with W and Mo together, The microstructures are change obviously, including Nb phase, the solid solubility phases of W and Mo atoms in Nb, and the solid solubility phases of Nb atoms in W are also found, but the solid solubility phenomenon of Nb 5 Si 3 phases is not detected. The microhardness of Nb and Nb 5 Si 3 phases increases obviously because of solid solution strengthening. The Nb/Nb 5 Si 3 composite alloyed with W and Mo together hashing high fracture toughness is attributable to the big eutectic Nb and interface of eutectic phases, which can bear large deformation to absorb the crack energy and form the decohesion between eutectic phases

  8. 99Mo Yield Using Large Sample Mass of MoO3 for Sustainable Production of 99Mo

    Science.gov (United States)

    Tsukada, Kazuaki; Nagai, Yasuki; Hashimoto, Kazuyuki; Kawabata, Masako; Minato, Futoshi; Saeki, Hideya; Motoishi, Shoji; Itoh, Masatoshi

    2018-04-01

    A neutron source from the C(d,n) reaction has the unique capability of producing medical radioisotopes such as 99Mo with a minimum level of radioactive waste. Precise data on the neutron flux are crucial to determine the best conditions for obtaining the maximum yield of 99Mo. The measured yield of 99Mo produced by the 100Mo(n,2n)99Mo reaction from a large sample mass of MoO3 agrees well with the numerical result estimated with the latest neutron data, which are a factor of two larger than the other existing data. This result establishes an important finding for the domestic production of 99Mo: approximately 50% of the demand for 99Mo in Japan could be met using a 100 g 100MoO3 sample mass with a single accelerator of 40 MeV, 2 mA deuteron beams.

  9. Syntheses, structures, and properties of Ag4(Mo2O5)(SeO4)2(SeO3) and Ag2(MoO3)3SeO3

    International Nuclear Information System (INIS)

    Ling Jie; Albrecht-Schmitt, Thomas E.

    2007-01-01

    Ag 4 (Mo 2 O 5 )(SeO 4 ) 2 (SeO 3 ) has been synthesized by reacting AgNO 3 , MoO 3 , and selenic acid under mild hydrothermal conditions. The structure of this compound consists of cis-MoO 2 2+ molybdenyl units that are bridged to neighboring molybdenyl moieties by selenate anions and by a bridging oxo anion. These dimeric units are joined by selenite anions to yield zigzag one-dimensional chains that extended down the c-axis. Individual chains are polar with the C 2 distortion of the Mo(VI) octahedra aligning on one side of each chain. However, the overall structure is centrosymmetric because neighboring chains have opposite alignment of the C 2 distortion. Upon heating Ag 4 (Mo 2 O 5 )(SeO 4 ) 2 (SeO 3 ) looses SeO 2 in two distinct steps to yield Ag 2 MoO 4 . Crystallographic data: (193 K; MoKα, λ=0.71073 A): orthorhombic, space group Pbcm, a=5.6557(3), b=15.8904(7), c=15.7938(7) A, V=1419.41(12), Z=4, R(F)=2.72% for 121 parameters with 1829 reflections with I>2σ(I). Ag 2 (MoO 3 ) 3 SeO 3 was synthesized by reacting AgNO 3 with MoO 3 , SeO 2 , and HF under hydrothermal conditions. The structure of Ag 2 (MoO 3 ) 3 SeO 3 consists of three crystallographically unique Mo(VI) centers that are in 2+2+2 coordination environments with two long, two intermediate, and two short bonds. These MoO 6 units are connected to form a molybdenyl ribbon that extends along the c-axis. These ribbons are further connected together through tridentate selenite anions to form two-dimensional layers in the [bc] plane. Crystallographic data: (193 K; MoKα, λ=0.71073 A): monoclinic, space group P2 1 /n, a=7.7034(5), b=11.1485(8), c=12.7500(9) A, β=105.018(1) V=1002.7(2), Z=4, R(F)=3.45% for 164 parameters with 2454 reflections with I>2σ(I). Ag 2 (MoO 3 ) 3 SeO 3 decomposes to Ag 2 Mo 3 O 10 on heating above 550 deg. C. - Graphical abstract: A view of the one-dimensional [(Mo 2 O 5 )(SeO 4 ) 2 (SeO 3 )] 4- chains that extend down the c-axis in the structure of Ag 4 (Mo 2 O 5 )(SeO 4

  10. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom)

    2012-12-07

    Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] (A) is inert to oxidation, but after two-electron reduction to [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-} (1), it can be desilylated to form [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U{sup VI/V} couple in dioxygen reduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Urinary 8-oxo-7,8-dihydro-2'-deoxyguanosine as a biomarker in type 2 diabetes

    DEFF Research Database (Denmark)

    Broedbaek, Kasper; Weimann, Allan; Stovgaard, Elisabeth Ida Specht

    2011-01-01

    The increasing prevalence of diabetes together with the associated morbidity and mortality calls for additional preventive and therapeutic strategies. New biomarkers that can be used in therapy control and risk stratification as alternatives to current methods are needed and can facilitate a more...... individualized and sufficient treatment of diabetes. Evidence derived from both epidemiological and mechanistic studies suggests that oxidative stress has an important role in mediating the pathologies of diabetic complications. A marker of intracellular oxidative stress that potentially could be used...... as a valuable biomarker in diabetes is the DNA oxidation marker 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG), which can be assessed noninvasively in the urine, with minimal discomfort for the patient. In this review the analytical validity of 8-oxodG is addressed by highlighting important methodological issues...

  12. Influence of colorant and film thickness on thermal aging characteristics of oxo-biodegradable plastic bags

    Science.gov (United States)

    Leuterio, Giselle Lou D.; Pajarito, Bryan B.; Domingo, Carla Marie C.; Lim, Anna Patricia G.

    2016-05-01

    Functional, lightweight, strong and cheap plastic bags incorporated with pro-oxidants undergo accelerated degradation under exposure to heat and oxygen. This work investigated the effect of colorant and film thickness on thermal aging characteristics of commercial oxo-biodegradable plastic bag films at 70 °C. Degradation is monitored through changes in infrared absorption, weight, and tensile properties of thermally aged films. The presence of carbonyl band in infrared spectrum after 672 h of thermal aging supports the degradation behavior of exposed films. Results show that incorporation of colorant and increasing thickness exhibit low maximum weight uptake. Titanium dioxide as white colorant in films lowers the susceptibility of films to oxygen uptake but enhances physical degradation. Higher amount of pro-oxidant loading also contributes to faster degradation. Opaque films are characterized by low tensile strength and high elastic modulus. Decreasing the thickness contributes to lower tensile strength of films. Thermally aged films with colorant and low thickness promote enhanced degradation.

  13. Metal-oxo containing polymer nanobeads as potential contrast agents for magnetic resonance imaging

    Science.gov (United States)

    Pablico, Michele Huelar

    Magnetic resonance imaging (MRI) has greatly revolutionized the way diseases are detected and treated, as it is a non-invasive imaging modality solely based on the interaction of radiowaves and hydrogen nuclei in the presence of an external magnetic field. It is widely used today for the diagnosis of diseases as it offers an efficient method of mapping structure and function of soft tissues in the body. Most MRI examinations utilize paramagnetic materials known as contrast agents, which enhance the MR signal by decreasing the longitudinal (T1) and transverse (T2) relaxation times of the surrounding water protons in biological systems. This results into increased signal intensity differences thereby allowing better interpretation and analysis of pathological tissues. Contrast agents function by lowering the T1 or lowering the T2, resulting into bright and dark contrasts, respectively. The most common MRI contrast agents that are in clinical use today are gadolinium chelates and superparamagnetic iron oxide nanoparticles, both of which have their own advantages in terms of contrast enhancement properties. In the past few years, however, there has been interest in utilizing metal-containing clusters for MRI contrast enhancement as these materials bridge the gap between the constrained structure and magnetic properties of the gadolinium chelates with the superparamagnetic behavior of the iron oxide nanoparticles. Recently, metallic clusters containing Mn and Fe metal centers have received increased attention mainly because of their potential for high spin states and benign nature. In the quest to further develop novel imaging agents, this research has focused on investigating the use of metal-oxo clusters as potential contrast agents for MRI. The primary goal of this project is to identify clusters that meet the following criteria: high paramagnetic susceptibility, water-soluble, stable, cheap, contain environmentally benign metals, and easily derivatized. This work is

  14. Dipole strength distribution below the giant dipole resonance in {sup 92}Mo, {sup 98}Mo and {sup 100}Mo

    Energy Technology Data Exchange (ETDEWEB)

    Rusev, G.Y.

    2006-07-01

    Investigations of the dipole-strength distributions in {sup 92}Mo, {sup 98}Mo and {sup 100}Mo were carried out by means of the method of nuclear resonance fluorescence. The low-lying excitations in the nuclides {sup 92}Mo, {sup 98}Mo and {sup 100}Mo have been studied in photon-scattering experiments at an electron energy of 6 MeV at the ELBE accelerator and at electron energies from 3.2 to 3.8 MeV at the Dynamitron accelerator. Five levels were observed in {sup 92}Mo. Five levels in {sup 98}Mo and 14 in {sup 100}Mo were identified for the first time in the energy range from 2 to 4 MeV. Dipole-strength distributions up to the neutron-separation energies in the nuclides {sup 92}Mo, {sup 98}Mo and {sup 100}Mo have been investigated at the ELBE accelerator. Because of the possible observation of transitions in the neighboring nuclei produced via ({gamma},n) reaction, additional measurements at electron energies of 8.4 and 7.8 MeV, below the neutron-separation energy, were performed on {sup 98}Mo and {sup 100}Mo, respectively. The number of transitions assigned to {sup 92}Mo, {sup 98}Mo and {sup 100}Mo is 340, 485 and 499, respectively, the main part of them being dipole transitions. Statistical properties of the observed transitions are obtained. The continuum contains the ground-state transitions as well as the branching transitions to the low-lying levels and the subsequent deexcitations of these levels. (orig.)

  15. Electronic structures of B1 MoN, fcc Mo2N, and hexagonal MoN

    International Nuclear Information System (INIS)

    Ihara, H.; Kimura, Y.; Senzaki, K.; Kezuka, H.; Hirabayashi, M.

    1985-01-01

    The electronic structures of B1 MoN, fcc Mo 2 N, and hexagonal MoN were observed by photoelectron spectroscopic measurement. The B1-MoN phase has been predicted to be a high-T/sub c/ superconductor because of a large density of states at Fermi level. The observed electronic structure of the stoichiometric B1-MoN phase is different from that of the real B1-MoN type. The nitrogen excess B1-MoN/sub x/ (x> or =1.3) phase, however, shows the B1-type electronic structure. This is explained by the occurrence of a nitrogen vacancy in the apparent stoichiometric B1 phase and the occupation of the nitrogen vacancy in the nitrogen-excess B1 phase. This property is related to the previously reported low T/sub c/ of the B1-MoN crystals

  16. Microstructure and properties of MoSi2-MoB and MoSi2-Mo5Si3 molybdenum silicides

    International Nuclear Information System (INIS)

    Schneibel, J.H.; Sekhar, J.A.

    2003-01-01

    MoSi 2 -based intermetallics containing different volume fractions of MoB or Mo 5 Si 3 were fabricated by hot-pressing MoSi 2 , MoB, and Mo 5 Si 3 powders in vacuum. Both classes of alloys contained approximately 5 vol.% of dispersed silica phase. Additions of MoB or Mo 5 Si 3 caused the average grain size to decrease. The decrease in the grain size was typically accompanied by an increase in flexure strength, a decrease in the room temperature fracture toughness, and a decrease in the hot strength (compressive creep strength) measured around 1200 deg. C, except when the Mo 5 Si 3 effectively became the major phase. Oxidation measurements on the two classes of alloys were carried out in air. Both classes of alloys were protected from oxidation by an in-situ adherent scale that formed on exposure to high temperature. The scale, although not analyzed in detail, is commonly recognized in MoSi 2 containing materials as consisting mostly of SiO 2 . The MoB containing materials showed an increase in the scale thickness and the cyclic oxidation rate at 1400 deg. C when compared with pure MoSi 2 . However, in contrast with the pure MoSi 2 material, oxidation at 1400 deg. C began with a weight loss followed by a weight gain and the formation of the protective silica layer. The Mo 5 Si 3 containing materials experienced substantial initial weight losses followed by regions of small weight changes. Overall, the MoB and Mo 5 Si 3 additions to MoSi 2 tended to be detrimental for the mechanical and oxidative properties

  17. Bio-dissolution of Ni, V and Mo from spent petroleum catalyst using iron oxidizing bacteria.

    Science.gov (United States)

    Pradhan, Debabrata; Kim, Dong J; Roychaudhury, Gautam; Lee, Seoung W

    2010-01-01

    Bioleaching studies of spent petroleum catalyst containing Ni, V and Mo were carried out using iron oxidizing bacteria. Various leaching parameters such as Fe(II) concentration, pulp density, pH, temperature and particle size were studied to evaluate their effects on the leaching efficiency as well as the kinetics of dissolution. The percentage of leaching of Ni and V were higher than Mo. The leaching process followed a diffusion controlled model and the product layer was observed to be impervious due to formation of ammonium jarosite (NH(4))Fe(3)(SO(4))(2)(OH)(6). Apart from this, the lower leaching efficiency of Mo was due to a hydrophobic coating of elemental sulfur over Mo matrix in the spent catalyst. The diffusivities of the attacking species for Ni, V and Mo were also calculated.

  18. Chemistry of phosphido-bridged dimolybdenum complexes. Part 2: the reaction of [(η-C5H5)2Mo2(μ-H)(μ-PMe2) (CO)4] with alkynes: X-ray crystal structure of [(η-C5H5)2Mo2 (μ-σ:η2-C(Me) = CHMe) (μ-PMe2) (CO)3

    International Nuclear Information System (INIS)

    Conole, G.; Henrick, K.; McPartlin, M.; Horton, A.D.; Mays, M.J.

    1988-01-01

    The photolytic reactions with alkynes have been studied. With MeC ≡ CMe the major product is the μ-vinyl complex which has been characterised by a single crystal X-ray diffraction study. This shows that the methyl groups on the μ-vinyl ligand adopt a mutually trans orientation; the Mo - Mo bond length is 3.056 (1) A (mean for two independent molecules). The unsymmetrical alkynes give inseparable isomeric mixtures but HC ≡ CH and PhC ≡ CPh do not give simple μ-vinyl products. Each of the above μ-vinyl complexes is accompanied by a minor yield of the corresponding oxo complex and a low yield of such a complex is also obtained in the reaction with acetylene itself. 21 refs

  19. Impact of Reduced Graphene Oxide on MoS2 Grown by Sulfurization of Sputtered MoO3 and Mo Precursor Films (Postprint)

    Science.gov (United States)

    2016-05-26

    1,2 intercalation assisted exfoliation,8–11 physical vapor deposition (PVD),12,13 and a wet chemistry approach involving thermal decomposition of a... annealed MoO3, MoS2 films S1 (MoS2 using Mo precursor), S2 (MoS2 using MoO3 precursor), S1r (MoS2 using Mo pre- cursor and rGO), and S2r (MoS2 using...MoO3 precursor and rGO). The annealed MoO3 (a) shows Mo(IV) peaks which are indicative of MoO2, and Mo(VI) peaks that occur when MoO3 is present. Both

  20. Nucleation-growth of salicylic acid-oxoTiO{sub 2} colloids synthesized by sol-gel processing

    Energy Technology Data Exchange (ETDEWEB)

    Tieng, S.; Jia, Z. [Laboratoire des Sciences des Procédés et des Matériaux, CNRS, Université Paris 13, Sorbonne Paris Cité, 99 avenue J.-B. Clément, 93430 Villetaneuse (France); Subra-Paternault, P. [Laboratoire de Chimie et Biologie des Membranes et Nanoobjets, CBMN – UMR 5248, Bâtiment, 14B, Allée Geoffroy Saint Hilaire, 33600 Pessac (France); Kanaev, A. [Laboratoire des Sciences des Procédés et des Matériaux, CNRS, Université Paris 13, Sorbonne Paris Cité, 99 avenue J.-B. Clément, 93430 Villetaneuse (France); Chhor, K., E-mail: khay.chhor@lspm.cnrs.fr [Laboratoire des Sciences des Procédés et des Matériaux, CNRS, Université Paris 13, Sorbonne Paris Cité, 99 avenue J.-B. Clément, 93430 Villetaneuse (France)

    2014-12-15

    In this work, the preparation of hybrid oxo-TiO{sub 2} nanoparticles modified by salicylic acid (SA) is reported. The size-selected TiO{sub 2} nanoparticles were synthesized in a sol-gel reactor with rapid micromixing of reagents and binding of SA molecules occurs at the nucleation stage. UV-visible absorption, Raman spectroscopy and Light scattering measurements evidence the formation of a SA–oxo-TiO{sub 2} charge-transfer complex. In particularly, the C=O vibration mode of SA shifts to lower frequencies upon complexation while the C-O vibration modes of both carboxylate and phenolic groups retain their position. The absence of C-O shift comes from two effects that cancel each other, i.e. the hardening of this mode related to the C=O mode changes and its softening due to the replacement of hydrogen in COH group by Ti atoms. Kinetic studies of the oxo-TiO{sub 2} nanoparticles nucleation and growth in presence of SA show that the acidic ligand at the nanoparticle surface acts as an attractor for another oxo-TiO{sub 2} nanoparticle leading to polycondensation. This mechanism is responsible for the acceleration of the nanoparticle aggregation kinetics and shortening of the induction time. The hybrid nanoparticles are stable at pH ≤ 7.7 and release SA molecules at pH ≥ 8.5. - Highlights: • Hybrid oxo-TiO{sub 2} nanoparticles modified by salicylic acid (SA) are prepared. • The synthesis is achieved during the nucleation stage of sol-gel process. • The formation of SA–oxo-TiO{sub 2} charge-transfer complex is evidenced. • Mechanism responsible for the acceleration of the nanoparticle aggregation kinetics is proposed. • SA-TiO{sub 2} nanoparticles are stable at pH ≤ 7.7 and release SA molecules at pH ≥ 8.5.

  1. Reactions of 1-methyl-derivatives of 2-oxo-1,2,3,4-tetrahydropyrimidine with phosphorus pentachloride and phosphorus oxychloride

    International Nuclear Information System (INIS)

    Khanina, E.L.; Liepin'sh, E.E.; Mutsenietse, D.Kh.; Dubur, G.Ya.

    1987-01-01

    In the reaction of 4-phenyl-and 4,6-diphenyl-1-methyl-2-oxo-5-ethoxycarbonyl-1,2,3,4-tetrahydropyrimidines with phosphorus pentachloride, oxidation and dealkylation takes place in addition to chlorination and as a result one obtained 4-phenyl- and 4,6-diphenyl-1-methyl-5-ethoxycarbonyl-2-pyrimidones and also 4-phenyl-, (4,6-diphenyl)-5-ethoxycarbonyl-2-chloropyrimidines. 1,6-Dimethyl-2-oxo-4-phenyl-5-ethoxycarbonyl-1,2,3,4-tetrahydropyrimidine in the same reaction gives 1-methyl-2-oxo-4-phenyl-5-ethoxycarbonyl 6-dichloromethyl-1,2,3,4-tetrahydropyrimidine, together with 6-chloromethylene- and 6-dichloromethylene-1-methyl-2-oxo-4-phenyl-5-chloro-5-ethoxycarbonylhexahydropyrimidines. The structure was established on the basis of elemental analysis, proton NMR spectra, and carbon-13 NMR spectra, taking into account the long-range 2 H- 13 C coupling constants

  2. Measurement of target and double-spin asymmetries for the e<mo>→>p<mo>→mo><mo>→mo>eπ<mo>+mo><mo>(n)> reaction in the nucleon resonance region at low Q2

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, X.; Adhikari, K. P.; Bosted, P.; Deur, A.; Drozdov, V.; El Fassi, L.; Kang, Hyekoo; Kovacs, K.; Kuhn, S.; Long, E.; Phillips, S. K.; Ripani, M.; Slifer, K.; Smith, L. C.; Adikaram, D.; Akbar, Z.; Amaryan, M. J.; Anefalos Pereira, S.; Asryan, G.; Avakian, H.; Badui, R. A.; Ball, J.; Baltzell, N. A.; Battaglieri, M.; Batourine, V.; Bedlinskiy, I.; Biselli, A. S.; Briscoe, W. J.; Bültmann, S.; Burkert, V. D.; Carman, D. S.; Celentano, A.; Chandavar, S.; Charles, G.; Chen, J. -P.; Chetry, T.; Choi, Seonho; Ciullo, G.; Clark, L.; Colaneri, L.; Cole, P. L.; Compton, N.; Contalbrigo, M.; Crede, V.; D' Angelo, A.; Dashyan, N.; De Vita, R.; De Sanctis, E.; Djalali, C.; Dodge, G. E.; Dupre, R.; Egiyan, H.; El Alaoui, A.; Elouadrhiri, L.; Eugenio, P.; Fanchini, E.; Fedotov, G.; Fersch, R.; Filippi, A.; Fleming, J. A.; Gevorgyan, N.; Ghandilyan, Y.; Gilfoyle, G. P.; Giovanetti, K. L.; Girod, F. X.; Gleason, C.; Golovach, E.; Gothe, R. W.; Griffioen, K. A.; Guidal, M.; Guler, N.; Guo, L.; Hanretty, C.; Harrison, N.; Hattawy, M.; Hicks, K.; Holtrop, M.; Hughes, S. M.; Ilieva, Y.; Ireland, D. G.; Ishkhanov, B. S.; Isupov, E. L.; Jenkins, D.; Jiang, H.; Jo, H. S.; Joosten, S.; Keller, D.; Khachatryan, G.; Khandaker, M.; Kim, A.; Kim, W.; Klein, F. J.; Kubarovsky, V.; Lanza, L.; Lenisa, P.; Livingston, K.; MacGregor, I. J. D.; Markov, N.; McKinnon, B.; Mirazita, M.; Mokeev, V.; Movsisyan, A.; Munevar, E.; Munoz Camacho, C.; Murdoch, G.; Nadel-Turonski, P.; Net, L. A.; Ni, A.; Niccolai, S.; Niculescu, G.; Niculescu, I.; Osipenko, M.; Ostrovidov, A. I.; Paolone, M.; Paremuzyan, R.; Park, K.; Pasyuk, E.; Peng, P.; Pisano, S.; Pogorelko, O.; Price, J. W.; Puckett, A. J. R.; Raue, B. A.; Rizzo, A.; Rosner, G.; Rossi, P.; Roy, P.; Sabatié, F.; Salgado, C.; Schumacher, R. A.; Sharabian, Y. G.; Skorodumina, Iu.; Smith, G. D.; Sokhan, D.; Sparveris, N.; Stankovic, I.; Strakovsky, I. I.; Strauch, S.; Taiuti, M.; Tian, Ye; Ungaro, M.; Voskanyan, H.; Voutier, E.; Walford, N. K.; Watts, D. P.; Wei, X.; Weinstein, L. B.; Wood, M. H.; Zachariou, N.; Zhang, J.; Zonta, I.

    2016-10-01

    We report measurements of target- and double-spin asymmetries for the exclusive channel e<mo>→>p<mo>→mo><mo>→mo>eπ<mo>+mo><mo>(n)> in the nucleon resonance region at Jefferson Lab using the CEBAF Large Acceptance Spectrometer (CLAS). These asymmetries were extracted from data obtained using a longitudinally polarized NH3 target and a longitudinally polarized electron beam with energies 1.1, 1.3, 2.0, 2.3, and 3.0 GeV. The new results are consistent with previous CLAS publications but are extended to a low Q2 range from 0.0065 to 0.35 (GeV/c)2. The Q2 access was made possible by a custom-built Cherenkov detector that allowed the detection of electrons for scattering angles as low as 6 degrees. These results are compared with the unitary isobar models JANR and MAID, the partial-wave analysis prediction from SAID, and the dynamic model DMT. In many kinematic regions our results, in particular results on the target asymmetry, help to constrain the polarization-dependent components of these models.

  3. Estudio de la biodegradación de bolsas oxo - biodegradables en agua dulce y salada, simulando condiciones ambientales de Costa, Sierra y Oriente Ecuatoriano.

    OpenAIRE

    Escobar Silva, Nelly Jacqueline

    2014-01-01

    This work allowed the study of biodegradation of four types of oxo-biodegradable bags by environmental conditions simulated in fresh and salt water of the Costa, Sierra and Oriente regions. El presente trabajo permitió el estudio de la biodegradación de cuatro tipos de bolsas oxo-biodegradables mediante condiciones ambientales simuladas en el agua dulce y salada de las regiones Costa, Sierra y Oriente ecuatoriano.

  4. Ethyl (1R*,10S*,12R*,15S*-4-Hydroxy-2-oxo-15- (2-oxo-1-pyrrolidinyl-9-oxatetracyclo[10.2.2.01,10.03,8]hexadeca-3,5,7,13-tetraene-13-carboxylate

    Directory of Open Access Journals (Sweden)

    Jorge Heredia-Moya

    2017-01-01

    Full Text Available N-Vinylpirrolidinone reacts with (E-ethyl 5-hydroxy-3-(4-oxo-4H-chromen-3-yl acrylate (1 through a domino reaction similar to that reported reaction for ethyl vinyl ether. Inverse electron demand Diels–Alder (IEDDA–elimination-IEDDA generates isomeric tetracycles 5 and 6. The assignment of the relative stereochemistry of the products was made by comparing the proton couplings with those obtained by reaction with ethyl vinyl ether.

  5. Assembly of crosslinked oxo-cyanoruthenate and zirconium oxide bilayers: Application in electrocatalytic films based on organically modified silica with templated pores

    International Nuclear Information System (INIS)

    Rutkowska, Iwona A.; Sek, Jakub P.; Mehdi, B. Layla; Kulesza, Pawel J.; Cox, James A.

    2014-01-01

    Electrochemical deposition of crosslinked oxo-cyanoruthenate, Ru-O/CN-O, from a mixture of RuCl 3 and K 4 Ru(CN) 6 is known to yield a film on glassy carbon that promotes oxidations by a combination of electron and oxygen transfer. Layer-by-layer (LbL) deposition of this species at a film formed by cycling of the electrode potential in a ZrO 2 solution systematically increases the number of catalytically active sites of the Ru-O/CN-O on the electrode. The evaluation of the electrocatalytic activity was by cyclic voltammetric oxidation of cysteine at pH 2. Plots of the anodic peak current vs. the square root of scan rate were indicative of linear diffusion control of this oxidation, even in the absence of ZrO 2 , but the slopes of these linear plots increased with bilayer number, n, of (ZrO 2 | Ru-O/CN-O) n . The latter observation is hypothesized to be due to an increased number of active sites for a given geometric electrode area, but proof requires further study. To optimize utilization of the catalyst and to provide a size-exclusion characteristic to the electrode, the study was extended to LbL deposition of the composite in 50-nm pores of an organically modified silica film deposited by electrochemically assisted sol-gel processing using surface-bound poly(styrene sulfonate) nanospheres as a templating agent

  6. Evaluation of Stability of Complexes of Inner Transition Metal Ions with 2-Oxo-1-pyrrolidine Acetamide and Role of Systematic Errors

    Directory of Open Access Journals (Sweden)

    Sangita Sharma

    2011-01-01

    Full Text Available BEST FIT models were used to study the complexation of inner transition metal ions like Y(III, La(III, Ce(III, Pr(III, Nd(III, Sm(III, Gd(III, Dy(III and Th(IV with 2-oxo-1-pyrrolidine acetamide at 30 °C in 10%, 20, 30, 40, 50% and 60% v/v dioxane-water mixture at 0.2 M ionic strength. Irving Rossotti titration method was used to get titration data. Calculations were carried out with PKAS and BEST Fortran IV computer programs. The expected species like L, LH+, ML, ML2 and ML(OH3, were obtained with SPEPLOT. Stability of complexes has increased with increasing the dioxane content. The observed change in stability can be explained on the basis of electrostatic effects, non electrostatic effects, solvating power of solvent mixture, interaction between ions and interaction of ions with solvents. Effect of systematic errors like effect of dissolved carbon dioxide, concentration of alkali, concentration of acid, concentration of ligand and concentration of metal have also been explained here.

  7. Assessing the genotoxic effects of two lipid peroxidation products (4-oxo-2-nonenal and 4-hydroxy-hexenal) in haemocytes and midgut cells of Drosophila melanogaster larvae.

    Science.gov (United States)

    Demir, Eşref; Marcos, Ricard

    2017-07-01

    Lipid peroxidation products can induce tissue damage and are implicated in diverse pathological conditions, including aging, atherosclerosis, brain disorders, cancer, lung and various liver disorders. Since in vivo studies produce relevant information, we have selected Drosophila melanogaster as a suitable in vivo model to characterise the potential risks associated to two lipid peroxidation products namely 4-oxo-2-nonenal (4-ONE) and 4-hydroxy-hexenal (4-HHE). Toxicity, intracellular reactive oxygen species production, and genotoxicity were the end-points evaluated. Haemocytes and midgut cells were the evaluated targets. Results showed that both compounds penetrate the intestine of the larvae, affecting midgut cells, and reaching haemocytes. Significant genotoxic effects, as determined by the comet assay, were observed in both selected cell targets in a concentration/time dependent manner. This study highlights the importance of D. melanogaster as a model organism in the study of the different biological effects caused by lipid peroxidation products entering via ingestion. This is the first study reporting genotoxicity data in haemocytes and midgut cells of D. melanogaster larvae for the two selected compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Ethyl 3-oxo-2-(2,5-dioxopyrrolidin-3-yl)butanoate derivatives: Anthelmintic and cytotoxic potentials, antimicrobial and docking studies

    Science.gov (United States)

    Mahmood, Fawad; Jan, Muhammad S.; Ahmad, Sajjad; Rashid, Umer; Ayaz, Muhammad; Ullah, Farhat; Hussain, Fida; Ahmad, Ashfaq; Khan, Arif-ullah; Aasim, Muhammad; Sadiq, Abdul

    2017-12-01

    The development of novel and more effective drugs is slow asthe resistance produced by pathogens.From the current scenario it can be imagine that this field of research will enter into the pre-antibiotic era. This work aims to study and evaluate the preliminary antibacterial, anthelmintic and cytotoxic potentials of ethyl 3-oxo-2-(2,5-dioxopyrrolidin-3-yl)butanoates.Among all of the four compounds, compound 2 has displayed remarkable potency with MIC values of 0.125, 0.083, 0.073 and 0.109 mg/ml against E. sakazakii, E. coli. S. aureus and K. pneumonia respectively. Compared to etoposide (LC50 9.8 µg/ml), the compounds demonstrated LC50 values from 280 to 765 µg/ml. For anthelmintic assay, three concentrations of each compound and standard drug were studied in determination of time of death of the two species. Excellent anthelmintic activity was observed by all four compounds against P. posthuma and A. gallibetter than standard albendazole. High GOLD fitness score data from docking analysis towards the targets represent better protein–ligand binding affinity and thus indicate a high propensity for all the active compounds to bind to the active site.Thepromisingin-vitro antimicrobial, anthelmintic activity and cytotoxicity data conclusively revealed that these compounds may serve as viable lead compounds for the treatment of bacterial and parasitic infections, and therefore, could help the medicinal chemists to design future chemotherapeutic agents to avoid rapid drug resistance.

  9. Measurement and Estimation of the 99Mo Production Yield by 100Mo(n,2n)99Mo

    Science.gov (United States)

    Minato, Futoshi; Tsukada, Kazuaki; Sato, Nozomi; Watanabe, Satoshi; Saeki, Hideya; Kawabata, Masako; Hashimoto, Shintaro; Nagai, Yasuki

    2017-11-01

    We, for the first time, measured the yield of 99Mo, the mother nuclide of 99mTc used in nuclear medicine diagnostic procedures, produced by the 100Mo(n,2n)99Mo reaction with accelerator neutrons. The neutrons with a continuous energy spectrum from the thermal energy up to about 40 MeV were provided by the C(d,n) reaction with 40 MeV deuteron beams. It was proved that the 99Mo yield agrees with that estimated by using the latest data on neutrons from the C(d,n) reaction and the evaluated cross section of the 100Mo(n,2n)99Mo reaction given in the Japanese Evaluated Nuclear Data Library. On the basis of the agreement, a systematic calculation was carried out to search for an optimum condition that enables us to produce as much 99Mo as possible with a good 99Mo/100Mo value from an economical point of view. The calculated 99Mo yield from a 150 g 100MoO3 sample indicated that about 30% of the demand for 99Mo in Japan can be met with a single accelerator capable of 40 MeV, 2 mA deuteron beams. Here, by referring to an existing 18F-fluorodeoxyglucose (FDG) distribution system we assumed that 99mTc radiopharmaceuticals formed after separating 99mTc from 99Mo can be delivered to hospitals from a radiopharmaceutical company within 6 h. The elution of 99mTc from 99Mo twice a day would meet about 50% of the demand for 99Mo.

  10. Single-molecule magnetism in a single-ion triamidoamine uranium(V) terminal mono-oxo complex

    Energy Technology Data Exchange (ETDEWEB)

    King, David M.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [Nottingham Univ. (United Kingdom). School of Chemistry; Tuna, Floriana; McInnes, Eric J.L. [Manchester Univ. (United Kingdom). School of Chemistry

    2013-04-26

    Straightforward oxidation of a triamidoamine uranium(III) complex with trimethyl-N-oxide affords a uranium(V) terminal mono-oxo complex which is the first clear-cut example of a uranium(V) single-molecule magnet (SMM). This monometallic complex unambiguously shows that a strongly axially ligated and thus anisotropic ligand field can be used to overcome the limited magnetic anisotropy of uranium(V). [German] Die direkte Oxidation eines Triamidoamin-Uran(III)-Komplexes mit Trimethyl-N-oxid liefert einen terminalen Uran(V)-Mono(oxo)komplex, der das erste gesicherte Beispiel eines Uran(V)-Einzelmolekuelmagnets ist. Dieser monometallische Komplex zeigt eindeutig, dass ein starkes axiales und somit anisotropes Ligandenfeld die begrenzte magnetische Anisotropie von Uran(V) beseitigen kann.

  11. Synthesis and Microbiological Activity of Some Newly Synthesized Derivatives of 2-Oxo-2H-chromen-2-one

    OpenAIRE

    Daci-Ajvazi, Majlinda; Govori, Sevdije; Omeragiq, Shuhreta

    2011-01-01

    By the action of 2-amino-5-methylthio-1,3,4-thiadiazole, 3-amino-5-methylisoxazole, 2-amino-6-fluorobenzothiazole, 2-amino-5-chloropyridine, respectively, on 4-chloro-2-oxo-2H-chromene-3-sulfonyl chloride, the corresponding 9-methylthio-7,7-dioxo-7,7a-dihydro-5-oxo-7λ6,10-dithia-8,11-diaza-cyclopenta[b] phenantren-6-one, 9-methyl-7,7-dioxo-7H-5,8-dioxa-7λ6-thia-7a,11-diaza-cyclopenta[b] phenantren-6-one, 9-fluoro-7,7-dioxo-7H-5-oxa-7λ6,12-dithia-7a,13-diaza-indeno[1,2-b] phenantren-6-one and ...

  12. Synthesis of deuterium-labeled analogs of the lipid hydroperoxide-derived bifunctional electrophile 4-oxo-2(E)-nonenal

    OpenAIRE

    Arora, Jasbir S.; Oe, Tomoyuki; Blair, Ian A.

    2011-01-01

    Lipid hydroperoxides undergo homolytic decomposition into the bifunctional 4-hydroxy-2(E)-nonenal and 4-oxo-2(E)-nonenal (ONE). These bifunctional electrophiles are highly reactive and can readily modify intracellular molecules including glutathione (GSH), deoxyribonucleic acid (DNA) and proteins. Lipid hydroperoxide-derived bifunctional electrophiles are thought to contribute to the pathogenesis of a number of diseases. ONE is an α,β-unsaturated aldehyde that can react in multiple ways and w...

  13. Synthesis of 1-Methyl-3-oxo-7-oxabicyclo[2.2.1]hept-5-ene-2-carboxylic Acid Methyl Ester

    Directory of Open Access Journals (Sweden)

    Gil Valdo José da Silva

    2005-11-01

    Full Text Available A simple and efficient method for the preparation of 1-methyl-3-oxo-7- oxabicyclo[2.2.1]hept-5-en-2-carboxylic acid methyl ester (1 is described. The first step is a highly regioselective Diels-Alder reaction between 2-methylfuran and methyl-3-bromo- propiolate. A remarkably difficult ketal hydrolysis reaction was effected by treatment with HCl, a simple reagent that was shown to be more efficient, in this case, than commonly used more elaborate methods.

  14. Synthesis, structure and properties of oxo- and dioxochloride complexes of molybdenum(VI) and tungsten(VI) with 8-oxyquinoline

    International Nuclear Information System (INIS)

    Abramenko, V.L.; Sergienko, V.S.; Egorova, O.A.

    2005-01-01

    Complexes of oxo- and dioxochlorides of molybdenum(VI) and tungsten(VI) with 8-oxyquinoline of molecular and intracomplex type are synthesized and studied by the method of IR spectroscopy. The complexes have octahedral structure. It is proposed that 8-oxyquinoline in molecular complexes is coordinated by central atom through nitrogen atom of heterocycle, but in intracomplex compounds - through heterocyclic nitrogen atom and oxygen atom of deprotonated OH-group. Thermal stability of the complexes is studied [ru

  15. Comparative study of reactions between µ-nitrido- or µ-oxo-bridged iron tetrasulfophthalocyanines and sulfur-containing reductants

    Directory of Open Access Journals (Sweden)

    Dereven’kov Ilia A.

    2013-01-01

    Full Text Available A comparative study of reactivity of μ-nitrido- and μ-oxo-dimers of iron tetrasulfophthalocyanine has been performed in aqueous solutions of various acidity. The substantially higher stability of nitrido-bridged structure under both strongly acidic and strongly alkaline environments was demonstrated. Reactions of the complexes with sulfur-containing reductants (sodium dithionite, thiourea dioxide, sodium hydroxymethanesulfinate, L-cysteine has been studied. Differences in reduction processes were explained.

  16. Single-molecule magnetism in a single-ion triamidoamine uranium(V) terminal mono-oxo complex

    International Nuclear Information System (INIS)

    King, David M.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.; Tuna, Floriana; McInnes, Eric J.L.

    2013-01-01

    Straightforward oxidation of a triamidoamine uranium(III) complex with trimethyl-N-oxide affords a uranium(V) terminal mono-oxo complex which is the first clear-cut example of a uranium(V) single-molecule magnet (SMM). This monometallic complex unambiguously shows that a strongly axially ligated and thus anisotropic ligand field can be used to overcome the limited magnetic anisotropy of uranium(V). [de

  17. (E-3-Methyl-6-(3-oxo-3-(thiophen-2-yl-1-propenyl-2(3H-benzothiazolone

    Directory of Open Access Journals (Sweden)

    Yordanka Ivanova

    2016-04-01

    Full Text Available The title compound, (E-3-methyl-6-(3-oxo-3-(thiophen-2-yl-1-propenyl-2(3H-benzothiazolone, was synthesized by Claisen-Schmidt condensation of 3-methyl-2(3H-benzothiazolone-6-carbaldehyde with 2-acetylthiophene in 94% yield. The structure of the target compound was confirmed using 1H-NMR, 13C-NMR, IR, MS, and elemental analysis.

  18. Carboxylate ligands drastically enhance the rates of oxo exchange and hydrogen peroxide disproportionation by oxo manganese compounds of potential biological significance.

    Science.gov (United States)

    Dubois, Lionel; Pécaut, Jacques; Charlot, Marie-France; Baffert, Carole; Collomb, Marie-Noëlle; Deronzier, Alain; Latour, Jean-Marc

    2008-01-01

    To mimic the carboxylate-rich active site of the manganese catalases more closely we introduced carboxylate groups into dimanganese complexes in place of nitrogen ligands. The series of dimanganese(III,IV) complexes of tripodal ligands [Mn(2)(L)(2)(O)(2)](3+/+/-/3-) was extended from those of tpa (1) and H(bpg) (2) to those of H(2)(pda) (3) and H(3)(nta) (4) (tpa=tris-picolylamine, H(bpg)=bis-picolylglycylamine, H(2)(pda)=picolyldiglycylamine, H(3)(nta)=nitrilotriacetic acid). While 3 [Mn(2)(pda)(2)(O)(2)][Na(H(2)O)(3)] could be synthesized at -20 degrees C and characterized in the solid state, 4 [Mn(2)(nta)(2)(O)(2)](3-) could be obtained and studied only in solution at -60 degrees C. A new synthetic procedure for the dimanganese(III,III) complexes was devised, using stoichiometric reduction of the dimanganese(III,IV) precursor by the benzil radical with EPR monitoring. This enabled the preparation of the parent dimanganese(III,III) complex 5 [Mn(2)(tpa)(2)(O)(2)](ClO(4))(2), which was structurally characterized. The UV/visible, IR, EPR, magnetic, and electrochemical properties of complexes 1-3 and 5 were analyzed to assess the electronic changes brought about by the carboxylate replacement of pyridine ligands. The kinetics of the oxo ligand exchanges with labeled water was examined in acetonitrile solution. A dramatic effect of the number of carboxylates was evidenced. Interestingly, the influence of the second carboxylate substitution differs from that of the first one probably because this substitution occurs on an out-of-plane coordination while the former occurs in the plane of the [Mn(2)O(2)] core. Indeed, on going from 1 to 3 the exchange rate was increased by a factor of 50. Addition of triethylamine caused a rate increase for 1, but not for 3. The abilities of 1-3 to disproportionate H(2)O(2) were assessed volumetrically. The disproportionation exhibited a sensitivity corresponding to the carboxylate substitution. These observations strongly suggest that

  19. Synergistic complexes of uranyl ion with 1-phenyl-3-methyl-4-acetyl-pyrazolone-5 and some oxo-donors

    International Nuclear Information System (INIS)

    Nagar, M.S.; Ruikar, P.B.; Subramanian, M.S.

    1987-01-01

    Complexes of uranyl ion with 1-phenyl-3-methyl-4-acetyl-pyrazolone-5(PMAP) and various oxo-donors such as aliphatic sulphoxides [R 2 SO, where R = i-C 5 H 11 (DISO), n-C 6 H 13 (DHSO), n-C 7 H 15 (DSSO), n-C 8 H 17 (DOSO), n-C 9 H 19 (DNSO), n-C 10 H 21 (DDSO), n-C 11 H 23 (DUDSO) and n-C 4 H 9 (DBUSO)] tributylphosphate (TBP) and tri-n-octyl phosphine oxide (TOPO) have been synthesised and characterized. Analytical data establish that they have the stoichiometry UO 2 (PMAP) 2 X where X is the oxo-donor. The IR spectra of the sulphoxide complexes in the S - O stretching region indicate that the ligands R 2 SO are O-bonded. The methyl protons of the pyrazole ring and acetyl group in the PMAP ligand are equivalent giving rise to a single sharp peak in the PMR spectra, whereas in the synergistic complexes with the oxo-donors, two deshielded peaks of equal intensity are observed which indicate the non-equivalence of the methyl groups. The peak which is more deshielded has been ascribed to the methyl of the acetyl group. The higher deshielding of these methyl protons arises due to the transfer of electron density to the metal atom on complexation. (author)

  20. SBA-15-functionalized 3-oxo-ABNO as recyclable catalyst for aerobic oxidation of alcohols under metal-free conditions.

    Science.gov (United States)

    Karimi, Babak; Farhangi, Elham; Vali, Hojatollah; Vahdati, Saleh

    2014-09-01

    The nitroxyl radical 3-oxo-9-azabicyclo [3.3.1]nonane-N-oxyl (3-oxo-ABNO) has been prepared using a simple protocol. This organocatalyst is found to be an efficient catalyst for the aerobic oxidation of a wide variety of alcohols under metal-free conditions. In addition, the preparation and characterization of a supported version of 3-oxo-ABNO on ordered mesoporous silica SBA-15 (SABNO) is described for the first time. The catalyst has been characterized using several techniques including simultaneous thermal analysis (STA), transmission electron microscopy (TEM), and nitrogen sorption analysis. This catalyst exhibits catalytic performance comparable to its homogeneous analogue and much superior catalytic activity in comparison with (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) for the aerobic oxidation of almost the same range of alcohols under identical reaction conditions. It is also found that SABNO can be conveniently recovered and reused at least 12 times without significant effect on its catalytic efficiency. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Poly[[[[1-ethyl-6,8-difluoro-7-(3-methylpiperazin-1-yl-4-oxo-1,4-dihydroquinoline-3-carboxylato]cadmium]-μ-benzene-1,4-dicarboxylato] trihydrate

    Directory of Open Access Journals (Sweden)

    Xin-Ping Kang

    2010-11-01

    Full Text Available In the title layered coordination polymer, {[Cd(C17H18F2N3O3(C8H4O4]·3H2O}n, the CdII atom exhibits a very distorted CdO6 octahedral geometry defined by one O3,O4-bidentate 1-ethyl-6,8-difluoro-7-(3-methylpiperazin-1-yl-4-oxo-1,4-dihydroquinoline-3-carboxylate (lome ligand, one O,O′-bidentate benzene-1,4-dicarboxylate (bdc dianion and two O-monodentate bdc dianions. Both the bdc species in the asymmetric unit are completed by crystallographic inversion symmetry. The bridging bdc dianions link the cadmium nodes into a rectangular grid lying parallel to (01overline{1}. A network of N—H...O and O—H...O hydrogen bonds helps to establish the packing.

  2. Effects of surface acidities of MCM-41 modified with MoO{sub 3} on adsorptive desulfurization of gasoline

    Energy Technology Data Exchange (ETDEWEB)

    Shao Xinchao, E-mail: sxc86@yahoo.cn [Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning ShiHua University, Fushun 113001 (China); Zhang Xiaotong; Yu Wenguang; Wu Yuye [Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning ShiHua University, Fushun 113001 (China); Qin Yucai [Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning ShiHua University, Fushun 113001 (China); College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao, Shandong 257061 (China); Sun Zhaolin [Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning ShiHua University, Fushun 113001 (China); School of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Song Lijuan, E-mail: lsong56@263.net [Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning ShiHua University, Fushun 113001 (China) and College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao, Shandong 257061 (China)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer The MoO{sub 3}-MCM-41 samples prepared by spontaneous monolayer dispersion and impregnation with a different MoO{sub 3} filling have been studied. Black-Right-Pointing-Pointer The relative concentration of hydroxyl groups present on before and after containing MoO{sub 3} samples was monitored by in situ FTIR to speculate the bonding style of MoO{sub 3} and MCM-41. Black-Right-Pointing-Pointer The surface acidities of the MoO{sub 3}-MCM-41 adsorbents were investigated systematically and correlated with the desulfurization performance. - Abstract: A series of MCM-41 samples containing molybdenum oxide as active species in the mesoporous channels loaded by spontaneous monolayer dispersion (SMD) and impregnation (IM) have been prepared and characterized using XRD, N{sub 2} adsorption-desorption analysis, Fourier transform infrared spectroscopy (FTIR) and intelligent gravimetric analyzer (IGA). The relative number of hydroxy on the adsorbents was investigated by in situ FTIR. Surface acidities of the adsorbents were studied by infrared spectroscopy of adsorbed pyridine and correlated with reactivity for adsorptive desulfurization. The IGA technique was employed to investigate adsorption behavior of thiophene and benzene on the adsorbents at 303 K. It is shown that MoO{sub 3} can be highly dispersed up to 0.2 g g{sup -1} in the MCM-41 channels by the SMD strategy with the ordered mesoporous structure of the MoMM samples remaining intact. The ordered mesostructure of MCM-41 is, however, destroyed at higher MoO{sub 3} contents of 0.26 and 0.32 g g{sup -1} with particle sizes of 1.2 nm and 3.6 nm, respectively, observed. For the MoMI(0.2) sample prepared by the IM method, the aggregation of the MoO{sub 3} particles takes place with a particle size of 6.5 nm obtained. The results are also revealed that the dispersion extent of the MoO{sub 3} species is related to the abundant surface hydroxy of MCM-41. The host species and guest

  3. Effects of surface acidities of MCM-41 modified with MoO3 on adsorptive desulfurization of gasoline

    International Nuclear Information System (INIS)

    Shao Xinchao; Zhang Xiaotong; Yu Wenguang; Wu Yuye; Qin Yucai; Sun Zhaolin; Song Lijuan

    2012-01-01

    Highlights: ► The MoO 3 -MCM-41 samples prepared by spontaneous monolayer dispersion and impregnation with a different MoO 3 filling have been studied. ► The relative concentration of hydroxyl groups present on before and after containing MoO 3 samples was monitored by in situ FTIR to speculate the bonding style of MoO 3 and MCM-41. ► The surface acidities of the MoO 3 -MCM-41 adsorbents were investigated systematically and correlated with the desulfurization performance. - Abstract: A series of MCM-41 samples containing molybdenum oxide as active species in the mesoporous channels loaded by spontaneous monolayer dispersion (SMD) and impregnation (IM) have been prepared and characterized using XRD, N 2 adsorption–desorption analysis, Fourier transform infrared spectroscopy (FTIR) and intelligent gravimetric analyzer (IGA). The relative number of hydroxy on the adsorbents was investigated by in situ FTIR. Surface acidities of the adsorbents were studied by infrared spectroscopy of adsorbed pyridine and correlated with reactivity for adsorptive desulfurization. The IGA technique was employed to investigate adsorption behavior of thiophene and benzene on the adsorbents at 303 K. It is shown that MoO 3 can be highly dispersed up to 0.2 g g −1 in the MCM-41 channels by the SMD strategy with the ordered mesoporous structure of the MoMM samples remaining intact. The ordered mesostructure of MCM-41 is, however, destroyed at higher MoO 3 contents of 0.26 and 0.32 g g −1 with particle sizes of 1.2 nm and 3.6 nm, respectively, observed. For the MoMI(0.2) sample prepared by the IM method, the aggregation of the MoO 3 particles takes place with a particle size of 6.5 nm obtained. The results are also revealed that the dispersion extent of the MoO 3 species is related to the abundant surface hydroxy of MCM-41. The host species and guest species undergo solid-state reaction to form Si-O-Mo bonds in the mixtures which enhance both the Lewis acid and Brönsted acid of

  4. Retention data of bile acids and their oxo derivatives in characterization of pharmacokinetic properties and in silico ADME modeling.

    Science.gov (United States)

    Trifunović, Jovana; Borčić, Vladan; Vukmirović, Saša; Kon, Svetlana Goločorbin; Mikov, Momir

    2016-09-20

    Information on ADME properties of examined bile acids and their oxo derivatives are scarce, although the interest for bile acids and their use in nanochemistry and macromolecular chemistry is increasing. The purpose of this research was to evaluate the lipophilicity, a crucial physicochemical parameter for describing ADME properties of selected bile acids and their oxo derivatives, and to compare two approaches: experimentally determined hydrophobicity parameters and calculated logP values. Commercially available bile acids - deoxycholic, chenodeoxycholic, hyodeoxycholic and ursodeoxycholic acid were used to synthesize oxo derivatives. Lipophilicity was evaluated in two solvent systems: toluene/ethanol and toluene/butanol. Retention parameters were acquired by normal-phase TLC. The correlations between calculated logP values obtained using five different software and experimentally determined hydrophobicity parameters (RM(0)(tol/eth), RM(0)(tol/but), b(tol/eth) and b(tol/but)) were examined. Correlation analysis confirmed significant dependence between experimental RM(0) values and software calculated parameters. Results suggest satisfactory intestinal absorption after oral administration for all of the examined compounds as well as low volumes of distribution, and high affinity for binding with plasma proteins. Penetration through blood-brain barrier and skin is not satisfactory. All of the examined compounds show high affinity for binding with G-protein coupled receptors and consequently inhibition of ionic channels. Results also suggest possible binding with nuclear receptors. Established lipophilicity testing model of studied compounds showed excellent predictive ability and might represent significant tool in development of relations between chromatographic behavior and ADME properties. Compounds 3α-hydroxy-7,12-dioxo-5β-cholanoic and 12α-hydroxy-3,7-dioxo-5β-cholanoic acid might be the most suitable candidates for further development studies (satisfactory

  5. Causes and consequences of plant radio-resistance. Formation of DNA basis lesions and self-repairing activity of one of them, the 8-oxo-7,8-dihydro-guanine in Arabidopsis thaliana

    International Nuclear Information System (INIS)

    Dany, A.L.

    2001-01-01

    In this research thesis, the author first explains how and why DNA is injured when it is submitted to an oxidizing stress, and describes precisely the formation and the biological consequences of lesions of DNA bases, the 8-oxo-7,8-dihydro-guanine (8-oxoGua). She describes the repairing activities of the oxidized DNA, and more particularly the repairing of 8-oxoGua, in prokaryotes as well as in yeast, mammals and plants. Methodologies used are described, together with the repair activities of the 8-oxo-7,8-dihydro-guanine following a biochemical type approach and a molecular biology approach

  6. Aging and defense against generation of 8-oxo-7,8-dihydro-2'-deoxyguanosine in DNA

    DEFF Research Database (Denmark)

    Mikkelsen, Lone; Bialkowski, Karol; Risom, Lotte

    2009-01-01

    damaged DNA and the activity of the DNA repair system and 8-oxo-7,8-dihydro-2'-deoxyguanosine 5'-triphosphate pyrophosphohydrolase (8-oxodGTPase) activity in liver and lung tissue from mice at 10-100 weeks of age. The level of 8-oxodG increased with age, whereas the level of formamidopyrimidine DNA...... glycosylase sites was unaltered. The enzyme activity toward single oxygen-induced DNA damage and mRNA expression levels of Ercc1, Neil1, and Ogg1 remained unaltered with age. However, the 8-oxodGTPase activity in the liver was 18% (95% CI: 0.2-37%) lower in mice at 25 and 50 weeks than in 10-week-old mice....... The 10- and 100-week-old mice had similar 8-oxodGTPase activity. In contrast, the mRNA expression of Nudt1 was statistically unaltered that likely resulted from higher variation of measurements. The accumulation of 8-oxodG with age is not a direct consequence of decreased enzyme activity toward singlet...

  7. Chemoproteomics Reveals Chemical Diversity and Dynamics of 4-Oxo-2-nonenal Modifications in Cells.

    Science.gov (United States)

    Sun, Rui; Fu, Ling; Liu, Keke; Tian, Caiping; Yang, Yong; Tallman, Keri A; Porter, Ned A; Liebler, Daniel C; Yang, Jing

    2017-10-01

    4-Oxo-2-nonenal (ONE) derived from lipid peroxidation modifies nucleophiles and transduces redox signaling by its reactions with proteins. However, the molecular interactions between ONE and complex proteomes and their dynamics in situ remain largely unknown. Here we describe a quantitative chemoproteomic analysis of protein adduction by ONE in cells, in which the cellular target profile of ONE is mimicked by its alkynyl surrogate. The analyses reveal four types of ONE-derived modifications in cells, including ketoamide and Schiff-base adducts to lysine, Michael adducts to cysteine, and a novel pyrrole adduct to cysteine. ONE-derived adducts co-localize and exhibit crosstalk with many histone marks and redox sensitive sites. All four types of modifications derived from ONE can be reversed site-specifically in cells. Taken together, our study provides much-needed mechanistic insights into the cellular signaling and potential toxicities associated with this important lipid derived electrophile. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  8. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [Edinburgh Univ. (United Kingdom). EaStCHEM School of Chemistry

    2012-12-07

    The silylated uranium(V) dioxo complex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] is inert to oxidation, but after two-electron reduction to [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-}, it can be desilylated to form [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U{sup VI/V} couple in dioxygen reduction. [German] Der silylierte Dioxouran(V)-Komplex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] (A) ist inert gegen Oxidation, kann aber nach Zweielektronenreduktion zu [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-} (1) zu [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} (2) mit wiederhergestelltem Uranylcharakter desilyliert werden. Beim Entfernen der Silylgruppe zeigt sich eine neue Redox- und Oxoumlagerungschemie des Urans unter Rueckbildung des Uranylmotivs sowie der Beteiligung des U{sup VI/V}-Paars an einer Disauerstoffreduktion.

  9. Direct evidence for the inactivation of branched-chain oxo-acid dehydrogenase by enzyme phosphorylation

    International Nuclear Information System (INIS)

    Odessey, R.

    1980-01-01

    The branched-chain 2-oxo-acid dehydrogenase (BCOAD) from mitochondria of several different rat tissues is inactivated by ATP and can be reactivated by incubation in Mg 2+ -containing buffers. Work carried out on the system from skeletal muscle mitochondria has shown that inactivation requires the cleavage of the γ-phosphate group of ATP and that modification is covalent. The non-metabolized ATP analog, p[NH]ppA, can block the inhibitory effect of ATP when added prior to ATP addition, but cannot reverse the inhibition of the inactivated dehydrogenase. These and other data raise the possibility that BCOAD may be regulated by enzyme phosphorylation. This hypothesis is supported by the finding that various procedures which separate the enzyme from its mitochondrial environment (e.g. detergent treatment, ammonium sulfate precipitation and freeze-thawing) do not alter the degree of inhibition induced by ATP in the mitochondrial preincubation. These experiments suggested the feasibility of labelling the enzyme with 32 P and purifying it. (Auth.)

  10. Redox-controlled dinitrosyl formation at the diiron-oxo center of NorA.

    Science.gov (United States)

    Cramm, Rainer; Strube, Katja

    2008-01-01

    In the denitrifying bacterium Ralstonia eutropha H16, the NorA protein is coproduced with the respiratory nitric oxide (NO) reductase. NorA contains a diiron-oxo center, which can form stable adducts with dioxygen and NO. In contrast to other diiron proteins, the formation of NorA-NO requires both fully reduced protein and additional electrons. A minor fraction of in vitro NorA-NO represents a paramagnetic dinitrosyl iron complex (DNIC), while the major fraction is attributed to a DNIC of the structure {Fe(NO)(2)}, which shows no electron paramagnetic resonance. The NorA-DNIC may be formed either upon direct reaction of the protein with NO or upon incubation with nitrite due to an intrinsic nitrite reduction activity of NorA that liberates NO. NorA can be purified rapidly as a six histidine-tagged derivative from overproducing cells of Escherichia coli. This chapter describes procedures for the preparation of different redox forms of NorA for the formation of NorA adducts with NO, dioxygen, and azide, as well as for the quantification of NorA-bound NO.

  11. Polynuclear Iron-Oxo/Hydroxy Complexes of Ketoacidoximate Ligands: Synthesis, Structures and Conversion to Ferric Oxide

    KAUST Repository

    Davaasuren, Bambar

    2017-06-13

    The polynuclear iron-oxo/hydroxy complexes containing ketoacidoximate ligands described in this report are [Fe3(μ3-O){O2C-C(C6H5)=NOCH3}6(py)3] (1) (py=pyridine), [Fe2(μ3-O){O2C-C(CH2-C6H5)=NO}2(H2O)(CH3OH)]2 (2) and [{Fe(μ2-OH)(O2C-C(CH3)=NO)}(dmso)]6 (3) (dmso=dimethyl sulfoxide). 1–3 are isolated from the reaction of Fe(NO3)3⋅9H2O and in situ generated anions of ketoacidoximate ligand [(HO2C-C(R1)=NOR2), where R1=CH3, C6H5 and CH2-C6H5; R2=H or CH3] in H2O, followed by crystallization in donor solvents. 1–3 undergo thermal decomposition above 200 °C and form crystalline α-Fe2O3 at 600 °C.

  12. Cis-12-oxo-phytodienoic acid stimulates rice defense response to a piercing-sucking insect.

    Science.gov (United States)

    Guo, Hui-Min; Li, Hai-Chao; Zhou, Shi-Rong; Xue, Hong-Wei; Miao, Xue-Xia

    2014-11-01

    The brown planthopper (BPH, Nilaparvata lugens) is a destructive, monophagous, piercing-sucking insect pest of rice. Previous studies indicated that jasmonic acid (JA) positively regulates rice defense against chewing insect pests but negatively regulates it against the piercing-sucking insect of BPH. We here demonstrated that overexpression of allene oxide cyclase (AOC) but not OPR3 (cis-12-oxo-phytodienoic acid (OPDA) reductase 3, an enzyme adjacent to AOC in the JA synthetic pathway) significantly increased rice resistance to BPH, mainly by reducing the feeding activity and survival rate. Further analysis revealed that plant response to BPH under AOC overexpression was independent of the JA pathway and that significantly higher OPDA levels stimulated rice resistance to BPH. Microarray analysis identified multiple candidate resistance-related genes under AOC overexpression. OPDA treatment stimulated the resistance of radish seedlings to green peach aphid Myzus persicae, another piercing-sucking insect. These results imply that rice resistance to chewing insects and to sucking insects can be enhanced simultaneously through AOC-mediated increases of JA and OPDA and provide direct evidence of the potential application of OPDA in stimulating plant defense responses to piercing-sucking insect pests in agriculture. © The Author 2014. Published by the Molecular Plant Shanghai Editorial Office in association with Oxford University Press on behalf of CSPB and IPPE, SIBS, CAS.

  13. Synthesis, spectroscopic and DFT studies of novel 4-(morpholinomethyl)-5-oxo-1-phenylpyrrolidine-3-carboxylic acid

    Science.gov (United States)

    Devi, Poornima; Fatma, Shaheen; Bishnoi, Abha; Srivastava, Krishna; Shukla, Shraddha; Kumar, Roop

    2018-04-01

    A novel 4-(morpholinomethyl)-5-oxo-1-phenylpyrrolidine-3-carboxylic acid has been synthesized and its structural elucidation has been done by UV, FT-IR, 1H and 13C NMR spectroscopy. All quantum chemical calculations were carried out at level of density functional theory (DFT) with B3LYP function using 6-31G (d, p) basis atomic set. AIM approach has been incorporated for the analysis of various intermolecular interactions. Polarizability and hyperpolarizabilities values have been calculated along with the exploration of nonlinear optical properties of the title compound. DFT computed total first static hyperpolarizability (β0 = 0.2747 × 10-30 esu) indicates that title molecule could be an area of interest as an attractive future NLO material. For the analysis of thermal behaviour of title molecule, thermodynamic properties such as heat capacity, entropy and enthalpy change at various temperatures have been calculated. The NBO computations were done for the correlation of possible transitions with the electronic transitions. Electrophilic and nucleophilic regions were identified with the help of MESP plot. Determination of energy gap has been done by using HOMO and LUMO energy values, along with the computation of electronegativity and electrophilicity indices.

  14. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

    KAUST Repository

    Qureshi, Ziyauddin

    2017-01-05

    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  15. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

    KAUST Repository

    Qureshi, Ziyauddin; Hamieh, Ali Imad Ali; Barman, Samir; Maity, Niladri; Samantaray, Manoja; Ould-Chikh, Samy; Abou-Hamad, Edy; Falivene, Laura; D’ Elia, Valerio; Rothenberger, Alexander; Llorens, Isabelle; Hazemann, Jean-Louis; Basset, Jean-Marie

    2017-01-01

    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  16. Ternary system of Na2MoO4-Cs2MoO4-MoO3

    International Nuclear Information System (INIS)

    Zueva, V.P.; Shabanova, A.N.; Drobasheva, T.I.

    1982-01-01

    Using the methods of thermal analysis interaction of components in ternary system Na 2 MoO 4 -Cs 2 MoO 4 -MoO 3 has been studied. Crystallization surface consists of nine fields belonging to initial components and compounds of lateral sides. Triangulation of the system is carried out and the character of nonvariant points is clarified, the temperature of 360 deg C corresponds to low-melting eutectics

  17. Interplay of Electronic Cooperativity and Exchange Coupling in Regulating the Reactivity of Diiron(IV)-oxo Complexes towards C-H and O-H Bond Activation.

    Science.gov (United States)

    Ansari, Azaj; Ansari, Mursaleem; Singha, Asmita; Rajaraman, Gopalan

    2017-07-26

    Activation of inert C-H bonds such as those of methane are extremely challenging for chemists but in nature, the soluble methane monooxygenase (sMMO) enzyme readily oxidizes methane to methanol by using a diiron(IV) species. This has prompted chemists to look for similar model systems. Recently, a (μ-oxo)bis(μ-carboxamido)diiron(IV) ([Fe IV 2 O(L) 2 ] 2+ L=N,N-bis-(3',5'-dimethyl-4'-methoxypyridyl-2'-methyl)-N'-acetyl-1,2-diaminoethane) complex has been generated by bulk electrolysis and this species activates inert C-H bonds almost 1000 times faster than mononuclear Fe IV =O species and at the same time selectively activates O-H bonds of alcohols. The very high reactivity and selectivity of this species is puzzling and herein we use extensive DFT calculations to shed light on this aspect. We have studied the electronic and spectral features of diiron {Fe III -μ(O)-Fe III } +2 (complex I), {Fe III -μ(O)-Fe IV } +3 (II), and {Fe IV -μ(O)-Fe IV } +4 (III) complexes. Strong antiferromagnetic coupling between the Fe centers leads to spin-coupled S=0, S=3/2, and S=0 ground state for species I-III respectively. The mechanistic study of the C-H and O-H bond activation reveals a multistate reactivity scenario where C-H bond activation is found to occur through the S=4 spin-coupled state corresponding to the high-spin state of individual Fe IV centers. The O-H bond activation on the other hand, occurs through the S=2 spin-coupled state corresponding to an intermediate state of individual Fe IV centers. Molecular orbital analysis reveals σ-π/π-π channels for the reactivity. The nature of the magnetic exchange interaction is found to be switched during the course of the reaction and this offers lower energy pathways. Significant electronic cooperativity between two metal centers during the course of the reaction has been witnessed and this uncovers the reason behind the efficiency and selectivity observed. The catalyst is found to prudently choose the desired spin

  18. Physical and chemical transformations of μ-oxo dimers and alkoxy complexes of Fe-octaethylporphyrins in solids and in solutions

    Science.gov (United States)

    Ivashin, N. V.; Shulga, A. M.; Terekhov, S. N.; Dzilinski, K.

    1996-11-01

    It has been found that relatively small changes in conditions of crystallization in the synthesis process of μ-oxo dimers can lead to quite different products with dimeric or monomeric structures. Molecular structures of these products, discussed on the basis of Fe-octaethylporphyrin (FeOEP) complexes, have been studied using IR, NMR, EPR, resonance Raman (RR), mass and Mössbauer spectroscopies. The use of chloroform with admixture of alcohols (methanol, deuteromethanol and ethanol) in place of pure chloroform for crystallization of the eluate obtained during synthesis of μ-oxo dimers leads to the formation of alkoxy complexes instead of the μ-oxo dimers. It has been also established that dissolution of the μ-oxo dimers in chloroform-ethanol or chloroform-methanol mixtures leads to conversion of the μ-oxo dimers into the alkoxy complexes after evaporation of the solvents. Methoxy and ethoxy ligands in Fe(OEP)OCH 3 and Fe(OEP)OC 2H 5 complexes can exchange the positions during addition of ethanol to the former and methanol to the latter complex in solution. The possibility of generation of doubly bridged structures of the type: OEP Fe< RRFe OEP where R is OCH 3 or OC 2H 5 is discussed.

  19. Possible doping strategies for MoS 2 monolayers: An ab initio study

    KAUST Repository

    Dolui, Kapildeb; Rungger, Ivan; Das Pemmaraju, Chaitanya; Sanvito, Stefano

    2013-01-01

    Density functional theory is used to systematically study the electronic properties of doped MoS2 monolayers, where the dopants are incorporated both via S/Mo substitution or as adsorbates. Among the possible substitutional dopants at the Mo site, Nb is identified as suitable p-type dopant, while Re is the donor with the lowest activation energy. When dopants are simply adsorbed on a monolayer we find that alkali metals shift the Fermi energy into the MoS2 conduction band, making the system n type. Finally, the adsorption of charged molecules is considered, mimicking an ionic liquid environment. We find that molecules adsorption can lead to both n- and p-type conductivity, depending on the charge polarity of the adsorbed species. © 2013 American Physical Society.

  20. Possible doping strategies for MoS 2 monolayers: An ab initio study

    KAUST Repository

    Dolui, Kapildeb

    2013-08-14

    Density functional theory is used to systematically study the electronic properties of doped MoS2 monolayers, where the dopants are incorporated both via S/Mo substitution or as adsorbates. Among the possible substitutional dopants at the Mo site, Nb is identified as suitable p-type dopant, while Re is the donor with the lowest activation energy. When dopants are simply adsorbed on a monolayer we find that alkali metals shift the Fermi energy into the MoS2 conduction band, making the system n type. Finally, the adsorption of charged molecules is considered, mimicking an ionic liquid environment. We find that molecules adsorption can lead to both n- and p-type conductivity, depending on the charge polarity of the adsorbed species. © 2013 American Physical Society.

  1. Evaluation of genetic toxicity of 6-diazo-5-oxo-l-norleucine (DON).

    Science.gov (United States)

    Kulkarni, Rohan M; Dakoulas, Emily W; Miller, Ken E; Terse, Pramod S

    2017-09-01

    DON (6-diazo-5-oxo-l-norleucine), a glutamine antagonist, was demonstrated to exhibit analgesic, antibacterial, antiviral and anticancer properties. The study was performed to characterize its in vitro and in vivo genetic toxicity potential. DON was tested in the bacterial reverse mutation assay (Ames test) using Salmonella typhimurium tester strains (TA98, TA100, TA1535 and TA1537) and Escherichia coli tester strain (WP2 uvrA) with and without S9 and also with reductive S9. In addition, DON was tested for the chromosome aberrations in Chinese hamster ovary (CHO) cells with or without S9 to evaluate the clastogenic potential. Furthermore, DON was also evaluated for its in vivo clastogenic activity by detecting micronuclei in polychromatic erythrocyte (PCE) cells in bone marrow collected from the male mice dosed intravenously with 500, 100, 10, 1 and 0.1 mg/kg at 24 and 48-h post-dose. The Ames mutagenicity assay showed no positive mutagenic responses. However, the in vitro chromosome aberration assay demonstrated dose dependent statistically positive increase in structural aberrations at 4 and 20-h exposure without S9 and also at 4-h exposure with S9. The in vivo micronucleus assay also revealed a statistically positive response for micronucleus formation at 500, 100 and 10 mg/kg at 24 and 48-h post-dose. Thus, DON appears to be negative in the Ames test but positive in the in vitro chromosome aberration assay and in the in vivo micronucleus assay. In conclusion, the results indicate DON is a genotoxic compound with a plausible epigenetic mechanism.

  2. Electronic structure of structural open derivatives of the [Mo6X14]2- cluster: [Mo5Cl13]2- and [Mo4I11]2-

    International Nuclear Information System (INIS)

    Miessner, H.; Korol'kov, D.V.

    1983-01-01

    The electronic structure of structural open derivatives of the [Mo 6 X 14 ] 2 - -cluster [Mo 5 Cl 13 ] 2 - and [Mo 4 I 11 ] 2 - has been studied by the EHMO method. In [Mo 5 Cl 13 ] 2 - 9 occupied MO's with dominant Mo4d character are responsible for the formation of the 8 metal-metal bonds. In [Mo 4 I 11 ] 2 - the stronger covalent character of the Mo-I bonds affects the localization and the energy of molecular orbitals and also the charge distribution. The metal-metal bonds are formed by 8 MO's containing considerable participation of halogen AO's contrary to the chloride cluster. There is no bonding between the Mo atoms at the wing tips of the Mo 4 butterfly and the reason for decreasing the dihedral angle between the Mo 3 planes in [Mo 4 I 11 ] 2 - compared with the octahedral angle is apparently the stabilization of the whole system (Mo-Mo and Mo-I bonds). The unpaired electron occupies in both clusters a slightly antibonding (with regard to the Mo-Mo bonds) orbital. (author)

  3. Creep and shrinkage of Mo(Ni)

    International Nuclear Information System (INIS)

    Kaysser, W.A.; Hofmann-Amtenbrink, M.; Petzow, G.

    1984-01-01

    To avoid some of the errors inherent in a quantitative interpretation of shrinkage of powder compacts as Mo-Ni, other experiments were looked for, where the influence of Ni on the material transport properties of Mo could be measured semi-quantitatively during heating up to temperature and subsequent isothermal annealing. The bending of thin Mo foils under small loads was found to be an experimental arrangement, where variations in stress, in Ni-concentration and in intrinsic material properties could be realized. The results of these creep experiments will be compared in a qualitative sense with sintering experiments in Mo-Ni done under similar conditions as the creep experiments

  4. Atom-type-based AI topological descriptors: application in structure-boiling point correlations of oxo organic compounds.

    Science.gov (United States)

    Ren, Biye

    2003-01-01

    Structure-boiling point relationships are studied for a series of oxo organic compounds by means of multiple linear regression (MLR) analysis. Excellent MLR models based on the recently introduced Xu index and the atom-type-based AI indices are obtained for the two subsets containing respectively 77 ethers and 107 carbonyl compounds and a combined set of 184 oxo compounds. The best models are tested using the leave-one-out cross-validation and an external test set, respectively. The MLR model produces a correlation coefficient of r = 0.9977 and a standard error of s = 3.99 degrees C for the training set of 184 compounds, and r(cv) = 0.9974 and s(cv) = 4.16 degrees C for the cross-validation set, and r(pred) = 0.9949 and s(pred) = 4.38 degrees C for the prediction set of 21 compounds. For the two subsets containing respectively 77 ethers and 107 carbonyl compounds, the quality of the models is further improved. The standard errors are reduced to 3.30 and 3.02 degrees C, respectively. Furthermore, the results obtained from this study indicate that the boiling points of the studied oxo compound dominantly depend on molecular size and also depend on individual atom types, especially oxygen heteroatoms in molecules due to strong polar interactions between molecules. These excellent structure-boiling point models not only provide profound insights into the role of structural features in a molecule but also illustrate the usefulness of these indices in QSPR/QSAR modeling of complex compounds.

  5. On the reduction of orthorhombic MoO3 to MoO2

    International Nuclear Information System (INIS)

    Delannay, F.

    1982-01-01

    Electron diffraction shows evidence of topotactic orientation relationships between the original MoO 3 crystal and MoO 2 crystals formed under mild reduction conditions. These relationships differ from previously published literature data. A possible mechanism of formation of the [100] strings of edge sharing octahedra in the MoO 2 structure is tentatively proposed. (author)

  6. Microwave effects on NiMoS and CoMoS single-sheet catalysts.

    Science.gov (United States)

    Borges, I; Silva, Alexander M; Modesto-Costa, Lucas

    2018-05-04

    Single-sheet nanoclusters of MoS 2 , NiMoS or CoMoS are widely used in hydrodesulfurization (HDS) catalysis in the petroleum industry. In HDS reactions under microwave irradiation, experiments indirectly pointed out that for pristine MoS 2 reaction rates are accelerated because hot spots are generated on the catalyst bed. In this work, we investigated NiMoS and CoMoS isolated single-sheet substituted catalysts before and after thiophene adsorption focusing on quantifying the effect of microwave irradiation. For that purpose, density functional theory (DFT) molecular charge densities of each system were decomposed according to the distributed multipole analysis (DMA) of Stone. Site dipole values of each system were directly associated with a larger or smaller interaction with the microwave field according to a proposed general approach. We showed that microwave enhancement of HDS reaction rates can occur more efficiently in the CoMoS and NiMoS promoted clusters compared to pristine MoS 2 in the following order: CoMoS > NiMoS > MoS 2 . The atomic origin of the catalyst hot spots induced by microwaves was clearly established in the promoted clusters.

  7. Edge termination of MoS2 and CoMoS catalyst particles

    DEFF Research Database (Denmark)

    Byskov, Line Sjolte; Nørskov, Jens Kehlet; Clausen, B. S.

    2000-01-01

    The edge termination of MoS2 and CoMoS catalyst particles is studied by density functional calculations. We show that for structures without vacancies Mo-terminated edges have the lowest edge energies. Creation of vacancies, which are believed to be active sites in these catalyst systems, leads...

  8. Postirradiation tensile properties of Mo and Mo alloys irradiated with 600 MeV protons

    International Nuclear Information System (INIS)

    Mueller, G.V.; Gavillet, D.; Victoria, M.; Martin, J.L.

    1994-01-01

    Tensile specimens of pure Mo and Mo-5 Re, Mo-41 Re and TZM alloys have been irradiated with 600 MeV protons in the PIREX facility at 300 and 660 K to 0.5 dpa. Results of the postirradiation tensile testing show a strong radiation hardening and a severe loss of ductility for all the materials tested at room temperature. ((orig.))

  9. Derivatives of 16alpha-hydroxy-dehydroepiandrosterone with an additional 7-oxo or 7-hydroxy substituent: synthesis and gas chromatography/mass spectrometry analysis.

    Science.gov (United States)

    Pouzar, Vladimír; Cerný, Ivan; Hill, Martin; Bicíková, Marie; Hampl, Richard

    2005-10-01

    Derivatives of 16alpha-hydroxy-dehydroepiandrosterone, which have an additional oxygen substituent at position 7 (oxo or hydroxy group), were synthesized. Firstly, 17,17-dimethoxyandrost-5-ene-3beta,16alpha-diyl diacetate was prepared and then oxidized with a complex of chromium(VI) oxide and 2,5-dimethylpyrazole to the respective 7-oxo derivative. This key intermediate was both deprotected or reduced by l-Selectride or sodium borohydride in the presence of cerium(III) chloride and then deprotected to give 7-oxo, 7alpha-hydroxy and 7beta-hydroxy derivatives of 16alpha-hydroxy-dehydroepiandrosterone. The target compounds were characterized by (1)H and (13)C NMR spectra and in the form of O-methyloxime-trimethylsilyl derivatives, by gas chromatography/mass spectrometry methods.

  10. The gas–liquid chromatography of carboxylic acid esters of the urinary 11-deoxy-17-oxo steroids

    Science.gov (United States)

    Sadler, Patricia A.; Kellie, A. E.

    1967-01-01

    1. The gas–liquid-chromatographic separations of the acetate, propionate, n-butyrate, isobutyrate and n-valerate esters of androsterone, aetiocholanolone and dehydroepiandrosterone were studied on a 1% neopentyl glycol sebacate column. The n-butyrate, isobutyrate and n-valerate esters were well resolved. 2. The three steroids derived from hydrolysed urinary 17-oxo steroid conjugate extracts were analysed by gas–liquid chromatography after conversion into their n-butyrate esters. The results were compared with independent determinations involving chromatography on alumina. PMID:4227802

  11. Single-molecule magnetism in a single-ion triamidoamine uranium(V) terminal mono-oxo complex

    Energy Technology Data Exchange (ETDEWEB)

    King, David M.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [School of Chemistry, University of Nottingham (United Kingdom); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, University of Manchester (United Kingdom)

    2013-04-26

    Straightforward oxidation of a triamidoamine uranium(III) complex with trimethyl-N-oxide affords a uranium(V) terminal mono-oxo complex which is the first clear-cut example of a uranium(V) single-molecule magnet (SMM). This monometallic complex unambiguously shows that a strongly axially ligated and thus anisotropic ligand field can be used to overcome the limited magnetic anisotropy of uranium(V). (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Reactions of 5-Aroylmethylene-3-benzyl-4-oxo-2-thioxo-1,3-thiazolidines with Nitrile Oxides

    Directory of Open Access Journals (Sweden)

    Ahmed S. A. Youssef

    2001-05-01

    Full Text Available E,Z-5-Aroylmethylene-3-benzyl-4-oxo-2-thioxo-1,3-thiazolidines (3a-c react with 4-methoxy and 4-chlorophenylnitrile oxides (4a and b in pyridine solution to afford one or more of the following compounds: Z-3, Z-2,4-dioxo analogues 5 and 3,6-diaryl-1,4,2,5-dioxadiazines (6a-b. The interconversion route is discussed and the structures of all of the synthesised compounds are proven by microanalytical and spectral data.

  13. Hydration energies and specific influence of oxo complexes and high coordination numbers on the predicted chemistry of superheavy elements

    International Nuclear Information System (INIS)

    Jorgensen, C.K.; Penneman, R.A.

    1975-01-01

    On the basis of an analysis of the known ionization energies of gaseous ions and aqua ions of the 3d, 4f, and 6d transition groups and the radius effects, the chemistry of the superheavy elements is predicted. The formation of aqua ion and oxo complexes in the elements with Z below 121 is considered. It is probable that the series from 123 to 140 constitute a close analogy to the lanthanides with Th-like chemistry. Above Z = 140 the elements will probably displace a transition group behavior. A brief comment is made on the analytical aspects to be expected. (U.S.)

  14. Single-molecule magnetism in a single-ion triamidoamine uranium(V) terminal mono-oxo complex

    International Nuclear Information System (INIS)

    King, David M.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.; Tuna, Floriana; McInnes, Eric J.L.

    2013-01-01

    Straightforward oxidation of a triamidoamine uranium(III) complex with trimethyl-N-oxide affords a uranium(V) terminal mono-oxo complex which is the first clear-cut example of a uranium(V) single-molecule magnet (SMM). This monometallic complex unambiguously shows that a strongly axially ligated and thus anisotropic ligand field can be used to overcome the limited magnetic anisotropy of uranium(V). (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Six-coordinate oxo-vanadium(V) dimer complex with methoxy bridging: synthesis, crystal structure, biological activity and molecular docking

    Czech Academy of Sciences Publication Activity Database

    Heidari, F.; Fatemi, S.J.A.; Yousef Ebrahimipour, S.; Ebrahimnejad, H.; Castro, J.; Dušek, Michal; Eigner, Václav

    2017-01-01

    Roč. 76, Feb (2017), s. 1-4 ISSN 1387-7003 R&D Projects: GA MŠk(CZ) LO1603; GA ČR(CZ) GA14-03276S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : oxo-vanadium(V) * Schiff base complex * antimicrobial activity * X-ray crystal structure Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 1.640, year: 2016

  16. NMR structural studies of the ionizing radiation adduct 7-hydro-8-oxodeoxyguanosine (8-oxo-7H-dG) opposite deoxyadenosine in a DNA duplex. 8-oxo-7H-dG(syn)·dA(anti) alignment at lesion site

    International Nuclear Information System (INIS)

    Kouchakdjian, M.; Patel, D.J.; Bodepudi, V.; Shibutani, S.; Eisenberg, M.; Johnson, F.; Grollman, A.P.

    1991-01-01

    Proton NMR studies are reported on the complementary d(C1-C2-A3-C4-T5-A6-oxo-G7-T8-C9-A10-C11-C12)·d(G13-G14-T15-G16-A17-A18-T19-A20-G21-T22-G23-G24) dodecanucleotide duplex (designated 8-oxo-7H-dG·dA 12-mer), which contains a centrally located 7-hydro-8-oxodeoxyguanosine (8-oxo-7H-dG) residue, a group commonly found in DNA that has been exposed to ionizing radiation or oxidizing free radicals. From the NMR spectra it can be deduced that this moiety exists as two tautomers, or gives rise to two DNA conformations, that are in equilibrium and that exchange slowly. The present study focuses on the major component of the equilibrium that originates in the 6,8-dioxo tautomer of 8-oxo-7H-dG. The authors have assigned the exchangeable NH1, NH7, and NH 2 -2 base protons located on the Watson-Crick and Hoogsteen edges of 8-oxo-7H-dG7 in the 8-oxo-7H-dG·dA 12-mer duplex, using an analysis of one- and two-dimensional nuclear Overhauser enhancement (NOE) data in H 2 O solution. They were able to detect a set of intra- and interstrand NOEs between protons (exchangeable and nonexchangeable) on adjacent residues in the d(A6-oxo-G7-T8)·d(A17-A18-T19) trinucleotide segment centered about the lesion site that establishes stacking of the oxo-dG7(syn)·dA(anti) pair between stable Watson-Crick dA6·dT19 and dT8·A17 base pairs with minimal perturbation of the helix. The structural studies demonstrate that 8-oxo-7H-dG(syn)·dA(anti) forms a stable pair in the interior of the helix, providing a basis for the observed incorporation of dA opposite 8-oxo-7H-dG when readthrough occurs past this oxidized nucleoside base

  17. LC-mS analysis of human urine specimens for 2-oxo-3-hydroxy LSD: method validation for potential interferants and stability study of 2-oxo-3-hydroxy LSD under various storage conditions.

    Science.gov (United States)

    Klette, Kevin L; Horn, Carl K; Stout, Peter R; Anderson, Cynthia J

    2002-01-01

    2-Oxo-3-hydroxy lysergic acid diethylamide (O-H-LSD), a major LSD metabolite, has previously been demonstrated to be a superior marker for identifying LSD use compared with the parent drug, LSD. Specifically, O-H-LSD analyzed using liquid chromatography-mass spectrometry has been reported to be present in urine at concentrations 16 to 43 times greater than LSD. To further support forensic application of this procedure, the specificity of the assay was assessed using compounds that have structural and chemical properties similar to O-H-LSD, common over-the-counter products, prescription drugs and some of their metabolites, and other drugs of abuse. Of the wide range of compounds studied, none were found to interfere with the detection of O-H-LSD or the internal standard 2-oxo-3-hydroxy lysergic acid methyl propylamide. The stability of O-H-LSD was investigated from 0 to 9 days at various temperatures, pH conditions, and exposures to fluorescent light. Additionally, the effect of long-term frozen storage and pH was investigated from 0 to 60 days. There was no significant loss of O-H-LSD under both refrigerated and frozen conditions within the normal human physiological pH range of urine (4.6-8.4). However, significant loss of O-H-LSD was observed in samples prepared at pH 4.6-8.4 and stored at room temperature or higher (24-50 degrees C).

  18. Synthesis, characterization and vibrational spectra analysis of ethyl (2Z)-2-(2-amino-4-oxo-1,3-oxazol-5(4H)-ylidene)-3-oxo-3-phenylpropanoate

    Science.gov (United States)

    Kıbrız, İbrahim Evren; Sert, Yusuf; Saçmacı, Mustafa; Şahin, Ertan; Yıldırım, İsmail; Ucun, Fatih

    2013-10-01

    In the present study, the experimental and theoretical vibrational spectra of ethyl (2Z)-2-(2-amino-4-oxo-1,3-oxazol-5(4H)-ylidene)-3-oxo-3-phenylpropanoate (AOX) were investigated. The experimental FT-IR (400-4000 cm-1) and Laser-Raman spectra (100-4000 cm-1) of the molecule in the solid phase were recorded. Theoretical vibrational frequencies and geometric parameters (bond lengths, bond angles and torsion angles) were calculated using ab initio Hartree Fock (HF), Density Functional Theory (B3LYP and B3PW91) methods with 6-311++G(d,p) basis set by Gaussian 03 program, for the first time. The computed values of frequencies are scaled using a suitable scale factor to yield good coherence with the observed values. The assignments of the vibrational frequencies were performed by potential energy distribution (PED) analysis by using VEDA 4 program. The theoretical optimized geometric parameters and vibrational frequencies were compared with the corresponding experimental X-ray diffraction data, and they were seen to be in a good agreement with each other. The hydrogen bonding geometry of the molecule was also simulated to evaluate the effect of intermolecular hydrogen bonding on the vibrational frequencies. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were found.

  19. Formation of Conjugated Double Bonds to Induce Polystyrene Conductivity by using Different Concentrations of Methoxo-Oxo Bis (8-Quinolyloxo Vanadium (V

    Directory of Open Access Journals (Sweden)

    Basim Mohamad Hasan

    2017-02-01

    Full Text Available The effect of different concentrations of additive compound methoxo–oxo bis (8-quinolyloxo vanadium (v on formation of conjugated double bonds as part of photo transformation of polystyrene has been investigated. The UV-Vis spectrophotometery has been used in this work. The results are show that additive concentrations applied increase the formation of conjugated double bond as compared with polystyrene. In this study methoxo – oxo bis (8-quinolyloxo vanadium (v indicates great activity to enhance the conductivity of polystyrene by formation of conjugated double bonds.

  20. On the Mo-Papas equation

    Science.gov (United States)

    Aguirregabiria, J. M.; Chamorro, A.; Valle, M. A.

    1982-05-01

    A new heuristic derivation of the Mo-Papas equation for charged particles is given. It is shown that this equation cannot be derived for a point particle by closely following Dirac's classical treatment of the problem. The Mo-Papas theory and the Bonnor-Rowe-Marx variable mass dynamics are not compatible.

  1. A new indium metal-organic 3D framework with 1,3,5-benzenetricarboxylate, MIL-96 (In), containing μ 3-oxo-centered trinuclear units and a hexagonal 18-ring network

    International Nuclear Information System (INIS)

    Volkringer, Christophe; Loiseau, Thierry

    2006-01-01

    A new indium trimesate In 12 O(OH) 12 ({OH} 4 ,{H 2 O} 5 )[btc] 6 .∼31H 2 O, called MIL-96 (btc = 1,3,5-benzenetricarboxylate or trimesate species) was hydrothermally synthesized under mild condition (210 deg. C, 5 h) in the presence of trimethyl 1,3,5-benzenetricarboxylate in water and characterized by single-crystal X-ray diffraction technique. The MIL-96 (In) structure exhibits a three-dimensional metal-organic framework containing isolated trinuclear μ 3 -oxo-bridged indium clusters and infinite chains of InO 4 (OH) 2 and InO 2 (OH) 3 (H 2 O) octahedra generating a hexagonal network based on 18-membered ring. The two types of indium entities are connected to each other through the trimesate species which induce corrugated chains of indium octahedra, linked via μ 2 -hydroxo bonds with the specific -cis-cis-trans- sequence. The 3D framework of MIL-96 reveals three kind of cavities (two of them have estimated ∼ 400 A 3 volumes), in which are encapsulated free water molecules. The latter species are removed upon heating at 150 deg. C

  2. Mo(ve)ment-methodology

    DEFF Research Database (Denmark)

    Mørck, Line Lerche; Christian Celosse-Andersen, Martin

    2018-01-01

    This paper describes the theoretical basis for and development of a moment-movement research methodology, based on an integration of critical psychological practice research and critical ethnographic social practice theory. Central theoretical conceptualizations, such as human agency, life...... conditions and identity formation, are discussed in relation to criminological theories of gang desistance. The paper illustrates how the mo(ve)ment methodology was applied in a study of comprehensive processes of identity (re)formation and gang exit processes. This study was conducted with Martin, a former....... This is a moment which captures Martin’s complex and ambiguous feelings of conflictual concerns, frustration, anger, and a new feeling of insecurity in his masculinity, as well as engagement and a sense of deep meaningfulness as he becomes a more reflective academic. All these conflicting feelings also give...

  3. Development of fission Mo-99 production technology

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jin Ho; Choung, W. M.; Lee, K. I. and others

    2000-05-01

    Fission Mo-99 is the only parent nuclide of Tc-99m, an extremely useful tool for mdeical diagnosis, with an estimated usage of greater than 80% of nuclear medicine applicatons. HEU and LEU targets to optimize in HANARO irradiation condition suggested and designed for domestic production of fission Mo-99. The optimum process conditions are established in each unit process to meet quality requirements of fission Mo-99 products, and the results of performance test in combined process show Mo separation and purification yield of the above 97%. The concept of Tc generator production process is established, and the result of performance test show Tc production yield of 98.4% in Tc generator procuction process. The drafts is prepared for cooperation of technical cooperation and business investment with foreign country. Evaluation on economic feasibility is accompanied for fission Mo-99 and Tc-99m generator production.

  4. Development of fission Mo-99 production technology

    International Nuclear Information System (INIS)

    Park, Jin Ho; Choung, W. M.; Lee, K. I. and others

    2000-05-01

    Fission Mo-99 is the only parent nuclide of Tc-99m, an extremely useful tool for mdeical diagnosis, with an estimated usage of greater than 80% of nuclear medicine applicatons. HEU and LEU targets to optimize in HANARO irradiation condition suggested and designed for domestic production of fission Mo-99. The optimum process conditions are established in each unit process to meet quality requirements of fission Mo-99 products, and the results of performance test in combined process show Mo separation and purification yield of the above 97%. The concept of Tc generator production process is established, and the result of performance test show Tc production yield of 98.4% in Tc generator procuction process. The drafts is prepared for cooperation of technical cooperation and business investment with foreign country. Evaluation on economic feasibility is accompanied for fission Mo-99 and Tc-99m generator production

  5. 57Fe Moessbauer Studies in Mo-Fe Supported Catalysts

    International Nuclear Information System (INIS)

    Castelao-Dias, M.; Costa, B. F. O.; Quinta-Ferreira, R. M.

    2001-01-01

    Industrially, the Mo-Fe catalysts used in the selective oxidation of methanol to formaldehyde can rapidly deactivate. The use of support materials may reduce the high temperatures in the catalytic bed and/or increase thermal and mechanical resistance. However, during the preparation of these catalysts, or even during reaction conditions, the active species may react with the support material losing their catalytic activity. In this work silica, silicium carbide and titania were studied as supported catalysts by Moessbauer spectroscopy which proved to be a useful technique in the choice of supported materials

  6. Spent 99Mo/99mTc generator as an economical source of 99Mo

    International Nuclear Information System (INIS)

    El-Kolaly, M.T.

    1990-01-01

    An improved method for utilization and purification of 99 Mo from spent 90 Mo/ 99m Tc generators has been described. After washing the generator with saline to remove the generated 99m Tc, followed by 2 mL 5 M NaOH containing a few drops of H 2 O 2 , the 99 Mo was quantitatively eluted from the generator with 5 mL 5 M NaOH. The alkaline eluate containing 99 Mo was contaminated with partially dissolved alumina. In the present method, an anion-exchange resin Dowex 1 x 8 column was used for purification of 99 Mo from the contaminating alumina. The resultant 99 Mo was of high purity and contained 3+ /mL 99 Mo solution, as estimated by atomic absorption. (author)

  7. Probing the Compound I-like reactivity of a bare high-valent oxo iron porphyrin complex: the oxidation of tertiary amines.

    Science.gov (United States)

    Chiavarino, Barbara; Cipollini, Romano; Crestoni, Maria Elisa; Fornarini, Simonetta; Lanucara, Francesco; Lapi, Andrea

    2008-03-12

    The mechanisms of oxidative N-dealkylation of amines by heme enzymes including peroxidases and cytochromes P450 and by functional models for the active Compound I species have long been studied. A debated issue has concerned in particular the character of the primary step initiating the oxidation sequence, either a hydrogen atom transfer (HAT) or an electron transfer (ET) event, facing problems such as the possible contribution of multiple oxidants and complex environmental effects. In the present study, an oxo iron(IV) porphyrin radical cation intermediate 1, [(TPFPP)*+ Fe(IV)=O]+ (TPFPP = meso-tetrakis (pentafluorophenyl)porphinato dianion), functional model of Compound I, has been produced as a bare species. The gas-phase reaction with amines (A) studied by ESI-FT-ICR mass spectrometry has revealed for the first time the elementary steps and the ionic intermediates involved in the oxidative activation. Ionic products are formed involving ET (A*+, the amine radical cation), formal hydride transfer (HT) from the amine ([A(-H)]+, an iminium ion), and oxygen atom transfer (OAT) to the amine (A(O), likely a carbinolamine product), whereas an ionic product involving a net initial HAT event is never observed. The reaction appears to be initiated by an ET event for the majority of the tested amines which included tertiary aliphatic and aromatic amines as well as a cyclic and a secondary amine. For a series of N,N-dimethylanilines the reaction efficiency for the ET activated pathways was found to correlate with the ionization energy of the amine. A stepwise pathway accounts for the C-H bond activation resulting in the formal HT product, namely a primary ET process forming A*+, which is deprotonated at the alpha-C-H bond forming an N-methyl-N-arylaminomethyl radical, A(-H)*, readily oxidized to the iminium ion, [A(-H)]+. The kinetic isotope effect (KIE) for proton transfer (PT) increases as the acidity of the amine radical cation increases and the PT reaction to the base

  8. Reviving Lonidamine and 6-Diazo-5-oxo-L-norleucine to Be Used in Combination for Metabolic Cancer Therapy

    Directory of Open Access Journals (Sweden)

    Diana Cervantes-Madrid

    2015-01-01

    Full Text Available Abnormal metabolism is another cancer hallmark. The two most characterized altered metabolic pathways are high rates of glycolysis and glutaminolysis, which are natural targets for cancer therapy. Currently, a number of newer compounds to block glycolysis and glutaminolysis are being developed; nevertheless, lonidamine and 6-diazo-5-oxo-L-norleucine (DON are two old drugs well characterized as inhibitors of glycolysis and glutaminolysis, respectively, whose clinical development was abandoned years ago when the importance of cancer metabolism was not fully appreciated and clinical trial methodology was less developed. In this review, a PubMed search using the words lonidamine and 6-diazo-5-oxo-L-norleucine (DON was undertaken to analyse existing information on the preclinical and clinical studies of these drugs for cancer treatment. Data show that they exhibit antitumor effects; besides there is also the suggestion that they are synergistic. We conclude that lonidamine and DON are safe and potentially effective drugs that need to be reevaluated in combination as metabolic therapy of cancer.

  9. Reviving Lonidamine and 6-Diazo-5-oxo-L-norleucine to Be Used in Combination for Metabolic Cancer Therapy

    Science.gov (United States)

    Cervantes-Madrid, Diana; Romero, Yair; Dueñas-González, Alfonso

    2015-01-01

    Abnormal metabolism is another cancer hallmark. The two most characterized altered metabolic pathways are high rates of glycolysis and glutaminolysis, which are natural targets for cancer therapy. Currently, a number of newer compounds to block glycolysis and glutaminolysis are being developed; nevertheless, lonidamine and 6-diazo-5-oxo-L-norleucine (DON) are two old drugs well characterized as inhibitors of glycolysis and glutaminolysis, respectively, whose clinical development was abandoned years ago when the importance of cancer metabolism was not fully appreciated and clinical trial methodology was less developed. In this review, a PubMed search using the words lonidamine and 6-diazo-5-oxo-L-norleucine (DON) was undertaken to analyse existing information on the preclinical and clinical studies of these drugs for cancer treatment. Data show that they exhibit antitumor effects; besides there is also the suggestion that they are synergistic. We conclude that lonidamine and DON are safe and potentially effective drugs that need to be reevaluated in combination as metabolic therapy of cancer. PMID:26425550

  10. Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework.

    Science.gov (United States)

    Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei; Sanchez-Sanchez, Maricruz; Ortuño, Manuel A; Pahls, Dale R; Fulton, John L; Camaioni, Donald M; Li, Zhanyong; Ray, Debmalya; Mehdi, B Layla; Browning, Nigel D; Farha, Omar K; Hupp, Joseph T; Cramer, Christopher J; Gagliardi, Laura; Lercher, Johannes A

    2017-08-02

    Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu + and ∼85% Cu 2+ . The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu 2+ to Cu + . The products, methanol, dimethyl ether, and CO 2 , were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.

  11. Two Ti13-oxo-clusters showing non-compact structures, film electrode preparation and photocurrent properties.

    Science.gov (United States)

    Hou, Jin-Le; Luo, Wen; Wu, Yin-Yin; Su, Hu-Chao; Zhang, Guang-Lin; Zhu, Qin-Yu; Dai, Jie

    2015-12-14

    Two benzene dicarboxylate (BDC) and salicylate (SAL) substituted titanium-oxo-clusters, Ti13O10(o-BDC)4(SAL)4(O(i)Pr)16 (1) and Ti13O10(o-BDC)4(SAL-Cl)4(O(i)Pr)16 (2), are prepared by one step in situ solvothermal synthesis. Single crystal analysis shows that the two Ti13 clusters take a paddle arrangement with an S4 symmetry. The non-compact (non-sphere) structure is stabilized by the coordination of BDC and SAL. Film photoelectrodes are prepared by the wet coating process using the solution of the clusters and the photocurrent response properties of the electrodes are studied. It is found that the photocurrent density and photoresponsiveness of the electrodes are related to the number of coating layers and the annealing temperature. Using ligand coordinated titanium-oxo-clusters as the molecular precursors of TiO2 anatase films is found to be effective due to their high solubility, appropriate stability in solution and hence the easy controllability.

  12. Synthesis and Microbiological Activity of Some Newly Synthesized Derivatives of 2-Oxo-2H-chromen-2-one

    Directory of Open Access Journals (Sweden)

    Majlinda Daci-Ajvazi

    2011-01-01

    Full Text Available By the action of 2-amino-5-methylthio-1,3,4-thiadiazole, 3-amino-5-methylisoxazole, 2-amino-6-fluorobenzothiazole, 2-amino-5-chloropyridine, respectively, on 4-chloro-2-oxo-2H-chromene-3-sulfonyl chloride, the corresponding 9-methylthio-7,7-dioxo-7,7a-dihydro-5-oxo-7λ6,10-dithia-8,11-diaza-cyclopenta[b] phenantren-6-one, 9-methyl-7,7-dioxo-7H-5,8-dioxa-7λ6-thia-7a,11-diaza-cyclopenta[b] phenantren-6-one, 9-fluoro-7,7-dioxo-7H-5-oxa-7λ6,12-dithia-7a,13-diaza-indeno[1,2-b] phenantren-6-one and 9-Chloro-7,7-dioxo-7H-5-oxa-7λ6-thia-7a,12-diaza-benzo[α]anthracen -6-one were formed and they have been isolated in satisfying yields. Based on the biological activity of chromene-2-ones and heterocyclic compounds condensed in position 3 and 4, we also studied microbiological activity of these new compounds (5-8, against Staphylococcus aureus ATCC 25923, Streptococcus pneumoniae, Aeromonas Salmonicida, Bacillus spp and some of them exhibited significant activity.

  13. Phase formation in Na2MoO4 - MgMoO4 - Cr2(MoO4)3 system

    International Nuclear Information System (INIS)

    Kotova, I.Yu.; Kozhevnikova, N.M.

    1998-01-01

    Interaction within Na 2 MoO 4 - MgMoO 4 - Cr 2 (MoO 4 ) 3 ternary system is studied by X ray phase and DTA methods. State diagram of NaCr(MoO 4 ) 2 - MgMoO 4 section is plotted. Production of ternary molybdates of Na 1-x Mg 1-x Cr 1+x (MoO 4 ) 3 , where 0 ≤ x ≤ 0.3, and NaMg 3 Cr(MoO 4 ) 5 composition is ascertained [ru

  14. AMORE Mo-99 Spike Test Results

    Energy Technology Data Exchange (ETDEWEB)

    Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Krebs, John F. [Argonne National Lab. (ANL), Argonne, IL (United States); Quigley, Kevin J. [Argonne National Lab. (ANL), Argonne, IL (United States); Byrnes, James P. [Argonne National Lab. (ANL), Argonne, IL (United States); Rotsch, David A [Argonne National Lab. (ANL), Argonne, IL (United States); Brossard, Thomas [Argonne National Lab. (ANL), Argonne, IL (United States); Wesolowski, Kenneth [Argonne National Lab. (ANL), Argonne, IL (United States); Alford, Kurt [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2017-09-27

    With funding from the National Nuclear Security Administrations Material Management and Minimization Office, Argonne National Laboratory (Argonne) is providing technical assistance to help accelerate the U.S. production of Mo-99 using a non-highly enriched uranium (non-HEU) source. A potential Mo-99 production pathway is by accelerator-initiated fissioning in a subcritical uranyl sulfate solution containing low enriched uranium (LEU). As part of the Argonne development effort, we are undertaking the AMORE (Argonne Molybdenum Research Experiment) project, which is essentially a pilot facility for all phases of Mo-99 production, recovery, and purification. Production of Mo-99 and other fission products in the subcritical target solution is initiated by putting an electron beam on a depleted uranium (DU) target; the fast neutrons produced in the DU target are thermalized and lead to fissioning of U-235. At the end of irradiation, Mo is recovered from the target solution and separated from uranium and most of the fission products by using a titania column. The Mo is stripped from the column with an alkaline solution. After acidification of the Mo product solution from the recovery column, the Mo is concentrated (and further purified) in a second titania column. The strip solution from the concentration column is then purified with the LEU Modified Cintichem process. A full description of the process can be found elsewhere [1–3]. The initial commissioning steps for the AMORE project include performing a Mo-99 spike test with pH 1 sulfuric acid in the target vessel without a beam on the target to demonstrate the initial Mo separation-and-recovery process, followed by the concentration column process. All glovebox operations were tested with cold solutions prior to performing the Mo-99 spike tests. Two Mo-99 spike tests with pH 1 sulfuric acid have been performed to date. Figure 1 shows the flow diagram for the remotely operated Mo-recovery system for the AMORE project

  15. Effect of oxygen partial pressure on oxidation of Mo-metal

    Science.gov (United States)

    Sharma, Rabindar Kumar; Kumar, Prabhat; Singh, Megha; Gopal, Pawar; Reddy, G. B.

    2018-05-01

    This report explains the effect of oxygen partial pressure (PO2 ) on oxidation of Mo-metal in oxygen plasma. XRD results indulge that oxide layers formed on Mo-surfaces at different oxygen partial pressures have two different oxide phases (i.e. orthorhombic MoO3 and monoclinic Mo8O23). Intense XRD peaks at high pressure (i.e. 2.0×10-1 Torr) points out the formation of thick oxide layer on Mo-surface due to presence of large oxygen species in chamber and less oxide volatilization. Whereas, at low PO2 (6.5×10-2 and 7.5×10-2 Torr.) the reduced peak strength is owing to high oxide volatilization rate. SEM micrographs and thickness measurements also support XRD results and confirm that the optimum -2value of PO2 to deposited thicker and uniform oxide film on glass substrate is 7.5×10-2 Torr through plasma assistedoxidation process. Further to study the compositional properties, EDX of the sample M2 (the best sample) is carried out, which confirms that the stoichiometric ratio is less than 3 (i.e. 2.88). Less stoichiometric ratio again confirms the presence of sub oxides in oxide layers on Mo metal as evidenced by XRD results. All the observed results are well in consonance with each other.

  16. Properties of vacancies type defects in intermetallic compounds of the Al-Mo system

    International Nuclear Information System (INIS)

    Pascuet, M.I; Fernandez, J.R; Monti, A.M

    2006-01-01

    There are five intermetallic compounds in the Al-Mo system that are stable at low temperatures. Of these, the richest phases in some of the two components are the compounds Al 12 Mo and AlMo 3 , whose Pearson symbols are cI26 and cP8, respectively. In both structures, the atoms of the minority component occupy positions bcc and each one of them is surrounded by 12 atoms first neighbors of the other component. These 13 atoms form icosahedron shaped units or heaps. Unlike what occurs in Al 12 Mo, the AlMo 3 heaps are superposed by sharing atoms from the majority component. The neighboring environment of the majority component is mixed but differs considerably in one or another intermetallic. In each structure, the sites occupied by any given species are crystallographically equivalent, that is, they can self generate from one of the positions and from the crystalline structure's elements of symmetry. This work studies the energy of vacancies and antisites in both compounds and the atomic-jump processes to vacant sites. Computer simulation techniques were used based on minimizing the system's energy. Many-body embedded-atom potentials were used to represent the atomic interactions. The potential mixture used resulted in an adjustment to the crystalline structure of the AlMo 3 phase at low temperatures and to its formation energy (cw)

  17. In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

    Science.gov (United States)

    Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

    2014-04-01

    Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with S pecies, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene ``painting'' on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis.

  18. Hydrogen-induced blistering of Mo/Si multilayers: Uptake and distribution

    NARCIS (Netherlands)

    Kuznetsov, Alexey; Gleeson, M.A.; Bijkerk, Frederik

    2013-01-01

    We report on the uptake of deuterium by thin-film Mo/Si multilayer samples as a result of exposure to fluxes of predominantly thermal atomic and molecular species, but also containing a small fraction of energetic (800–1000 eV) ions. These exposures result in blister formation characterized by layer

  19. Hydrogen-induced blistering of Mo/Si multilayers: Uptake and distribution

    NARCIS (Netherlands)

    Kuznetsov, A. S.; Gleeson, M. A.; F. Bijkerk,

    2013-01-01

    Abstract We report on the uptake of deuterium by thin-film Mo/Si multilayer samples as a result of exposure to fluxes of predominantly thermal atomic and molecular species, but also containing a small fraction of energetic (800 1000 eV) ions. These exposures result in blister formation

  20. The Magnaporthe oryzae Alt A 1-like protein MoHrip1 binds to the plant plasma membrane.

    Science.gov (United States)

    Zhang, Yi; Liang, Yingbo; Dong, Yijie; Gao, Yuhan; Yang, Xiufen; Yuan, Jingjing; Qiu, Dewen

    2017-10-07

    MoHrip1, a protein isolated from Magnaporthe oryzae, belongs to the Alt A 1 (AA1) family. mohrip1 mRNA levels showed inducible expression throughout the infection process in rice. To determine the location of MoHrip1 in M. oryzae, a mohrip1-gfp mutant was generated. Fluorescence microscopy observations and western blotting analysis showed that MoHrip1 was both present in the secretome and abundant in the fungal cell wall. To obtain MoHrip1 protein, we carried out high-yield expression of MoHrip1 in Pichia pastoris. Treatment of tobacco plants with MoHrip1 induced the formation of necrosis, accumulation of reactive oxygen species and expression of several defense-related genes, as well as conferred disease resistance. By fusion to green fluorescent protein, we showed that MoHrip1 was able to bind to the tobacco and rice plant plasma membrane, causing rapid morphological changes at the cellular level, such as cell shrinkage and chloroplast disorganization. These findings indicate that MoHrip1 is a microbe-associated molecular pattern that is perceived by the plant immune system. This is the first study on an AA1 family protein that can bind to the plant plasma membrane. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. A simple and sensitive separation technique of 99Mo and 99mTc from their equilibrium mixture

    International Nuclear Information System (INIS)

    Swadesh Mandal; Ajoy Mandal

    2014-01-01

    The present work describes a simple and inexpensive separation method of 99 Mo from the equilibrium mixture. The liquid-liquid extraction technique has been employed to separate 99 Mo and 99m Tc using triisooctylamine (TIOA). The 99 Mo and 99m Tc were quantitatively separated out in 2 M TIOA with tripled distilled water; 99m Tc was back extracted from TIOA organic phase to aqueous phase by 0.1 M DTPA. The species information or indirect speciation of molybdenum was also established by the extraction profile of the molybdenum. (author)

  2. Endangered Species

    Science.gov (United States)

    EPA's Endangered Species Protection Program helps promote recovery of listed species. The ESPP determines if pesticide use in a geographic area may affect any listed species. Find needed limits on pesticide use in Endangered Species Protection Bulletins.

  3. Development of fission Mo-99 production technology

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jin Ho; Choung, W. M.; Lee, K. I. and others

    2001-05-01

    This R and D project is planed to supply domestic demands of Mo-99 through fission route, and consequently this project will be expected to rise up utilization of HANARO and KAERI's capability for marketing extension into domestic and oversea radiopharmaceutical market. HEU and LEU target types are decided and designed for fission Mo-99 production in domestic. Experimental study of target fabrication technology was performed and developed processing equipments. And conceptual design of target loading/unloading in/from HANARO device are performed. Tracer test of Mo-99 separation and purification process was performed, test results reach to Mo-99 recovery yield above 80% and decontamination factor above 1600. Combined Mo-99 separation and purification process was decided for hot test scheduled from next year, and performance test was performed. Conceptual design for modification of existing hot cell for fission Mo-99 production facility was performed and will be used for detail design. Assumption for the comparison of LEU and HEU target in fission Mo-99 production process were suggested and compared of merits and demerits in view of fabrication technology and economy feasibility.

  4. Development of fission Mo-99 production technology

    International Nuclear Information System (INIS)

    Park, Jin Ho; Choung, W. M.; Lee, K. I. and others

    2001-05-01

    This R and D project is planed to supply domestic demands of Mo-99 through fission route, and consequently this project will be expected to rise up utilization of HANARO and KAERI's capability for marketing extension into domestic and oversea radiopharmaceutical market. HEU and LEU target types are decided and designed for fission Mo-99 production in domestic. Experimental study of target fabrication technology was performed and developed processing equipments. And conceptual design of target loading/unloading in/from HANARO device are performed. Tracer test of Mo-99 separation and purification process was performed, test results reach to Mo-99 recovery yield above 80% and decontamination factor above 1600. Combined Mo-99 separation and purification process was decided for hot test scheduled from next year, and performance test was performed. Conceptual design for modification of existing hot cell for fission Mo-99 production facility was performed and will be used for detail design. Assumption for the comparison of LEU and HEU target in fission Mo-99 production process were suggested and compared of merits and demerits in view of fabrication technology and economy feasibility

  5. Effect of zirconia morphology on sulfur-resistant methanation performance of MoO3/ZrO2 catalyst

    Science.gov (United States)

    Liu, Chen; Wang, Weihan; Xu, Yan; Li, Zhenhua; Wang, Baowei; Ma, Xinbin

    2018-05-01

    Two kinds of ZrO2 support with different morphologies were prepared by facile solvothermal method in different solvents. The obtained two supports showed monoclinic zirconia (m-ZrO2) and tetragonal zirconia (t-ZrO2) phase with similar crystalline size. Their supported Mo-based catalysts were prepared by impregnation method and the effect of zirconia morphology on the performance of sulfur-resistant methanation was examined. The results indicated that the MoO3/m-ZrO2 has higher CO conversion than the MoO3/t-ZrO2 catalyst. Characterizations by XRD, Raman, H2-TPR and IR confirmed that the m-ZrO2 is superior to t-ZrO2 for dispersing molybdenum species. In addition, the MoO3/m-ZrO2 catalyst has weaker interaction between support and active Mo speices than the MoO3/t-ZrO2 catalyst, which facilitates to forming active species of nanocrystalline MoS2 layers for sulfur-resistant methanation. The weaker interaction of molybdenum species with m-ZrO2 is related with the more covalent character of the Zrsbnd O bond and more oxygen defective structure of m-ZrO2. A larger number of Lewis acid centers appear on the surface of m-ZrO2, which verified the substantial vacancies on m-ZrO2 exposing coordinately unsaturated Zr3+ and Zr4+ cations. Meanwhile, the less Lewis acid of t-ZrO2 result in stronger interaction between support and molybdenum species and trigger crystalline phase MoO3 and Mosbnd Osbnd Zr linkages.

  6. Enhanced electrocatalytic activity of MoSx on TCNQ-treated electrode for hydrogen evolution reaction

    KAUST Repository

    Chang, Yunghuang

    2014-10-22

    Molybdenum sulfide has recently attracted much attention because of its low cost and excellent catalytical effects in the application of hydrogen evolution reaction (HER). To improve the HER efficiency, many researchers have extensively explored various avenues such as material modification, forming hybrid structures or modifying geometric morphology. In this work, we reported a significant enhancement in the electrocatalytic activity of the MoSx via growing on Tetracyanoquinodimethane (TCNQ) treated carbon cloth, where the MoSx was synthesized by thermolysis from the ammonium tetrathiomolybdate ((NH4)2MoS4) precursor at 170 °C. The pyridinic N- and graphitic N-like species on the surface of carbon cloth arising from the TCNQ treatment facilitate the formation of Mo5+ and S2 2- species in the MoSx, especially with S2 2- serving as an active site for HER. In addition, the smaller particle size of the MoSx grown on TCNQ-treated carbon cloth reveals a high ratio of edge sites relative to basal plane sites, indicating the richer effective reaction sites and superior electrocatalytic characteristics. Hence, we reported a high hydrogen evolution rate for MoSx on TCNQ-treated carbon cloth of 6408 mL g-1 cm-2 h-1 (286 mmol g-1 cm-2 h-1) at an overpotential of V = 0.2 V. This study provides the fundamental concepts useful in the design and preparation of transition metal dichalcogenide catalysts, beneficial in the development in clean energy.

  7. Ternary reduced-graphene-oxide/Bi2MoO6/Au nanocomposites with enhanced photocatalytic activity under visible light

    International Nuclear Information System (INIS)

    Bi, Jinhong; Fang, Wei; Li, Li; Li, Xiaofen; Liu, Minghua; Liang, Shijing; Zhang, Zizhong; He, Yunhui; Lin, Huaxiang; Wu, Ling; Liu, Shengwei; Wong, Po Keung

    2015-01-01

    A novel ternary nanocomposite photocatalyst consisted of reduced-graphene-oxide (RGO), Bi 2 MoO 6 and plasmonic Au nanoparticles were successfully fabricated by multiple steps including a simple solvothermal process and photochemical reduction process. RGO/Bi 2 MoO 6 /Au was characterized by X-ray powder diffraction patterns, transmission electron microscopy, UV–vis diffuse reflectance spectra, Raman spectroscopy and X-ray photoelectron spectroscopy. In comparison with Bi 2 MoO 6 , RGO/Bi 2 MoO 6 and Au/Bi 2 MoO 6 , RGO/Bi 2 MoO 6 /Au exhibits an enhanced photocatalytic activity for decomposition of Rhodamine B under visible light. The separation efficiency of the photogenerated holes and electrons on Bi 2 MoO 6 is promoted by the combined effect of both RGO and Au in the ternary composite, and thus enhances photocatalytic activity. The scavenger study revealed that both hole and superoxide are the major reactive species for the photocatalytic degradation of Rhodamine B using RGO/Bi 2 MoO 6 /Au photocatalyst. - Graphical abstract: A novel ternary nanocomposite photocatalyst consisted of reduced-graphene-oxide (RGO), Bi 2 MoO 6 and plasmonic Au nanoparticles were successfully fabricated by multiple steps including a simple solvothermal process and photochemical reduction process. The resulted ternary nanocomposites greatly enhanced the visible light photocatalytic properties compared to Bi 2 MoO 6 , RGO/Bi 2 MoO 6 or Au/Bi 2 MoO 6 binary systems. The improved photocatalytic activity was mainly attributed to the synergistic effect of Au and RGO with better separation of the photogenerated holes and electrons, resulting from the surface plasmonic resonance and extra strong electron magnetic field of Au nanoparticles and the high electron conductivity of RGO. - Highlights: • The ternary nanocomposites RGO/Bi 2 MoO 6 /Au were constructed for the first time. • RGO/Bi 2 MoO 6 /Au showed much higher visible photoactivity than RGO (Au)/Bi 2 MoO 6 . • The improved

  8. Synthesis and crystal structures of 2-methyl-4-aryl-5-oxo-5H-indeno [1,2-b] pyridine carboxylate derivatives

    DEFF Research Database (Denmark)

    Pandian, Ramesh; Naushad, Edayadulla; Vijayakumar, Vinodhkumar

    2014-01-01

    pyridine derivatives through oxidation. Consequently, the interest in this aromatization reaction, investigation of a wide range of 1, 4-DHPs continues to attract the attention of researchers. Herein, we report the preparation of pyridine derivatives and the crystal structures determined by X......-ray crystallographic methods.Results: The crystal structures and conformational studies of two organic compounds, namely ethyl 2-methyl-4-phenyl-5-oxo-5H-indeno [1,2-b] pyridine-3-carboxylate (I) and ethyl 2-methyl-4-(4 chlorophenyl)-5-oxo-5H-indeno [1,2-b] pyridine-3-carboxylate (II) are reported. The terminal ethyl......) dimer running along 011 direction.Conclusion: The crystal structures ethyl 2-methyl-4-phenyl-5-oxo-5H-indeno [1,2-b] pyridine-3-carboxylate and ethyl 2-methyl-4-(4 chlorophenyl)-5-oxo-5H-indeno [1,2-b] pyridine-3-carboxylate have been investigated in detail. The terminal ethyl group of compound I...

  9. 16-Cyclopentadienyl tricarbonyl 99mTc 16-oxo-hexadecanoic acid: synthesis and evaluation of fatty acid metabolism in mouse myocardium.

    Science.gov (United States)

    Lee, Byung Chul; Kim, Dong Hyun; Lee, Iljung; Choe, Yearn Seong; Chi, Dae Yoon; Lee, Kyung-Han; Choi, Yong; Kim, Byung-Tae

    2008-06-26

    We synthesized 16-cyclopentadienyl tricarbonyl 99mTc 16-oxo-hexadecanoic acid (99mTc-CpTT-16-oxo-HDA, 1) and investigated its potential as a radiotracer for evaluating fatty acid metabolism in myocardium. Radiotracer 1 was synthesized in 22.6 +/- 6.3% decay-corrected yield by a double ligand transfer reaction between the ferrocene adduct of methyl hexadecanoate ( 2) and Na99mTcO 4 in the presence of Cr(CO)6 and CrCl3, followed by hydrolysis of the methyl ester group. Radiotracer 1 was found to be chemically stable (99% at 6 h) when incubated in human serum. A tissue distribution study in mice showed that high radioactivity accumulated in heart (9.03%ID/g at 1 min and 5.41%ID/g at 5 min postinjection) with rapid clearance and that heart to blood uptake ratios increased with time (2.13 at 5 min and 3.76 at 30 min postinjection). Metabolite analysis of the heart tissues using a simple extraction method showed that 99mTc-CpTT-4-oxo-butyric acid was detected as the major radioactive metabolite by HPLC, suggesting that 1 is metabolized to 99mTc-CpTT-4-oxo-butyric acid via beta-oxidation in myocardium.

  10. Synthesis of 3 alpha-deuterated 7 alpha-hydroxy-DHEA and 7-oxo-DHEA and application in LC-MS/MS plasma analysis

    Czech Academy of Sciences Publication Activity Database

    Sosvorova, L.K.; Sarek, J.; Vitku, J.; Kvasnica, Miroslav

    2016-01-01

    Roč. 112, AUG (2016), s. 88-94 ISSN 0039-128X Institutional support: RVO:61389030 Keywords : 7 alpha-Hydroxy-DHEA * 7-Oxo-DHEA * Deuterated standard Subject RIV: CE - Biochemistry Impact factor: 2.282, year: 2016

  11. Mass spectrometric determination of stability of gaseous BaMoO2, Ba2MoO4, Ba2MoO5, Ba2Mo2O8 molecules

    International Nuclear Information System (INIS)

    Kudin, L.S.; Balduchchi, Dzh.; Dzhil'i, G.; Gvido, M.

    1982-01-01

    During the mass spectrometric investigation of BaCrO 4 evaporation Cr + , Ba + , BaO + main ions are recorded as well as BaMoO 4 + , BaMoO 3 + , BaMoO 2 + , BaMoO + , BaMoO 4 + , Ba 2 MoO 5 + , BaMo 2 O 8 + ions - the products of ionization of three-component (Ba, Mo, M) molecules, forming as a result of substance chemical interaction with the material of an effusion cell (Mo). Heats of formation of BaMoO 2 , Ba 2 MoO 4 , Ba 2 MoO 5 and Ba 2 Mo 2 O 8 molecules which constituted - 577+-70, -1343+-115, -1464+-70, -2393+-90 k J/mol respectively are determined on the base of the analysis of curves of ionisation efficiency and of reaction heats Ba 2 MoO 5 =BaO+BaMoO 4 , ΔH 0 0 =322+-60 kJ/mol Ba 2 Mo 2 O 8 =2BaMoO 4 , ΔH 0 0 =351+-80 kJ/mol calculated with the use of third low of thermodynamics [ru

  12. Experimental and time-dependent density functional theory characterization of the UV-visible spectra of monomeric and μ-oxo dimeric ferriprotoporphyrin IX.

    Science.gov (United States)

    Kuter, David; Venter, Gerhard A; Naidoo, Kevin J; Egan, Timothy J

    2012-10-01

    Speciation of ferriprotoporphyrin IX, Fe(III)PPIX, in aqueous solution is complex. Despite the use of its characteristic spectroscopic features for identification, the theoretical basis of the unique UV-visible absorbance spectrum of μ-[Fe(III)PPIX](2)O has not been explored. To investigate this and to establish a structural and spectroscopic model for Fe(III)PPIX species, density functional theory (DFT) calculations were undertaken for H(2)O-Fe(III)PPIX and μ-[Fe(III)PPIX](2)O. The models agreed with related Fe(III)porphyrin crystal structures and reproduced vibrational spectra well. The UV-visible absorbance spectra of H(2)O-Fe(III)PPIX and μ-[Fe(III)PPIX](2)O were calculated using time-dependent DFT and reproduced major features of the experimental spectra of both. Transitions contributing to calculated excitations have been identified. The features of the electronic spectrum calculated for μ-[Fe(III)PPIX](2)O were attributed to delocalization of electron density between the two porphyrin rings of the dimer, the weaker ligand field of the axial ligand, and antiferromagnetic coupling of the Fe(III) centers. Room temperature magnetic circular dichroism (MCD) spectra have been recorded and are shown to be useful in distinguishing between these two Fe(III)PPIX species. Bands underlying major spectroscopic features were identified through simultaneous deconvolution of UV-visible and MCD spectra. Computed UV-visible spectra were compared to deconvoluted spectra. Interpretation of the prominent bands of H(2)O-Fe(III)PPIX largely conforms to previous literature. Owing to the weak paramagnetism of μ-[Fe(III)PPIX](2)O at room temperature and the larger number of underlying excitations, interpretation of its experimental UV-visible spectrum was necessarily tentative. Nonetheless, comparison with the calculated spectra of antiferromagnetically coupled and paramagnetic forms of the μ-oxo dimer of Fe(III)porphine suggested that the composition of the Soret band involves

  13. Antidiabetic Bis-Maltolato-OxoVanadium(IV: Conversion of inactive trans- to bioactive cis-BMOV for possible binding to target PTP-1B

    Directory of Open Access Journals (Sweden)

    Thomas Scior

    2008-11-01

    Full Text Available Thomas Scior1, Hans-Georg Mack2, José Antonio Guevara García3, Wolfhard Koch41Departamento de Farmacia. Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, Colonia San Manuel, Puebla, Mexico; 2Institut für Physikalische Chemie, Universität Tübingen, Tübingen, Germany; 3Laboratorio de Investigación en Bioinorgánica y Biorremediación (LIByB. Departamento de Ciencias Básicas, Ingeniería y Tecnología, Universidad Autónoma de Tlaxcala, Apizaco, Tlaxcala, Mexico; 4Facultad de Estudios Superiores Zaragoza (FESZ, Universidad Nacional Autónoma de México (UNAM, Colonia Ejército de Oriente, Delegación Iztapalapa, Mexico City, MexicoAbstract: The postulated transition of Bis-Maltolato-OxoVanadium(IV (BMOV from its inactive trans- into its cis-aquo-BMOV isomeric form in solution was simulated by means of computational molecular modeling. The rotational barrier was calculated with DFT – B3LYP under a stepwise optimization protocol with STO-3G, 3-21G, 3-21G*, and 6-31G ab initio basis sets. Our computed results are consistent with reports on the putative molecular mechanism of BMOV triggering the insulin-like cellular response (insulin mimetic as a potent inhibitor of the protein tyrosine phosphatase-1B (PTP-1B. Initially, trans-BMOV is present in its solid dosage form but in aqueous solution, and during oral administration, it is readily converted into a mixture of “open-type” and “closed-type” complexes of cis-aquo-BMOV under equilibrium conditions. However, in the same measure as the “closed-type” complex binds to the cytosolic PTP-1B, it disappears from solution, and the equilibrium shifts towards the “closed-type” species. In full accordance, the computed binding mode of cis-BMOV is energetically favored over sterically hindered trans-BMOV. In view of our earlier report on prodrug hypothesis of vanadium organic compounds the present results suggest that cis-BMOV is the bioactive species

  14. Extended analysis of Mo VI

    International Nuclear Information System (INIS)

    Edlen, B.; Rahimullah, K.; Tauheed, A.; Chaghtai, M.S.Z.

    1985-01-01

    The analysis of the RbI-like spectrum Mo VI has been extended to include a total of some 110 classified lines and 44 energy levels belonging to the one-electron configurations 4s 2 4p 6 ( 1 S)nl with n ranging up to 9 and l up to 7. The analysis is based on recordings of vacuum spark spectra made at Lund in the region 230-2350 A, complemented by a list of lines from 2193 to 6336 A observed and identified by Romanov and Striganov in a Penning type arc discharge. The one-electron level system is partly mixed with core-excited configurations, not treated in the present paper. Especially the nf series is strongly perturbed by 4s 2 4p 5 4d 2 , and an anomalous behaviour of the ng series is explained by interaction with the 2 G term of 4s4p 6 4d 2 . The ionization limit, derived from 6h, 7i and 8k by means of the polarization formula, is found to be 555 132+-2 cm -1 . (orig.)

  15. Nanoparticles of superconducting γ-Mo2N and δ-MoN

    International Nuclear Information System (INIS)

    Gomathi, A.; Sundaresan, A.; Rao, C.N.R.

    2007-01-01

    We have been able to prepare nanoparticles (∼4 nm diameter) of cubic γ-Mo 2 N by a simple procedure involving the reaction of MoCl 5 with urea at 873 K. The nanoparticles show a superconducting transition around 6.5 K. The γ-Mo 2 N nanoparticles are readily transformed to nanoparticles of δ-MoN with a slightly larger diameter on heating in a NH 3 atmosphere at 573 K. Phase-pure δ-MoN obtained by this means shows a superconducting transition around 5 K. - Graphical abstract: TEM image of the γ-Mo 2 N particles with the inset showing the resistivity of the sample as a function of temperature

  16. Stacking change in MoS2 bilayers induced by interstitial Mo impurities.

    Science.gov (United States)

    Cortés, Natalia; Rosales, Luis; Orellana, Pedro A; Ayuela, Andrés; González, Jhon W

    2018-02-01

    We use a theoretical approach to reveal the electronic and structural properties of molybdenum impurities between MoS 2 bilayers. We find that interstitial Mo impurities are able to reverse the well-known stability order of the pristine bilayer, because the most stable form of stacking changes from AA' (undoped) into AB' (doped). The occurrence of Mo impurities in different positions shows their split electronic levels in the energy gap, following octahedral and tetrahedral crystal fields. The energy stability is related to the accommodation of Mo impurities compacted in hollow sites between layers. Other less stable configurations for Mo dopants have larger interlayer distances and band gaps than those for the most stable stacking. Our findings suggest possible applications such as exciton trapping in layers around impurities, and the control of bilayer stacking by Mo impurities in the growth process.

  17. Stability study on an anti-cancer drug 4-(3,5-bis(2-chlorobenzylidene-4-oxo-piperidine-1-yl-4-oxo-2-butenoic acid (CLEFMA using a stability-indicating HPLC method

    Directory of Open Access Journals (Sweden)

    Dhawal Raghuvanshi

    2017-02-01

    Full Text Available CLEFMA, 4-(3,5-bis(2-chlorobenzylidene-4-oxo-piperidine-1-yl-4-oxo-2-butenoic acid, is a new chemical entity with anti-cancer and anti-inflammatory activities. Here, we report its stability in solution against stress conditions of exposure to acid/base, light, oxidant, high temperature, and plasma. The identity of the degradation products was ascertained by mass and proton nuclear magnetic resonance spectroscopy. To facilitate this study, we developed and validated a reverse phase high performance liquid chromatography method for detection of CLEFMA and its degradation. The method was linear over a range of 1–100 µg/mL; the accuracy and precision were within acceptable limits; it was stability-indicating as it successfully separated cis-/trans-isomers of CLEFMA as well as its degradation product. The major degradation product was produced from amide hydrolysis at maleic acid functionality caused by an acidic buffer, oxidant (3% hydrogen peroxide, or temperature stress (40–60 °C. The log k-pH profile showed that CLEFMA was most stable at neutral pH. In accelerated stability study we found that the shelf-life (T90% of CLEFMA at 25 °C and 4 °C was 45 days and 220 days, respectively. Upon exposure to UV-light (365 nm, the normally prevalent trans-CLEFMA attained cis-configuration. This isomerization also involved the maleic acid moiety. CLEFMA was stable in plasma from which it could be efficiently extracted by an acetonitrile precipitation method. These results indicate that CLEFMA is sensitive to hydrolytic cleavage at its maleic acid moiety, and it is recommended that its samples should be stored under refrigerated and light-free conditions, and under inert environment.

  18. Floodplain Mapping Submission for Oregon County, MO

    Data.gov (United States)

    Federal Emergency Management Agency, Department of Homeland Security — The Floodplain Mapping study deliverables depict and quantify the flood risks for Oregon County, MO. The City of Thayer and the Missouri State Emergency Management...

  19. Alternative energy resources for MoDOT

    Science.gov (United States)

    2011-02-01

    This research investigates environmentally friendly alternative energy sources that could be used by MoDOT in various areas, and develops applicable and sustainable strategies to implement those energy sources.

  20. Phase transformations in Mo-doped FINEMETs

    Energy Technology Data Exchange (ETDEWEB)

    Silveyra, Josefina M., E-mail: jsilveyra@fi.uba.a [Lab. de Solidos Amorfos, INTECIN, FIUBA-CONICET, Paseo Colon 850, (C1063ACV) Buenos Aires (Argentina); Illekova, Emilia; Svec, Peter; Janickovic, Dusan [Institute of Physics SAS, Dubravska cesta 9, 845 11 Bratislava (Slovakia); Rosales-Rivera, Andres [Laboratorio de Magnetismo y Materiales Avanzados, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Manizales (Colombia); Cremaschi, Victoria J. [Lab. de Solidos Amorfos, INTECIN, FIUBA-CONICET, Paseo Colon 850, (C1063ACV) Buenos Aires (Argentina)

    2010-06-15

    In this paper, the phase transformations occurring during the crystallization process of FINEMETs in which Nb has been gradually replaced by Mo have been studied by a variety of techniques including DSC, DTA, TGA, XRD and TEM. The thermal stability of the alloy was deteriorated as a consequence of Mo's smaller atomic size. The gradual replacement of Nb by Mo reduced the onset temperature of Fe-Si and of the borides. The Curie temperature of the amorphous phase slightly decreased from 594 K for x=0 to 587 K for x=3. The borides compounds Fe{sub 2}B and Fe{sub 23}B{sub 6} as well as the (Nb,Mo){sub 5}Si{sub 3} phase were found to precipitate in the second and third crystallization.

  1. PRoMoTo 2013 proceedings

    OpenAIRE

    Bishop, Judith; Tillmann, Nikolai; Puder, Arno; Naik, Vinayak

    2013-01-01

    Programming for Mobile and Touch (PRoMoTo'13) was held at the 2013 ACM SIGPLAN conference on Systems, Programming, Languages and Applications (SPLASH 2013), October 2013 in Indianapolis, USA. Submissions for this event were invited in the general area of mobile and touch-oriented programming languages and programming environments, and teaching of programming for mobile devices. These are proceedings of the PRoMoTo'13.

  2. 99Mo production using MoO3 pellets obtained by mechanical compression and heat treatment

    International Nuclear Information System (INIS)

    Rojas, Jorge; Mendoza, Pablo; Lopez, Alcides

    2014-01-01

    This paper shows the results of the MoO 3 pellets fabrication by mechanical compression and the heat treatment method (MCHT) in order to optimize the production of 99 Mo in the RACSO Nuclear Center. The effects of polyvinyl alcohol (PVA) as binder are assessed by heat treatment of pellets in air atmosphere, evaluating the elimination process with increasing temperature and solubility in 5N NaOH. The results show that the pellets fabrication technique is suitable because fulfills the required technical specifications, allows to irradiate 50 % more of 98 Mo mass and facilitate a safer radiological handling of the irradiated MoO 3 . (authors).

  3. Biodistribution of 99Mo in rats

    International Nuclear Information System (INIS)

    Souza, Raphael Sancho Sisley de; Ribeiro, Bianca da Silva; Dantas, Ana Leticia Almeida; Dantas, Bernardo Maranhao; Bernardo Filho, Mario

    2009-01-01

    The modification of 99 Mo standard metabolism in the presence of MDP would alter the dosimetry of this radionuclide in nuclear medicine patients. Therefore, the objective of this work is to evaluate the influence of MDP in the biodistribution of 99 Mo. Wistar rats were divided in two groups of six animals, being inoculated respectively 99 Molibdate and 99 Mo+MDP via plex ocular. The biodistribution study was carried out after 10 and 120 minutes respectively. The organs were counted with a NaI(Tl) detector. The uptake values did not present significant differences among the groups. An in vitro study through planar chromatography was carried out to determine the affinity between molybdenum and MDP. The results show that 99 Mo has low affinity both to propanone and NaCl-0.9% solution. However, 99 Mo in the presence of MDP presented affinity to NaCl-0.9% solution and low affinity to propanone suggesting that 99 Mo was bound to MDP under the conditions of the experiment. (author)

  4. Carbon supported Pd-Co-Mo alloy as an alternative to Pt for oxygen reduction in direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Rao, Ch. Venkateswara [National Centre for Catalysis Research, Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, TN (India); Viswanathan, B., E-mail: bvnathan@acer.iitm.ernet.i [National Centre for Catalysis Research, Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, TN (India)

    2010-03-01

    Carbon black (CDX975) supported Pd and Pd-Co-Mo alloy nanoparticles are prepared by the reduction of metal precursors with hydrazine in reverse microemulsion of water/Triton-X-100/propanol-2/cyclohexane. The as-synthesized Pd-Co-Mo/CDX975 is heat treated at 973, 1073 and 1173 K to promote alloy formation. The prepared materials are characterized by powder XRD and EDX. Face-centred cubic structure of Pd is evident from XRD. The chemical composition of the respective elements in the catalysts is evaluated from the EDX analysis and observed that it is in good agreement with initial metal precursor concentrations. Oxygen reduction measurements performed by linear sweep voltammetry indicate the good catalytic activity of Pd-Co-Mo alloys compared to Pd. This is due to the suppression of (hydr)oxy species on Pd surface by the presence of alloying elements, Co and Mo. Among the investigated catalysts, heat-treated Pd-Co-Mo/CDX975 at 973 K exhibited good ORR activity compared to the catalysts heat treated at 1073 and 1173 K. This is due to the small crystallite size and high surface area. Rotating disk electrode (RDE) measurements indicated the comparable ORR activity of heat-treated Pd-Co-Mo/CDX975 at 973 K with that of commercial Pt/C. Kinetic analysis reveals that the ORR on Pd-Co-Mo/CDX975 follows the four-electron pathway leading to water. Moreover, Pd-Co-Mo/CDX975 exhibited substantially higher ethanol tolerance during the ORR than Pt/C. Good dispersion of metallic nanoparticles on the carbon support is observed from HRTEM images. Single-cell direct ethanol fuel cell tests indicated the comparable performance of Pd-Co-Mo/CDX975 with that of commercial Pt/C. Stability under DEFC operating conditions for 50 h indicated the good stability of Pd-Co-Mo/CDX975 compared with that of Pt/C.

  5. Preparation, characterization of Mo catalysts supported on Ni- containing calcium deficient hydroxyapatite and reactivity for the thiophene HDS reaction

    Directory of Open Access Journals (Sweden)

    Cherif A.

    2013-09-01

    Full Text Available Ni-containing Calcium Hydroxyapatite (NiCaHAp; 3.31 wt.% Ni was synthesized by coprecipitation and used as catalyst support. Molybdenum was supported on NiCaHAp by impregnation using ammonium heptamolybdate. The prepared catalysts Mo(x/NiCaHAp (x: 2 to 8 wt % in Mo were characterized by elemental analysis, XRD, FT-IR, N2 adsorption-desorption and TEM-EDX. The catalysts were sulfided in-situ at 673 K under flowing H2S/H2 (15 Vol.% H2S and tested in hydrodesulfurization (HDS of thiophene at 673 K. The main XRD peaks of hydroxyapatite CaHAp phase were observed in all samples and a peak due probably to crystalline MoO3 phase was also identified from the results. However, no crystalline phase of NiO was found for the catalysts, which showed its Ni species were highly dispersed. The sulfided catalysts Mo(x/NiCaHAp presented are active in HDS of thiophene, despite the presence of some large MoO3 crystallites and incomplete sulfidation. This activity may be due to interaction of NiO and MoO3 on CaHAp resulting in the formation of Ni-Mo-S phase under flowing H2S/H2. When the molybdenum content increased the HDS activity increasead slightly, which was caused by the agglomeration of MoO3. The Mo(8/NiCaHAp catalyst is about two times less active for thiophene HDS than the commercial NiMoP/Al2O3.

  6. Stereochemistry of 16a-Hydroxyfriedelin and 3-Oxo-16-methylfriedel-16-ene Established by 2D NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Vagner Fernandes Knupp

    2009-02-01

    Full Text Available Friedelin (1, 3b-friedelinol (2, 28-hydroxyfriedelin (3, 16a-hydroxyfriedelin (4, 30-hydroxyfriedelin (5 and 16a,28-dihydroxyfriedelin (6 were isolated through fractionation of the hexane extract obtained from branches of Salacia elliptica. After a week in CDCl3 solution, 16a-hydroxyfriedelin (4 reacted turning into 3-oxo-16-methylfriedel-16-ene (7. This is the first report of a dehydration followed by a Nametkin rearrangement of a pentacyclic triterpene in CDCl3 solution occurring in the NMR tube. These seven pentacyclic triterpenes was identified through NMR spectroscopy and the stereochemistry of compound 4 and 7 was established by 2D NMR (NOESY spectroscopy and mass spectrometry (GC-MS. It is also the first time that all the 13C-NMR and 2D NMR spectral data are reported for compounds 4 and 7.

  7. Increased urinary excretion of 8-oxo-2'-deoxyguanosine, a biomarker of oxidative DNA damage, in urban bus drivers

    DEFF Research Database (Denmark)

    Loft, S; Poulsen, H E; Vistisen, K

    1999-01-01

    Oxidative damage to DNA could be involved in the increased risk of cancer associated with exposure to polluted urban air, which contains a number of oxidants. CYP1A2 is induced by and metabolizes polyaromatic hydrocarbons (PAH) and aromatic amines and could modify effects of exposure to ambient air...... pollution. Similarly, DNA repair may be influenced by occupational and other exposures as well as modify the effect of DNA damaging agents. As part of a large investigation of the genotoxic burden to diesel exposed workers in transport sectors we studied oxidative DNA damage in 57 non-smoking bus drivers...... from the greater Copenhagen area. The drivers were studied on a workday and on a day off work. Comparisons were made between drivers from the central (n=30) and rural/suburban (n=27) areas of Copenhagen. The rate of oxidative DNA damage was estimated from 24 h urinary excretion of 8-oxo-2...

  8. Microstructural defects modeling in the Al-Mo system

    International Nuclear Information System (INIS)

    Pascuet, Maria I.; Fernandez, Julian R.; Monti, Ana M.

    2006-01-01

    In this work we have utilized computer simulation techniques to study microstructural defects, such as point defects and interfaces, in the Al-Mo alloy. Such alloy is taken as a model to study the Al(fcc)/U-Mo(bcc) interface. The EAM interatomic potential used has been fitted to the formation energy and lattice constant of the AlMo 3 intermetallic. Formation of vacancies for both components Al and Mo and anti-sites, Al Mo and Mo Al , as well as vacancy migration was studied in this structure. We found that the lowest energy defect complex that preserves stoichiometry is the antisite pair Al Mo +Mo Al , in correspondence with other intermetallics of the same structure. Our results also suggest that the structure of the Al(fcc)/Mo(bcc) interface is unstable, while that of the Al(fcc)/Al 5 Mo interface is stable, as observed experimentally. (author) [es

  9. Microstructure and tribological properties of NiMo/Mo2Ni3Si intermetallic 'in-situ' composites

    International Nuclear Information System (INIS)

    Gui Yongliang; Song Chunyan; Yang Li; Qin Xiaoling

    2011-01-01

    Research highlights: → Wear resistant NiMo/Mo 2 Ni 3 Si intermetallic 'in-situ' composites was fabricated successfully with Mo-Ni-Si powder blends as the starting materials. Microstructure of the NiMo/Mo 2 Ni 3 Si composites consists of Mo 2 Ni 3 Si primary dendrites, binary intermetallic phase NiMo and small amount of Ni/NiMo eutectics structure. The NiMo/Mo 2 Ni 3 Si composites exhibited high hardness and outstanding tribological properties under room-temperature dry-sliding wear test conditions which were attributed to the covalent-dominant strong atomic bonds and excellent combination of strength and ductility and toughness. - Abstract: Wear resistant NiMo/Mo 2 Ni 3 Si intermetallic 'in-situ' composites with a microstructure of ternary metal silicide Mo 2 Ni 3 Si primary dendritic, the long strip-like NiMo intermetallic phase, and a small amount of Ni/NiMo eutectics structure were designed and fabricated using molybdenum, nickel and silicon elemental powders. Friction and wear properties of NiMo/Mo 2 Ni 3 Si composites were evaluated under different contact load at room-temperature dry-sliding wear test conditions. Microstructure, worn surface morphologies and subsurface microstructure were characterized by OM, XRD, SEM and EDS. Results indicate that NiMo/Mo 2 Ni 3 Si composites have low fiction coefficient, excellent wear resistance and sluggish wear-load dependence. The dominant wear mechanisms of NiMo/Mo 2 Ni 3 Si composites are soft abrasion and slightly superficial oxidative wear.

  10. Impact of reduced graphene oxide on MoS{sub 2} grown by sulfurization of sputtered MoO{sub 3} and Mo precursor films

    Energy Technology Data Exchange (ETDEWEB)

    Pacley, Shanee, E-mail: shanee.pacley@us.af.mil; Brausch, Jacob; Beck-Millerton, Emory [U.S. Air Force Research Laboratory (AFRL)/Wright Patterson Air Force Base, Wright Patterson, Ohio 45433-7707 (United States); Hu, Jianjun; Jespersen, Michael [University of Dayton Research Institute, 300 College Park, Dayton, Ohio 45469 (United States); Hilton, Al [Wyle Laboratories, 4200 Colonel Glenn Hwy, Beavercreek, Ohio 45431 (United States); Waite, Adam [University Technology Corporation, 1270 N Fairfield Rd., Beavercreek, Ohio 45432 (United States); Voevodin, Andrey A. [Department of Materials Science and Engineering, University of North Texas, 1155 Union Circle, Denton, Texas 76203 (United States)

    2016-07-15

    Monolayer molybdenum disulfide (MoS{sub 2}), a two dimensional semiconducting dichalcogenide material with a bandgap of 1.8–1.9 eV, has demonstrated promise for future use in field effect transistors and optoelectronics. Various approaches have been used for MoS{sub 2} processing, the most common being chemical vapor deposition. During chemical vapor deposition, precursors such as Mo, MoO{sub 3}, and MoCl{sub 5} have been used to form a vapor reaction with sulfur, resulting in thin films of MoS{sub 2}. Currently, MoO{sub 3} ribbons and powder, and MoCl{sub 5} powder have been used. However, the use of ribbons and powder makes it difficult to grow large area-continuous films. Sputtering of Mo is an approach that has demonstrated continuous MoS{sub 2} film growth. In this paper, the authors compare the structural properties of MoS{sub 2} grown by sulfurization of pulse vapor deposited MoO{sub 3} and Mo precursor films. In addition, they have studied the effects that reduced graphene oxide (rGO) has on MoS{sub 2} structure. Reports show that rGO increases MoS{sub 2} grain growth during powder vaporization. Herein, the authors report a grain size increase for MoS{sub 2} when rGO was used during sulfurization of both sputtered Mo and MoO{sub 3} precursors. In addition, our transmission electron microscopy results show a more uniform and continuous film growth for the MoS{sub 2} films produced from Mo when compared to the films produced from MoO{sub 3}. Atomic force microscopy images further confirm this uniform and continuous film growth when Mo precursor was used. Finally, x-ray photoelectron spectroscopy results show that the MoS{sub 2} films produced using both precursors were stoichiometric and had about 7–8 layers in thickness, and that there was a slight improvement in stoichiometry when rGO was used.

  11. Rapid water disinfection using vertically aligned MoS_2 nanofilms and visible light

    International Nuclear Information System (INIS)

    Liu, Chong; Kong, Desheng; Hsu, Po-Chun; Yuan, Hongtao; Lee, Hyun-Wook

    2016-01-01

    Here, solar energy is readily available in most climates and can be used for water purification. However, solar disinfection of drinking water (SODIS) mostly relies on ultraviolet light, which represents only 4% of total solar energy, and this leads to slow treatment speed. The development of new materials that can harvest visible light for water disinfection, and speed up solar water purification, is therefore highly desirable. Here, we show that few-layered vertically aligned MoS_2 (FLV-MoS_2) films can be used to harvest the whole spectrum of visible light (~ 50% of solar energy) and achieve highly efficient water disinfection. The bandgap of MoS_2 was increased from 1.3 eV to 1.55 eV by decreasing the domain size, which allowed the FLV-MoS_2 to generate reactive oxygen species (ROS) for bacterial inactivation in water. The FLV-MoS_2 showed ~15 times better log inactivation efficiency of indicator bacteria compared to bulk MoS_2, and much faster inactivation of bacteria under both visible light and sunlight illumination compared to widely used TiO_2. Moreover, by using a 5 nm copper film on top of the FLV-MoS_2 as a catalyst to facilitate electron-hole pair separation and promote the generation of ROS, the disinfection rate was further increased 6 fold. With our approach, we achieved water disinfection of >99.999% inactivation of bacteria in 20 minutes with a small amount of material (1.6 mg/L) under simulated visible light.

  12. Rapid water disinfection using vertically aligned MoS2 nanofilms and visible light

    International Nuclear Information System (INIS)

    Liu, Chong; Kong, Desheng; Hsu, Po-Chun; Yuan, Hongtao; Lee, Hyun-Wook

    2016-01-01

    In most climates, solar energy is readily available and can be used for water purification. But, solar disinfection of drinking water mostly relies on ultraviolet light, which represents only 4% of the total solar energy, and this leads to a slow treatment speed. Therefore, the development of new materials that can harvest visible light for water disinfection, and so speed up solar water purification, is highly desirable. Here we show that few-layered vertically aligned MoS_2 (FLV-MoS_2) films can be used to harvest the whole spectrum of visible light (~50% of solar energy) and achieve highly efficient water disinfection. The bandgap of MoS_2 was increased from 1.3 to 1.55 eV by decreasing the domain size, which allowed the FLV-MoS_2 to generate reactive oxygen species (ROS) for bacterial inactivation in the water. The FLV-MoS_2 showed a ~15 times better log inactivation efficiency of the indicator bacteria compared with that of bulk MoS_2, and a much faster inactivation of bacteria under both visible light and sunlight illumination compared with the widely used TiO_2. Moreover, by using a 5 nm copper film on top of the FLV-MoS_2 as a catalyst to facilitate electron–hole pair separation and promote the generation of ROS, the disinfection rate was increased a further sixfold. Here, we achieved water disinfection of >99.999% inactivation of bacteria in 20 min with a small amount of material (1.6 mg l–1) under simulated visible light.

  13. Tailoring of the structure of Fe-cationic species in Fe-ZSM-5 by distribution of Al atoms in the framework for N2O decomposition and NH3-SCR-NOx

    Czech Academy of Sciences Publication Activity Database

    Sazama, Petr; Wichterlová, Blanka; Tabor, Edyta; Šťastný, Petr; Sathu, Naveen Kumar; Sobalík, Zdeněk; Dědeček, Jiří; Sklenák, Štěpán; Klein, Petr; Vondrová, Alena

    2014-01-01

    Roč. 312, APR 2014 (2014), s. 123-138 ISSN 0021-9517 R&D Projects: GA ČR GAP106/11/0624; GA TA ČR TA01021377 Institutional support: RVO:61388955 Keywords : Fe-ZSM-5 zeolite * Structure of Fe species * Fe(III)-oxo species Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.921, year: 2014

  14. Measurement of Mo-99 column activity in the evaluation of Mo-99/Tc-99m generator

    International Nuclear Information System (INIS)

    Kuster, Z.

    1994-01-01

    In order to calculate the real elution efficiency of Mo-99/Tc-99m generator the Mo-99 content on the column has to be previously determined. As found in this work, the external measurement of Mo-99-column activity by means of Geiger-Mueller counter is a simple, fast and reliable method. Generally, Mo-99-column is placed slightly out of the center of the generator; therefore the externally measured flux of photons (φ) is an angular-dependent function. If the thickness of the lead container is radially uniform, the flux measured at some distance from the generator (which is rotated in 2π/3 steps) is given by the equation φ = A (1 + Bcos (α-2π(i - 2)/3)) -1 , i=1,2 or 3 (Eq.1) where A is a numerical constant depending on the Mo-99-column activity, B is a numerical constant depending on the Mo-99- column position within the lead container, the angle α depends on the initial orientation of the generator. A total of 20 generator were studied. The measured Mo-99-column activities (Capintec dose calibrator) were in the range 13.1- 35.11 GBq. Contrary to the findings of Vinberg and Kristensen (Eur J Nucl Med 1/1976(219), values of A (Eq. 1) are in good correlation (r 2 =0.9794) with the measured Mo-99-column activities. (author)

  15. EXAFS study of Mo2N and Mo nitrides supported on zeolites

    International Nuclear Information System (INIS)

    Liu Zhenlin; Meng Ming; Fu Yilu; Jiang Ming; Hu Tiandou; Xie Yaning; Liu Tao

    2002-01-01

    In the present study, the reaction is applied to prepare molybdenum nitrides with high surface area, and zeolites are used as supports. The EXAFS of the Mo K-absorption edge is measured and the change of coordination environment of Mo atoms before and after the nitridation is revealed

  16. DFT study of the reactions of Mo and Mo with CO2 in gas phase

    Indian Academy of Sciences (India)

    understanding the mechanism of second-row metal reacting with CO2. The minimum energy ... et al.18 performed an IR study on the reaction of laser- ablated Mo atom .... indicate that the weak electrostatic interaction between. Mo. + and CO2 ...

  17. Cu4Pr6(MoO4)11-Pr2(MoO4)3 system

    International Nuclear Information System (INIS)

    Arzumanyan, G.A.

    1982-01-01

    Existence boundaries and Dalton compositions (CuPr(MoO 4 ) 2 , CuPr 3 (MoO 4 ) 5 ) of solid solutions that in the mojority are of shcheelite dsitored structure have been determined in the Cu 4 Pr 6 (MoO 4 ) 11 -Pr 2 (MoO 4 ) 3 system. It has been revealed that regions of homogeneity near the CuPr(MoO 4 ) 2 composition have a horseshoeshaped profile

  18. Effect of Ni on the characteristics and hydrogenation activity of sulfide Mo/γ-Al2O3

    International Nuclear Information System (INIS)

    Schachtl, E.; Wuttke, E.; Gutierrez, O.Y.; Lercher, J.A.

    2012-01-01

    The hydrogenation of phenanthrene was explored on sulfide Mo/γ-Al 2 O 3 catalysts promoted with increasing concentrations of Ni. The characterization of the materials was done by N 2 -physisorption, X-ray diffraction, transmission electron microscopy, temperature programmed sulfidation and NO adsorption experiments. Increasing loading of Ni improves the dispersion of MoS 2 species; however, at Ni/(Mo+Ni) molar ratio higher than 0.5, segregation of Ni-sulfides is observed. The presence of Ni also facilitates the sulfidation of oxidic catalyst precursors by lowering the reduction temperature of Mo species. In the sulfide catalysts, Ni changes the structure of MoS 2 leading to shorter slabs with higher stacking degree than on Mo/γ-Al 2 O 3 , and increases the concentration of coordinatively unsaturated sites. The kinetic results (increased hydrogenation rate and changed reaction network in the presence of Ni) suggest that a highly active kind of active site is created by Ni promotion. (orig.)

  19. Metabolism of Oxo-Bile Acids and Characterization of Recombinant 12α-Hydroxysteroid Dehydrogenases from Bile Acid 7α-Dehydroxylating Human Gut Bacteria.

    Science.gov (United States)

    Doden, Heidi; Sallam, Lina A; Devendran, Saravanan; Ly, Lindsey; Doden, Greta; Daniel, Steven L; Alves, João M P; Ridlon, Jason M

    2018-05-15

    Bile acids are important cholesterol-derived nutrient signaling hormones, synthesized in the liver, that act as detergents to solubilize dietary lipids. Bile acid 7α-dehydroxylating gut bacteria generate the toxic bile acids deoxycholic acid and lithocholic acid from host bile acids. The ability of these bacteria to remove the 7-hydroxyl group is partially dependent on 7α-hydroxysteroid dehydrogenase (HSDH) activity, which reduces 7-oxo-bile acids generated by other gut bacteria. 3α-HSDH has an important enzymatic activity in the bile acid 7α-dehydroxylation pathway. 12α-HSDH activity has been reported for the low-activity bile acid 7α-dehydroxylating bacterium Clostridium leptum ; however, this activity has not been reported for high-activity bile acid 7α-dehydroxylating bacteria, such as Clostridium scindens , Clostridium hylemonae , and Clostridium hiranonis Here, we demonstrate that these strains express bile acid 12α-HSDH. The recombinant enzymes were characterized from each species and shown to preferentially reduce 12-oxolithocholic acid to deoxycholic acid, with low activity against 12-oxochenodeoxycholic acid and reduced activity when bile acids were conjugated to taurine or glycine. Phylogenetic analysis suggests that 12α-HSDH is widespread among Firmicutes , Actinobacteria in the Coriobacteriaceae family, and human gut Archaea IMPORTANCE 12α-HSDH activity has been established in the medically important bile acid 7α-dehydroxylating bacteria C. scindens , C. hiranonis , and C. hylemonae Experiments with recombinant 12α-HSDHs from these strains are consistent with culture-based experiments that show a robust preference for 12-oxolithocholic acid over 12-oxochenodeoxycholic acid. Phylogenetic analysis identified novel members of the gut microbiome encoding 12α-HSDH. Future reengineering of 12α-HSDH enzymes to preferentially oxidize cholic acid may provide a means to industrially produce the therapeutic bile acid ursodeoxycholic acid. In

  20. Doping of two-dimensional MoS2 by high energy ion implantation

    Science.gov (United States)

    Xu, Kang; Zhao, Yuda; Lin, Ziyuan; Long, Yan; Wang, Yi; Chan, Mansun; Chai, Yang

    2017-12-01

    Two-dimensional (2D) materials have been demonstrated to be promising candidates for next generation electronic circuits. Analogues to conventional Si-based semiconductors, p- and n-doping of 2D materials are essential for building complementary circuits. Controllable and effective doping strategies require large tunability of the doping level and negligible structural damage to ultrathin 2D materials. In this work, we demonstrate a doping method utilizing a conventional high-energy ion-implantation machine. Before the implantation, a Polymethylmethacrylate (PMMA) protective layer is used to decelerate the dopant ions and minimize the structural damage to MoS2, thus aggregating the dopants inside MoS2 flakes. By optimizing the implantation energy and fluence, phosphorus dopants are incorporated into MoS2 flakes. Our Raman and high-resolution transmission electron microscopy (HRTEM) results show that only negligibly structural damage is introduced to the MoS2 lattice during the implantation. P-doping effect by the incorporation of p+ is demonstrated by Photoluminescence (PL) and electrical characterizations. Thin PMMA protection layer leads to large kinetic damage but also a more significant doping effect. Also, MoS2 with large thickness shows less kinetic damage. This doping method makes use of existing infrastructures in the semiconductor industry and can be extended to other 2D materials and dopant species as well.

  1. Comparison of the redox activities of sol-gel and conventionally prepared Bi-Mo-Ti mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Wildberger, M.; Grundwaldt, J.D.; Mallat, T.; Baiker, A. [Lab. of Technical Chemistry, Swiss Federal Inst. of Technology, ETH-Zentrum, Zuerich (Switzerland)

    1998-12-31

    Novel sol-gel Bi-Mo-Ti oxides have been prepared and characterized by XRD, XPS, FT-Raman and HRTEM. The surface Bi{sup 3+} and Mo{sup 6+} species of some xerogels and an aerogel could be reduced and oxidized at room temperature, whereas the conventionally prepared reference materials were not reduced by H{sub 2} below 300 C. The unusual redox properties, under very mild conditions, are likely due to the unique morphology of Bi-Mo-oxides stabilized by titania. During butadiene oxidation to furan at above 400 C to sol-gel mixed oxides restructured considerably and their performance was barely better than that of titania-supported Bi-Mo oxides. (orig.)

  2. Estudio de la biodegradación de bolsas oxo - biodegradables utilizando compost maduro seco, con aireación y simulando condiciones ambientales de humedad y temperatura de un relleno sanitario ubicado en la Costa Ecuatoriana.

    OpenAIRE

    Sandoval Moreira, María Isabel

    2014-01-01

    This work allowed the study of biodegradability of four types of oxo-biodegradable bags used to sell products, simulating environmental conditions of a landfill located in the city of Manta. El presente trabajo permitió el estudio de la biodegrabilidad de cuatro tipos de bolsas oxo-biodegradables utilizadas para la venta de productos, simulando condiciones ambientales de un relleno sanitario ubicado en la ciudad de Manta.

  3. ITO-free flexible organic photovoltaics with multilayer MoO3/LiF/MoO3/Ag/MoO3 as the transparent electrode

    International Nuclear Information System (INIS)

    Chen, Shilin; Dai, Yunjie; Zhang, Hongmei; Zhao, Dewei

    2016-01-01

    We present efficient flexible organic photovoltaics (OPVs) with multiple layers of molybdenum oxide (MoO 3 )/LiF/MoO 3 /Ag/MoO 3 as the transparent electrode, where the thin Ag layer yields high conductivity and the dielectric layer MoO 3 /LiF/MoO 3 has high transparency due to optical interference, leading to improved power conversion efficiency compared with indium tin oxide (ITO) based devices. The MoO 3 contacting organic active layer is used as a buffer layer for good hole extraction. Thus, the multilayer MoO 3 /LiF/MoO 3 /Ag/MoO 3 can improve light transmittance and also facilitate charge carrier extraction. Such an electrode shows excellent mechanical bendability with a 9% reduction of efficiency after 1000 cycles of bending due to the ductile nature of the thin metal layer and dielectric layer used. Our results suggest that the MoO 3 /LiF/MoO 3 /Ag/MoO 3 multilayer electrode is a promising alternative to ITO as an electrode in OPVs. (paper)

  4. Room temperature isotherms for Mo and Ni

    International Nuclear Information System (INIS)

    Masse, J.L.

    1986-11-01

    Isotherms at room temperature for Mo and Ni are proposed. They are of three types: BIRCH, KEANE and BORN-MIE. The adjustable constants appearing in these isotherms have been determined from experimental quantities at zero pressure. An evaluation of the limit of (δB T /δP) T as P #-> # ∞, where B T is the isothermal bulk modulus, has been also used. These three isotherms obtained for Mo and Ni are compared with isotherms derived from shock-wave data according to the PRIETO's model. There is a good agreement between these and these derived from shock-wave data. The three isotherms proposed for Mo and Ni can be considered as valid until pressures of several B To , where B To is the bulk modulus B T at P = o [fr

  5. Wetting of metals and glasses on Mo

    Energy Technology Data Exchange (ETDEWEB)

    Saiz, Eduardo; Tomsia, Antoni P.; Saiz, Eduardo; Lopez-Esteban, Sonia; Benhassine, Mehdi; de Coninck, Joel; Rauch, Nicole; Ruehle, Manfred

    2008-01-08

    The wetting of low melting point metals and Si-Ca-Al-Ti-O glasses on molybdenum has been investigated. The selected metals (Au, Cu, Ag) form a simple eutectic with Mo. Metal spreading occurs under nonreactive conditions without interdiffusion or ridge formation. The metals exhibit low (non-zero) contact angles on Mo but this requires temperatures higher than 1100 C in reducing atmospheres in order to eliminate a layer of adsorbed impurities on the molybdenum surface. By controlling the oxygen activity in the furnace, glass spreading can take place under reactive or nonreactive conditions. We have found that in the glass/Mo system the contact angle does not decrease under reactive conditions. In all cases, adsorption from the liquid seems to accelerate the diffusivity on the free molybdenum surface.

  6. Catalytic upgrading of oleic acid into biofuel using Mo modified zeolite supported Ni oxalate catalyst functionalized with fluoride ion

    International Nuclear Information System (INIS)

    Ayodele, O.B.; Abbas, Hazzim F.; Daud, Wan Mohd Ashri Wan

    2014-01-01

    Highlights: • Modification of zeolite with freshly prepared molybdenum oxalate. • Functionalization of Ni oxalate with HF and incorporation into Mo modified zeolite. • Characterization of synthesized Mo modified zeolite supported Ni oxalate catalyst. • Deoxygenation of oleic acid with the synthesized zeolite supported catalyst. • Reusability study on the synthesized zeolite supported catalyst. - Abstract: In this study, fluoride ion functionalized nickel oxalate supported on molybdenum modified zeolite (NiMoFOx/Zeol) catalyst was synthesized, characterized and tested on the hydrodeoxygenation (HDO) of oleic acid (OA) into paraffinic fuel. The NiMoFOx/Zeol characterization results confirmed the presence of both Ni and Mo as well as the formation of NiMoO 4 which is a highly HDO reactive specie at 2θ value of 43.6° according to the XRD result. NiMoFOx/Zeol also showed loss in crystallinity and reduction in the average particle size leading to increase in the pore volume and specific surface area due to the combined effects of fluoride ion presence, oxalic acid functionalization and calcination. The effect of temperature, pressure and NiMoFOx/Zeol loading studied showed that initial increase in their values increased the yield of the target fractions until some points where reduction was observed. The best observed experimental conditions to hydrodeoxygenate 40 g (∼45 mL) of OA into 75% n-C 18 and 23% i-C 18 were 360 °C, 30 mg NiMoFOx/Zeol loading and 20 bar using 100 mL H 2 /min. The presence of i-C 18 was due to the functionalization of the catalyst with fluoride ion. The catalyst reusability result displayed excellent qualities with marginal loss of only 2% in activity after third reuse due to the improved synthesis protocol that employed organometallic precursor. The results are strongly encouraging for further studies toward industrialization of HDO process

  7. Vedinių su priesaga *-mo- raida

    Directory of Open Access Journals (Sweden)

    Saulius Ambrazas

    2011-12-01

    Full Text Available DEVELOPMENT OF DERIVATIVES WITH THE SUFFIX *-mo-SummaryAdjectives with the suffix *-mo- have been formed from substantives (cf. Lith. tólimas / tólymas and Latv. dial. tuôl’eims ‘distant’; Pruss. *auktimas ‘high’; Skr. agrimá- ‘the first, who is at the head’ and verbs (cf. Lith. dial. ãpsukmas ‘sewn round’, pliùkšmas ‘deflated, limp’; OLith. laimas ‘happy’ and Pruss. etnīstislaims (gnadenreich III 631; Lith. liñksmas and Latv. lìksms ‘merry, gay, joyfull’, Gmc. *werma- ‘warm’, Skr. bhīmá- ‘terrible, frightfull’, Toch. A, B cämpamo- ‘well-to-do, rich’, Hitt. kišamma- ‘combed’ from the Late Proto-Indo-European. The gratest part of them became participles in the Baltic, Slavic and Albanian languages.On the other hand, the use of derivatives with the suffix *-mo- in the position of abstract nouns is also very old, cf. semanticaly concretized and derivationaly indissoluble abstract noun, in herited from Proto-Indo-European, Lith. dmas (dmai, Latv. dũmi, Pruss. dumis (rauch E 39, Slav. *dymъ, Latv. fūmus, Skr. dhūmó- ‘smoke’ and Gk. θῡ‑μός with abstract meaning ‘soal, vitality, passion,    need’ : dhe-/dh-/dhū- ‘blow; breathe; choke; smoke; rush; disperse; whirl, move, stir’.In the East Baltic languages abstract nouns with the derived suffixes, based on *-mo-, became productive, cf. nomina actionis with *-i-mo- in Lithuanian (cf. gyvẽnimas ‘life’ and corresponding derivatives with *-u-mo- in Latvian (cf. ìeradums ‘custom, habit’.

  8. 2 : 2 Fe(III): ligand and "adamantane core" 4 : 2 Fe(III): ligand (hydr)oxo complexes of an acyclic ditopic ligand

    DEFF Research Database (Denmark)

    Ghiladi, Morten; Larsen, Frank B.; McKenzie, Christine J.

    2005-01-01

    A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X-ray struct......A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X...

  9. Synthesis and pharmacological evaluation of N-substituted 2-(2-oxo-2H-chromen-4-yloxy)propanamide as cyclooxygenase inhibitors.

    Science.gov (United States)

    Rambabu, D; Mulakayala, Naveen; Ismail; Kumar, K Ravi; Kumar, G Pavan; Mulakayala, Chaitanya; Kumar, Chitta Suresh; Kalle, Arunasree M; Rao, M V Basaveswara; Oruganti, Srinivas; Pal, Manojit

    2012-11-01

    A series of novel N-substituted 2-(2-oxo-2H-chromen-4-yloxy)propanamide derivatives were synthesized via converting the readily available 4-hydroxy coumarin to the corresponding ethyl 2-(2-oxo-2H-chromen-4-yloxy)propanoate followed by hydrolysis and then reacting with different substituted amines. The molecular structures of two representative compounds, that is, 3 and 5l were confirmed by single crystal X-ray diffraction study. All the compounds synthesized were evaluated for their cyclooxygenase (COX) inhibiting properties in vitro. The compound 5i showed balanced selectivity towards COX-2 over COX-1 inhibition and good docking scores when docked into the COX-2 protein. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. Biocatalytic Conversion of Avermectin to 4"-Oxo-Avermectin: Characterization of Biocatalytically Active Bacterial Strains and of Cytochrome P450 Monooxygenase Enzymes and Their Genes

    Science.gov (United States)

    Jungmann, Volker; Molnár, István; Hammer, Philip E.; Hill, D. Steven; Zirkle, Ross; Buckel, Thomas G.; Buckel, Dagmar; Ligon, James M.; Pachlatko, J. Paul

    2005-01-01

    4"-Oxo-avermectin is a key intermediate in the manufacture of the agriculturally important insecticide emamectin benzoate from the natural product avermectin. Seventeen biocatalytically active Streptomyces strains with the ability to oxidize avermectin to 4"-oxo-avermectin in a regioselective manner have been discovered in a screen of 3,334 microorganisms. The enzymes responsible for this oxidation reaction in these biocatalytically active strains were found to be cytochrome P450 monooxygenases (CYPs) and were termed Ema1 to Ema17. The genes for Ema1 to Ema17 have been cloned, sequenced, and compared to reveal a new subfamily of CYPs. Ema1 to Ema16 have been overexpressed in Escherichia coli and purified as His-tagged recombinant proteins, and their basic enzyme kinetic parameters have been determined. PMID:16269732

  11. Elevated Temperature Tensile Tests on DU–10Mo Rolled Foils

    Energy Technology Data Exchange (ETDEWEB)

    Schulthess, Jason [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2014-09-01

    Tensile mechanical properties for uranium-10 wt.% molybdenum (U–10Mo) foils are required to support modeling and qualification of new monolithic fuel plate designs. It is expected that depleted uranium-10 wt% Mo (DU–10Mo) mechanical behavior is representative of the low enriched U–10Mo to be used in the actual fuel plates, therefore DU-10Mo was studied to simplify material processing, handling, and testing requirements. In this report, tensile testing of DU-10Mo fuel foils prepared using four different thermomechanical processing treatments were conducted to assess the impact of foil fabrication history on resultant tensile properties.

  12. 8-oxo-7,8-dihydroguanine level - the DNA oxidative stress marker - recognized by fluorescence image analysis in sporadic uterine adenocarcinomas in women.

    Science.gov (United States)

    Postawski, Krzysztof; Przadka-Rabaniuk, Dorota; Piersiak, Tomasz

    2013-01-01

    In the case of carcinogenesis in human endometrium no information exists on tissue concentration of 8-oxo-7,8-dihydroguanine, the DNA oxidative stress marker This was the main reason to undertake the investigation of this DNA modification in human uterine estrogen-dependent tissue cancers. In order to estimate the level of oxidative damage, 8-oxo-7,8-dihydroguanine was determined directly in cells of tissue microscope slides using OxyDNA Assay Kit, Fluorometric. Cells were investigated under confocal microscope. Images of individual cells were captured by computer-interfaced digital photography and analyzed for fluorescence intensities (continuous inverted 8-bit gray-scale = 0 [black]-255 [white]). Fluorescence scores were calculated for each of 13 normal endometrial samples and 31 uterine adenocarcinoma specimens. Finally the level of the oxidative stress marker was also analyzed according to histological and clinical features of the neoplasms. The obtained data revealed that: 8-oxo-7,8-dihydroguanine levels were higher in uterine adenocarcinomas than in normal endometrial samples (48,32 vs. 38,64; p<0,001); in contrast to normal endometrium there was no correlation between age and DNA oxidative modification content in uterine cancer; highest mean fluorescence intensity was recognized in G2 endometrial adenocarcinomas; level of 8-oxo-7,8-dihydroguanine does not depend on Body Mass Index (BMI) and cancer uterine wall infiltration or tumor FIGO stage. Our study indicates that accumulation of the oxidized DNA base may contribute to the development of endometrial neoplasia, however oxidative DNA damage does not seem to increase with tumor progression.

  13. (E-3-Methyl-6-(3-oxo-3-(3,4,5-trimethoxyphenylprop-1-en-1-yl-2(3H-benzothiazolone

    Directory of Open Access Journals (Sweden)

    Yordanka Ivanova

    2016-09-01

    Full Text Available The title compound, (E-3-methyl-6-(3-oxo-3-(3,4,5-trimethoxyphenylprop-1-en-1-yl-2(3H-benzothiazolone, was synthesized by both an acid- and base-catalyzed aldol condensation of 3-methyl-6-acetyl-2(3H-benzothiazolone and 3,4,5-trimethoxyacetophenone. The structure of the target compound was confirmed using 1H-NMR, 13C-NMR, IR, MS, and elemental analysis.

  14. Study of 2-methyl -2-oxo-3,5-di-tert.-butyl-Δ4-1,3,2-oxazaphospholine interaction with lanthanide shifting reagents

    International Nuclear Information System (INIS)

    Turov, A.V.; Povolotskij, M.I.; Balitskij, Yu.V.; Kornilov, M.Yu.; Boldeskul, I.E.

    1983-01-01

    2-methyl-2-oxo-3.5-di-tret.-butyl-Δ 4 -1, 3, 2-oxazaphospholine in CDCl 3 solution reacts with lanthanide shifting reagents-tris (dipivaloylmethanates) of europium (3) and praseodymium (3)-with the formation of adducts of constant composition. At that, in ( + H, 13 C) NMR spectra considerable pseudocontact induced shifts of substratum signals take place. Geometry of the adducts formed is calculated

  15. One-Pot Two-Step Multicomponent Process of Indole and Other Nitrogenous Heterocycles or Amines toward α-Oxo-acetamidines.

    Science.gov (United States)

    Martinez-Ariza, Guillermo; McConnell, Nicholas; Hulme, Christopher

    2016-04-15

    A cesium carbonate promoted three-component reaction of N-H containing heterocycles, primary or secondary amines, arylglyoxaldehydes, and anilines is reported. The key step involves a tandem sequence of N-1 addition of a heterocycle or an amine to preformed α-iminoketones, followed by an air- or oxygen-mediated oxidation to form α-oxo-acetamidines. The scope of the reaction is enticingly broad, and this novel methodology is applied toward the synthesis of various polycyclic heterocycles.

  16. On flotation separation of oxo-anions of transition metals by the use of fine-emulsified solutions of cationic collector in non-polar liquids

    International Nuclear Information System (INIS)

    Skrylev, L.D.; Purich, A.N.; Babinets, S.K.

    1980-01-01

    Experimentally shown is a principle possibility of flotation separation of oxo-anions of transition metals by the use of fine-emulsified solutions of cationic collector in non-polar liquids. Ammonium vanadate and sodium tuno.state solutions have been the objects of study. Hexadezilamine has been used as collector. The collector has been introduced in the form of hexadecylamine emulsions in n-decane, in tetrachloromethane or alcohol. Optimum pH value ranges are determined for separation processes

  17. The modulation of Schottky barriers of metal-MoS2 contacts via BN-MoS2 heterostructures.

    Science.gov (United States)

    Su, Jie; Feng, Liping; Zhang, Yan; Liu, Zhengtang

    2016-06-22

    Using first-principles calculations within density functional theory, we systematically studied the effect of BN-MoS2 heterostructure on the Schottky barriers of metal-MoS2 contacts. Two types of FETs are designed according to the area of the BN-MoS2 heterostructure. Results show that the vertical and lateral Schottky barriers in all the studied contacts, irrespective of the work function of the metal, are significantly reduced or even vanish when the BN-MoS2 heterostructure substitutes the monolayer MoS2. Only the n-type lateral Schottky barrier of Au/BN-MoS2 contact relates to the area of the BN-MoS2 heterostructure. Notably, the Pt-MoS2 contact with n-type character is transformed into a p-type contact upon substituting the monolayer MoS2 by a BN-MoS2 heterostructure. These changes of the contact natures are ascribed to the variation of Fermi level pinning, work function and charge distribution. Analysis demonstrates that the Fermi level pinning effects are significantly weakened for metal/BN-MoS2 contacts because no gap states dominated by MoS2 are formed, in contrast to those of metal-MoS2 contacts. Although additional BN layers reduce the interlayer interaction and the work function of the metal, the Schottky barriers of metal/BN-MoS2 contacts still do not obey the Schottky-Mott rule. Moreover, different from metal-MoS2 contacts, the charges transfer from electrodes to the monolayer MoS2, resulting in an increment of the work function of these metals in metal/BN-MoS2 contacts. These findings may prove to be instrumental in the future design of new MoS2-based FETs with ohmic contact or p-type character.

  18. Phase relations in the M2MoO4 - Ag2MoO4 - Hf(MoO4)2 (M=Li, Na) systems

    International Nuclear Information System (INIS)

    Bazarova, Zh.G.; Bazarov, B.G.; Balsanova, L.V.

    2002-01-01

    The M 2 MoO 4 - Ag 2 MoO 4 - Hf(MoO 4 ) 2 (M=Li, Na) systems were studied by X-ray diffraction and differential thermal analyses in the subsolidus area (450 - 500 Deg C) for the first time. The formation of the binary compound with the variable composition Li 4-x Hf 1+0.2x (MoO 4 ) 4 (0 ≤ x ≤ 0.6) in the Li 2 MoO 4 - Hf(MoO 4 ) 2 system and the ternary molybdates Li 4 Ag 2 Hf(MoO 4 ) 5 (S 1 ) and Na 2 Ag 2 Hf(MoO 4 ) 4 (S 2 ) was established and the thermal characteristics of the prepared compounds were examined. The new binary molybdate Ag 2 Hf(MoO 4 ) 3 was prepared by the reaction between Ag 2 MoO 4 and Hf(MoO 4 ) 2 [ru

  19. Subtle interactions and electron transfer between UIII, NpIII, or PuIII and uranyl mediated by the oxo group

    International Nuclear Information System (INIS)

    Arnold, Polly L.; Zegke, Markus; Hollis, Emmalina; Pecharman, Anne-Frederique; Love, Jason B.; Dutkiewicz, Michal S.; Walter, Olaf; Apostolidis, Christos; Magnani, Nicola; Griveau, Jean-Christophe; Colineau, Eric; Caciuffo, Roberto; Zhang, Xiaobin; Schreckenbach, Georg

    2016-01-01

    A dramatic difference in the ability of the reducing An III center in AnCp 3 (An=U, Np, Pu; Cp=C 5 H 5 ) to oxo-bind and reduce the uranyl(VI) dication in the complex [(UO 2 )(THF)(H 2 L)] (L=''Pacman'' Schiff-base polypyrrolic macrocycle), is found and explained. These are the first selective functionalizations of the uranyl oxo by another actinide cation. At-first contradictory electronic structural data are explained by combining theory and experiment. Complete one-electron transfer from Cp 3 U forms the U IV -uranyl(V) compound that behaves as a U V -localized single molecule magnet below 4 K. The extent of reduction by the Cp 3 Np group upon oxo-coordination is much less, with a Np III -uranyl(VI) dative bond assigned. Solution NMR and NIR spectroscopy suggest Np IV U V but single-crystal X-ray diffraction and SQUID magnetometry suggest a Np III -U VI assignment. DFT-calculated Hirshfeld charge and spin density analyses suggest half an electron has transferred, and these explain the strongly shifted NMR spectra by spin density contributions at the hydrogen nuclei. The Pu III -U VI interaction is too weak to be observed in THF solvent, in agreement with calculated predictions. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Syntheses and catalytic oxotransfer activities of oxo molybdenum(vi) complexes of a new aminoalcohol phenolate ligand.

    Science.gov (United States)

    Hossain, M K; Haukka, M; Sillanpää, R; Hrovat, D A; Richmond, M G; Nordlander, E; Lehtonen, A

    2017-05-30

    The new aminoalcohol phenol 2,4-di-tert-butyl-6-(((2-hydroxy-2-phenylethyl)amino)methyl)phenol (H2L) was prepared by a facile solvent-free synthesis and used as a tridentate ligand for new cis-dioxomolybdenum(vi)(L) complexes. In the presence of a coordinating solvent (DMSO, MeOH, pyridine), the complexes crystallise as monomeric solvent adducts while in the absence of such molecules, a trimer with asymmetric Mo[double bond, length as m-dash]O→Mo bridges crystallises. The complexes can catalyse epoxidation of cis-cyclooctene and sulfoxidation of methyl-p-tolylsulfide, using tert-butyl hydroperoxide as oxidant.

  1. Mo-V-Te-Nb oxides as catalysts for ethene production by oxidative dehydrogenation of ethane

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, D. [Technische Universitaet Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center; Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany)

    2013-11-01

    The availability of ethane in shale gas, as well as the interest in valorising previously underutilized carbon feedstocks, makes the oxidative dehydrogenation (ODH) of ethane an attractive alternative to the industrially established processes for production of ethylene. Mo-V-Te-Nb mixed oxide has been chosen as catalyst for the ODH reaction in view of its outstanding ability to activate alkane molecules. Catalytic test results showed that this type of catalyst can selectively oxidize ethane to ethene at moderate temperatures (350-400 C) with minor production of CO{sub x}. The catalytic performance of Mo-V-Te-Nb mixed-oxide is mainly attributable to the crystalline phase 'M1'. Rietveld analysis of the X-Ray diffractograms allowed us to quantify the amount of MoVTeNb oxide that has crystallized as M1. In this way, it was possible to find a linear correlation of the reaction rate with the abundance of M1 in the solid. Therefore, it is clear that for improving the efficiency of MoVTeNb oxide in ODH, the amount of M1 in the catalyst should be maximized. With this purpose, several MoVTeNb oxides were subject to different thermal treatments prior to the catalytic test. Structural changes in the catalyst were monitored by in-situ XRD technique. Under oxidative atmosphere, it was observed a recrystallization of M2 and possibly, amorphous oxide, into M1 phase, leading to correspondingly more active and selective catalysts (selectivities above 95 % for ethane conversions up to 40 % under industrially relevant conditions). The active site of M1 involves V species, likely with redox properties enhanced by the proximity of Mo and Te species, while the function of the crystalline structure itself is to provide the spatial configuration that allows interaction between these species. However, ethene formation rate was observed to be independent of the V content of the samples. The vanadium species exposed at the surface were studied by LEIS and by IR spectroscopy of CO

  2. Investigation of BaMoO4-Ln2(MoO4)3 systems (Ln = Nd, Sm, Yb)

    International Nuclear Information System (INIS)

    Vakulyuk, V.V.; Evdokimov, A.A.; Khomchenko, G.P.

    1982-01-01

    Using the methods of X-ray phase and differential-thermal analyses phase ratios in the systems BaMoO 4 -Ln 2 (MoO 4 ) 3 (Ln=Nd, Sm, Yb); BaNd 2 (MoO 4 ) 4 -MaGd 2 (MoO 4 ) are studied. Unit cell parameters and the character of melting of the compounds BaLn 2 (MoO 4 ) 4 are specified. Effect of growth conditions on laminated nature of BaGd 2 (MoO 4 ) 4 monocrystals is studied

  3. Metabolic characteristics of 13-cis-retinoic acid (isotretinoin) and anti-tumour activity of the 13-cis-retinoic acid metabolite 4-oxo-13-cis-retinoic acid in neuroblastoma.

    Science.gov (United States)

    Sonawane, Poonam; Cho, Hwang Eui; Tagde, Ashujit; Verlekar, Dattesh; Yu, Alice L; Reynolds, C Patrick; Kang, Min H

    2014-12-01

    Isotretinoin (13-cis-retinoic acid; 13-cRA) is a differentiation inducer used to treat minimal residual disease after myeloablative therapy for high-risk neuroblastoma. However, more than 40% of children develop recurrent disease during or after 13-cRA treatment. The plasma concentrations of 13-cRA in earlier studies were considered subtherapeutic while 4-oxo-13-cis-RA (4-oxo-13-cRA), a metabolite of 13-cRA considered by some investigators as inactive, were greater than threefold higher than 13-cRA. We sought to define the metabolic pathways of 13-cRA and investigated the anti-tumour activity of its major metabolite, 4-oxo-13-cRA. Effects of 13-cRA and 4-oxo-13-cRA on human neuroblastoma cell lines were assessed by DIMSCAN and flow cytometry for cell proliferation, MYCN down-regulation by reverse transcription PCR and immunoblotting, and neurite outgrowth by confocal microscopy. 13-cRA metabolism was determined using tandem MS in human liver microsomes and in patient samples. Six major metabolites of 13-cRA were identified in patient samples. Of these, 4-oxo-13-cRA was the most abundant, and 4-oxo-13-cRA glucuronide was also detected at a higher level in patients. CYP3A4 was shown to play a major role in catalysing 13-cRA to 4-oxo-13-cRA. In human neuroblastoma cell lines, 4-oxo-13-cRA and 13-cRA were equi-effective at inducing neurite outgrowth, inhibiting proliferation, decreasing MYCN mRNA and protein, and increasing the expression of retinoic acid receptor-β mRNA and protein levels. We showed that 4-oxo-13-cRA is as active as 13-cRA against neuroblastoma cell lines. Plasma levels of both 13-cRA and 4-oxo-13-cRA should be evaluated in pharmacokinetic studies of isotretinoin in neuroblastoma. © 2014 The British Pharmacological Society.

  4. Teens join the MoEDAL collaboration

    CERN Multimedia

    Stephanie Hills

    2013-01-01

    The principal investigator for any institute joining an experimental collaboration is generally a self-assured researcher with evident leadership skills and an in-depth knowledge of their subject gained over many years. Katherine Evans fits the brief in every respect, except that she is 17 years old and her research institute is the Langton Star Centre, based at the Simon Langton Grammar School for Boys. The school has just joined the MoEDAL experiment.   Teacher Becky Parker (left) with two students from the Simon Langton Grammar School for Boys in the MoEDAL experimental area. MoEDAL, the latest LHC experiment has detectors located close to the interaction point of the LHCb experiment. This new experiment is designed to search for the highly ionizing avatars of new physics at the LHC, specifically the magnetic monopole or dyon and other highly ionizing stable massive particles from a number of beyond-the-Standard-Model scenarios. MoEDAL was approved in 2010 and is due to start taking data i...

  5. Ventilation system for 99Mo production apparatus

    International Nuclear Information System (INIS)

    Izumo, Mishiroku; Okane, Shougo; Sorita, Takami; Aoyama, Saburou

    1978-04-01

    In production of 20 Ci 99 Mo from 235 U fission, about 120 Ci of radioiodine ( 131 I, 132 I, and 133 I) is involved. To remove airborne radioiodine from the exhaust air from production apparatus and minimize radioiodine release to the atmosphere, the ventilation system is equipped with 2 units of Model-FD charcoal filter (KI 3 -Impregnated charcoal 2 inch thick of Barnebey-Cheney Co.). From September 1976 to December 1977, 21 runs of 99 Mo production involving airborne radioiodine were carried out. The ventilation system was operated continuously for the whole 15 months period; variation in removal efficiency of airborne radioiodine from the exhaust air stream was observed. In the runs valuable experiences were gained in operation and maintenance of the ventilation system including activated charcoal filter and health-physics management of such facility. Following are the results: (1) Airborne radioiodine from 99 Mo production apparatus is reduced to 10 -3 % of the original quantity. (2) When the ventilation system is operated at a maximum air flow rate through the filter, the average efficiency during 15 months is over 98%. (3) Airborne radioiodine released from 99 Mo production apparatus to the ventilation system is less than 5% particulate iodine and alkyl iodines and more than 95% inorganic iodine. (4) Airborne radioiodine released from the stack is less than 28 μCi/run, which is below the limit in regulations on Radioisotope Production Laboratory. (auth.)

  6. Analysis of MoDOT communication and outreach effectiveness

    Science.gov (United States)

    2008-07-01

    Personal interviews were held with MoDOT personnel to assess MoDOTs current communication practices and existing customer segmentation practices. Focus groups were then held to help gauge the effectiveness of existing communication practices and t...

  7. Fixation Of Mo In Uranium Leach Liquor By Activated Carbon

    International Nuclear Information System (INIS)

    Mainar, S.; Guswita, A.; Erni, R.A.; Susilaningtyas

    1996-01-01

    The use of activated carbon for Mo fixation by bulk system is reported. Several factors influencing the fixation process were examined, including contact time, carbon particle size, carbon porosity and the effect of other elements present in Mo containing solutions. Experimental data showed that an adsorption equilibrium of Mo on of activated carbon and 0,85 to 1,18 mm of carbon particle size under forced-convection mass transfer in 100 ml solution that contains + 0,56 m mol of Mo and +. 0,25 m mol Of U was reached after 6 hours period. Under those conditions, about 0,50 m mol of Mo and 0,026 m mol of U were adsorbed into carbon. High concentration of rare earth elements decreased Mo adsorption, hence, the use of activated carbon was not effective to separate Mo from the digestion liquor of Rirang are where Mo was adsorbed, into the carbon + 34,5 %

  8. X-ray fluorescence analysis of Fe - Ni - Mo systems

    International Nuclear Information System (INIS)

    Belyaev, E.E.; Ershov, A.V.; Mashin, A.I.; Mashin, N.I.; Rudnevskij, N.K.

    1998-01-01

    Procedures for the X-ray fluorescence determination of the composition and thickness of Fe - Ni - Mo thin films and the concentration of elements in thick films of the Fe - Ni - Mo alloy are developed [ru

  9. Interdiffusion between U(Mo,Pt) or U(Mo,Zr) and Al or Al A356 alloy

    International Nuclear Information System (INIS)

    Komar Varela, C.; Mirandou, M.; Arico, S.; Balart, S.; Gribaudo, L.

    2009-01-01

    Solid state reactions in chemical diffusion couples U-7 wt.%Mo-0.9 wt.%Pt/Al at 580 deg. C and U-7 wt.%Mo-0.9 wt.%Pt/Al A356 alloy, U-7 wt.%Mo-1 wt.%Zr/Al and U-7 wt.%Mo-1 wt.%Zr/Al A356 alloy at 550 deg. C were characterized. Results were obtained from optical and scanning electron microscopy, electron probe microanalysis and X-ray diffraction. The UAl 3, UAl 4 and Al 20 Mo 2 U phases were identified in the interaction layers of γU(Mo,Pt)/Al and γU(Mo,Zr)/Al diffusion couples. Al 43 Mo 4 U 6 ternary compound was also identified in γU(Mo,Zr)/Al due to the decomposition of γU(Mo,Zr) phase. The U(Al,Si) 3 and U 3 Si 5 phases were identified in the interaction layers of γU(Mo,Pt)/Al A356 and γU(Mo,Zr)/Al A356 diffusion couples. These phases are formed due to the migration of Si to the interaction layer. In the diffusion couple U(Mo,Zr)/Al A356, Zr 5 Al 3 phase was also identified in the interaction layer. The use of synchrotron radiation at Brazilian Synchrotron Light Laboratory (LNLS, CNPq, Campinas, Brazil) was necessary to achieve a complete crystallographic characterization.

  10. Transfer matrix approach to electron transport in monolayer MoS2/MoO x heterostructures

    Science.gov (United States)

    Li, Gen

    2018-05-01

    Oxygen plasma treatment can introduce oxidation into monolayer MoS2 to transfer MoS2 into MoO x , causing the formation of MoS2/MoO x heterostructures. We find the MoS2/MoO x heterostructures have the similar geometry compared with GaAs/Ga1‑x Al x As semiconductor superlattice. Thus, We employ the established transfer matrix method to analyse the electron transport in the MoS2/MoO x heterostructures with double-well and step-well geometries. We also considere the coupling between transverse and longitudinal kinetic energy because the electron effective mass changes spatially in the MoS2/MoO x heterostructures. We find the resonant peaks show red shift with the increasing of transverse momentum, which is similar to the previous work studying the transverse-momentum-dependent transmission in GaAs/Ga1‑x Al x As double-barrier structure. We find electric field can enhance the magnitude of peaks and intensify the coupling between longitudinal and transverse momentums. Moreover, higher bias is applied to optimize resonant tunnelling condition to show negative differential effect can be observed in the MoS2/MoO x system.

  11. Effect of Mo/B atomic ratio on the properties of Mo2NiB2-based cermets

    International Nuclear Information System (INIS)

    Xie, Lang; Li, XiaoBo; Zhang, Dan; Yi, Li; Gao, XiaoQing; Xiangtan Univ.

    2015-01-01

    Using three elementary substances, Mo, Ni, and amorphous B as raw materials, four series of Mo 2 NiB 2 -based cermets with the Mo/B atomic ratio ranging from 0.9 to 1.2 were successfully prepared via reaction sintering. The effect of Mo/B atomic ratio on the microstructure and properties was studied for the cermets. The results indicate that there is a strong correlation between the Mo/B atomic ratio and properties. The transverse rupture strength of the cermets increases with an increase in Mo/B ratio and shows a maximum value of 1 872 MPa at an Mo/B atomic ratio of 1.1 and then decreases with increasing Mo/B atomic ratio. The hardness and the corrosion resistance of the cermets increase monotonically with an increase in Mo/B atomic ratio. In Mo-rich cermets with an atomic ratio of Mo/B above 1.1, a small amount Ni-Mo intermetallic compound is found precipitated at the interface of Mo 2 NiB 2 grains.

  12. Phase transitions in alloys of the Ni-Mo system

    International Nuclear Information System (INIS)

    Ustinovshikov, Y.; Shabanova, I.

    2011-01-01

    Graphical abstract: The structure of Ni-20 at.% Mo and Ni-25 at.% Mo alloys was studied by methods of TEM and XPS. It is shown that at high temperatures the tendency toward phase separation takes place in the alloys and crystalline bcc Mo particles precipitate in the liquid solution. At 900 deg. C and below, the tendency toward ordering leads to the dissolution of Mo particles and precipitation of the particles of Ni 3 Mo, Ni 2 Mo or Ni 4 Mo chemical compounds. Highlights: → 'Chemical' phase transition 'ordering-phase separation' is first discovered in alloys of the Ni-Mo system. → It is first shown that the phase separation in the alloys studied begins at temperatures above the liquidus one. → The formation of Ni 3 Mo from A1 has gone through the intervening stage of the Ni 4 Mo and Ni 2 Mo coexistence. - Abstract: The structure of Ni-20 at.% Mo and Ni-25 at.% Mo alloys heat treated at different temperatures was studied by the method of transmission electron microscopy. X-ray photoelectron spectroscopy was used to detect the sign of the chemical interaction between Ni and Mo atoms at different temperatures. It is shown that at high temperatures the tendency toward phase separation takes place. The system of additional reflections at positions {1 1/2 0} on the electron diffraction patterns testifies that the precipitation of crystalline bcc Mo particles begins in the liquid solution. At 900 deg. C and below, the tendency toward ordering leads to the precipitation of the particles of the chemical compounds. A body-centered tetragonal phase Ni 4 Mo (D1 a ) is formed in the Ni-20 at.% Mo alloy. In the Ni-25 at.% Mo alloy, the formation of the Ni 3 Mo (D0 22 ) chemical compound from the A1 solid solution has gone through the intervening stage of the Ni 4 Mo (D1 a ) and Ni 2 Mo (Pt 2 Mo) formation.

  13. Preparation of NO-doped β-MoO{sub 3} and its methanol oxidation property

    Energy Technology Data Exchange (ETDEWEB)

    Pham, Thi Thuy Phuong, E-mail: pttphuong@ict.vast.vn; Nguyen, Phuc Hoang Duy; Vo, Tan Tai; Luu, Cam Loc; Nguyen, Huu Huy Phuc

    2016-12-01

    The major drawback of the industrial iron molybdate catalysts which is their deactivation problem has driven the study of alternative catalysts for formaldehyde production from methanol. In this paper, NO-doped β-MoO{sub 3} was successfully synthesized from the commercial molybdic acid powder (H{sub 2}MoO{sub 4}) and characterized by differential thermal analysis (DTA), X-ray Diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Results obtained from XRD and Raman spectroscopy indicated that the synthesized sample has all features of the well-known β-MoO{sub 3} except for the presence of a new small peak. The curve-fitting of XPS spectra revealed that nitrogen-containing species may be present in the form of negatively charged nitrogen oxide in the prepared sample. Due to its metastable nature, NO-doped β-MoO{sub 3} may be transformed into the thermally stable α-MoO{sub 3} at temperature higher than 400 °C as pointed out by DTA study. However, when the reaction temperature was as low as 300 °C, the catalyst was stable for partial methanol oxidation with no significant change in activity during 30 h of catalytic study. Methanol conversion and formaldehyde selectivity were maintained at about 98% and 99%, respectively. - Highlights: • NO-doped β-MoO{sub 3} was synthesized by a facile and effective method. • Its structure was confirmed by XRD, Raman and XPS analysis. • X{sub MeOH} and S{sub HCHO} were stabilized at 98% and 99%, respectively, for the first 30 h.

  14. Tunneling microscopy of 2H-MoS2: A compound semiconductor surface

    OpenAIRE

    Weimer, M.; Kramar, J.; Bai, C.; Baldeschwieler, J. D.

    1988-01-01

    Molybdenum disulfide, a layered semiconductor, is an interesting material to study with the tunneling microscope because two structurally and electronically different atomic species may be probed at its surface. We report on a vacuum scanning tunneling microscopy study of 2H-MoS2. Atomic resolution topographs and current images show the symmetry of the surface unit cell and clearly reveal two distinct atomic sites in agreement with the well-known x-ray crystal structure.

  15. 12-Oxo-Phytodienoic Acid Accumulation during Seed Development Represses Seed Germination in Arabidopsis[C][W][OA

    Science.gov (United States)

    Dave, Anuja; Hernández, M. Luisa; He, Zhesi; Andriotis, Vasilios M.E.; Vaistij, Fabián E.; Larson, Tony R.; Graham, Ian A.

    2011-01-01

    Arabidopsis thaliana COMATOSE (CTS) encodes an ABC transporter involved in peroxisomal import of substrates for β-oxidation. Various cts alleles and mutants disrupted in steps of peroxisomal β-oxidation have previously been reported to exhibit a severe block on seed germination. Oxylipin analysis on cts, acyl CoA oxidase1 acyl CoA oxidase2 (acx1 acx2), and keto acyl thiolase2 dry seeds revealed that they contain elevated levels of 12-oxo-phytodienoic acid (OPDA), jasmonic acid (JA), and JA-Ile. Oxylipin and transcriptomic analysis showed that accumulation of these oxylipins occurs during late seed maturation in cts. Analysis of double mutants generated by crossing cts with mutants in the JA biosynthesis pathway indicate that OPDA, rather than JA or JA-Ile, contributes to the block on germination in cts seeds. We found that OPDA was more effective at inhibiting wild-type germination than was JA and that this effect was independent of CORONATINE INSENSITIVE1 but was synergistic with abscisic acid (ABA). Consistent with this, OPDA treatment increased ABA INSENSITIVE5 protein abundance in a manner that parallels the inhibitory effect of OPDA and OPDA+ABA on seed germination. These results demonstrate that OPDA acts along with ABA to regulate seed germination in Arabidopsis. PMID:21335376

  16. Synthesis of deuterium-labeled analogs of the lipid hydroperoxide-derived bifunctional electrophile 4-oxo-2(E)-nonenal.

    Science.gov (United States)

    Arora, Jasbir S; Oe, Tomoyuki; Blair, Ian A

    2011-05-15

    Lipid hydroperoxides undergo homolytic decomposition into the bifunctional 4-hydroxy-2( E )-nonenal and 4-oxo-2( E )-nonenal (ONE). These bifunctional electrophiles are highly reactive and can readily modify intracellular molecules including glutathione (GSH), deoxyribonucleic acid (DNA) and proteins. Lipid hydroperoxide-derived bifunctional electrophiles are thought to contribute to the pathogenesis of a number of diseases. ONE is an α , β -unsaturated aldehyde that can react in multiple ways and with glutathione, proteins and DNA. Heavy isotope-labeled analogs of ONE are not readily available for conducting mechanistic studies or for use as internal standards in mass spectrometry (MS)-based assays. An efficient onestep cost-effective method has been developed for the preparation of C-9 deuterium-labeled ONE. In addition, a method for specific deuterium labeling of ONE at C-2, C-3 or both C-2 and C-3 has been developed. This latter method involved the selective reduction of an intermediate alkyne either by lithium aluminum hydride or lithium aluminum deuteride and quenching with water or deuterium oxide. The availability of these heavy isotope analogs will be useful as internal standards for quantitative studies employing MS and for conducting mechanistic studies of complex interactions between ONE and DNA bases as well as between ONE and proximal amino acid residues in peptides and proteins.

  17. Biocatalytic Conversion of Avermectin to 4"-Oxo-Avermectin: Heterologous Expression of the ema1 Cytochrome P450 Monooxygenase

    Science.gov (United States)

    Molnár, István; Hill, D. Steven; Zirkle, Ross; Hammer, Philip E.; Gross, Frank; Buckel, Thomas G.; Jungmann, Volker; Pachlatko, Johannes Paul; Ligon, James M.

    2005-01-01

    The cytochrome P450 monooxygenase Ema1 from Streptomyces tubercidicus R-922 and its homologs from closely related Streptomyces strains are able to catalyze the regioselective oxidation of avermectin into 4"-oxo-avermectin, a key intermediate in the manufacture of the agriculturally important insecticide emamectin benzoate (V. Jungmann, I. Molnár, P. E. Hammer, D. S. Hill, R. Zirkle, T. G. Buckel, D. Buckel, J. M. Ligon, and J. P. Pachlatko, Appl. Environ. Microbiol. 71:6968-6976, 2005). The gene for Ema1 has been expressed in Streptomyces lividans, Streptomyces avermitilis, and solvent-tolerant Pseudomonas putida strains using different promoters and vectors to provide biocatalytically competent cells. Replacing the extremely rare TTA codon with the more frequent CTG codon to encode Leu4 in Ema1 increased the biocatalytic activities of S. lividans strains producing this enzyme. Ferredoxins and ferredoxin reductases were also cloned from Streptomyces coelicolor and biocatalytic Streptomyces strains and tested in ema1 coexpression systems to optimize the electron transport towards Ema1. PMID:16269733

  18. Nanoparticulate iron(III) oxo-hydroxide delivers safe iron that is well absorbed and utilised in humans

    Science.gov (United States)

    Pereira, Dora I.A.; Bruggraber, Sylvaine F.A.; Faria, Nuno; Poots, Lynsey K.; Tagmount, Mani A.; Aslam, Mohamad F.; Frazer, David M.; Vulpe, Chris D.; Anderson, Gregory J.; Powell, Jonathan J.

    2014-01-01

    Iron deficiency is the most common nutritional disorder worldwide with substantial impact on health and economy. Current treatments predominantly rely on soluble iron which adversely affects the gastrointestinal tract. We have developed organic acid-modified Fe(III) oxo-hydroxide nanomaterials, here termed nano Fe(III), as alternative safe iron delivery agents. Nano Fe(III) absorption in humans correlated with serum iron increase (P solubility. The most promising preparation (iron hydroxide adipate tartrate: IHAT) showed ~80% relative bioavailability to Fe(II) sulfate in humans and, in a rodent model, IHAT was equivalent to Fe(II) sulfate at repleting haemoglobin. Furthermore, IHAT did not accumulate in the intestinal mucosa and, unlike Fe(II) sulfate, promoted a beneficial microbiota. In cellular models, IHAT was 14-fold less toxic than Fe(II) sulfate/ascorbate. Nano Fe(III) manifests minimal acute intestinal toxicity in cellular and murine models and shows efficacy at treating iron deficiency anaemia. From the Clinical Editor This paper reports the development of novel nano-Fe(III) formulations, with the goal of achieving a magnitude less intestinal toxicity and excellent bioavailability in the treatment of iron deficiency anemia. Out of the tested preparations, iron hydroxide adipate tartrate met the above criteria, and may become an important tool in addressing this common condition. PMID:24983890

  19. Antitumor activity of newly synthesized oxo and ethylidene derivatives of bile acids and their amides and oxazolines.

    Science.gov (United States)

    Bjedov, Srđan; Jakimov, Dimitar; Pilipović, Ana; Poša, Mihalj; Sakač, Marija

    2017-04-01

    Bile acid derivatives with modifications in side chain and modifications on steroid skeleton were synthetized and their antitumor activity against five human cancer cell lines was investigated. Modifications in side chain include amid group, formed in reaction with 2-amino-2-methylpropanol, and 4,4-dimethyloxazoline group, obtained after cyclization of amides. In the steroid skeleton oxo groups were introduced in position 7 (2, 2a, 2b) and 7,12 (3, 3a, 3b). Ethylidene groups were introduced regio- and stereoselectively on C-7, and/or without stereoselectivity on C-3 by Wittig reaction. By combination of these modifications, a series of 19 bile acid derivatives were synthesized. Compounds containing both C-7 ethylidene and C-12 carbonyl groups (6, 6a, 6b) shown very good antitumor activity with IC 50 amide or oxazoline group has positive effect on cytotoxicity. Different molecular descriptors were determined in silico and after principal component analysis was found that molecular descriptor BLTF96 can be used for fast assessment of experimental cytotoxicity of bile acid derivatives. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Selective kappa-opioid agonists: synthesis and structure-activity relationships of piperidines incorporating on oxo-containing acyl group.

    Science.gov (United States)

    Giardina, G; Clarke, G D; Dondio, G; Petrone, G; Sbacchi, M; Vecchietti, V

    1994-10-14

    This study describes the synthesis and the structure-activity relationships (SARs) of the (S)-(-)-enantiomers of a novel class of 2-(aminomethyl)piperidine derivatives, using kappa-opioid binding affinity and antinociceptive potency as the indices of biological activity. Compounds incorporating the 1-tetralon-6-ylacetyl residue (30 and 34-45) demonstrated an in vivo antinociceptive activity greater than predicted on the basis of their kappa-binding affinities. In particular, (2S)-2-[(dimethylamino)methyl]-1-[(5,6,7,8-tetrahydro-5-oxo-2- naphthyl)acetyl]piperidine (34) was found to have a potency similar to spiradoline in animal models of antinociception after subcutaneous administration, with ED50s of 0.47 and 0.73 mumol/kg in the mouse and in the rat abdominal constriction tests, respectively. Further in vivo studies in mice and/or rats revealed that compound 34, compared to other selective kappa-agonists, has a reduced propensity to cause a number of kappa-related side effects, including locomotor impairment/sedation and diuresis, at antinociceptive doses. For example, it has an ED50 of 26.5 mumol/kg sc in the rat rotarod model, exhibiting a ratio of locomotor impairment/sedation vs analgesia of 36. Possible reasons for this differential activity and its clinical consequence are discussed.

  1. 4-Hydroxy-5-methoxy-N,1-dimethyl-2-oxo-N-[4-(trifluoromethylphenyl]-1,2-dihydroquinoline-3-carboxamide

    Directory of Open Access Journals (Sweden)

    Emmanuel S. Akinboye

    2014-03-01

    Full Text Available The title compound, C20H17F3N2O4, named tasquinimod, is a second-generation oral quinoline-3-carboxamide analogue, which is currently in phase III clinical trials for the treatment of metastatic prostate cancer. The quinoline unit is almost planar (r.m.s. deviation of fitted atoms = 0.0075 Å. The carboxamide side chain, substituted at position 3, is tilted by 88.07 (7° to the quinoline plane. Both the methyl and carbonyl groups of this carboxamide side chain are in a syn conformation. The 4-(trifluoromethylphenyl plane is inclined at 50.62 (17° to the plane of the carboxamide side chain, and at 87.14 (4° to the plane of the quinoline ring system. The 4-hydroxy H atom acts as a double proton donor in an intramolecular hydrogen bond to the 5-position methoxy O atom and in an intermolecular contact to the 2-oxo group, generating a chain along [010] in the crystal structure.

  2. Interstitial Mo-Assisted Photovoltaic Effect in Multilayer MoSe2 Phototransistors.

    Science.gov (United States)

    Kim, Sunkook; Maassen, Jesse; Lee, Jiyoul; Kim, Seung Min; Han, Gyuchull; Kwon, Junyeon; Hong, Seongin; Park, Jozeph; Liu, Na; Park, Yun Chang; Omkaram, Inturu; Rhyee, Jong-Soo; Hong, Young Ki; Yoon, Youngki

    2018-03-01

    Thin-film transistors (TFTs) based on multilayer molybdenum diselenide (MoSe 2 ) synthesized by modified atmospheric pressure chemical vapor deposition (APCVD) exhibit outstanding photoresponsivity (103.1 A W -1 ), while it is generally believed that optical response of multilayer transition metal dichalcogenides (TMDs) is significantly limited due to their indirect bandgap and inefficient photoexcitation process. Here, the fundamental origin of such a high photoresponsivity in the synthesized multilayer MoSe 2 TFTs is sought. A unique structural characteristic of the APCVD-grown MoSe 2 is observed, in which interstitial Mo atoms exist between basal planes, unlike usual 2H phase TMDs. Density functional theory calculations and photoinduced transfer characteristics reveal that such interstitial Mo atoms form photoreactive electronic states in the bandgap. Models indicate that huge photoamplification is attributed to trapped holes in subgap states, resulting in a significant photovoltaic effect. In this study, the fundamental origin of high responsivity with synthetic MoSe 2 phototransistors is identified, suggesting a novel route to high-performance, multifunctional 2D material devices for future wearable sensor applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Electron microscopy studies on MoS2 nanocrystals

    DEFF Research Database (Denmark)

    Hansen, Lars Pilsgaard

    Industrial-style MoS2-based hydrotreating catalysts are studied using electron microscopy. The MoS2 nanostructures are imaged with single-atom sensitivity to reveal the catalytically important edge structures. Furthermore, the in-situ formation of MoS2 crystals is imaged for the first time....

  4. Ternary alloying study of MoSi2

    International Nuclear Information System (INIS)

    Yi, D.; Li, C.; Akselsen, O.M.; Ulvensoen, J.H.

    1998-01-01

    Ternary alloying of MoSi 2 with adding a series of transition elements was investigated by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy (TEM), and energy dispersive spectroscopy (EDS). Iron, Co, Ni, Cr, V, Ti, and Nb were chosen as alloying elements according to the AB 2 structure map or the atomic size factor. The studied MoSi 2 base alloys were prepared by the arc melting process from high-purity metals. The EDS analysis showed that Fe, Co, and Ni have no solid solubility in as-cast MoSi 2 , while Cr, V, Ti, and Nb exhibit limited solid solubilities, which were determined to be 1.4 ± 0.7, 1.4 ± 0.4, 0.4 ± 0.1, and 0.8 ± 0.1. Microstructural characterization indicated that Mo-Si-M VIII (M VIII = Fe, Co, Ni) and Mo-Si-Cr alloys have a two-phase as-cast microstructure, i.e., MoSi 2 matrix and the second-phase FeSi 2 , CoSi, NiSi 2 , and CrSi 2 , respectively. In as-cast Mo-Si-V, Mo-Si-Ti, and Mo-Si-Nb alloys, besides MoSi 2 and C40 phases, the third phases were observed, which have been identified to be (Mo, V) 5 Si 3 , TiSi 2 , and (Mo, Nb) 5 Si 3

  5. 76 FR 43576 - Amendment of Class E Airspace; Hannibal, MO

    Science.gov (United States)

    2011-07-21

    ...-0046; Airspace Docket No. 11-ACE-1] Amendment of Class E Airspace; Hannibal, MO AGENCY: Federal... Hannibal, MO. Decommissioning of the Hannibal non-directional beacon (NDB) at Hannibal Regional Airport, Hannibal, MO, has made this action necessary to enhance the safety and management of Instrument Flight Rule...

  6. Demonstration of resonant photopumping of Mo VII by Mo XII for a VUV laser near 600 Angstrom

    International Nuclear Information System (INIS)

    Ilcisin, K.J.; Aumayr, F.; Schwob, J.L.; Suckewer, S.

    1993-09-01

    We present data of experiments on the resonant photopumping of Mo VII by Mo XII as a method of generating a coherent VUV source near 600 angstrom. The experiment is based on a scheme proposed by Feldman and Reader in which the 4p 6 -- 4p 5 6s transition in Mo VII in resonantly photopumped by the 5s 2 S 1/2 -- 4p 2 P 1/2 transition in Mo XII. Results of the laser produced plasma experiments show the successful enhancement of the population of the Mo VII 4p 5 6s upper lasing level when pumped by an adjacent Mo VII plasma. No enhancement was seen in a control experiment where the Mo VII plasma was pumped by a Zr X plasma. Improvements of the intensity of the Mo XII pump source, achieved using an additional pump laser, lead to the generation of a population inversion for the VUV transition

  7. The reactive transport benchmark proposed by GdR MoMaS: presentation and first results

    Energy Technology Data Exchange (ETDEWEB)

    Carrayrou, J. [Institut de Mecanique des Fluides et des Solides, UMR ULP-CNRS 7507, 67 - Strasbourg (France); Lagneau, V. [Ecole des Mines de Paris, Centre de Geosciences, 77 - Fontainebleau (France)

    2007-07-01

    We present here the actual context of reactive transport modelling and the major numerical challenges. GdR MoMaS proposes a benchmark on reactive transport. We present this benchmark and some results obtained on it by two reactive transport codes HYTEC and SPECY. (authors)

  8. The reactive transport benchmark proposed by GdR MoMaS: presentation and first results

    International Nuclear Information System (INIS)

    Carrayrou, J.; Lagneau, V.

    2007-01-01

    We present here the actual context of reactive transport modelling and the major numerical challenges. GdR MoMaS proposes a benchmark on reactive transport. We present this benchmark and some results obtained on it by two reactive transport codes HYTEC and SPECY. (authors)

  9. Hydrogen Doping into MoO3 Supports toward Modulated Metal-Support Interactions and Efficient Furfural Hydrogenation on Iridium Nanocatalysts.

    Science.gov (United States)

    Xie, Lifang; Chen, Ting; Chan, Hang Cheong; Shu, Yijin; Gao, Qingsheng

    2018-03-16

    As promising supports, reducible metal oxides afford strong metal-support interactions to achieve efficient catalysis, which relies on their band states and surface stoichiometry. In this study, in situ and controlled hydrogen doping (H doping) by means of H 2 spillover was employed to engineer the metal-support interactions in hydrogenated MoO x -supported Ir (Ir/H-MoO x ) catalysts and thus promote furfural hydrogenation to furfuryl alcohol. By easily varying the reduction temperature, the resulting H doping in a controlled manner tailors low-valence Mo species (Mo 5+ and Mo 4+ ) on H-MoO x supports, thereby promoting charge redistribution on Ir and H-MoO x interfaces. This further leads to clear differences in H 2 chemisorption on Ir, which illustrates its potential for catalytic hydrogenation. As expected, the optimal Ir/H-MoO x with controlled H doping afforded high activity (turnover frequency: 4.62 min -1 ) and selectivity (>99 %) in furfural hydrogenation under mild conditions (T=30 °C, PH2 =2 MPa), which means it performs among the best of current catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Controllable synthesis of carbon nanotubes by changing the Mo content in bimetallic Fe-Mo/MgO catalyst

    International Nuclear Information System (INIS)

    Xu Xiangju; Huang Shaoming; Yang Zhi; Zou Chao; Jiang Junfan; Shang Zhijie

    2011-01-01

    Research highlights: → Increasing the Mo content in the Fe-Mo/MgO catalysts resulted in an increase in wall number, diameter and growth yield of carbon nanotubes. → The Fe interacts with MgO to form complex (MgO) x (FeO) 1-x (0 4 and relative large metal Mo particles can be generated after reduction. → The avalanche-like reduction of MgMoO 4 makes the catalyst particles to be small thus enhances the utilize efficiency of Fe nanoparticles. - Abstract: A series of Fe-Mo/MgO catalysts with different Mo content were prepared by combustion method and used as catalysts for carbon nanotube (CNT) growth. Transmission electron microscopy studies of the nanotubes show that the number of the CNT walls and the CNT diameters increase with the increasing of Mo content in the bimetallic catalyst. The growth yield determined by thermogravimetric analysis also follows the trend: the higher the Mo content, the higher the yield of the CNTs. However, the increase of Mo content leads to the lower degree of graphitization of CNTs. A comparative study on the morphology and catalytic functions of Fe/MgO, Mo/MgO and Fe-Mo/MgO catalysts was carried out by scanning electron microscopy and X-ray diffraction. It is found that the Fe interacts with MgO to form complexes and is then dispersed into the MgO support uniformly, resulting in very small Fe nanoparticles after reduction. The Mo interacts with MgO to form stoichiometry compound MgMoO 4 and relative large metal Mo particles can be generated after reduction. High yield CNTs with small diameter can be generated from Fe-Mo/MgO because the avalanche-like reduction of MgMoO 4 makes the catalyst particles to be small thus enhances the utilize efficiency of Fe nanoparticles.

  11. Adsorption of oxyanions of As, B, Cr, Mo and Se from coal fly ash leachates using Al3+/Fe3+modified bentonite clay

    CSIR Research Space (South Africa)

    Vhahangwele, M

    2013-01-01

    Full Text Available ponds. On disposal, coal fly ash leaches out toxic chemical species on contact with the aqueous media hence posing hazardous effects to the aquatic and terrestrial environment. Of prime concern are Oxyanionic species such as As, B, Cr, Mo and Se...

  12. Controlling magnetism of MoS2 sheets by embedding transition-metal atoms and applying strain.

    Science.gov (United States)

    Zhou, Yungang; Su, Qiulei; Wang, Zhiguo; Deng, Huiqiu; Zu, Xiaotao

    2013-11-14

    Prompted by recent experimental achievement of transition metal (TM) atoms substituted in MoS2 nanostructures during growth or saturating existing vacancies (Sun et al., ACS Nano, 2013, 7, 3506; Deepak et al., J. Am. Chem. Soc., 2007, 129, 12549), we explored, via density functional theory, the magnetic properties of a series of 3d TM atoms substituted in a MoS2 sheet, and found that Mn, Fe, Co, Ni, Cu and Zn substitutions can induce magnetism in the MoS2 sheet. The localizing unpaired 3d electrons of TM atoms respond to the introduction of a magnetic moment. Depending on the species of TM atoms, the substituted MoS2 sheet can be a metal, semiconductor or half-metal. Remarkably, the applied elastic strain can be used to control the strength of the spin-splitting of TM-3d orbitals, leading to an effective manipulation of the magnetism of the TM-substituted MoS2 sheet. We found that the magnetic moment of the Mn- and Fe-substituted MoS2 sheets can monotonously increase with the increase of tensile strain, while the magnetic moment of Co-, Ni-, Cu- and Zn-substituted MoS2 sheets initially increases and then decreases with the increase of tensile strain. An instructive mechanism was proposed to qualitatively explain the variation of magnetism with elastic strain. The finding of the magnetoelastic effect here is technologically important for the fabrication of strain-driven spin devices on MoS2 nanostructures, which allows us to go beyond the current scope limited to the spin devices within graphene and BN-based nanostructures.

  13. A systematic first principle method to study magnetic properties of FeMo, CoMo and NiMo

    International Nuclear Information System (INIS)

    Bhattacharjee, Ashis Kumar; Touheed, Md.; Ahmed, Mesbahuddin; Halder, A.; Mookerjee, A.

    2003-06-01

    We use the first principle TB-LMTO (Tight-Binding Linear Muffin Tin Orbital) method combined with the ASM (Augmented Space Method) to take care of disorder beyond the mean field (CPA - Cohetent Potential Approximation) approximation. We analyze binary alloys between magnetic transition metals Fe, Co, Ni and non-magnetic Mo to find out the effect of disorder on electronic structure and consequently magnetic properties of the alloys. (author)

  14. High pressure effect on MoS2 and MoSe2 single crystals grown by ...

    Indian Academy of Sciences (India)

    Unknown

    tetrahedral anvil apparatus up to 5 GPa. In this paper we report room temperature resistance mea- surements as a function of pressure on MoS2 and MoSe2 single crystals. In each case the resistance decreases un- der pressure due to an increase in the carrier concentration. 2. Experimental. Single crystals of MoS2 and ...

  15. Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl)(PMe3)3.

    Science.gov (United States)

    Khalimon, Andrey Y; Shirobokov, Oleg G; Peterson, Erik; Simionescu, Razvan; Kuzmina, Lyudmila G; Howard, Judith A K; Nikonov, Georgii I

    2012-04-02

    The reaction of (ArN=)MoCl(2)(PMe(3))(3) (Ar = 2,6-diisopropylphenyl) with L-Selectride gives the hydrido-chloride complex (ArN=)Mo(H)(Cl)(PMe(3))(3) (2). Complex 2 was found to catalyze the hydrosilylation of carbonyls and nitriles as well as the dehydrogenative silylation of alcohols and water. Compound 2 does not show any productive reaction with PhSiH(3); however, a slow H/D exchange and formation of (ArN=)Mo(D)(Cl)(PMe(3))(3) (2(D)) was observed upon addition of PhSiD(3). Reactivity of 2 toward organic substrates was studied. Stoichiometric reactions of 2 with benzaldehyde and cyclohexanone start with dissociation of the trans-to-hydride PMe(3) ligand followed by coordination and insertion of carbonyls into the Mo-H bond to form alkoxy derivatives (ArN=)Mo(Cl)(OR)(PMe(2))L(2) (3: R = OCH(2)Ph, L(2) = 2 PMe(3); 5: R = OCH(2)Ph, L(2) = η(2)-PhC(O)H; 6: R = OCy, L(2) = 2 PMe(3)). The latter species reacts with PhSiH(3) to furnish the corresponding silyl ethers and to recover the hydride 2. An analogous mechanism was suggested for the dehydrogenative ethanolysis with PhSiH(3), with the key intermediate being the ethoxy complex (ArN=)Mo(Cl)(OEt)(PMe(3))(3) (7). In the case of hydrosilylation of acetophenone, a D-labeling experiment, i.e., a reaction of 2 with acetophenone and PhSiD(3) in the 1:1:1 ratio, suggests an alternative mechanism that does not involve the intermediacy of an alkoxy complex. In this particular case, the reaction presumably proceeds via Lewis acid catalysis. Similar to the case of benzaldehyde, treatment of 2 with styrene gives trans-(ArN=)Mo(H)(η(2)-CH(2)═CHPh)(PMe(3))(2) (8). Complex 8 slowly decomposes via the release of ethylbenzene, indicating only a slow insertion of styrene ligand into the Mo-H bond of 8.

  16. Electrochemistry of oxo-technetium(V) complexes containing Schiff base and 8-quinolinol ligands

    International Nuclear Information System (INIS)

    Refosco, F.; Mazzi, U.; Deutsch, E.; Kirchhoff, J.R.; Heineman, W.R.; Seeber, R.

    1988-01-01

    The electrochemistry of six-coordinate, monooxo technetium(V) complexes containing Schiff base ligands has been studied in acetonitrile and N,N'-dimethylformamide solutions. The complexes have the general formula TcOCl(L B ) 2 or TcO(L T )(L B ), where L B represents a bidentate-N,O Schiff base ligand or a bidentate-N,O 8-quinolinol ligand and L T represents a tridentate-O,N,O Schiff base ligand. Cyclic voltammetry at a platinum-disk electrode, controlled-potential coulometry, and thin-layer spectroelectrochemistry were used to probe both the oxidation and the reduction of these complexes. The results of these studies, and previously reported results on the analogous Re(V) complexes, can be understood within a single general reaction scheme. The salient features of this scheme are (i) one-electron reduction of Tc(V) to Tc(IV), (ii) subsequent loss of a ligand situated cis to the Tc≡O linkage, and (iii) subsequent isomerization of this unstable Tc(IV) product to more stable complex in which the site trans to the Tc≡O linkage is vacant. The Tc(IV) complexes can also be reduced to analogous Tc(III) species, which appear to undergo the same ligand loss and isomerization reactions. The technetium complexes are 400-500 mV easier to reduce than are their rhenium analogues. The 8-quinolinol ligands, and especially the 5-nitro derivative, both thermodynamically and kinetically stabilize the Tc(IV) and Tc(III) oxidation states. These electrogenerated species are unusual in that they constitute the bulk of the known examples of monomeric Tc(IV) and Tc(III) complexes containing only N- and O-donating ligands. 34 refs., 9 figs., 1 tab

  17. Relation between film thickness and surface doping of MoS2 based field effect transistors

    Science.gov (United States)

    Lockhart de la Rosa, César J.; Arutchelvan, Goutham; Leonhardt, Alessandra; Huyghebaert, Cedric; Radu, Iuliana; Heyns, Marc; De Gendt, Stefan

    2018-05-01

    Ultra-thin MoS2 film doping through surface functionalization with physically adsorbed species is of great interest due to its ability to dope the film without reduction in the carrier mobility. However, there is a need for understanding how the thickness of the MoS2 film is related to the induced surface doping for improved electrical performance. In this work, we report on the relation of MoS2 film thickness with the doping effect induced by the n-dopant adsorbate poly(vinyl-alcohol). Field effect transistors built using MoS2 films of different thicknesses were electrically characterized, and it was observed that the ION/OFF ratio after doping in thin films is more than four orders of magnitudes greater when compared with thick films. Additionally, a semi-classical model tuned with the experimental devices was used to understand the spatial distribution of charge in the channel and explain the observed behavior. From the simulation results, it was revealed that the two-dimensional carrier density induced by the adsorbate is distributed rather uniformly along the complete channel for thin films (<5.2 nm) contrary to what happens for thicker films.

  18. Study of the activation of targets containing Mo for the production of 99Mo by the 98Mo(n,γ)99Mo nuclear reaction and the behaviour of the radionuclidic impurities of the process

    International Nuclear Information System (INIS)

    Nieto, Renata Correa

    1998-01-01

    The most used radioisotope in Nuclear Medicine is 99m Tc, in the 99 Mo- 99m Tc generator form. 99 Mo can be produced by several nuclear reactions in reactors and cyclotrons. The cyclotron production is not technically and economically viable. The production in the reactor can be done in two different ways: by the fission of 235 U and by 98 Mo(n,γ) 99 Mo reaction. A project for the production of 99 Mo by the activation of Mo and the preparation of gel type generators is under development at the 'Instituto de Pesquisas Energeticas e Nucleares'. In the present work, the radionuclidic impurities produced in the activation of MOO 3 and MoZr gel were evaluated, and these represent the two possible ways of preparing the gel of MoZr. A target of metallic Mo was also studied. The radionuclidic purity of 99m Tc eluted from generators prepared in these ways was also measured and compared with the generators prepared with fission 99 Mo. The results showed that, by all the parameters analysed, the best way of preparing the generator of 99 Mo - 99m Tc is the irradiation of MOO 3 and further preparation of the gel and the generators. (author)

  19. Theoretical calculations of valence states in Fe-Mo compounds

    International Nuclear Information System (INIS)

    Estrada, F; Navarro, O; Noverola, H; Suárez, J R; Avignon, M

    2014-01-01

    The half-metallic ferromagnetic double perovskite compound Sr 2 FeMoO 6 is considered as an important material for spintronic applications. It appears to be fundamental to understand the role of electronic parameters controlling the half-metallic ground state. Fe-Mo double perovskites usually present some degree of Fe/Mo disorder which generally increases with doping. In this work, we study the valence states of Fe-Mo cations in the off-stoichiometric system Sr 2 Fe 1+x Mo 1−x O 6 (−1 ≤ x ≤ 1/3) with disorder. Our results for Fe and Mo valence states are obtained using the Green functions and the renormalization perturbation expansion method. The model is based on a correlated electron picture with localized Fe-spins and conduction Mo-electrons interacting with the local spins via a double-exchange-type mechanism

  20. Phase formation in the Li2MoO4-Rb2MoO4-Ln2(MoO4)3 systems and the properties of LiRbLn2(MoO4)4

    International Nuclear Information System (INIS)

    Basovich, O.M.; Khajkina, E.G.; Vasil'ev, E.V.; Frolov, A.M.

    1995-01-01

    Phase equilibria within subsolidus range of ternary salt systems Li 2 MoO 4 -Rb 2 MoO 4 -Ln 2 (MoO 4 ) 4 (Ln - Nd, Er) are analyzed. Formation of ternary molybdate LiRbNd 2 (MoO 4 ) 4 is proved along LiNd(MoO 4 ) 2 -RbNd(MoO 4 )-2 cross-section. Phase diagram of this cross-section is plotted. Similar compounds are synthesized for Ln = La-Eu. The parameters of their monoclinic elementary cells are determined. Luminescent properties of LiRbLa 2 (MoO 4 ) 4 -Nd 3+ are studied. 17 refs., 4 figs., 2 tabs

  1. Successful labeling of 99mTc-MDP using 99mTc separated from 99Mo produced by 100Mo(n,2n)99Mo

    International Nuclear Information System (INIS)

    Nagai, Yasuki; Hatsukawa, Yuichi; Kin, Tadahiro; Hashimoto, Kazuyuki; Motoishi, Shoji; Konno, Chikara; Ochiai, Kentaro; Takakura, Kosuke; Sato, Yuichi; Sato, Norihito; Ohta, Akio; Yamabayashi, Hisamichi; Tanase, Masakazu; Fujisaki, Saburo; Kawauchi, Yukimasa; Teranaka, Tomoyuki; Takeuchi, Nobuhiro; Igarashi, Takashi

    2011-01-01

    We have for the first time succeeded in separating 99m Tc from a MoO 3 sample irradiated with accelerator neutrons free from any radioactive impurities and in formulating 99m Tc-methylene diphosphonate ( 99 mTc-MDP). 99 Mo, the mother nuclide of 99m Tc, was produced by the 100 Mo(n,2n) 99 Mo reaction using about 14 MeV neutrons provided by the 3 H(d,n) 4 He reaction at the Fusion Neutronics Source of Japan Atomic Energy Agency. The 99m Tc was separated from 99 Mo by sublimation and its radionuclide purity was confirmed to be higher than 99.99% by γ-spectroscopy. The labeling efficiency of 99m Tc-MDP was shown to be higher than 99% by thin-layer chromatography. These values exceed the United States Pharmacopeia requirements for a fission product, 99 Mo. Consequently, a 99m Tc radiopharmaceutical preparation formed by using the mentioned 99 Mo can be a promising substitute for the fission product 99 Mo, which is currently produced using a highly enriched uranium target in aging research reactors. A longstanding problem to ensure a reliable and constant supply of 99 Mo in Japan can be partially mitigated. (author)

  2. Study of the 93Mo nucleus

    International Nuclear Information System (INIS)

    Mittal, V.K.; Avasthi, D.K.; Kumar, A; Govil, I.M.

    1981-01-01

    The level structure of 93 Mo has been studied through 93 Nb(p,nγ) reaction at incident proton energy of 4.2 MeV. Spin assignments and multipole mixing ratios for various levels and transitions have been deduced from the analysis of angular distributions of singles γ-ray spectra. Lifetimes of various levels have been obtained using Doppler Shift Attenuation (DSA) method. (author)

  3. MoS{sub 2} spaser

    Energy Technology Data Exchange (ETDEWEB)

    Jayasekara, Charith, E-mail: charith.jayasekara@monash.edu; Premaratne, Malin [Advanced Computing and Simulation Laboratory (A chi L), Department of Electrical and Computer Systems Engineering, Monash University, Clayton, Victoria 3800 (Australia); Gunapala, Sarath D. [Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California 91109 (United States); Stockman, Mark I. [Department of Physics and Astronomy, Georgia State University, Atlanta, Georgia 30303 (United States)

    2016-04-07

    We present a comprehensive analysis of a spaser made of a circular shaped highly doped molybdenum disulfide (MoS{sub 2}) resonator. “Spaser” is an acronym for “surface plasmon amplification by stimulated emission of radiation”–a nanoscale source of surface plasmons generated by stimulated emission in a plasmonic resonator which receives energy nonradiatively. By considering localized surface plasmon modes, operation characteristics of the model are analysed, and tunability of the design is demonstrated. We find the optimum geometric and material parameters of the spaser that provides efficient outputs and carryout a comparative analysis with a similar circular spaser made of graphene. Owing to physical and chemical properties of MoS{sub 2} and the active medium, the proposed design delivers efficient outputs in terms of spaser mode energy, operating thresholds, Q-factor, and electric field amplitude. Lower operating thresholds and higher mode energies are notable advantages of the design. Owing to having many superior features to existing similar designs, this MoS{sub 2} spaser may be much suited for applications in nanoplasmonic devices.

  4. Physicochemical investigation of Bi2MoO6 solid-phase interaction with Sm2MoO6

    International Nuclear Information System (INIS)

    Khajkina, E.G.; Kovba, L.M.; Bazarova, Zh.G.; Khal'baeva, K.M.; Khakhinov, V.V.; Mokhosoev, M.V.

    1986-01-01

    Bi 2 MoO 6 -Sm 2 MoO 6 interaction in the temperature range of 700-1000 deg C is studied using X-ray phase analysis and vibrational spectroscopy. Formation of monoclinic solid solutions based on γ'-Bi 2 MoO 6 and B 2-x Sm x MoO 6 varied composition phase with α-Ln 2 MoO 6 structure which homogeneity region extent at 1000 deg C constitutes ∼ 50 mol % (0.7≤x≤1.7) is stated. Crystallographic characteristics of the synthesized phases are determined

  5. Thermodynamic investigations in the system U-Mo-O

    International Nuclear Information System (INIS)

    Chattopadhyay, G.; Kerkar, A.S.; Tripathi, S.N.

    1984-01-01

    Thermodynamic data on materials are required to answer some practical questions regarding chemical equilibria and also for the ultimate purpose of quantifying the relative stabilities of all possible chemical species. The present work was undertaken to determine what role molybdenum, one of the most preponderant fission products, could play in determining the state of the chemical equilibrium in the fuel fission product complex in an oxide-based nuclear reactor or in the nuclear waste disposed in ceramic or glass forms. To understand and analyze such complex systems, it is necessary to know which are the possible phases and species that are to be considered and their thermodynamic properties. In the present work attention was given to the ternary oxides of uranium and molybdenum with regard to the equilibria among the various phases. This is a prerequisite for determining the thermodynamic properties of the relevant phases. Therefore, experiments were carried out to construct the phase diagram in the region UO 2 -MoO 2 -O in a more precise manner than hitherto and, hence, to determine the free energy of formation of UMoO 5

  6. Synthesis of Fine Mo2C Powder from Prereduced Mo in Undiluted CH4 Flow

    Science.gov (United States)

    Cetinkaya, S.; Eroglu, S.

    2017-10-01

    The carburization behavior of prereduced Mo was investigated in undiluted CH4 flow at 900-1000 K. Prior to the experiments, equilibrium thermodynamic analysis was carried out in the Mo-C-H system. The products were characterized by mass measurement, x-ray diffraction and scanning electron microscopy techniques. A single Mo2C phase was obtained within 45 min, 5 min, and 2.5 min at 900 K, 950 K, and 1000 K, respectively, at CH4 contents higher than the predicted ones. The reasons for this behavior were discussed in terms of CH4 stability, open tube flow, and self-created atmosphere in the powder bed. The fractional conversion-time curves indicated that the carburization kinetics followed a linear rate law. The Mo2C crystallite size (26-37 nm) and platelet thickness (50-100 nm) were found to be smaller than those of the parent Mo phase. These findings were attributable to the defects formed as a result of stresses associated with the reduction and the carburization.

  7. Deoxygenation of glycolaldehyde and furfural on Mo2C/Mo(100)

    Science.gov (United States)

    McManus, Jesse R.; Vohs, John M.

    2014-12-01

    The desire to produce fuels and chemicals in an energy conscious, environmentally sympathetic approach has motivated considerable research on the use of cellulosic biomass feedstocks. One of the major challenges facing the utilization of biomass is finding effective catalysts for the efficient and selective removal of oxygen from the highly-oxygenated, biomass-derived platform molecules. Herein, a study of the reaction pathways for the biomass-derived platform molecule furfural and biomass-derived sugar model compound glycolaldehyde provides insight into the mechanisms of hydrodeoxygenation (HDO) on a model molybdenum carbide catalyst, Mo2C/Mo(100). Using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS), it was found that the Mo2C/Mo(100) catalyst was active for selective deoxygenation of the aldehyde carbonyl by facilitating adsorption of the aldehyde in an η2(C,O) bonding configuration. Furthermore, the catalyst showed no appreciable activity for furanic ring hydrogenation, highlighting the promise of relatively inexpensive Mo2C catalysts for selective HDO chemistry.

  8. Bis(3-acetyl-6-methyl-2-oxo-2H-pyran-4-olatobis(dimethyl sulfoxidenickel(II

    Directory of Open Access Journals (Sweden)

    Amel Djedouani

    2009-10-01

    Full Text Available In the title compound, [Ni(C8H7O42{(CH32SO}2], the NiII atom is located on a crystallographic centre of symmetry and has a distorted octahedral coordination geometry of type MO6. The bidentate dehydroacetic acid (DHA ligands occupy the equatorial plane of the complex in a trans configuration, and the dimethyl sulfoxide (DMSO ligands are weakly coordinated through their O atoms in the axial positions.

  9. A Comparative Study of the Inclusion Complexes of 2-[5'-benzylidene-2'-phenyl-4'-oxo-1', 3'-thiazolidine]-1, 3-benzothiazole and 2-[5'-(p-N,N-dimethylamino- benzylidene-2'-phenyl-4'-oxo-1', 3'-thiazolidine]-1, 3-benzothiazole withβ-Cyclodextrin

    Directory of Open Access Journals (Sweden)

    S. Panda

    2011-01-01

    Full Text Available The compounds 2-[5'-benzylidene-2'-phenyl-4'-oxo-1', 3'-thiazolidine]-1, 3-benzothiazole and 2-[5'-(p-N,N-dimethylamino- benzylidene-2'-phenyl-4'-oxo-1', 3'-thiazolidine]-1, 3-benzothiazole have been synthesized in their purest forms starting from 2-aminobenzothiazole. The inclusion complexes of the above compounds have been prepared with β-cyclodextrin to increase their solubility and bioaccessibility in polar medium. The formation of inclusion complexes have been ascertained by study of spectral characteristic before and after inclusion complex formation. The stability of inclusion complexes and nature of interaction between the host and guest are known from the determination of thermodynamic parameters. Further the antibacterial and antifungal activities of the compounds are determined which is found to increase significantly after inclusion complex formation

  10. Structure of 6-diazo-5-oxo-norleucine-bound human gamma-glutamyl transpeptidase 1, a novel mechanism of inactivation.

    Science.gov (United States)

    Terzyan, Simon S; Cook, Paul F; Heroux, Annie; Hanigan, Marie H

    2017-06-01

    Intense efforts are underway to identify inhibitors of the enzyme gamma-glutamyl transpeptidase 1 (GGT1) which cleaves extracellular gamma-glutamyl compounds and contributes to the pathology of asthma, reperfusion injury and cancer. The glutamate analog, 6-diazo-5-oxo-norleucine (DON), inhibits GGT1. DON also inhibits many essential glutamine metabolizing enzymes rendering it too toxic for use in the clinic as a GGT1 inhibitor. We investigated the molecular mechanism of human GGT1 (hGGT1) inhibition by DON to determine possible strategies for increasing its specificity for hGGT1. DON is an irreversible inhibitor of hGGT1. The second order rate constant of inactivation was 0.052 mM -1 min -1 and the K i was 2.7 ± 0.7 mM. The crystal structure of DON-inactivated hGGT1 contained a molecule of DON without the diazo-nitrogen atoms in the active site. The overall structure of the hGGT1-DON complex resembled the structure of the apo-enzyme; however, shifts were detected in the loop forming the oxyanion hole and elements of the main chain that form the entrance to the active site. The structure of hGGT1-DON complex revealed two covalent bonds between the enzyme and inhibitor which were part of a six membered ring. The ring included the OG atom of Thr381, the reactive nucleophile of hGGT1 and the α-amine of Thr381. The structure of DON-bound hGGT1 has led to the discovery of a new mechanism of inactivation by DON that differs from its inactivation of other glutamine metabolizing enzymes, and insight into the activation of the catalytic nucleophile that initiates the hGGT1 reaction. © 2017 The Protein Society.

  11. 12-oxo-phytodienoic acid, a plant-derived oxylipin, attenuates lipopolysaccharide-induced inflammation in microglia

    Energy Technology Data Exchange (ETDEWEB)

    Taki-Nakano, Nozomi [Graduate School of Bioscience and Biotechnology, Tokyo Institute of Technology, 4259-B-65 Nagatsuta-cho, Midori-ku, Yokohama 226-8501 (Japan); Advanced Drug Research Laboratories, Sohyaku. Innovative Research Division, Mitsubishi Tanabe Pharma Corporation, 2-2-50, Kawagishi, Toda, Saitama 335-8505 (Japan); Kotera, Jun [Advanced Drug Research Laboratories, Sohyaku. Innovative Research Division, Mitsubishi Tanabe Pharma Corporation, 2-2-50, Kawagishi, Toda, Saitama 335-8505 (Japan); Ohta, Hiroyuki, E-mail: ohta.h.ab@m.titech.ac.jp [Graduate School of Bioscience and Biotechnology, Tokyo Institute of Technology, 4259-B-65 Nagatsuta-cho, Midori-ku, Yokohama 226-8501 (Japan); School of Life Science and Technology, Tokyo Institute of Technology, 4259-B-65 Nagatsuta-cho, Midori-ku, Yokohama 226-8501 (Japan)

    2016-05-13

    Jasmonates are plant lipid–derived oxylipins that act as key signaling compounds in plant immunity, germination, and development. Although some physiological activities of natural jasmonates in mammalian cells have been investigated, their anti-inflammatory actions in mammalian cells remain unclear. Here, we investigated whether jasmonates protect mouse microglial MG5 cells against lipopolysaccharide (LPS)–induced inflammation. Among the jasmonates tested, only 12-oxo-phytodienoic acid (OPDA) suppressed LPS-induced expression of the typical inflammatory cytokines interleukin-6 and tumor necrosis factor α. In addition, only OPDA reduced LPS-induced nitric oxide production through a decrease in the level of inducible nitric oxide synthase. Further mechanistic studies showed that OPDA suppressed neuroinflammation by inhibiting nuclear factor κB and p38 mitogen-activated protein kinase signaling in LPS-activated MG5 cells. In addition, OPDA induced expression of suppressor of cytokine signaling-1 (SOCS-1), a negative regulator of inflammation, in MG5 cells. Finally, we found that the nuclear factor erythroid 2-related factor 2 signaling cascade induced by OPDA is not involved in the anti-inflammatory effects of OPDA. These results demonstrate that OPDA inhibited LPS-induced cell inflammation in mouse microglial cells via multiple pathways, including suppression of nuclear factor κB, inhibition of p38, and activation of SOCS-1 signaling. -- Highlights: •OPDA attenuates LPS-induced inflammatory cytokines such as IL-6 and TNF-α. •OPDA reduces LPS-induced iNOS expression and NO production. •OPDA suppresses NF-κB and p38 pathways and activates SOCS-1 signaling.

  12. 12-oxo-phytodienoic acid, a plant-derived oxylipin, attenuates lipopolysaccharide-induced inflammation in microglia

    International Nuclear Information System (INIS)

    Taki-Nakano, Nozomi; Kotera, Jun; Ohta, Hiroyuki

    2016-01-01

    Jasmonates are plant lipid–derived oxylipins that act as key signaling compounds in plant immunity, germination, and development. Although some physiological activities of natural jasmonates in mammalian cells have been investigated, their anti-inflammatory actions in mammalian cells remain unclear. Here, we investigated whether jasmonates protect mouse microglial MG5 cells against lipopolysaccharide (LPS)–induced inflammation. Among the jasmonates tested, only 12-oxo-phytodienoic acid (OPDA) suppressed LPS-induced expression of the typical inflammatory cytokines interleukin-6 and tumor necrosis factor α. In addition, only OPDA reduced LPS-induced nitric oxide production through a decrease in the level of inducible nitric oxide synthase. Further mechanistic studies showed that OPDA suppressed neuroinflammation by inhibiting nuclear factor κB and p38 mitogen-activated protein kinase signaling in LPS-activated MG5 cells. In addition, OPDA induced expression of suppressor of cytokine signaling-1 (SOCS-1), a negative regulator of inflammation, in MG5 cells. Finally, we found that the nuclear factor erythroid 2-related factor 2 signaling cascade induced by OPDA is not involved in the anti-inflammatory effects of OPDA. These results demonstrate that OPDA inhibited LPS-induced cell inflammation in mouse microglial cells via multiple pathways, including suppression of nuclear factor κB, inhibition of p38, and activation of SOCS-1 signaling. -- Highlights: •OPDA attenuates LPS-induced inflammatory cytokines such as IL-6 and TNF-α. •OPDA reduces LPS-induced iNOS expression and NO production. •OPDA suppresses NF-κB and p38 pathways and activates SOCS-1 signaling.

  13. Immunomodulatory properties of 1,2-dihydro-4-hydroxy-2-oxo-1,8-naphthyridine-3-carboxamide derivative VL15.

    Science.gov (United States)

    Malfitano, Anna Maria; Laezza, Chiara; Bertini, Simone; Marasco, Daniela; Tuccinardi, Tiziano; Bifulco, Maurizio; Manera, Clementina

    2017-04-01

    1,2-Dihydro-4-hydroxy-2-oxo-1,8-naphthyridine-3-carboxamide derivative VL15 has been recently developed as a selective cannabinoid CB2 receptor compound. Given the high selectivity of this compound at the cannabinoid CB2 receptor and the well-known protective function of this receptor in neurological disorders with autoimmune component like multiple sclerosis, we assessed the immunomodulatory properties of VL15. We assessed on activated peripheral blood mononuclear cells), proliferation and viability, cell cycle progression and measured activation markers and the expression of phosphorylated proteins. We found that VL15 reduces PBMC proliferation slightly affecting cell vitality, blocks the cell cycle progression and down-regulates the levels of T cell activation markers as well as the expression of phosphorylated proteins, NF-kB, IKKαβ, IKBα, ERK and Akt. VL15 was also used in drug-permeability assays on Caco-2 cell line to evaluate its oral bioavailability and on MDCKII-hMDR1 cell lines to estimate its propensity to cross the blood-brain barrier by passive diffusion, in order to potentially maintain its efficiency on the infiltrating auto-reactive lymphocytes in the central nervous system. In these models, VL15 showed high intestinal absorption and good blood-brain barrier penetration. Our findings suggest that VL15, by controlling the immune response, might find potential application as orally administered drug in pathologies like multiple sclerosis. Copyright © 2017 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

  14. Metabolic Syndrome Is Associated with Increased Oxo-Nitrative Stress and Asthma-Like Changes in Lungs.

    Directory of Open Access Journals (Sweden)

    Vijay Pal Singh

    Full Text Available Epidemiological studies have shown an increased obesity-related risk of asthma. In support, obese mice develop airway hyperresponsiveness (AHR. However, it remains unclear whether the increased risk is a consequence of obesity, adipogenic diet, or the metabolic syndrome (MetS. Altered L-arginine and nitric oxide (NO metabolism is a common feature between asthma and metabolic syndrome that appears independent of body mass. Increased asthma risk resulting from such metabolic changes would have important consequences in global health. Since high-sugar diets can induce MetS, without necessarily causing obesity, studies of their effect on arginine/NO metabolism and airway function could clarify this aspect. We investigated whether normal-weight mice with MetS, due to high-fructose diet, had dysfunctional arginine/NO metabolism and features of asthma. Mice were fed chow-diet, high-fat-diet, or high-fructose-diet for 18 weeks. Only the high-fat-diet group developed obesity or adiposity. Hyperinsulinemia, hyperglycaemia, and hyperlipidaemia were common to both high-fat-diet and high-fructose-diet groups and the high-fructose-diet group additionally developed hypertension. At 18 weeks, airway hyperresponsiveness (AHR could be seen in obese high-fat-diet mice as well as non-obese high-fructose-diet mice, when compared to standard chow-diet mice. No inflammatory cell infiltrate or goblet cell metaplasia was seen in either high-fat-diet or high-fructose-diet mice. Exhaled NO was reduced in both these groups. This reduction in exhaled NO correlated with reduced arginine bioavailability in lungs. In summary, mice with normal weight but metabolic obesity show reduced arginine bioavailability, reduced NO production, and asthma-like features. Reduced NO related bronchodilation and increased oxo-nitrosative stress may contribute to the pathogenesis.

  15. Fabrication of Z-scheme Ag3PO4/MoS2 composites with enhanced photocatalytic activity and stability for organic pollutant degradation

    International Nuclear Information System (INIS)

    Zhu, Chaosheng; Zhang, Lu; Jiang, Bo; Zheng, Jingtang; Hu, Ping; Li, Sujuan; Wu, Mingbo; Wu, Wenting

    2016-01-01

    Highlights: • Ag 3 PO 4 /MoS 2 composite photocatalysts were prepared by precipitation method. • The composites showed enhanced visible-light photocatalytic activity. • The photocorrosion of Ag 3 PO 4 was inhibited due to the introduction of MoS 2 . • Z-scheme mechanism was proposed to explain the enhanced photoactivity. - Abstract: In this study, highly efficient visible-light-driven Ag 3 PO 4 /MoS 2 composite photocatalysts with different weight ratios of MoS 2 were prepared via the ethanol-water mixed solvents precipitation method and characterized by ICP, XRD, HRTEM, FE-SEM, BET, XPS, UV–vis DRS and PL analysis. Under visible-light irradiation, Ag 3 PO 4 /MoS 2 composites exhibit excellent photocatalytic activity towards the degradation of organic pollutants in aqueous solution. The optimal composite with 0.648 wt% MoS 2 content exhibits the highest photocatalytic activity, which can degrade almost all MB under visible-light irradiation within 60 min. Recycling experiments confirmed that the Ag 3 PO 4 /MoS 2 catalysts had superior cycle performance and stability. The photocatalytic activity enhancement of Ag 3 PO 4 /MoS 2 photocatalysts can be mainly ascribed to the efficient separation of photogenerated charge carriers and the stronger oxidation and reduction ability through a Z-scheme system composed of Ag 3 PO 4 , Ag and MoS 2 , in which Ag particles act as the charge separation center. The high photocatalytic stability is due to the successful inhibition of the photocorrosion of Ag 3 PO 4 by transferring the photogenerated electrons of Ag 3 PO 4 to MoS 2 . The evidence of the Z-scheme photocatalytic mechanism of the composite photocatalysts could be obtained from the active species trapping experiments and the photoluminescence technique.

  16. Electrochemical preparation of MoO{sub 3} buffer layer deposited onto the anode in organic solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Gacitua, M.; Soto, G.; Valle, M.A. del [Pontificia Universidad Catolica de Chile, Facultad de Quimica, Laboratorio de Electroquimica de Polimeros (LEP), Santiago (Chile); Boutaleb, Y.; Rehamnia, R. [Laboratoire d' Electrochimie, Universite Badji Mokhtar, Annaba (Algeria); Cattin, L.; Louarn, G. [Universite de Nantes, Nantes Atlantique Universites, Institut des Materiaux Jean Rouxel (IMN)-CNRS, Faculte des Sciences et Techniques, Nantes (France); Abe, S.Y. [Laboratoire de Physique de la Matiere Condensee et de Technologie (LPMCT), Universite de Cocody (Ivory Coast); Lare, Y. [Laboratoire d' Energie Solaire, Universite de Lome, Lome (Togo); Morsli, M; Bernede, J.C. [Universite de Nantes, Nantes Atlantique Universites, LAMP, EA 3825, Faculte des Sciences et des Techniques, Nantes (France); Drici, A. [LEREC Departement de physique, Universite Badji Mokhtar, Annaba (Algeria)

    2010-08-15

    In this work the authors have studied the advantages of using electrochemically deposited molybdenum oxide as a buffer layer in an organic bilayer heterojunction solar cell arrangement. Furthermore, it has been probed that electrochemistry provides an alternative low cost, reproducible and less laborious method to prepare thin layered deposits. The precursor solution is composed by a concentrated molybdic acid solution in a sulphuric media in order to ensure the obtainment of low reduced molybdenum species. Therefore, by means of potentiostatic techniques, ITO/molybdenum oxide transparent anodes were tested for the photovoltaic device showing improved surface properties. XDR and AFM techniques were used to characterize the morphology of the deposits. The films with optimum thickness (5 nm) are amorphous. XPS analysis indicates that the best results in solar cell performance are in hand with a heterogeneous composition of the molybdenum oxide film presenting Mo{sup V} and Mo{sup VI} as predominant species. The MoO{sub 3} films deposited by cyclic voltammetry are not as homogeneous as those deposited by potentiostatic technique and only Mo{sup VI} species are present. These differences may justify the different behaviour of the solar cells using these different buffer layers. Only buffer layers deposited by potentiostatic technique allow improving the cells performances in the same way than those achieved by evaporation. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  17. Metal Substitution in Keggin-Type Tridecameric Aluminum-Oxo-Hydroxy Clusters.

    Science.gov (United States)

    Parker, Wallace O'Neil; Millini, Roberto; Kiricsi, Imre

    1997-02-12

    The species resulting from a typical preparation for metal-substituted hybrids of the Keggin tridecamer, Al 13 or [AlO 4 Al 12 (OH) 24 (OH 2 ) 12 ] 7+ , were examined by performing 27 Al NMR on the solutions during aging and by studying the precipitated sulfate salts via solid state 27 Al NMR and powder X-ray diffraction (XRD). Aqueous mixtures (0.25 mol L -1 ) of AlCl 3 and another metal ion (M), in a 12:1 mole ratio (Al:M), where M = Fe 3+ , Zn 2+ , Ga 3+ , In 3+ , Sn 2+ , La 3+ , and Bi 3+ , were subjected to forced hydrolysis by addition of NaOH (1.0 mol L -1 ) until OH/(Al + M) = 2.25, and the kinetics of Al 13 formation and disappearance with aging at 80 °C was monitored by 27 Al NMR spectroscopy. Al 13 units polymerize on aging with an apparent rate constant (k) of 4.8(8) × 10 -2 h -1 to form a species referred to as AlP 2 . Only the solutions containing Ga 3+ and Sn 2+ exhibited faster Al 13 conversion rates. GaAl 12 forms quickly at 80 °C (k = 0.54 h -1 ) and is more stable than AlP 2 . Sn 2+ apparently promotes AlP 2 formation (k = 0.38 h -1 ). XRD and solid state NMR reveal that only the Ga hybrid can be prepared by this method. No hybrid formation was evidenced using M = Mg 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , In 3+ , La 3+ , or Ce 3+ at 25 °C or M = Co 2+ or La 3+ under reflux conditions. Isostructural (cubic symmetry) single crystals were obtained for the sulfate salts of Al 13 and GaAl 12 . Single-crystal XRD analysis of these two polyoxocations provides the first rigorous comparison between them and shows they have very similar structures. The main crystallographic data for Al 13 and GaAl 12 are as follows:  Na[AlO 4 Al 12 (OH) 24 (H 2 O) 12 ](SO 4 ) 4 ·10H 2 O, cubic, F4̄3m, a = 17.856(2) Å, Z = 4; Na[GaO 4 Al 12 (OH) 24 (H 2 O) 12 ](SO 4 ) 4 ·10H 2 O, cubic, F4̄3m, a = 17.869(3) Å, Z = 4. Thus, the greater thermal stability of GaAl 12 cannot be rationalized in terms of the overall geometric considerations, as suggested by

  18. Synthesis, structure and optical properties of two isotypic crystals, Na3MO4Cl (M=W, Mo)

    International Nuclear Information System (INIS)

    Han, Shujuan; Bai, Chunyan; Zhang, Bingbing; Yang, Zhihua; Pan, Shilie

    2016-01-01

    Two isotypic compounds, Na 3 MO 4 Cl (M = W, Mo) have been obtained from the high temperature solution, and their structures were determined by single-crystal X-ray diffraction. Both of them crystallize in the space group P4/nmm of tetragonal system with the unit cells: a=7.5181(15), c=5.360(2) for Na 3 WO 4 Cl and a=7.4942(12), c=5.3409(18) for Na 3 MoO 4 Cl. The structure exhibits a 3D network built up by the ClNa 6 groups, and the MO 4 groups reside in the tunnels of the 3D network. The structural similarities and differences between Na 3 MO 4 Cl (M=W, Mo) and Sr 3 MO 4 F (M=Al, Ga) have been discussed. Meanwhile, detailed structure comparison analyses between Na 3 MO 4 Cl (M=W, Mo) and Na 3 MO 4 F (M=W, Mo) indicate that the different connection modes of ClNa 6 and FNa 6 make Na 3 MO 4 Cl and Na 3 MO 4 F crystallize in different structures. The IR spectra were used to verify the validity of the structure. The diffuse reflectance spectra show that the UV absorption edges are about 249 nm (4.99 eV) and 265 nm (4.69 eV) for Na 3 WO 4 Cl and Na 3 MoO 4 Cl, respectively. In addition, the first-principles theoretical studies are also carried out to aid the understanding of electronic structures and linear optical properties. - Graphical abstract: Two isotypic compounds, Na 3 MO 4 Cl (M=W, Mo) have been obtained from the high temperature solution. Both of them crystallize in the space group P4/nmm of tetragonal system. The structure exhibits a 3D network built up by the ClNa 6 groups, and the MO 4 groups reside in the tunnels of the 3D network. - Highlights: • Structure and properties of Na 3 MO 4 Cl (M=W, Mo) are reported for the first time. • They show a 3D network built by ClNa 6 , and WO 4 lies in the tunnels of the network. • IR spectra were used to verify the validity of the structure. • Band structures and density of states have been calculated.

  19. Effects of Mo Content on Microstructure and Mechanical Property of PH13-8Mo Martensitic Precipitation-Hardened Stainless Steel

    Science.gov (United States)

    Yubing, Pei; Tianjian, Wang; Zhenhuan, Gao; Hua, Fan; Gongxian, Yang

    This paper introduces the effects of Mo content on microstructure and mechanical property of PH13-8Mo martensitic precipitation-hardened stainless steel which is used for LP last stage blade in steam turbine. Thermodynamic software Thermo-Calc has been used to calculate precipitation temperature and the mass fraction of precipitated phases in PH13-8Mo steel with different Mo content. The result shows that when the mass of Mo is below 0.6wt.%, chi-phase mu-phase and sigma-phase could disappear. The microstructure and mechanical property of high Mo PH13-8Mo (Mo=0.57wt.%) and low Mo PH13-8Mo (Mo=2.15wt.%)have been investigated in different heat treatments. The investigations reveal that austenitizing temperature decrease with the reduce of Mo content, so the optimum solution temperature for low Mo PH13-8Mo is lower than that for high Mo PH13-8Mo.The influence of solution temperature on grain size is weakened with the increase of Mo content, Mo rich carbides could retard coarsening of grain. An enormous amount of nano-size uniformly distributed β-NiAl particles are found in both kinds of steels using transmission electron microscopy, they are the most important strengthening phase in PH13-8Mo.

  20. Subtle interactions and electron transfer between U{sup III}, Np{sup III}, or Pu{sup III} and uranyl mediated by the oxo group

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, Polly L.; Zegke, Markus; Hollis, Emmalina; Pecharman, Anne-Frederique; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom); Dutkiewicz, Michal S. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom); European Commission, Directorate for Nuclear Safety and Security, Joint Research Centre, Karlsruhe (Germany); Walter, Olaf; Apostolidis, Christos; Magnani, Nicola; Griveau, Jean-Christophe; Colineau, Eric; Caciuffo, Roberto [European Commission, Directorate for Nuclear Safety and Security, Joint Research Centre, Karlsruhe (Germany); Zhang, Xiaobin; Schreckenbach, Georg [Department of Chemistry, University of Manitoba, Winnipeg, MB (Canada)

    2016-10-04

    A dramatic difference in the ability of the reducing An{sup III} center in AnCp{sub 3} (An=U, Np, Pu; Cp=C{sub 5}H{sub 5}) to oxo-bind and reduce the uranyl(VI) dication in the complex [(UO{sub 2})(THF)(H{sub 2}L)] (L=''Pacman'' Schiff-base polypyrrolic macrocycle), is found and explained. These are the first selective functionalizations of the uranyl oxo by another actinide cation. At-first contradictory electronic structural data are explained by combining theory and experiment. Complete one-electron transfer from Cp{sub 3}U forms the U{sup IV}-uranyl(V) compound that behaves as a U{sup V}-localized single molecule magnet below 4 K. The extent of reduction by the Cp{sub 3}Np group upon oxo-coordination is much less, with a Np{sup III}-uranyl(VI) dative bond assigned. Solution NMR and NIR spectroscopy suggest Np{sup IV}U{sup V} but single-crystal X-ray diffraction and SQUID magnetometry suggest a Np{sup III}-U{sup VI} assignment. DFT-calculated Hirshfeld charge and spin density analyses suggest half an electron has transferred, and these explain the strongly shifted NMR spectra by spin density contributions at the hydrogen nuclei. The Pu{sup III}-U{sup VI} interaction is too weak to be observed in THF solvent, in agreement with calculated predictions. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. A 3-hydroxy β-end group in xanthophylls is preferentially oxidized to a 3-oxo ε-end group in mammals.

    Science.gov (United States)

    Nagao, Akihiko; Maoka, Takashi; Ono, Hiroshi; Kotake-Nara, Eiichi; Kobayashi, Miyuki; Tomita, Mie

    2015-02-01

    We previously found that mice fed lutein accumulated its oxidative metabolites (3'-hydroxy-ε,ε-caroten-3-one and ε,ε-carotene-3,3'-dione) as major carotenoids, suggesting that mammals can convert xanthophylls to keto-carotenoids by the oxidation of hydroxyl groups. Here we elucidated the metabolic activities of mouse liver for several xanthophylls. When lutein was incubated with liver postmitochondrial fraction in the presence of NAD(+), (3'R,6'R)-3'-hydroxy-β,ε-caroten-3-one and (6RS,3'R,6'R)-3'-hydroxy-ε,ε-caroten-3-one were produced as major oxidation products. The former accumulated only at the early stage and was assumed to be an intermediate, followed by isomerization to the latter. The configuration at the C3' and C6' of the ε-end group in lutein was retained in the two oxidation products. These results indicate that the 3-hydroxy β-end group in lutein was preferentially oxidized to a 3-oxo ε-end group via a 3-oxo β-end group. Other xanthophylls such as β-cryptoxanthin and zeaxanthin, which have a 3-hydroxy β-end group, were also oxidized in the same manner as lutein. These keto-carotenoids, derived from dietary xanthophylls, were confirmed to be present in plasma of normal human subjects, and β,ε-caroten-3'-one was significantly increased by the ingestion of β-cryptoxanthin. Thus, humans as well as mice have oxidative activity to convert the 3-hydroxy β-end group of xanthophylls to a 3-oxo ε-end group. Copyright © 2015 by the American Society for Biochemistry and Molecular Biology, Inc.

  2. A 3-hydroxy β-end group in xanthophylls is preferentially oxidized to a 3-oxo ε-end group in mammals[S

    Science.gov (United States)

    Nagao, Akihiko; Maoka, Takashi; Ono, Hiroshi; Kotake-Nara, Eiichi; Kobayashi, Miyuki; Tomita, Mie

    2015-01-01

    We previously found that mice fed lutein accumulated its oxidative metabolites (3′-hydroxy-ε,ε-caroten-3-one and ε,ε-carotene-3,3′-dione) as major carotenoids, suggesting that mammals can convert xanthophylls to keto-carotenoids by the oxidation of hydroxyl groups. Here we elucidated the metabolic activities of mouse liver for several xanthophylls. When lutein was incubated with liver postmitochondrial fraction in the presence of NAD+, (3′R,6′R)-3′-hydroxy-β,ε-caroten-3-one and (6RS,3′R,6′R)-3′-hydroxy-ε,ε-caroten-3-one were produced as major oxidation products. The former accumulated only at the early stage and was assumed to be an intermediate, followed by isomerization to the latter. The configuration at the C3′ and C6′ of the ε-end group in lutein was retained in the two oxidation products. These results indicate that the 3-hydroxy β-end group in lutein was preferentially oxidized to a 3-oxo ε-end group via a 3-oxo β-end group. Other xanthophylls such as β-cryptoxanthin and zeaxanthin, which have a 3-hydroxy β-end group, were also oxidized in the same manner as lutein. These keto-carotenoids, derived from dietary xanthophylls, were confirmed to be present in plasma of normal human subjects, and β,ε-caroten-3′-one was significantly increased by the ingestion of β-cryptoxanthin. Thus, humans as well as mice have oxidative activity to convert the 3-hydroxy β-end group of xanthophylls to a 3-oxo ε-end group. PMID:25502844

  3. Imaging Tumor Vasculature Noninvasively with Positron Emission Tomography and RGD Peptides Labeled with Copper 64 Using the Bifunctonal Chelates DOTA, Oxo-DO3A. and PCTA

    Directory of Open Access Journals (Sweden)

    Donald T.T. Yapp

    2013-06-01

    Full Text Available Two novel bifunctional chelates, 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15,11,13-triene-3,6,9-triacetic acid (PCTA and 1-oxa-4,7,10-triazacyclododecane-4,7,10-triacetic acid (Oxo-DO3A, were found to radiolabel antibodies with copper 64 (64Cu well for positron emission tomography (PET. In this study, the same chelators were used to radiolabel peptides with 64Cu for PET imaging of angiogenesis. PCTA, Oxo-DO3A, and 1,4,7,10-tetraazacyclododecane-N,N‘,N“,N”’-tetraacetic acid (DOTA were conjugated to cyclic-(RGDyK, and their binding affinities were confirmed. Conditions for 64Cu radiolabeling were optimized for maximum yield and specific activity. The in vitro stability of the radiolabeled compounds was challenged with serum incubation. PET studies were carried out in a non-αvβ3-expressing tumor model to evaluate the compounds' specificity for proliferating tumor vasculature and their in vivo pharmacokinetics. The PCTA and Oxo-DO3A bioconjugates were labeled with 64Cu at higher effective specific activity and radiochemical yield than the DOTA bioconjugate. In the imaging studies, all the 64Cu bioconjugates could be used to visualize the tumor and the radiotracer uptake was blocked with cyclic-(RGDyK. Target uptake of each bioconjugate was similar, but differences in other tissues were observed. 64Cu-PCTA-RGD showed the best clearance from nontarget tissue and the highest tumor to nontarget ratios. PCTA was the most promising bifunctional chelate for 64Cu peptide imaging and warrants further investigation.

  4. Mo isotope fractionation during hydrothermal evolution of porphyry Cu systems

    Science.gov (United States)

    Shafiei, Behnam; Shamanian, GholamHossein; Mathur, Ryan; Mirnejad, Hassan

    2015-03-01

    We present Mo isotope compositions of molybdenite types from three successive stages of ore deposition in several porphyry copper deposits of the Kerman region, Iran. The data provide new insights into controlling processes on Mo isotope fractionation during the hydrothermal evolution of porphyry systems. The Mo isotope compositions of 27 molybdenite samples show wide variations in δ97Mo ranging from -0.37 to +0.92 ‰. The data reveal that molybdenites in the early and transitional stages of mineralization (preferentially 2H polytypes; δ97Mo mean = 0.35 ‰) have higher δ97Mo values than late stage (mainly 3R polytypes; δ97Mo mean = 0.02 ‰) molybdenites. This trend suggests that fractionation of Mo isotopes occurred in high-temperature stages of mineralization and that hydrothermal systems generally evolve towards precipitation of molybdenite with lower δ97Mo values. Taking into account the genetic models proposed for porphyry Cu deposits along with the temperature-dependent fractionation of Mo isotope ratios, it is proposed that large variations of Mo isotopes in the early and the transitional stages of ore deposition could be controlled by the separation of the immiscible ore-forming fluid phases with different density, pH, and ƒO2 properties (i.e., brine and vapor). The fractionation of Mo isotopes during fluid boiling and Rayleigh distillation processes likely dominates the Mo isotope budget of the remaining ore-forming fluids for the late stage of mineralization. The lower δ97Mo values in the late stage of mineralization can be explained by depletion of the late ore-forming hydrothermal solutions in 97Mo, as these fluids have moved to considerable distance from the source. Finally, the relationship observed between MoS2 polytypes (2H and 3R) and their Mo isotopic compositions can be explained by the molecular vibration theory, in which heavier isotopes are preferentially partitioned into denser primary 2H MoS2 crystals.

  5. Development of Mo recycle technique from generator materials

    Energy Technology Data Exchange (ETDEWEB)

    Tanimoto, Masataka; Kurosawa, Makoto; Kimura, Akihiro; Nishikata, Kaori; Tsuchiya, Kunihiko [Japan Atomic Energy Agency, Oarai Research and Development Center, Oarai, Ibaraki (Japan); Kakei, Sadanori; Yoshinaga, Hideo [Taiyo Koko Corp., Ako Laboratory, Ako, Hyogo (Japan)

    2012-03-15

    The domestic {sup 99}Mo production by the (n,{gamma}) method is proposed in JMTR because of low amount of radioactive wastes and easy {sup 99}Mo/{sup 99m}Tc production process. For the development of domestic production, it is necessary to use the enriched {sup 98}MoO{sub 3}, which is very expensive, for high specific activity of {sup 99}Mo. A large amount of used PZC/PTC embraced {sup 98}Mo is also generated after the decay of {sup 99}Mo. JAEA and Taiyo Koko is proposed to recover molybdenum from the used PZC/PTC for an effective use of resources and reduction of radioactive wastes. Preliminary experiments of Mo recycling with un-irradiated MoO{sub 3} were carried out by the elution and sublimation methods. From the results, Mo recovery rate from the PZC/PTC was more than 95% by two kinds of methods. The prospects are bright for Mo recycle and reduction of radioactive wastes using these methods. (author)

  6. Nanostructured Mo-based electrode materials for electrochemical energy storage.

    Science.gov (United States)

    Hu, Xianluo; Zhang, Wei; Liu, Xiaoxiao; Mei, Yueni; Huang, Yunhui

    2015-04-21

    The development of advanced energy storage devices is at the forefront of research geared towards a sustainable future. Nanostructured materials are advantageous in offering huge surface to volume ratios, favorable transport features, and attractive physicochemical properties. They have been extensively explored in various fields of energy storage and conversion. This review is focused largely on the recent progress in nanostructured Mo-based electrode materials including molybdenum oxides (MoO(x), 2 ≤ x ≤ 3), dichalconides (MoX2, X = S, Se), and oxysalts for rechargeable lithium/sodium-ion batteries, Mg batteries, and supercapacitors. Mo-based compounds including MoO2, MoO3, MoO(3-y) (0 energy storage systems because of their unique physicochemical properties, such as conductivity, mechanical and thermal stability, and cyclability. In this review, we aim to provide a systematic summary of the synthesis, modification, and electrochemical performance of nanostructured Mo-based compounds, as well as their energy storage applications in lithium/sodium-ion batteries, Mg batteries, and pseudocapacitors. The relationship between nanoarchitectures and electrochemical performances as well as the related charge-storage mechanism is discussed. Moreover, remarks on the challenges and perspectives of Mo-containing compounds for further development in electrochemical energy storage applications are proposed. This review sheds light on the sustainable development of advanced rechargeable batteries and supercapacitors with nanostructured Mo-based electrode materials.

  7. Phase equilibria of the Mo-Al-Ho ternary system

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yitai; Chen, Xiaoxian; Liu, Hao [Guangxi Univ., Nanning (China). College of Materials Science and Engineering; Guangxi Univ., Nanning (China). Guangxi Key Laboratory of Processing for Non-ferrous Metal and Featured Materials; Zhan, Yongzhong [Guangxi Univ., Nanning (China). College of Materials Science and Engineering; Guangxi Univ., Nanning (China). Guangxi Key Laboratory of Processing for Non-ferrous Metal and Featured Materials; Guangxi Univ., Nanning (China). Center of Ecological Collaborative Innovation for Aluminum Industry

    2017-08-15

    Investigation into the reactions and phase equilibria of transition metal elements (i.e. Mo, Zr, Cr, V and Ti), Al and rare earths is academically and industrially important for the development of both refractory alloys and lightweight high-temperature materials. In this work, the equilibria of the Mo-Al-Ho ternary system at 773 K have been determined by using X-ray powder diffraction and scanning electron microscopy equipped with energy dispersive X-ray analysis. A new ternary phase Al{sub 4}Mo{sub 2}Ho has been found and the other ternary phase Al{sub 43}Mo{sub 4}Ho{sub 6} is observed. Ten binary phases in the Al-Mo and Al-Ho systems, including Al{sub 17}Mo{sub 4} rather than Al{sub 4}Mo, have been determined to exist at 773 K. The homogeneity ranges of AlMo{sub 3} and Al{sub 8}Mo{sub 3} phase are 7.5 at.% and 1 at.%, respectively. According to the phase-disappearing method, the maximum solubility of Al in Mo is about 16 at.%.

  8. Gold nanoparticles on MoS2 layered crystal flakes

    International Nuclear Information System (INIS)

    Cao, Wei; Pankratov, Vladimir; Huttula, Marko; Shi, Xinying; Saukko, Sami; Huang, Zhongjia; Zhang, Meng

    2015-01-01

    Inorganic layered crystal MoS 2 is considered as one of the most promising and efficient semiconductor materials for future transistors, photoelectronics, and electrocatalysis. To boost MoS 2 -based material applications, one direction is to grow physically and chemically reactive nanoparticles onto MoS 2 . Here we report on a simple route to synthesis crystalized MoS 2 –Au complexes. The gold nanoparticles were grown on MoS 2 flakes through a wet method in the oxygen free environment at room temperature. Nanoparticles with diameters varying from 9 nm to 429 nm were controlled by the molar ratios of MoS 2 and HAuCl 4 precursors. MoS 2 host flakes keep intrinsic honeycomb layered structures and the Au nanoparticles cubic-center crystal microstructures. From product chemical states analysis, the synthesis was found driven by redox reactions between the sulphide and the chloroauric acid. Photoluminescence measurement showed that introducing Au nanoparticles onto MoS 2 stacks substantially prompted excitonic transitions of stacks, as an analogy for doping Si wafers with dopants. Such composites may have potential applications in wide ranges similar as the doped Si. - Highlights: • The Au nanoparticles were decorated on MoS 2 in oxygen free ambiences via a wet method. • The Au nanoparticles are size-controllable and crystalized. • Chemical reaction scheme was clarified. • The MoS 2 –Au complexes have strong photoluminescent properties

  9. In-situ fabrication of MoSi{sub 2}/SiC–Mo{sub 2}C gradient anti-oxidation coating on Mo substrate and the crucial effect of Mo{sub 2}C barrier layer at high temperature

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jun [School of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Key Laboratory for Advanced Materials Processing Technology, Ministry of Education, Beijing 100084 (China); State Key Laboratory of New Ceramics and Fine Processing, Beijing 100084 (China); Gong, Qianming, E-mail: gongqianming@mail.tsinghua.edu.cn [School of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Key Laboratory for Advanced Materials Processing Technology, Ministry of Education, Beijing 100084 (China); State Key Laboratory of New Ceramics and Fine Processing, Beijing 100084 (China); Shao, Yang; Zhuang, Daming [School of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Key Laboratory for Advanced Materials Processing Technology, Ministry of Education, Beijing 100084 (China); State Key Laboratory of New Ceramics and Fine Processing, Beijing 100084 (China); Liang, Ji [Key Laboratory for Advanced Materials Processing Technology, Ministry of Education, Beijing 100084 (China); Department of Mechanical Engineering, Tsinghua University, Beijing 100084 (China)

    2014-07-01

    MoSi{sub 2}/SiC–Mo{sub 2}C gradient coating on molybdenum was in situ prepared with pack cementation process by two steps: (1) carburizing with graphite powder to obtain a Mo{sub 2}C layer on Mo substrate, and (2) siliconizing with Si powder to get a composite MoSi{sub 2}/SiC layer on the upper part of Mo{sub 2}C layer. The microstructure and elemental distribution in the coating were investigated with scanning electron microscopy (SEM), backscattered electron (BSE), energy dispersive spectroscopy (EDS), electron probe microanalysis (EPMA) and X-ray diffraction (XRD). Cyclic oxidation tests (at 500 °C, 1200 °C, 1400 °C and 1600 °C) demonstrated excellent oxidation resistance for the gradient composite coating and the mass loss was only 0.23% in 60 min at 1600 °C. XRD, EPMA, thermal dynamic and phase diagram analyses indicated that the Mo{sub 2}C barrier layer played the key role in slowing down the diffusion of C and Si toward inner Mo substrate at high temperature and principally this contributed to the excellent anti-oxidation for Mo besides the outer MoSi{sub 2}/SiC composite layer.

  10. In-situ fabrication of MoSi2/SiC–Mo2C gradient anti-oxidation coating on Mo substrate and the crucial effect of Mo2C barrier layer at high temperature

    International Nuclear Information System (INIS)

    Liu, Jun; Gong, Qianming; Shao, Yang; Zhuang, Daming; Liang, Ji

    2014-01-01

    MoSi 2 /SiC–Mo 2 C gradient coating on molybdenum was in situ prepared with pack cementation process by two steps: (1) carburizing with graphite powder to obtain a Mo 2 C layer on Mo substrate, and (2) siliconizing with Si powder to get a composite MoSi 2 /SiC layer on the upper part of Mo 2 C layer. The microstructure and elemental distribution in the coating were investigated with scanning electron microscopy (SEM), backscattered electron (BSE), energy dispersive spectroscopy (EDS), electron probe microanalysis (EPMA) and X-ray diffraction (XRD). Cyclic oxidation tests (at 500 °C, 1200 °C, 1400 °C and 1600 °C) demonstrated excellent oxidation resistance for the gradient composite coating and the mass loss was only 0.23% in 60 min at 1600 °C. XRD, EPMA, thermal dynamic and phase diagram analyses indicated that the Mo 2 C barrier layer played the key role in slowing down the diffusion of C and Si toward inner Mo substrate at high temperature and principally this contributed to the excellent anti-oxidation for Mo besides the outer MoSi 2 /SiC composite layer.

  11. The gas-liquid chromatography of carboxylic acid esters of the urinary 11-deoxy-17-oxo steroids. Determination as n-butyrates.

    Science.gov (United States)

    Sadler, P A; Kellie, A E

    1967-06-01

    1. The gas-liquid-chromatographic separations of the acetate, propionate, n-butyrate, isobutyrate and n-valerate esters of androsterone, aetiocholanolone and dehydroepiandrosterone were studied on a 1% neopentyl glycol sebacate column. The n-butyrate, isobutyrate and n-valerate esters were well resolved. 2. The three steroids derived from hydrolysed urinary 17-oxo steroid conjugate extracts were analysed by gas-liquid chromatography after conversion into their n-butyrate esters. The results were compared with independent determinations involving chromatography on alumina.

  12. Cellular effects of bacterial N-3-Oxo-dodecanoyl-L-Homoserine lactone on the sponge Suberites domuncula (Olivi, 1792): insights into an intimate inter-kingdom dialogue.

    Science.gov (United States)

    Gardères, Johan; Henry, Joël; Bernay, Benoit; Ritter, Andrès; Zatylny-Gaudin, Céline; Wiens, Matthias; Müller, Werner E G; Le Pennec, Gaël

    2014-01-01

    Sponges and bacteria have lived together in complex consortia for 700 million years. As filter feeders, sponges prey on bacteria. Nevertheless, some bacteria are associated with sponges in symbiotic relationships. To enable this association, sponges and bacteria are likely to have developed molecular communication systems. These may include molecules such as N-acyl-L-homoserine lactones, produced by Gram-negative bacteria also within sponges. In this study, we examined the role of N-3-oxododecanoyl-L-homoserine lactone (3-oxo-C12-HSL) on the expression of immune and apoptotic genes of the host sponge Suberites domuncula. This molecule seemed to inhibit the sponge innate immune system through a decrease of the expression of genes coding for proteins sensing the bacterial membrane: a Toll-Like Receptor and a Toll-like Receptor Associated Factor 6 and for an anti-bacterial perforin-like molecule. The expression of the pro-apoptotic caspase-like 3/7 gene decreased as well, whereas the level of mRNA of anti-apoptotic genes Bcl-2 Homolog Proteins did not change. Then, we demonstrated the differential expression of proteins in presence of this 3-oxo-C12-HSL using 3D sponge cell cultures. Proteins involved in the first steps of the endocytosis process were highlighted using the 2D electrophoresis protein separation and the MALDI-TOF/TOF protein characterization: α and β subunits of the lysosomal ATPase, a cognin, cofilins-related proteins and cytoskeleton proteins actin, α tubulin and α actinin. The genetic expression of some of these proteins was subsequently followed. We propose that the 3-oxo-C12-HSL may participate in the tolerance of the sponge apoptotic and immune systems towards the presence of bacteria. Besides, the sponge may sense the 3-oxo-C12-HSL as a molecular evidence of the bacterial presence and/or density in order to regulate the populations of symbiotic bacteria in the sponge. This study is the first report of a bacterial secreted molecule acting on

  13. THE STATE OF MANGANESE IN THE PHOTOSYNTHETIC APPARATUS. I. EXAFS STUDIES ON CHLOROPLASTS AND di-u-oxo BRIDGED di-MANGANESE MODEL COMPOUNDS

    Energy Technology Data Exchange (ETDEWEB)

    Kirby, J. A.; Robertson, A. S.; Smith, J. P.; Thompson, A. C.; Thompson, A. C.; Klein, M. P.

    1980-11-01

    Extended X-ray Absorption Fine Structure (EXAFS) studies on the manganese contained in spinach chloroplasts and on certain di-u-oxo bridged manganese dimers of the form (X{sub 2}Mn)O{sub 2}(MnX{sub 2} (X=2,2'-bypyridine and 1,10-phenanthroline) are reported. From these studies, the manganese associated with photosynthetic oxygen evolution is suggested to occur as a bridged transition metal dimer with most likely another manganese. Extensive details on the analysis are included.

  14. Effects of clofibric acid on the activity and activity state of the hepatic branched-chain 2-oxo acid dehydrogenase complex.

    OpenAIRE

    Zhao, Y; Jaskiewicz, J; Harris, R A

    1992-01-01

    Feeding clofibric acid to rats caused little or no change in total activity of the liver branched-chain 2-oxo acid dehydrogenase complex (BCODC). No change in mass of liver BCODC was detected by immunoblot analysis in response to dietary clofibric acid. No changes in abundance of mRNAs for the BCODC E1 alpha, E1 beta and E2 subunits were detected by Northern-blot analysis. Likewise, dietary clofibric acid had no effect on the activity state of liver BCODC (percentage of enzyme in the dephosph...

  15. Design, synthesis, biological evaluation and docking study of 5-oxo-4,5-dihydropyrano[3,2-c]chromene derivatives as acetylcholinesterase and butyrylcholinesterase inhibitors.

    Science.gov (United States)

    Khoobi, Mehdi; Alipour, Masoumeh; Sakhteman, Amirhossein; Nadri, Hamid; Moradi, Alireza; Ghandi, Mehdi; Emami, Saeed; Foroumadi, Alireza; Shafiee, Abbas

    2013-10-01

    A series of fused coumarins namely 5-oxo-4,5-dihydropyrano[3,2-c]chromenes linked to N-benzylpyridinium scaffold were synthesized and evaluated as acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) inhibitors. The 1-(4-fluorobenzyl)pyridinium derivative 6g showed the most potent anti-AChE activity (IC50 value=0.038 μM) and the highest AChE/BuChE selectivity (SI>48). The docking study permitted us to rationalize the observed structure-affinity relationships and to detect possible binding modes. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

  16. Synthesis, characterization and biodistribution of new [sup 99m]Tc Oxo and nitrido complexes of unsaturated tetradentate (N[sub 2]S[sub 2]) ligands

    Energy Technology Data Exchange (ETDEWEB)

    Coulais, Y.; Gantet, P.; Tafani, J.A.M.; Vende, D.; Guiraud, R. (Faculte de Medecine Toulouse-Purpan, Toulouse (France). Lab. de Biophysique et de Medecine Nucleaire); Cros, G.; Darbieu, M.H. (Centre National de la Recherche Scientifique (CNRS), Toulouse (France). Lab. de Chimie de Coordination); Pasqualini, R. (Cis-Bio International, Gif-sur-Yvette (France))

    1993-04-01

    Three unsaturated Schiff base tetradentate (N[sub 2]S[sub 2] or N[sub 2]SO) ligands were synthesized and characterized. Oxo and nitrido 99m-technetium complexes were obtained with these ligands. The nitrido complexes were formed using a new easy method available as a kit. When injected into rats and mice, these lipophilic complexes were able to cross blood-brain barrier but brain perfusion imaging could not be performed due to the insufficient uptake and retention time. (author).

  17. Synthesis and Antitumor Activity of 3-Methyl-4-oxo-3,4-dihydroimidazo [5,1-d][1,2,3,5]tetrazine-8-carboxylates and -carboxamides

    Directory of Open Access Journals (Sweden)

    Lin-Xiang Zhao

    2010-12-01

    Full Text Available Seventeen novel 3-methyl-4-oxo-3,4-dihydroimidazo[5,1-d][1,2,3,5]tetrazine-8-carboxylate and -carboxamide derivatives were synthesized and evaluated for their growth inhibition in seven human solid tumor and a human leukemia HL-60 cell lines. Compound IVa showed more activity than the other compounds and the positive control temozolomide. In the presence of 40 mg/mL of IVa, the survival rate of all tested tumor cells was less than 10%. Esters displayed more potent antitumour activity than amides and temozolomide against HL-60 cells. These compounds also exhibited considerably enhanced water-solubility.

  18. 1-O-alkyl-2-(omega-oxo)acyl-sn-glycerols from shark oil and human milk fat are potential precursors of PAF mimics and GHR

    DEFF Research Database (Denmark)

    Hartvigsen, Karsten; Ravandi, A.; Harkewicz, R.

    2006-01-01

    This study examines the feasibility that peroxidation and lipolysis of 1-O-alkyl-2,3-diacyl-sn-glycerols (DAGE) found in shark liver oil and human milk fat constitutes a potential source of dietary precursors of platelet activating factor (PAF) mimics and of gamma-hydroxybutyrate (GHB). Purified...... yielded 1-O-octadecyl-2-(9-oxo)nonanoyl-sn-glycerol, as the major core aldehyde. Because diradylglycerols with short fatty chains are absorbed in the intestine and react with cytidine diphosphate-choline in the enterocytes, it is concluded that formation of such PAF mimics as 1-O-alkyl-2-(omega...

  19. Cellular effects of bacterial N-3-Oxo-dodecanoyl-L-Homoserine lactone on the sponge Suberites domuncula (Olivi, 1792: insights into an intimate inter-kingdom dialogue.

    Directory of Open Access Journals (Sweden)

    Johan Gardères

    Full Text Available Sponges and bacteria have lived together in complex consortia for 700 million years. As filter feeders, sponges prey on bacteria. Nevertheless, some bacteria are associated with sponges in symbiotic relationships. To enable this association, sponges and bacteria are likely to have developed molecular communication systems. These may include molecules such as N-acyl-L-homoserine lactones, produced by Gram-negative bacteria also within sponges. In this study, we examined the role of N-3-oxododecanoyl-L-homoserine lactone (3-oxo-C12-HSL on the expression of immune and apoptotic genes of the host sponge Suberites domuncula. This molecule seemed to inhibit the sponge innate immune system through a decrease of the expression of genes coding for proteins sensing the bacterial membrane: a Toll-Like Receptor and a Toll-like Receptor Associated Factor 6 and for an anti-bacterial perforin-like molecule. The expression of the pro-apoptotic caspase-like 3/7 gene decreased as well, whereas the level of mRNA of anti-apoptotic genes Bcl-2 Homolog Proteins did not change. Then, we demonstrated the differential expression of proteins in presence of this 3-oxo-C12-HSL using 3D sponge cell cultures. Proteins involved in the first steps of the endocytosis process were highlighted using the 2D electrophoresis protein separation and the MALDI-TOF/TOF protein characterization: α and β subunits of the lysosomal ATPase, a cognin, cofilins-related proteins and cytoskeleton proteins actin, α tubulin and α actinin. The genetic expression of some of these proteins was subsequently followed. We propose that the 3-oxo-C12-HSL may participate in the tolerance of the sponge apoptotic and immune systems towards the presence of bacteria. Besides, the sponge may sense the 3-oxo-C12-HSL as a molecular evidence of the bacterial presence and/or density in order to regulate the populations of symbiotic bacteria in the sponge. This study is the first report of a bacterial secreted

  20. Structural study of ethyl 3-methyl-9-oxo-3-azabicyclo63.3.19nonane-1-carboxylate by two-dimensional NMR spectroscopy

    Science.gov (United States)

    Arias-Pérez, M. S.; Alejo, A.; Gálvez, E.; Pérez, S. M.; Santos, M. J.

    1995-04-01

    Ethyl 3-methyl-9-oxo-3-azabicyclo[3.3.1]nonane-1-carboxylate has been studied by 1H, 13C and 2D NMR spectroscopy in order to establish its conformational behaviour. The combined use of COSY and 1H- 13C correlation spectra helped in the unambiguous and complete assignment of the bicyclic carbon and proton resonances. It is found that the piperidone ring displays a slightly fattened chair conformation with the N-methyl group in the equatorial position, while a twist-chair form seems to be favoured for the cyclohexanone one. Two preferred orientations migth be proposed for the ethoxycarbonyl moiety.

  1. Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U(V) oxo and nitrido complexes

    OpenAIRE

    Tsoureas, Nikolaos; Kilpatrick, Alexander; Inman, Christopher; Cloke, Frederick Geoffrey

    2016-01-01

    The synthesis and molecular structures of a U(V) neutral terminal oxo complex and a U(V) sodium uranium nitride contact ion pair are described. The synthesis of the former is achieved by the use of tBuNCO as a mild oxygen transfer reagent, whilst that of the latter is via the reduction of NaN3. Both mono-uranium complexes are stabilised by the presence of bulky silyl substituents on the ligand framework that facilitate a 2e- oxidation of a single U(III) centre. In contrast, when steric hindra...

  2. Corrosion resistance of Ni-Cr-Mo alloys. Chemical composition and metallurgical condition's effects

    International Nuclear Information System (INIS)

    Zadorozne, N.S.; Rebak, Raul B.

    2009-01-01

    Ni-Cr-Mo alloys offer an outstanding corrosion resistance in a wide variety of highly-corrosive environments. This versatility is due to the excellent performance of nickel in hot alkaline solutions and the beneficial effect of chromium and molybdenum in oxidizing and reducing conditions, respectively. Alloy C-22 (22 % Cr-13 % Mo-3% W) is a well known versatile member of this family. Due to its excellent corrosion resistance in a wide variety of environments, Alloy C-22 has been selected for the fabrication of the corrosion-resistant outer shell of the high-level nuclear waste container. The increasing demand of the industry for corrosion resistant alloys with particular properties of corrosion and mechanical resistance has led to the development of new alloys. Alloy C-22HS (Ni-21 % Cr-17 % Mo) is a new high-strength corrosion resistant material recently developed and introduced into the market. This alloy provides a corrosion resistance comparable with that of other C-type alloys, and it can also be age hardened to effectively double its yield strength. HASTELLOY HYBRID-BC1 (Ni-22 % Mo-15 % Cr) is a new development intended for filling the gap between Ni-Mo and Ni-Cr-Mo alloys. This novel alloy is able to withstand HCl and H 2 SO 4 , even in the presence of dissolved oxygen and other oxidizing species. Its resistance to chloride-induced pitting corrosion, crevice corrosion and stress corrosion cracking is also remarkable. Thermal aging of Ni-Cr-Mo alloys leads to microstructure changes depending on the temperature range and exposure time at temperature. A Long Range Ordering (LRO) reaction can occur in the range of 350 C degrees to 600 C degrees, producing an ordered Ni 2 (Cr,Mo) phase. This ordering reaction does not seem to affect the corrosion resistance and produces only a slight loss in ductility. LRO transformation is homogeneous and has proven to be useful to fabricate the age-hard enable Alloy C22-HS. Tetrahedral Close Packed (TCP) phases, like μ, σ and

  3. Grotrian diagrams for highly ionized molybdenum Mo VI through Mo XLII

    International Nuclear Information System (INIS)

    Shirai, Toshizo; Sugar, J.; Wiese, W.L.

    1997-07-01

    Grotrian diagrams are presented to provide graphical overviews for 1,930 spectral lines of highly ionized molybdenum, Mo VI through Mo XLII. In the usual diagram display such as that by Bashkin and Stoner (North-Holland, Amsterdam, 1975), the density of transitions is often too high to allow each transition to be drawn separately. Here in our modified diagrams, the transitions are also represented by lines connecting the upper and lower energy levels, but the lower energy levels are extended and repeated for successive configurations as needed. As a sequence, dense packing is avoided and all lines in a multiplet can be accommodated. (author)

  4. Structural transformation of MoO3 nanobelts into MoS2 nanotubes

    International Nuclear Information System (INIS)

    Deepak, Francis Leonard; Mayoral, Alvaro; Yacaman, Miguel Jose

    2009-01-01

    The structural transformation of MoO 3 nanobelts into MoS 2 nanotubes using a simple sulfur source has been reported. This transformation has been extensively investigated using electron microscopic and spectroscopic techniques including scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), and energy-dispersive X-ray analysis (SEM-EDAX and TEM-EDX). The method described in this report will serve as a generic route for the transformation of other oxide nanostructures into the chalcogenide nanostructures. (orig.)

  5. An octanuclear molybdenum(VI) complex containing coordinatively bound 4,4'-di-tert-butyl-2,2'-bipyridine, [Mo8O22(OH)4(di-tBu-bipy)4]: synthesis, structure, and catalytic epoxidation of bio-derived olefins.

    Science.gov (United States)

    Amarante, Tatiana R; Neves, Patrícia; Tomé, Cátia; Abrantes, Marta; Valente, Anabela A; Paz, Filipe A Almeida; Pillinger, Martyn; Gonçalves, Isabel S

    2012-03-19

    The reaction of [MoO(2)Cl(2)(di-tBu-bipy)] (1) (di-tBu-bipy = 4,4'-di-tert-butyl-2,2'-bipyridine) with water at 100-120 °C in a Teflon-lined stainless steel autoclave, in an open reflux system, or in a microwave synthesis system gave the octanuclear complex [Mo(8)O(22)(OH)(4)(di-tBu-bipy)(4)] (2) as a microcrystalline powder in good yields. Single crystals of 2 suitable for X-ray diffraction were obtained by the reaction of MoO(3) and di-tBu-bipy in water at 160 °C for 3 days. The molecular structure of 2 comprises a purely inorganic core, Mo(4)O(8)(μ(3)-OH)(2)(μ(2)-O)(2), attached to two peripheral oxo-bridged binuclear units, Mo(2)O(4)(μ(2)-O)(2)(OH)(di-tBu-bipy)(2). The inorganic core is composed of a unique assembly of four {MoO(5)} distorted square pyramids connected to each other via edge-sharing. Overall, the octanuclear complex adopts a highly distorted form strongly resembling an "S"-shaped molecular unit. Complex 2 was applied in the catalytic epoxidation of the biorenewable olefins DL-limonene (Lim) and methyl oleate (Ole), using tert-butylhydroperoxide (TBHP) as an oxygen donor, under mild reaction conditions (55 °C, air). The reactions of Lim and Ole gave the respective epoxide monomers in fairly high selectivities at high conversions (89% 1,2-epoxy-p-menth-8-ene selectivity at 96% Lim conversion; 99% methyl 9,10-epoxystearate selectivity at 94% Ole conversion, reached within 24 h reaction). Iodometric titrations revealed no measurable "non-productive" decomposition of TBHP. © 2012 American Chemical Society

  6. Oxygen isotope effect in 55Mn and 95Mo NMR spectra of the permanganate and molybdate ion

    International Nuclear Information System (INIS)

    Buckler, K.U.; Haase, A.R.; Lutz, O.; Mueller, M.; Nolle, A.

    1977-01-01

    By Fourier transform NMR spectroscopy the 55 Mn and 95 Mo resonance lines in the different permanganate and molybdate species Mn 16 Osub(4-n) 18 Osub(n) - and Mo 16 Osub(4-n) 18 Osub(n) 2- (n = 0,1,2,3,4) have been resolved in aqueous solutions of potassium permanganate and sodium molybdate. An isotopic effect on the Larmor frequency for 55 Mn of (0.59+-0.02)ppm and for 95 Mo of (0.25+-0.01)ppm to lower frequency has been found for the substitution of one 16 O atom by one 18 O atom. The relaxation rates 1/T 1 of 55 Mn in the different lines of the permanganate solution are equal within the limits of error. The oxygen exchange rate for the water-permanganate system has been evaluated. (orig.) [de

  7. Large intragrain magnetoresistance above room temperature in the double perovskite Ba2FeMoO6

    International Nuclear Information System (INIS)

    Maignan, A.; Raveau, B.; Martin, C.; Hervieu, M.

    1999-01-01

    Large intragrain magnetoresistance (MR) in the ordered double perovskite, Ba 2 FeMo 6 , is shown for the first time. The latter appears near T c (340 K), i.e., above room temperature. This effect originates from a double-exchange-like mechanism, based on antiferromagnetic coupling of localized high spin 3d 5 Fe 3+ , and itinerant 4d 1 Mo 5+ species. Besides this bulk MR, low field tunneling MR at lower temperatures (T 2 FeMoO 6 . Such a coexistence of both effects, intragrain and intergrain magnetoresistance, might extend to all members of this double perovskite family, suggesting the possibility of optimizing the MR for working at room temperature in a low magnetic field, by tuning the T c of solid solutions of such perovskites

  8. Physcomitrella patens activates reinforcement of the cell wall, programmed cell death and accumulation of evolutionary conserved defence signals, such as salicylic acid and 12-oxo-phytodienoic acid, but not jasmonic acid, upon Botrytis cinerea infection.

    Science.gov (United States)

    Ponce De León, Inés; Schmelz, Eric A; Gaggero, Carina; Castro, Alexandra; Álvarez, Alfonso; Montesano, Marcos

    2012-10-01

    The moss Physcomitrella patens is an evolutionarily basal model system suitable for the analysis of plant defence responses activated after pathogen assault. Upon infection with the necrotroph Botrytis cinerea, several defence mechanisms are induced in P. patens, including the fortification of the plant cell wall by the incorporation of phenolic compounds and the induced expression of related genes. Botrytis cinerea infection also activates the accumulation of reactive oxygen species and cell death with hallmarks of programmed cell death in moss tissues. Salicylic acid (SA) levels also increase after fungal infection, and treatment with SA enhances transcript accumulation of the defence gene phenylalanine ammonia-lyase (PAL) in P. patens colonies. The expression levels of the genes involved in 12-oxo-phytodienoic acid (OPDA) synthesis, including lipoxygenase (LOX) and allene oxide synthase (AOS), increase in P. patens gametophytes after pathogen assault, together with a rise in free linolenic acid and OPDA concentrations. However, jasmonic acid (JA) could not be detected in healthy or infected tissues of this plant. Our results suggest that, although conserved defence signals, such as SA and OPDA, are synthesized and are probably involved in the defence response of P. patens against B. cinerea infection, JA production appears to be missing. Interestingly, P. patens responds to OPDA and methyl jasmonate by reducing moss colony growth and rhizoid length, suggesting that jasmonate perception is present in mosses. Thus, P. patens can provide clues with regard to the evolution of different defence pathways in plants, including signalling and perception of OPDA and jasmonates in nonflowering and flowering plants. © 2012 THE AUTHORS. MOLECULAR PLANT PATHOLOGY © 2012 BSPP AND BLACKWELL PUBLISHING LTD.

  9. Radiochemical purity of Mo and Tc solution obtained after irradiation and dissolution of Mo-100-enriched and ultra-high-purity natural Mo disks

    Energy Technology Data Exchange (ETDEWEB)

    Tkac, Peter [Argonne National Lab. (ANL), Argonne, IL (United States); Gromov, Roman [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey D. [Argonne National Lab. (ANL), Argonne, IL (United States); Rotsch, David A. [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2016-09-01

    Four irradiations of ultra-high-purity natural Mo targets and one irradiation using 97.4% Mo-100-enriched material were performed. The purpose of these irradiations was to determine whether the presence of Sn stabilizer in the H2O2 used for the dissolution of sintered Mo disks can affect the radiochemical purity of the final K2MoO4 in 5M KOH solution. Results from radiochemical purity tests performed using thin-layer paper chromatography show that even 2– 3× excess of Sn-stabilized H2O2 typically used for dissolution of sintered Mo disks did not affect the radiochemical purity of the final product.

  10. EPR study of the coordination sphere of Mo5+ ions in UV-irradiated silica-supported molybdenum catalysts

    International Nuclear Information System (INIS)

    Canose, B.; Gonzalez-Elipe, A.R.; Che, M.

    1991-01-01

    The determination of the number of coordination vacancies existing at transition metal cations at the surface of bulk or supported oxides is of greater interest in relation to the adsorption and catalytic properties of such systems. In the case of paramagnetic cations, the authors have developed a method consisting of the recording of their first and third derivative EPR spectra after adsorption of 13 CO, ( 13 C, I = 1/2). In this way, the 13 C superhyperfine structure which is normally observed permits the determination of the number of CO molecules bonded to the metal center. In a recent EPR work published in this journal, Seyedmonir and Howe have reported the formation of a CO adduct of the tetrahedral Mo 5+ -OH - species formed by UV-irradiation at 20 K of a MoO 3 /SiO 2 catalyst in the presence of H 2 . In that work, although the structure of such an adduct could not be derived unambiguously on the basis of the g tensor values, the coordination of the Mo 5+ ion by two CO molecules was suggested. This would be in agreement with the previous results with thermally reduced V 2 O 5 /SiO 2 and MoO 3 /SiO 2 catalysts, where the coordination of, respectively, V 4+ and Mo 5+ tetrahedral centers by two CO molecules was proven by means of the combined use of 13 CO and third derivative EPR spectra. In the present work, using this approach, they have studied the structure of these Mo 5+ ions photochemically generated on MoO 3 /SiO 2 catalysts and concluded that only one CO molecule is bonded to the paramagnetic ion

  11. SALMONELLA SPECIES

    African Journals Online (AJOL)

    DR. AMINU

    ... of Salmonella species serotypes in relation to age and sex among children, ..... However, most antimicrobials show sufficient selective toxicity to be of value in ... salmonellosis should be given good attention (Barrow et al., 2007). To reduce ...

  12. Oxothiomolybdenum derivatives of the superlacunary crown heteropolyanion {P8W48}: structure of [K4{Mo4O4S4(H2O)3(OH)2}2(WO2)(P8W48O184)]30– and studies in solution.

    Science.gov (United States)

    Korenev, Vladimir S; Floquet, Sébastien; Marrot, Jérôme; Haouas, Mohamed; Mbomekallé, Israël-Martyr; Taulelle, Francis; Sokolov, Maxim N; Fedin, Vladimir P; Cadot, Emmanuel

    2012-02-20

    Reaction of the cyclic lacunary [H(7)P(8)W(48)O(184)](33-) anion (noted P(8)W(48)) with the [Mo(2)S(2)O(2)(H(2)O)(6)](2+) oxothiocation led to two compounds, namely, [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) (denoted 1) and [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) (denoted 2), which were characterized in the solid state and solution. In the solid state, the structure of [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) reveals the presence of two disordered {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) "handles" connected on both sides of the P(8)W(48) ring. Such a disorder is consistent with the presence of two geometrical isomers where the relative disposition of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles are arranged in a perpendicular or parallel mode. Such an interpretation is fully supported by (31)P and (183)W NMR solution studies. The relative stability of both geometrical isomers appears to be dependent upon the nature of the internal alkali cations, i.e., Na(+) vs K(+), and increased lability of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles, compared to the oxo analogous, was clearly identified by significant broadening of the (31)P and (183)W NMR lines. Solution studies carried out by UV-vis spectroscopy showed that formation of the adduct [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) occurs in the 1.5-4.7 pH range and corresponds to a fast and quantitative condensation process. Furthermore, (31)P NMR titrations in solution reveal formation of the "monohandle" derivative [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(P(8)W(48)O(184))](38-) as an intermediate prior to formation of the "bishandle" derivatives. Furthermore, the electrochemical behavior of [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) was studied in aqueous medium and compared with the parent anion P(8)W(48).

  13. Facile synthesis of stable structured MoS{sub 2}-Mo-CNFs heteroarchitecture with enhanced hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Mo, Qionghua [Research Institute for New Materials Technology, Chongqing University of Arts and Sciences, Chongqing 402160 (China); Faculty of Material and Energy, South West University, Chongqing 400700 (China); Yao, Yucen [Research Institute for New Materials Technology, Chongqing University of Arts and Sciences, Chongqing 402160 (China); Liu, Bitao, E-mail: liubitao007@163.com [Research Institute for New Materials Technology, Chongqing University of Arts and Sciences, Chongqing 402160 (China); Peng, Lingling; Yan, Hengqing; Hou, Zhupei; Wang, Jun [Research Institute for New Materials Technology, Chongqing University of Arts and Sciences, Chongqing 402160 (China); Lin, Yue, E-mail: linyue@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Anhui 230026 (China)

    2017-06-01

    3D structured MoS{sub 2} are grown in-situ on Mo particles embedded carbon nanofibers (CNFs) via a hydrothermal method. Due to this special structure, the bonding and effective electron delivery between CNFs and MoS{sub 2} are both enhanced, and which will exhibits a better hydrogen evolution activity. The onset potential of this MoS{sub 2}-Mo-CNFs catalyst will decreased to 60 mV compared to the 90 mV for the MoS{sub 2}-CNFs. And its current density nearly no change with 5000 cycles which is better than the 32.3% decrease of MoS{sub 2}-CNFs at η = 300 mV (V vs RHE). - Highlights: • Newly structured MoS{sub 2}-Mo-CNFs with effectively connection between MoS{sub 2} and CNFs successfully synthesized. • This structure can enhance the charge transfer and significantly increase electrocatalytic efficiency. • Nearly no HER activity loss after 5000 CV cycles.

  14. Effect of unlabelled monoclonal antibody (MoAb) on biodistribution of /sup 111/Indium labelled (MoAb)

    Energy Technology Data Exchange (ETDEWEB)

    Lamki, L M; Murray, J L; Rosenblum, M G; Patt, Y Z; Babaian, Richard; Unger, M W

    1988-08-01

    We have evaluated immunoscintigraphy in cancer patients using four /sup 111/In-labelled murine monoclonal antibodies (MoAb): 96.5 (anti-P97 of melanoma), ZME-018 (anti-high molecular weight antibody of melanoma), ZCE-025 (anti-CEA for colon cancer) and PAY-276 (anti-prostatic acid phosphatase for prostatic cancer). The effect of increasing the doses of unlabelled MoAb (co-infused with 1 mg labelled MoAb) on the relative body distribution of each labelled MoAb was assessed. Localization in the liver decreased significantly in all cases, with increasing MoAb dose, except for ZME-018. Localization in other organs increased significantly as the liver activity decreased. The spleen activity, however, fell in the case of MoAb ZME-018. Blood-pool activity increased with MoAb dose in all four MoAbs. These findings correlated with the rise in the detection rate of metastases, the plasma half-life, and other pharmacokinetic parameters. However, the dose level at which this correlation occurred varied with each antibody. These data demonstrate the co-infusion of unlabelled MoAb with /sup 111/In-labelled MoAb could alter the organ distribution, pharmacokinetics and tumour uptake in a favourable manner, though the degree to which this occurs depends on the antibody in question.

  15. Photo-transmutation of {sup 100}Mo to {sup 99}Mo with Laser-Compton Scattering Gamma-ray

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jiyoung; Rehman, Haseeb ur; Kim, Yonghee [KAIST, Daejeon (Korea, Republic of)

    2016-10-15

    This paper presents a photonuclear transmutation method using laser Compton scattering (LCS) gamma-ray beam. Potential production rate (reaction rate) of 99Mo using the photonuclear (γ,n) reaction is evaluated. Rigorous optimization of the LCS spectrum has also been performed to maximize production of the 99Mo. Cyclotron proton accelerators are used worldwide to produce many short-living medical isotopes. However, few are capable of producing Mo-99 and none are suitable for producing more than a small fraction of the required amounts. More than 90% of the world's demand of 99Mo is sourced from five nuclear reactors. Two of these reactors have already been decommissioned and the rest are more than 45 years old. Relatively short half-life of the parent 99Mo requires continuous re-supply to meet the requirements of medical industry. Therefore, there is an urgent need to produce the 99Mo and 99mTc isotopes by alternative ways. One such alternative is giant dipole resonance (GDR) based photonuclear transmutation of 100Mo to 99Mo. For 99Mo production with the LCS photons using GDR-based (γ,n) reaction, the gamma-ray energy should be around 15 MeV. This study indicates that optimization of LCS spectrum by varying the electron and laser energies within practical limits can enhance the transmutation of Mo-100 to M-99 quite significantly. It has been found that irradiation time should be rather short, e.g., less than 6 hours, to maximize the weekly production of Mo-99 in the GDR-based Mo-99 production facility using the LCS photons. The analysis shows that production of 99Mo using a high-performance LCS facility offers a potentially-promising alternative for the production of 99mTc.

  16. A study of the complexation of [99mTcO2+] by 2,4-dioxo-1,5,8,12-tetraazacyclotetradecane, 2-oxo-1,5,8,12-tetraazacyclotetradecane and their methylated derivatives in position 3

    International Nuclear Information System (INIS)

    Riche, F.; Vidal, M.; Pasqualini, R.; Duatti, A.

    1992-01-01

    The kinetics of complexation of TcO 2 + by 2,4-dioxo-1,5,8,12-tetraazacyclotetradecane, 2-oxo-1,5,8,12-tetraazacyclotetradecane and their methylated derivatives were studied by reducing 99m TcO 4 - with stannous tartrate. The charges of the complexes obtained were studied by electrophoresis; equilibration studies of the complexes with cyclam and a comparative study of the complexation kinetics have served to demonstrate the remarkable kinetic stability of [1,4,8,11-tetraazacyclotetradecane-TcO 2 + ] and [2-oxo-1,5,8,12-tetraazacyclotetradecane-TcO 2 + ]. (author)

  17. Synthesis and spectral studies of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and mercury(II) complexes of 4-oxo-4H-1-benzopyran-3-carboxaldehyde hydrazone derivatives

    International Nuclear Information System (INIS)

    Nawar, N.; Khattab, M.A.; Bekheit, M.M.; El-Kaddah, A.H.

    1996-01-01

    A few complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) with 4-oxo-4H-1-benzopyran-3-(carboxaldehyde-4-chlorobenzylhydrazone) (BCBH) and 4-oxo-4H-1-benzopyran-3-(carboxaldehyde-4-methylbenzylhydrazone) (BMBH) have been synthesised and characterized by elemental analysis, molar conductivities, magnetic measurements and infrared (IR) and visible spectral studies. The IR spectra show that BCBH and BMBH behave as bidentate ligands either in the keto or enol form. (author). 24 refs., 2 tabs

  18. Comparitive study of fluorescence lifetime quenching of rhodamine 6G by MoS2 and Au-MoS2

    Science.gov (United States)

    Shakya, Jyoti; Kasana, Parath; Mohanty, T.

    2018-04-01

    Time resolved fluorescence study of Rhodamine 6G (R6G) in the presence of Molybdenum disulfide (MoS2) nanosheets and gold doped MoS2 (Au-MoS2) have been carried out and discussed. We have analyzed the fluorescence decay curves of R6G and it is observed that Au-MoS2 is a better fluorescence lifetime quencher as compare to MoS2 nanosheets. Also, the energy transfer efficiency and energy transfer rate from R6G to MoS2 and Au-MoS2 has been calculated and found higher for Au-MoS2.

  19. Na2MoO2As2O7

    Directory of Open Access Journals (Sweden)

    Raja Jouini

    2012-12-01

    Full Text Available Disodium molybdenum dioxide diarsenate, Na2MoO2As2O7, has been synthesized by a solid-state reaction. The structure is built up from MoAs2O12 linear units sharing corners to form a three-dimensional framework containing tunnels running along the a-axis direction in which the Na+ cations are located. In this framework, the AsV atoms are tetrahedrally coordinated and form an As2O7 group. The MoVI atom is displaced from the center of an octahedron of O atoms. Two Na+ cations are disordered about inversion centres. Structural relationships between different compounds: A2MoO2As2O7 (A = K, Rb, AMOP2O7 (A = Na, K, Rb; M = Mo, Nb and MoP2O7 are discussed.

  20. Atomic scale onset of Al adhesion on Mo2BC

    International Nuclear Information System (INIS)

    Bolvardi, Hamid; Music, Denis; Schneider, Jochen M.

    2015-01-01

    We have explored interfacial interactions between a Mo–C terminated Mo 2 BC(040) surface and an Al cluster using ab initio molecular dynamics. The Al cluster is disrupted and wets the Mo 2 BC(040) surface. This can be understood based on the electronic structure. Across the Al–MoC interface C s–Al s hybridized states are formed. These bonds are stronger than the Al–Al intra-cluster bonds. Hence, the onset of Al adhesion is caused by bond formation across the Al–MoC interface. - Highlights: • Interfacial interactions between Mo 2 BC and an Al cluster were explored. • Al forms bonds to C constituting the onset of Al adhesion on Mo 2 BC. • These data are relevant for other carbide coatings

  1. U-Mo fuel qualification program in HANARO

    International Nuclear Information System (INIS)

    Lee, K.H.; Lee, C.S.; Kim, H.R.; Kuk, I.H.; Kim, C.K.

    2000-01-01

    Atomized U-Mo fuel has shown good performance from the results of previous out-of-pile tests and post-irradiation examinations. A qualification program of rod type U-Mo fuel is in progress and the fuel will be irradiated in HANARO. 6 gU/cm 3 U-7Mo, U-8Mo and U-9Mo are considered in this program. The laboratory test results of porosity, mechanical property, thermal conductivity, and thermal compatibility test are discussed in this paper. In parallel with this qualification program, the feasibility study on the core conversion from the present U 3 Si fuel to U-Mo in HANARO will be initiated to provide technical bases for the policy making. Several options of core conversion for HANARO are proposed and each option will be addressed briefly in terms of the operation policy, fuel management, and licensing of HANARO. (author)

  2. Effect of Ni on the characteristics and hydrogenation activity of sulfide Mo/{gamma}-Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Schachtl, E.; Wuttke, E.; Gutierrez, O.Y.; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center

    2012-07-01

    The hydrogenation of phenanthrene was explored on sulfide Mo/{gamma}-Al{sub 2}O{sub 3} catalysts promoted with increasing concentrations of Ni. The characterization of the materials was done by N{sub 2}-physisorption, X-ray diffraction, transmission electron microscopy, temperature programmed sulfidation and NO adsorption experiments. Increasing loading of Ni improves the dispersion of MoS{sub 2} species; however, at Ni/(Mo+Ni) molar ratio higher than 0.5, segregation of Ni-sulfides is observed. The presence of Ni also facilitates the sulfidation of oxidic catalyst precursors by lowering the reduction temperature of Mo species. In the sulfide catalysts, Ni changes the structure of MoS{sub 2} leading to shorter slabs with higher stacking degree than on Mo/{gamma}-Al{sub 2}O{sub 3}, and increases the concentration of coordinatively unsaturated sites. The kinetic results (increased hydrogenation rate and changed reaction network in the presence of Ni) suggest that a highly active kind of active site is created by Ni promotion. (orig.)

  3. Hydroconversion of Waste Cooking Oil into Green Biofuel over Hierarchical USY-Supported NiMo Catalyst: A Comparative Study of Desilication and Dealumination

    Directory of Open Access Journals (Sweden)

    Zongwei Zhang

    2017-09-01

    Full Text Available The hydroconversion of waste cooking oil into hydrocarbon fuel was investigated over the hierarchical USY zeolite-supported NiMo catalysts which were prepared by dealumination ((NH42SiF6/desilication (NaOH. The physical and acidity properties of the hierarchical catalysts were characterized by X-ray diffraction (XRD, the Brunauer-Emmett-Teller (BET infrared spectroscopy of adsorbed pyridine (Py-IR, ammonia temperature-programmed desorption (NH3-TPD, and H2 temperature-programmed reduction (H2-TPR. The Brønsted/Lewis (B/L acid distribution was little affected by dealumination and the acid density decreased significantly. However, the highly-desilicated catalysts decreased the B/L ratio obviously. Therefore, many more Mo species in the NiMoO4− and MoO3 phases were produced in the AHFS-treated catalysts, while more high-valence-state Mo species in the NiMoO4− phase were formed in the NaOH-treated catalysts. The AHFS-treated catalysts showed higher catalytic activity and better DCO2 selectivity and selective cracking for jet fuel. The 42.3% selectivity of jet fuel and 13.5% selectivity of jet-range aromatics was achieved over the 8 wt % (NH42SiF6-treated catalyst with 67% DCO2 selectivity.

  4. MoRM and Future Memories

    DEFF Research Database (Denmark)

    Rehder, Mads Middelboe; Ostrowski, Kasper

    2017-01-01

    for the experimental workshop we lunged into a process of devising both an interactive exhibition and an installation which explored the ‘big data’ citizens regularly produce in their everyday lives and how this data might be archived, packaged, and recycled - or even forgotten, primarily within social media. We...... wanted to explore what our daily routines connected to social media and sorting our data meant for the way we shape our memories, and therefore the traces of future memories. In this chapter we follow the trajectory of the exhibition entitled ‘MoRM’ (Museum of Random Memories)....

  5. Facile Preparation of Nano-Bi₂MoO₆/Diatomite Composite for Enhancing Photocatalytic Performance under Visible Light Irradiation.

    Science.gov (United States)

    Cai, Lu; Gong, Jiuyan; Liu, Jianshe; Zhang, Hailong; Song, Wendong; Ji, Lili

    2018-02-09

    In this work, a new nano-Bi₂MoO₆/diatomite composite photocatalyst was successfully synthesized by a facile solvothermal method. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and UV-vis diffuse reflection spectroscopy (DRS) were employed to investigate the morphology, crystal structure, and optical properties. It was shown that nanometer-scaled Bi₂MoO₆ crystals were well-deposited on the surface of Bi₂MoO₆/diatomite. The photocatalytic activity of the obtained samples was evaluated by the degradation of rhodamine B (RhB) under the visible light (λ > 420 nm) irradiation. Moreover, trapping experiments were performed to investigate the possible photocatalytic reaction mechanism. The results showed that the nano-Bi₂MoO₆/diatomite composite with the mass ratio of Bi₂MoO₆ to diatomaceous earth of 70% exhibited the highest activity, and the RhB degradation efficiency reached 97.6% within 60 min. The main active species were revealed to be h⁺ and•O 2- . As a photocatalytic reactor, its recycling performance showed a good stability and reusability. This new composite photocatalyst material holds great promise in the engineering field for the environmental remediation.

  6. Phase formation in the Li2MoO4–K2MoO4–In2(MoO4)3 system and crystal structures of new compounds K3InMo4O15 and LiK2In(MoO4)3

    International Nuclear Information System (INIS)

    Khal’baeva, Klara M.; Solodovnikov, Sergey F.; Khaikina, Elena G.; Kadyrova, Yuliya M.; Solodovnikova, Zoya A.; Basovich, Olga M.

    2012-01-01

    XRD study of solid-phase interaction in the Li 2 MoO 4 –K 2 MoO 4 –In 2 (MoO 4 ) 3 system was performed. The boundary K 2 MoO 4 –In 2 (MoO 4 ) 3 system is an non-quasibinary join of the K 2 O–In 2 O 3 –MoO 3 system where a new polymolybdate K 3 InMo 4 O 15 isotypic to K 3 FeMo 4 O 15 was found. In the structure (a=33.2905(8), b=5.8610(1), c=15.8967(4) Å, β=90.725(1)°, sp. gr. C2/c, Z=8, R(F)=0.0407), InO 6 octahedra, Mo 2 O 7 diortho groups and MoO 4 tetrahedra form infinite ribbons {[In(MoO 4 ) 2 (Mo 2 O 7 )] 3− } ∞ along the b-axis. Between the chains, 8- to 10-coordinate potassium cations are located. A subsolidus phase diagram of the Li 2 MoO 4 –K 2 MoO 4 –In 2 (MoO 4 ) 3 system was constructed and a novel triple molybdate LiK 2 In(MoO 4 ) 3 was revealed. Its crystal structure (a=7.0087(2), b=9.2269(3), c=10.1289(3) Å, β=107.401(1)°, sp. gr. P2 1 , Z=2, R(F)=0.0280) contains an open framework of vertex-shared MoO 4 tetrahedra, InO 6 octahedra and LiO 5 tetragonal pyramids with nine- and seven-coordinate potassium ions in the framework channels. - Graphical abstract: Exploring the Li 2 MoO 4 –K 2 MoO 4 –In 2 (MoO 4 ) 3 system showed its partial non-quasibinarity and revealed new compounds K 3 InMo 4 O 15 (isotypic to K 3 FeMo 4 O 15 ) and LiK 2 In(MoO 4 ) 3 which were structurally studied. An open framework of the latter is formed by vertex-shared MoO 4 tetrahedra, InO 6 octahedra and LiO 5 tetragonal pyramids. Highlights: ► Subsolidus phase relations in the Li 2 MoO 4 –K 2 MoO 4 –In 2 (MoO 4 ) 3 system were explored. ► The K 2 MoO 4 –In 2 (MoO 4 ) 3 system is a non-quasibinary join of the K 2 O–In 2 O 3 –MoO 3 system. ► New compounds K 3 InMo 4 O 15 and LiK 2 In(MoO 4 ) 3 were obtained and structurally studied. ► K 3 InMo 4 O 15 is isotypic to K 3 FeMo 4 O 15 and carries bands of InO 6 , MoO 4 and Mo 2 O 7 units. ► An open framework of LiK 2 In(MoO 4 ) 3 is formed by polyhedra MoO 4 , InO 6 and LiO 5 .

  7. Ordering in rapidly solidified Ni/sub 2/Mo

    International Nuclear Information System (INIS)

    Kulkarni, U.D.; Dey, G.K.; Banerjee, S.

    1988-01-01

    Ordering processes in the Ni-Mo system have been a subject of several investigations. Although the ordering behaviour of the Ni/sub 4/Mo and the Ni/sub 3/Mo has been examined in detail, no such study has been reported in the case of the Ni/sub 2/Mo alloy. The lack of experimental work on ordering transformations in Ni/sub 2/Mo is presumably due to the difficulty in obtaining a single phase fcc alloy of this composition. Enhanced solid solubility of Mo in Ni, which accompanies rapid solidification processing (RSP) makes the formation of such a phase possible. The ordering processes in Ni-Mo based alloys show several remarkable features. Firstly, the alloy (15 - 28 at % Mo) quenched from the α -phase filed exhibit a short range order (SRO) characterized by the presence of intensity maxima at /1 1/2 0/ fcc positions of the reciprocal space. This state of SRO has been attributed to the occurrence of 1 1/2 O spinodal ordering in the system. Secondly, the transformation from the state of SRO to the equilibrium/metastable coherent long range ordered (LRO) structures appears to take place in a continuous manner at relatively low temperatures of aging. Three different coherent LRO structures, namely: the equilibrium Ni/sub 4/Mo (prototype structure D1/sub a/) and the metastable Ni/sub 3/Mo (DO/sub 22/) and Ni/sub 2/Mo (Pt/sub 2/Mo) structures have reported to evolve from the SRO alloy, depending upon the aging treatment and the composition of the alloy

  8. Computational identification of MoRFs in protein sequences.

    Science.gov (United States)

    Malhis, Nawar; Gsponer, Jörg

    2015-06-01

    Intrinsically disordered regions of proteins play an essential role in the regulation of various biological processes. Key to their regulatory function is the binding of molecular recognition features (MoRFs) to globular protein domains in a process known as a disorder-to-order transition. Predicting the location of MoRFs in protein sequences with high accuracy remains an important computational challenge. In this study, we introduce MoRFCHiBi, a new computational approach for fast and accurate prediction of MoRFs in protein sequences. MoRFCHiBi combines the outcomes of two support vector machine (SVM) models that take advantage of two different kernels with high noise tolerance. The first, SVMS, is designed to extract maximal information from the general contrast in amino acid compositions between MoRFs, their surrounding regions (Flanks), and the remainders of the sequences. The second, SVMT, is used to identify similarities between regions in a query sequence and MoRFs of the training set. We evaluated the performance of our predictor by comparing its results with those of two currently available MoRF predictors, MoRFpred and ANCHOR. Using three test sets that have previously been collected and used to evaluate MoRFpred and ANCHOR, we demonstrate that MoRFCHiBi outperforms the other predictors with respect to different evaluation metrics. In addition, MoRFCHiBi is downloadable and fast, which makes it useful as a component in other computational prediction tools. http://www.chibi.ubc.ca/morf/. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  9. Atomic structure calculations of Mo XV-XL

    International Nuclear Information System (INIS)

    Kubo, Hirotaka; Sugie, Tatsuo; Shiho, Makoto; Suzuki, Yasuo; Ishii, Keishi; Maeda, Hikosuke.

    1986-06-01

    Energy levels and oscillator strengths were calculated for Mo XV - Mo XL. The computer program for atomic structure calculation, developed by Dr. Robert D. Cowan, Los Alamos National Laboratory, was used in the present work. The scaled energy parameters were empirically determined from the observed spectral data. We present wavelengths and transition probabilities of Mo XV-XL. Energy levels and spectral patterns are presented in figures that are useful for the identification of spectral lines. (author)

  10. Intermediate report of MoReMo. Modelling resilience for maintenance and outage

    Energy Technology Data Exchange (ETDEWEB)

    Oedewald, P.; Macchi, L. (VTT Technical Research Centre of Finland (Finland)); Axelsson, C. (Ringhals AB, Vattenfall AB (Sweden)); Eitrheim, M.H.R. (Institute for Energy Technology (Norway))

    2012-02-15

    Resilience Engineering (RE) is a new approach to safety that helps organisations and individuals adapt to unforeseen events and long-term changes. Such an approach is needed by nuclear power plants (NPPs) as they face demanding modification projects, high staff turnover and increased pressures to maintain and improve safety. The goal of the Modelling Resilience for Maintenance and Outage (MoReMO) project is to develop and test models and methods to identify and analyse resilience in safety-critical activities in natural everyday settings. In 2011, we have applied four approaches in different case studies: Organisational Core Task modelling (OCT), Functional Resonance Analysis Method (FRAM), Efficiency Thoroughness Trade-Off (ETTO) analysis, and Work Practice and Culture Characterisation. The project has collected data through observations, interviews and document reviews at two NPPs. Together, the four approaches have provided valuable insights for understanding the rationale behind work practices, their effects on safety, and the support of flexibility and adaptability. In 2012, the MoReMO project will complete the data collection and integrate results on how resilience can be operationalized in practical safety management tools for the companies. (Author)

  11. Sheet-like of Mo –Sm assembly containing [Mo (CN)8 ] and Sm ions ...

    Indian Academy of Sciences (India)

    Administrator

    421–427. © Indian Academy of Sciences. 421 ... Department of Chemistry, Nankai University, Tianjin, 300071, PR China e-mail: ... [Mo(CN)8]3– building blocks, this paper details the ..... 20601014), and National Basic Research Program of.

  12. IEA Mobility Model (MoMo) and its use in the ETP 2008

    International Nuclear Information System (INIS)

    Fulton, Lew; Cazzola, Pierpaolo; Cuenot, Francois

    2009-01-01

    The IEA published 'Energy Technology Perspectives' (ETP) in June 2008. That document reports on IEA scenarios for baseline and low-CO 2 alternative scenarios to 2050, across the energy economy. The study included creating scenarios for transport, using the IEA Mobility Model (MoMo). This paper reports on the transport-related ETP scenarios and describes the model used in the analysis. According to the ETP Baseline scenario, world transport energy use and CO 2 emissions will more than double by 2050. In the most challenging scenario, called 'BLUE', transport emissions are reduced by 70% in 2050 compared to their baseline level in that year (and about 25% below their 2005 levels). There are several versions of the BLUE scenario, but all involve: a 50% or greater improvement in LDV efficiency, 30-50% improvement in efficiency of other modes (e.g. trucks, ships and aircraft), 25% substitution of liquid fossil fuels by biofuels, and considerable penetration of electric and/or fuel-cell vehicles. In the second half of this paper, an overview of the MoMo model is provided. Details on the complete analysis are contained in the ETP 2008 document, available at (www.iea.org). Details of the LDV fuel economy analysis are contained in a separate paper in this collection.

  13. Intermediate report of MoReMo. Modelling resilience for maintenance and outage

    International Nuclear Information System (INIS)

    Oedewald, P.; Macchi, L.; Axelsson, C.; Eitrheim, M.H.R.

    2012-02-01

    Resilience Engineering (RE) is a new approach to safety that helps organisations and individuals adapt to unforeseen events and long-term changes. Such an approach is needed by nuclear power plants (NPPs) as they face demanding modification projects, high staff turnover and increased pressures to maintain and improve safety. The goal of the Modelling Resilience for Maintenance and Outage (MoReMO) project is to develop and test models and methods to identify and analyse resilience in safety-critical activities in natural everyday settings. In 2011, we have applied four approaches in different case studies: Organisational Core Task modelling (OCT), Functional Resonance Analysis Method (FRAM), Efficiency Thoroughness Trade-Off (ETTO) analysis, and Work Practice and Culture Characterisation. The project has collected data through observations, interviews and document reviews at two NPPs. Together, the four approaches have provided valuable insights for understanding the rationale behind work practices, their effects on safety, and the support of flexibility and adaptability. In 2012, the MoReMO project will complete the data collection and integrate results on how resilience can be operationalized in practical safety management tools for the companies. (Author)

  14. Conceptual study of 99Mo production in JRR-3

    International Nuclear Information System (INIS)

    Hirose, Akira; Komeda, Masao; Kinase, Masami; Sorita, Takami; Wada, Shigeru

    2010-06-01

    We investigated the production process of 99 Mo, which is parent nuclide of 99m Tc, in JRR-3. 99m Tc is most commonly used as a radiopharmaceutical in the field of nuclear medicine. Currently the supplying of 99 Mo is only dependent on imports from foreign countries, so JAEA is aiming at domestic production of a part of 99 Mo in cooperation with the industrial arena. This report presents the technical study for the production process of 99 Mo by using the neutron radiation method of (n, γ) reaction in JRR-3. (author)

  15. Development of Commercial-scale Fission Mo-99 Production System

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seung-Kon; Lee, Suseung; Hong, Soon-Bog; Jang, Kyung-Duk; Park, Ul Jael; Lee, Jun Sig [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2016-10-15

    These days, worldwide {sup 99} Mo supply is not only insufficient but also unstable. Because, most of the main {sup 99}Mo production reactors are more than years old and suffered from frequent and unscheduled shutdown. Therefore, movement to replace old reactors to keep stable supply is now active. Under these conditions, KAERI (Korea Atomic Energy Research Institute) is developing LEU-based fission {sup 99}Mo production process which is connected to the new research reactor (Kijang New Research Reactor, KJRR), which is being constructed in Gijang, Busan, Korea. Historically, the most fission {sup 99}Mo producers have been used highly enriched uranium (HEU) targets so far. However, to reduce the use of HEU in private sector for non-proliferation, {sup 99}Mo producers are forced to convert their HEU-based process to use low enriched uranium (LEU) targets. Economic impact of a target conversion from HEU to LEU is significant. In this study, fission {sup 99}Mo process with non-irradiated LEU targets was presented except separation and purification steps. Pre- and post-irradiation tests of the fission {sup 99}Mo target will be done in 4th quarter of 2016. For the fission Mo production process development, hot experiments with irradiated LEU targets will be done in 4th quarter of 2016. Then, verification of the production process with quality control will be followed until the commercial production of fission {sup 99}Mo scheduled in 2019.

  16. Faceted MoS2 nanotubes and nanoflowers

    International Nuclear Information System (INIS)

    Deepak, Francis Leonard; Mayoral, Alvaro; Yacaman, Miguel Jose

    2009-01-01

    A simple synthesis of novel faceted MoS 2 nanotubes (NTs) and nanoflowers (NFs) starting from molybdenum oxide and thiourea as the sulphur source is reported. The MoS 2 nanotubes with the faceted morphology have not been observed before. Further the as-synthesized MoS 2 nanotubes have high internal surface area. The nanostructures have been characterized by a variety of electron microscopy techniques. It is expected that these MoS 2 nanostrutures will find important applications in energy storage, catalysis and field emission.

  17. Synthesis of nanometre-thick MoO3 sheets

    Science.gov (United States)

    Kalantar-Zadeh, Kourosh; Tang, Jianshi; Wang, Minsheng; Wang, Kang L.; Shailos, Alexandros; Galatsis, Kosmas; Kojima, Robert; Strong, Veronica; Lech, Andrew; Wlodarski, Wojtek; Kaner, Richard B.

    2010-03-01

    The formation of MoO3 sheets of nanoscale thickness is described. They are made from several fundamental sheets of orthorhombic α-MoO3, which can be processed in large quantities via a low cost synthesis route that combines thermal evaporation and mechanical exfoliation. These fundamental sheets consist of double-layers of linked distorted MoO6 octahedra. Atomic force microscopy (AFM) measurements show that the minimum resolvable thickness of these sheets is 1.4 nm which is equivalent to the thickness of two double-layers within one unit cell of the α-MoO3 crystal.

  18. MoMoSat -- Mobile Service for Monitoring with GeoNotes via Satellite

    Energy Technology Data Exchange (ETDEWEB)

    Niemeyer, Irmgard [Forschungszentrum Juelich (Germany). Programme Group Systems Analysis and Technology Evaluation (STE); Jonas, Karl [Univ. of Applied Science Bonn-Rhein-Sieg, Sankt Augustin (Germany). FhG FOKUS CC SATCom; Horz, Alexander [horz informatik, Sankt Augustin (Germany); Wettschereck, Dietrich; Schmidt, Dirk [DIALOGIS GmbH, Bonn (Germany)

    2003-05-01

    The MoMoSat service will enable mobile end-users to view, manage, annotate, and communicate mapbased information in the field. The handled information exists of a huge volume of raster (satellite or aerial images) and vector data (i.e. street networks, cadastral maps or points of interest), as well as text-specific geo-referenced textual notes (the so-called 'GeoNotes') and real-time voice. A secure real-time communication between mobile units and the primary data store is an essential task of the MoMoSat service. The basic information is stored in the primary database that is accessible through a virtual private network (VPN) and cached at a server at a base station in order to ensure data availability. The base station may be installed in a car or another mobile vehicle. The two servers will periodically communicate with each other via secure satellite communication in order to check for updates. The base station supplies the relevant GIS data for the mobile units (people or even robots in the field at remote solutions). The communication between the mobile units is based on a peer-to-peer wireless local area network (WLAN) architecture. The mobile units are equipped with mobile computers (i.e. laptop, tablet PC or PDA) combined with a satellite-based positioning system (GPS) that enables them to request the proper geographic data sets from yhe base station's map server. An interactive mapping software shows the actual location on the map and allows the user to navigate (zoom, pan) through the high-resolution map display. The user can switch 'on' or 'off' several thematic layers (i.e. street network or points of interest) on the map. The software also supports collaborative aspects of MoMoSat by offering tools for the management of the GeoNotes that can be visualized by categories. The user can extend the existing GeoNotes with his personnel comments or create new GeoNotes by defining categories, recipients and the level of

  19. N-(Pivaloyloxy)alkoxy-carbonyl Prodrugs of the Glutamine Antagonist 6-Diazo-5-oxo-l-norleucine (DON) as a Potential Treatment for HIV Associated Neurocognitive Disorders.

    Science.gov (United States)

    Nedelcovych, Michael T; Tenora, Lukáš; Kim, Boe-Hyun; Kelschenbach, Jennifer; Chao, Wei; Hadas, Eran; Jančařík, Andrej; Prchalová, Eva; Zimmermann, Sarah C; Dash, Ranjeet P; Gadiano, Alexandra J; Garrett, Caroline; Furtmüller, Georg; Oh, Byoungchol; Brandacher, Gerald; Alt, Jesse; Majer, Pavel; Volsky, David J; Rais, Rana; Slusher, Barbara S

    2017-08-24

    Aberrant excitatory neurotransmission associated with overproduction of glutamate has been implicated in the development of HIV-associated neurocognitive disorders (HAND). The glutamine antagonist 6-diazo-5-oxo-l-norleucine (DON, 14) attenuates glutamate synthesis in HIV-infected microglia/macrophages, offering therapeutic potential for HAND. We show that 14 prevents manifestation of spatial memory deficits in chimeric EcoHIV-infected mice, a model of HAND. 14 is not clinically available, however, because its development was hampered by peripheral toxicities. We describe the synthesis of several substituted N-(pivaloyloxy)alkoxy-carbonyl prodrugs of 14 designed to circulate inert in plasma and be taken up and biotransformed to 14 in the brain. The lead prodrug, isopropyl 6-diazo-5-oxo-2-(((phenyl(pivaloyloxy)methoxy)carbonyl)amino)hexanoate (13d), was stable in swine and human plasma but liberated 14 in swine brain homogenate. When dosed systemically in swine, 13d provided a 15-fold enhanced CSF-to-plasma ratio and a 9-fold enhanced brain-to-plasma ratio relative to 14, opening a possible clinical path for the treatment of HAND.

  20. The effect of smoking on the urinary excretion of 8-oxodG and 8-oxoGuo in patients with type 2 diabetes

    DEFF Research Database (Denmark)

    Sørensen, Anne-Sofie; Kjær, Laura Kofoed; Petersen, Kasper Meidahl

    2017-01-01

    as urinary 8-oxo-7, 8-dihydro-2'-deoxyguanosine (8-oxodG) excretion in smokers compared with non-smokers in a healthy population. We aimed to investigate if an increased urinary excretion of 8-oxodG in smokers versus never smokers and former smokers could be verified in a population with type 2 diabetes......Over the past decades, attention has been paid to understanding the impact of oxidative stress and related modifications of DNA and RNA on various human health risks. A recent meta-analysis comprising 1915 smokers and 3462 non-smokers found a significantly higher level of DNA oxidation measured...... to examine the relationship between daily smokers (n = 462) versus former (n = 1341) and never smokers (n = 918) regarding the RNA and DNA oxidation, respectively. We did not find any significant effect of smoking on urinary excretion of 8-oxodG or 8-oxoGuo in our study. Due to a sparse study area...

  1. Synthesis, screening and QSAR studies of 3-benzoyl-2-oxo/thioxo-1,2,3,4-tetrahydro-pyrimidine analogues as antibacterial agents

    Directory of Open Access Journals (Sweden)

    Ramesh L. Sawant

    2008-12-01

    Full Text Available The purpose of this study was to synthesize several 3-benzoyl-5-acyl-6-methyl-4-substituted-2-oxo/thioxo-1,2,3,4-tetrahydropyrimidines, evaluate them for their antibacterial activity and to establish correlation between the activity and physicochemical properties. 5-Acyl-6-methyl-4-substituted-2-oxo/thioxo-1,2,3,4-tetrahydropyrimidines (A were synthesized by cyclocondensation reaction between appropriate aldehyde, acetoacetate and urea/thiourea in presence of aluminium chloride and hydrochloric acid which upon treatment with benzoyl chloride in presence of pyridine in benzene furnish the title compounds (1-28. The structures of all title compounds have been confirmed on the basis of their analytical, IR and NMR spectral data. The title compounds have been tested for antibacterial activity against Staphylococcus aureus. The compounds were divided into training and test sets. A quantitative structure activity relationship study was made using various descriptors. Several statistical expressions were developed using stepwise multiple linear regression analysis. The best quantitative structure activity relationship model was further cross validated. The study revealed that total positive partial charge (PC+ and total polar negative Van der Waals surface area (Q_VSA_PNEG contributes negatively where as contribution of Van der Waals surface area to molar refractivity (SMR_VSA7 contributes positively to the antibacterial activity. The compounds with improved antibacterial potential can be successfully designed with selected quantitative structure activity relationship model.

  2. Long-Lived Photoinduced Charge Separation in a Trinuclear Iron-μ 3 -oxo-based Metal–Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Hanna, Lauren [Department; Kucheryavy, Pavel [Department; Liu, Cunming [X-ray; Zhang, Xiaoyi [X-ray; Lockard, Jenny V. [Department

    2017-06-14

    The presence of long-lived charge-separated excited states in metal-organic frameworks (MOFs) can enhance their photocatalytic activity by decreasing the probability that photogenerated electrons and holes recombine before accessing adsorbed reactants. Detecting these charge separated states via optical transient absorption, however, can be challenging when they lack definitive optical signatures. Here, we investigate the long-lived excited state of a MOF with such vague optical properties, MIL-100(Fe), comprised of Fe3-μ3-oxo clusters and trimesic acid linkers using Fe K-edge X-ray transient absorption (XTA) spectroscopy, to unambiguously determine its ligand-to-metal charge transfer character. Spectra measured at time delays up to 3.6 μs confirm the long lived nature of the charge separated excited state. Several trinuclear iron μ3- oxo carboxylate complexes, which model the trinuclear cores of the MOF structure, are measured for comparison using both steady state XAS and XTA to further support this assignment and corresponding decay time. The MOF is prepared as a colloidal nanoparticle suspension for these measurements so both its fabrication and particle size analysis are presented, as well.

  3. Production of 3-Oxo-2-(2'-pentenyl)-cyclopentane-1-octanoic Acid in the Fungus Aspergillus oryzae: A Step Towards Heterologous Production of Pyrethrins in Fungi.

    Science.gov (United States)

    Mohamed, Maged E; Pahirulzaman, Khomaizon A K; Lazarus, Colin M

    2016-03-01

    Pyrethrins are natural insecticides, which accumulate to high concentrations in pyrethrum (Chrysanthemum cinerariaefolium) flowers. Synthetic pyrethroids are more stable, more efficacious and cheaper, but contemporary requirements for safe and environmentally friendly pesticides encourage a return to the use of natural pyrethrins, and this would be favoured by development of an efficient route to their production by microbial fermentation. The biosynthesis of pyrethrins involves ester linkage between an acid moiety (chrysanthemoyl or pyrethroyl, synthesised via the mevalonic acid pathway from glucose), and an alcohol (pyrethrolone). Pyrethrolone is generated from 3-oxo-2-(2'-pentenyl)-cyclopentane-1-octanoic acid, which originates from α-linolenic acid via the jasmonic acid biosynthetic cascade. The first four genes in this cascade, encoding lipoxygenase 2, allene-oxide synthase, allene-oxide cyclase 2 and 12-oxophytodienoic acid reductase 3, were amplified from an Arabidopsis thaliana cDNA library, cloned in a purpose-built fungal multigene expression vector and expressed in Aspergillus oryzae. HPLC-MS analysis of the transgenic fungus homogenate gave good evidence for the presence of 3-oxo-2-(2'-pentenyl)-cyclopentane-1-octanoic acid.

  4. Forensic engineering of advanced polymeric materials Part IV: Case study of oxo-biodegradable polyethylene commercial bag - Aging in biotic and abiotic environment.

    Science.gov (United States)

    Musioł, Marta; Rydz, Joanna; Janeczek, Henryk; Radecka, Iza; Jiang, Guozhan; Kowalczuk, Marek

    2017-06-01

    The public awareness of the quality of environment stimulates the endeavor to safe polymeric materials and their degradation products. The aim of the forensic engineering case study presented in this paper is to evaluate the aging process of commercial oxo-degradable polyethylene bag under real industrial composting conditions and in distilled water at 70°C, for comparison. Partial degradation of the investigated material was monitored by changes in molecular weight, thermal properties and Keto Carbonyl Bond Index and Vinyl Bond Index, which were calculated from the FTIR spectra. The results indicate that such an oxo-degradable product offered in markets degrades slowly under industrial composting conditions. Even fragmentation is slow, and it is dubious that biological mineralization of this material would occur within a year under industrial composting conditions. The slow degradation and fragmentation is most likely due to partially crosslinking after long time of degradation, which results in the limitation of low molecular weight residues for assimilation. The work suggests that these materials should not be labeled as biodegradable, and should be further analyzed in order to avoid the spread of persistent artificial materials in nature. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Comparative study of NiW, NiMo and MoW prepared by mechanical alloying

    International Nuclear Information System (INIS)

    Gonzalez, G.; Sagarzazu, A.; Villalba, R.; Ochoa, J.

    2007-01-01

    The present work concern the amorphisation process induced by mechanical alloying in the NiW, NiMo and MoW systems. The alloys chosen combine a group of transition elements varying from very similar atomic radius and electronic valences (MoW) to different ones (NiW and NiMo). The three systems achieved an amorphous state after 50 h of milling. The mechanism of amorphisation proposed for NiW and NiMo was the combined effect of an excess concentration of the solute atoms entering into the structure of one of the elements and a critical concentration of defects. Continuous formation of an amorphous phase at the interface of the crystalline phase was observed during the process. MoW seems to amorphize by continuous reduction of grain size down to a critical value where the amorphisation takes place

  6. Phase equilibria in the CdMoO4-Gd2(MoO4)3 system

    International Nuclear Information System (INIS)

    Tunik, T.A.; Fedorov, N.F.; Razumovskij, S.N.

    1980-01-01

    The constitutional diagram of the CdMoO 4 -Cd 2 (MoO 4 ) 3 system has been plotted using statistical and dynamic methods as well as a complex of instrumental analysis procedures. Three major phases have been found to occur in the systems, viz.: CdMoO 4 based solid solutions that crystallize in the range from 0 to 25 mol.percent of Cd 2 (MoO 4 ) 3 and pass in transit the two-phase narrow region becoming then solid solutions having a distorted scheelite structure and existing in concentrations from 40 to 65 mol.% of Cd 2 (MoO 4 ) 3 . The entire range, in which the Cd 2 (MoO 4 ) 3 solid solutions can exist, amounts to less than 5 mol.%. Certain crystallochemical constants of the phases that occur in the system have been determined [ru

  7. Crystal structures of three 1-oxo-1,2-dihydronaphthalene derivatives: dimethyl 4-(4-methoxyphenyl-2-(4-methylphenyl-1-oxo-1,2-dihydronaphthalene-2,3-dicarboxylate, dimethyl 1-oxo-2-(pyren-4-yl-4-(thiophen-2-yl-1,2-dihydronaphthalene-2,3-dicarboxylate and ethyl 1-oxo-2-phenyl-2,4-bis(thiophen-2-yl-1,2-dihydronaphthalene-3-carboxylate

    Directory of Open Access Journals (Sweden)

    S. Gopinath

    2017-02-01

    Full Text Available In the title 1-oxo-1,2-dihydronaphthalene derivatives, C28H24O6, (I, C34H22O5S, (II, and C27H20O3S2, (III, the cyclohexa-1,3-diene rings of the 1,2-dihydronaphthalene ring systems adopt half-chair, boat and half-chair conformations, respectively. The carbonyl O atoms attached to the dihydronaphthalene ring systems are each significantly deviated from the mean plane of the 1,2-dihydronaphthalene ring system, by 0.6162 (12 Å in (I, 0.6016 (16 Å in (II and 0.515 (3 Å in (III. The mean planes of the 1,2-dihydronaphthalene ring systems make dihedral angles of 85.83 (3, 88.19 (3 and 81.67 (8°, respectively, with the methylphenyl ring in (I, the pyrene ring in (II and the phenyl ring in (III. In (I, the molecular structure is stabilized by an intramolecular C—H...O hydrogen bond, generating an S(6 ring motif. In the crystal of (I, molecules are linked by an intermolecular C—H...O hydrogen bond, which generates a C(8 zigzag chain running along [100]. Adjacent chains are further connected by C—H...π and offset π–π interactions [centroid–centroid distance = 3.6572 (9 Å], forming a double-chain structure. In the crystals of (II and (III, molecules are linked into chain structures by offset π–π interactions with centroid–centroid distances of 3.5349 (12 and 3.8845 (13 Å for (II and 3.588 (2 Å for (III. In (II and (III, the thiophene rings are orientationally disordered over two sites, with occupancy ratios of 0.69:0.31 for (II, and 0.528 (4:0.472 (4 and 0.632 (5:0.368 (5 for (III.

  8. Phase equilibria in the system Li2O - MoO3 - Sc2O3

    International Nuclear Information System (INIS)

    Safonov, V.V.; Chaban, N.G.; Porotnikov, N.V.

    1984-01-01

    Using the methods of DTA and X-ray phase analysis, interaction of components in the system Li 2 O-MoO 3 -Sc 2 O 3 in concentration range, adjacent to the vertex of MoO 3 , has been studied. Projection of the Li 2 MoO 4 -MoO 3 -Sc 2 (MoO 4 ) 3 system liquidus on concentrational triangle of the compositions Li 2 O-MoO 3 -Sc 2 O 3 , which consists of the fields of primary separation of Li 2 MoO 4 , Li 2 Mo 5 O 17 , Li 2 Mo 4 O 13 , MoO 3 , Sc 2 (MoO 4 ) 3 , Li 3 Sc(MoO 4 ) 3 and LiSc(MoO 4 ) 2 , is built

  9. -MoS2 Lateral Heterojunctions

    KAUST Repository

    Li, Ming-yang

    2018-02-28

    2D layered heterostructures have attracted intensive interests due to their unique optical, transport, and interfacial properties. The laterally stitched heterojunction based on dissimilar 2D transition metal dichalcogenides forms an intrinsic p–n junction without the necessity of applying an external voltage. However, no scalable processes are reported to construct the devices with such lateral heterostructures. Here, a scalable strategy, two-step and location-selective chemical vapor deposition, is reported to synthesize self-aligned WSe2–MoS2 monolayer lateral heterojunction arrays and demonstrates their light-emitting devices. The proposed fabrication process enables the growth of high-quality interfaces and the first successful observation of electroluminescence at the WSe2–MoS2 lateral heterojunction. The electroluminescence study has confirmed the type-I alignment at the interface rather than commonly believed type-II alignment. This self-aligned growth process paves the way for constructing various 2D lateral heterostructures in a scalable manner, practically important for integrated 2D circuit applications.

  10. Epitaxial (100)-oriented Mo/V superlattice grown on MgO(100) by dcMS and HiPIMS

    International Nuclear Information System (INIS)

    Shayestehaminzadeh, S.; Magnusson, R.L.; Gislason, H.P.; Olafsson, S.

    2013-01-01

    Epitaxial (100)-oriented Mo/V superlattices have been grown by High Power Impulse Magnetron Sputtering (HiPIMS) and dc Magnetron Sputtering (dcMS) on single-crystalline MgO(100) substrates at growth temperatures ranging from 30 °C to 600 °C. Superlattice bilayer period of Mo/V around 12/12 monolayers and 15 repeat periods was studied. This study aims to investigate the effect of the HiPIMS process on reducing the growth temperature of Mo/V superlattices using the high energy ionized Mo, V species in the HiPIMS plasma. In one case, the Mo layer was only grown with the HiPIMS process and V layer grown using the dcMS process while in another both layers were grown with the HiPIMS process. The as-deposited films were characterized by X-ray reflection and diffraction techniques. The dcMS process was found to give superior superlattice growth at high growth temperatures while a mixed Mo HiPIMS and V dcMS process gives better result at lower growth temperatures (300 °C). Room temperature growth reveals that neither the mixed Mo HiPIMS and V dcMS process nor the pure HiPIMS for both materials can produce better result compared to the pure dcMS process, which gives a relatively better result. - Highlights: • Epitaxial (100)-oriented Mo/V superlattices have been grown by HiPIMS and dcMS on MgO(100) for various temperatures. • The study was aimed to investigate the effect of ionized HiPIMS process onlowering the growth temperature. • The dcMS process was found to give superior superlattice growth at high growth temperature. • The mixed Mo HiPIMS and V dcMS process gives best result at lower growth temperatures

  11. Voltage profile, structural prediction, and electronic calculations for MgxMo6S8

    CSIR Research Space (South Africa)

    Kganyago, KR

    2003-03-01

    Full Text Available the binary Mo6S8 and MgAMo6S8 ~see Table III!, the Mo-Mo distances decrease by (0.521)%. This decrease corresponds to an an- isotropic contraction of the Mo6 octahedron. The Mo cluster of the rhombohedral compounds forms an elongated octahe- dron of symmetry...

  12. Lattice structures and electronic properties of MO/MoSe2 interface from first-principles calculations

    Science.gov (United States)

    Zhang, Yu; Tang, Fu-Ling; Xue, Hong-Tao; Lu, Wen-Jiang; Liu, Jiang-Fei; Huang, Min

    2015-02-01

    Using first-principles plane-wave calculations within density functional theory, we theoretically studied the atomic structure, bonding energy and electronic properties of the perfect Mo (110)/MoSe2 (100) interface with a lattice mismatch less than 4.2%. Compared with the perfect structure, the interface is somewhat relaxed, and its atomic positions and bond lengths change slightly. The calculated interface bonding energy is about -1.2 J/m2, indicating that this interface is very stable. The MoSe2 layer on the interface has some interface states near the Fermi level, the interface states are mainly caused by Mo 4d orbitals, while the Se atom almost have no contribution. On the interface, Mo-5s and Se-4p orbitals hybridize at about -6.5 to -5.0 eV, and Mo-4d and Se-4p orbitals hybridize at about -5.0 to -1.0 eV. These hybridizations greatly improve the bonding ability of Mo and Se atom in the interface. By Bader charge analysis, we find electron redistribution near the interface which promotes the bonding of the Mo and MoSe2 layer.

  13. First-principles study of van der Waals interactions in MoS2 and MoO3

    International Nuclear Information System (INIS)

    Peelaers, H; Van de Walle, C G

    2014-01-01

    Van der Waals interactions play an important role in layered materials such as MoS 2 and MoO 3 . Within density functional theory, several methods have been developed to explicitly include van der Waals interactions. We compare the performance of several of these functionals in describing the structural and electronic properties of MoS 2 and MoO 3 . We include functionals based on the local density or generalized gradient approximations, but also based on hybrid functionals. The coupling of the semiempirical Grimme D2 method with the hybrid functional HSE06 is shown to lead to a very good description of both structural and electronic properties. (paper)

  14. The fracture toughness and DBTT of MoB particle-reinforced MoSi2 composites

    International Nuclear Information System (INIS)

    Xiong Zhi; Wang Gang; Jiang Wan

    2005-01-01

    The room temperature fracture toughness and the high temperature DBTT of MoB particle-reinforced MoSi 2 composites were investigated using Vickers indentation technique and MSP testing method, respectively. Modified small punch (MSP) test is a method for evaluation of mechanical properties using very small specimens, and it's appropriate for the determination of strength and DBTT. It was found that the approximate fracture toughness of the composite is 1.3 times that of monolithic MoSi 2 , and its DBTT is 100 C higher than that of monolithic MoSi 2 materials. Cracks deflection is a probable mechanism responsible for this behavior. (orig.)

  15. Magnetoresistance in Co/2D MoS2/Co and Ni/2D MoS2/Ni junctions.

    Science.gov (United States)

    Zhang, Han; Ye, Meng; Wang, Yangyang; Quhe, Ruge; Pan, Yuanyuan; Guo, Ying; Song, Zhigang; Yang, Jinbo; Guo, Wanlin; Lu, Jing

    2016-06-28

    Semiconducting single-layer (SL) and few-layer MoS2 have a flat surface, free of dangling bonds. Using density functional theory coupled with non-equilibrium Green's function method, we investigate the spin-polarized transport properties of Co/2D MoS2/Co and Ni/2D MoS2/Ni junctions with MoS2 layer numbers of N = 1, 3, and 5. Well-defined interfaces are formed between MoS2 and metal electrodes. The junctions with a SL MoS2 spacer are almost metallic owing to the strong coupling between MoS2 and the ferromagnets, while those are tunneling with a few layer MoS2 spacer. Both large magnetoresistance and tunneling magnetoresistance are found when fcc or hcp Co is used as an electrode. Therefore, flat single- and few-layer MoS2 can serve as an effective nonmagnetic spacer in a magnetoresistance or tunneling magnetoresistance device with a well-defined interface.

  16. Mo-99 supply issues: Status report and lessons learned

    International Nuclear Information System (INIS)

    Ponsard, B.

    2010-01-01

    The worldwide supply of 99 Mo relies on a limited number of research reactors and processing facilities. Its production is essential for the nuclear medicine as 99m Tc, obtained from 99 Mo/ 99m Tc generators, is used in about 80% of the diagnostic nuclear imaging procedures. These applications represent yearly approximately 30 million examinations worldwide. The short half-life's of 99 Mo (66 hours) and its daughter 99m Tc (6 hours) require a regular supply of 99 Mo/ 99m Tc generators to hospitals or central radiopharmacies. Currently, there are only five nuclear reactors involved in the production of 99 Mo on industrial scale: NRU (Canada), HFR (Netherlands), BR2 (Belgium), OSIRIS (France) and SAFARI (South Africa). They irradiate highly enriched uranium targets for the production of about 95% of the available 99 Mo by four processing facilities: AECL/MDS NORDION (Canada), COVIDIEN (Netherlands), IRE (Belgium) and NTP (South Africa). However, these ageing reactors are subject to unscheduled shutdowns and longer maintenance periods making the 99 Mo supply chain vulnerable and unreliable. Several severe disruptions have been experienced since the fall 2005 due to the occurrence of problems at different stages of the supply chain: reactor outages, release of activity from processing facilities, recall of 99 Mo/ 99m Tc generators by the manufacturers, ... It is not expected that the situation will improve significantly in the near future. Therefore, several workshops have been organized in 2009 by the OECD Nuclear Energy Agency (NEA), the International Atomic Energy Agency (IAEA) and the Association of Imaging Producers and Equipment Suppliers (AIPES) to define measures that should be taken to secure the 99 Mo supply in the short, medium and long term. This paper summarizes the current status of the 99 Mo supply, discusses the ongoing plans for additional 99 Mo production capacity and outlines the issues for a reliable global supply chain. (author)

  17. Physical properties of monolithic U8 wt.%-Mo

    Science.gov (United States)

    Hengstler, R. M.; Beck, L.; Breitkreutz, H.; Jarousse, C.; Jungwirth, R.; Petry, W.; Schmid, W.; Schneider, J.; Wieschalla, N.

    2010-07-01

    As a possible high density fuel for research reactors, monolithic U8 wt.%-Mo ("U8Mo") was examined with regard to its structural, thermal and electric properties. X-ray diffraction by the Bragg-Brentano method was used to reveal the tetragonal lattice structure of rolled U8Mo. The specific heat capacity of cast U8Mo was determined by differential scanning calorimetry, its thermal diffusivity was measured by the laser flash method and its mass density by Archimedes' principle. From these results, the thermal conductivity of U8Mo in the temperature range from 40 °C to 250 °C was calculated; in the measured temperature range, it is in good accordance with literature data for UMo with 8 and 9 wt.% Mo, is higher than for 10 wt.% Mo and lower than for 5 wt.% Mo. The electric conductivity of rolled and cast U8Mo was measured by a four-wire method and the electron based part of the thermal conductivity calculated by the Wiedemann-Frantz law. Rolled and cast U8Mo was irradiated at about 150 °C with 80 MeV 127I ions to receive the same iodine ion density in the damage peak region as the fission product density in the fuel of a typical high flux reactor after the targeted nuclear burn-up. XRD analysis of irradiated U8Mo showed a change of the lattice parameters as well as the creation of UO 2 in the superficial sample regions; however, a phase change by irradiation was not observed. The determination of the electron based part of the thermal conductivity of the irradiated samples failed due to high measurement errors which are caused by the low thickness of the damage region in the ion irradiated samples.

  18. Five (or so) challenges for species distribution modelling

    DEFF Research Database (Denmark)

    Bastos Araujo, Miguel; Guisan, Antoine

    2006-01-01

    Species distribution modelling is central to both fundamental and applied research in biogeography. Despite widespread use of models, there are still important conceptual ambiguities as well as biotic and algorithmic uncertainties that need to be investigated in order to increase confidence in mo...

  19. Selective adsorption of molybdenum(VI) from Mo-Re bearing effluent by chemically modified astringent persimmon

    Energy Technology Data Exchange (ETDEWEB)

    Xiong Ying, E-mail: xiongying_1977@hotmail.com [School of Chemistry, Key Laboratory of Rare-scattered Elements of Liaoning Province, Liaoning University, Shenyang 110036 (China); Wang Haitao; Lou Zhenning; Shan Weijun; Xing Zhiqiang; Deng Guichun [School of Chemistry, Key Laboratory of Rare-scattered Elements of Liaoning Province, Liaoning University, Shenyang 110036 (China); Wu Dongbei [Department of Chemistry, Tongji University, 200092 (China); Fang Dawei [School of Chemistry, Key Laboratory of Rare-scattered Elements of Liaoning Province, Liaoning University, Shenyang 110036 (China); Biswas, Biplob Kumar [Department of Applied Chemistry, Saga University, Honjo 1, Saga 840-8502 (Japan); Department of Applied Chemistry and Chemical Engineering, Jessore Science and Technology University, Jessore (Bangladesh)

    2011-02-28

    Graphical abstract: The use of persimmon for the recovery of Mo(VI) from aqueous chloride medium was investigated. The excellent adsorption characteristics for Mo(VI) were confirmed by adsorption and elution tests using a column packed with the APF gel. Research highlights: {yields} Astringent persimmon was chemically cross-linked by formaldehyde to obtain a novel kind of adsorption gel. By comparing with the adsorption of some other metal ions, especially for Re(VII), this new gel exhibited selectivity only for molybdenum with a remarkably high capacity for Mo(VI) (1.05 mol/kg dry gel). {yields} The adsorption mechanisms of molybdenum on the astringent persimmon gel have been determined for deferent molybdenum species. And, the endothermic adsorption process followed pseudo-second order kinetics, and the adsorption behavior obeys the Langmuir mode. {yields} The excellent adsorption characteristics for Mo(VI) were confirmed by adsorption and elution tests using a column packed with the APF gel, especially from an actual industrial waste effluent. - Abstract: Astringent persimmon was chemically cross-linked by formaldehyde to obtain a novel kind of adsorption gel, which was named as APF gel. The adsorption behaviors of Mo(VI) and Re(VII) along with other coexisting metals onto the APF gel were studied in the present paper. The APF gel was found to be effective for the adsorption of Mo(VI) while the gel is almost completely inert toward rhenium and calcium over the whole hydrochloric acid concentration region. The APF gel has a low affinity for iron, copper, lead, nickel, manganese and zinc ions when the concentration of HCl is higher than 1 mol/L. The gel exhibited selectivity only for Mo(VI) with a remarkably high adsorption capacity 1.05 mol/kg, and the adsorption behavior obeys the Langmuir model. According to the thermodynamic and kinetic studies, the endothermic adsorption process followed pseudo-second order kinetics. Also, its excellent adsorption

  20. Thermal expansion studies on Th(MoO4)2, Na2Th(MoO4)3 and Na4Th(MoO4)4

    International Nuclear Information System (INIS)

    Keskar, Meera; Krishnan, K.; Dahale, N.D.

    2008-01-01

    Thermal expansion behavior of Th(MoO 4 ) 2 , Na 2 Th(MoO 4 ) 3 and Na 4 Th(MoO 4 ) 4 was studied under vacuum in the temperature range of 298-1123 K by high temperature X-ray diffractometer. Th(MoO 4 ) 2 was synthesized by reacting ThO 2 with 2 mol of MoO 3 , at 1073 K in air and Na 2 Th(MoO 4 ) 3 and Na 4 Th(MoO 4 ) 4 were prepared by reacting Th(MoO 4 ) 2 with 1 and 2 mol of Na 2 MoO 4 , respectively at 873 K in air. The XRD data of Th(MoO 4 ) 2 was indexed on orthorhombic system where as XRD data of Na 2 Th(MoO 4 ) 3 and Na 4 Th(MoO 4 ) 4 were indexed on tetragonal system. The lattice parameters and cell volume of all the three compounds, fit into polynomial expression with respect to temperature, showed positive thermal expansion (PTE) up to 1123 K. The average value of thermal expansion coefficients for Th(MoO 4 ) 2 , Na 2 Th(MoO 4 ) 3 and Na 4 Th(MoO 4 ) 4 were determined from the high temperature data

  1. Effects of eight weeks of an alleged aromatase inhibiting nutritional supplement 6-OXO (androst-4-ene-3,6,17-trione on serum hormone profiles and clinical safety markers in resistance-trained, eugonadal males

    Directory of Open Access Journals (Sweden)

    Kreider Richard

    2007-10-01

    Full Text Available Abstract The purpose of this study was to determine the effects of 6-OXO, a purported nutritional aromatase inhibitor, in a dose dependent manner on body composition, serum hormone levels, and clinical safety markers in resistance trained males. Sixteen males were supplemented with either 300 mg or 600 mg of 6-OXO in a double-blind manner for eight weeks. Blood and urine samples were obtained at weeks 0, 1, 3, 8, and 11 (after a 3-week washout period. Blood samples were analyzed for total testosterone (TT, free testosterone (FT, dihydrotestosterone (DHT, estradiol, estriol, estrone, SHBG, leutinizing hormone (LH, follicle stimulating hormone (FSH, growth hormone (GH, cortisol, FT/estradiol (T/E. Blood and urine were also analyzed for clinical chemistry markers. Data were analyzed with two-way MANOVA. For all of the serum hormones, there were no significant differences between groups (p > 0.05. Compared to baseline, free testosterone underwent overall increases of 90% for 300 mg 6-OXO and 84% for 600 mg, respectively (p 0.05 and clinical safety markers were not adversely affected with ingestion of either supplement dose (p > 0.05. While neither of the 6-OXO dosages appears to have any negative effects on clinical chemistry markers, supplementation at a daily dosage of 300 mg and 600 mg for eight weeks did not completely inhibit aromatase activity, yet significantly increased FT, DHT, and T/E.

  2. Hybrid conducting polymer materials incorporating poly-oxo-metalates for extraction of actinides; Materiaux polymeres conducteurs hybrides incorporant des polyoxometallates pour l'extraction d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Racimor, D

    2003-09-15

    The preparation and characterization of hybrid conducting polymers incorporating poly-oxo-metalates for extracting actinides is discussed. A study of the coordination of various lanthanide cations (Ce(III), Ce(IV), Nd(III)) by the mono-vacant poly-oxo-metalate {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} showed significant differences according to the cation.. Various {alpha}-A-[PW{sub 9}O{sub 34}(RPO){sub 2}]{sup 5-} hybrids were synthesized and their affinity for actinides or lanthanides was demonstrated through complexation. The first hybrid poly-oxo-metallic lanthanide complexes were then synthesized, as was the first hybrid functionalized with a pyrrole group. The electro-polymerization conditions of this pyrrole remain still to be optimized. Poly-pyrrole materials incorporating {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} or its neodymium or cerium complexes as doping agents proved to be the first conducting polymer incorporating poly-oxo-metalates capable of extracting plutonium from nitric acid. (author)

  3. Synthesis, crystal structure, and spectra of 3,3- dimethyl-1-N-(1'-phenyl-2',3'-dimethyl-5'-oxo-3'- pyrazolin-4'-yl)imino-1,2,3,4-tetrahydroisoquinoline

    International Nuclear Information System (INIS)

    Sokol, V.I.; Ryabov, M.A.; Merkur'eva, N.Yu.; Davydov, V.V.; Zaitsev, B.E.; Shklyaev, Yu.V.; Sergienko, V.S.; Zaitsev, B.E.

    1996-01-01

    The synthesis and the crystal and molecular structure of 3,3-dimethyl-1-N-(1'-phenyl-2',3'- dimethyl-5'-oxo-3'-pyrazolin-4'-yl)imino-1,2,3,4-tetrahydroisoquinoline are reported. As is evidenced by the 1H NMR, IR, and electron spectra, the tautomeric form of the compounds observed in the crystal is also retained in solutions

  4. Study of the water-gas shift reaction on Mo2C/Mo catalytic coatings for application in microstructured fuel processors

    NARCIS (Netherlands)

    Rebrov, E.V.; Kuznetsov, S.A.; Croon, de M.H.J.M.; Schouten, J.C.

    2007-01-01

    The activity and stability of two types of molybdenum carbide coatings deposited on molybdenum substrates (Mo2C/Mo) were compared in the water-gas shift reaction at 513–631 K. The activity of the Mo2C/Mo coatings obtained by carburization of preoxidized molybdenum substrates in a CH4/H2 mixture at

  5. LEUbased Fission Mo-99 Process with Reduced Solid Wastes

    International Nuclear Information System (INIS)

    Lee, Seungkon; Lee, Suseung; Jung, Sunghee; Hong, Soonbog; Jang, Kyungduk; Choi, Sang Mu; Lee, Jun Sig; Lim, Incheol

    2014-01-01

    99m Tc emits 140 keV of very low gamma-ray radiation energy, as low as conventional diagnostic X-ray, and has short half-life of 6.0058 hours. Therefore, as radioactive tracer, 99m Tc provides high quality diagnostic images but keeps total patient radiation exposure low. Depending on the tagging pharmaceuticals and procedures, 99m Tc can be applied for the diagnostics of various target organs and diseases: brain, myocardium, thyroid, lungs, liver, gallbladder, kidneys, skeleton, blood and tumors. More than 95% of 99 Mo is produced through fission of 235 U worldwide because, 99m o generated from the fission (fission 99 Mo) exhibits very high specific activity (<100 Ci/g). Over 90% of fission 99 Mo producers have been used highly enriched uranium (HEU) targets so far. However, the IAEA recommends the use of low enriched uranium (LEU) to the 99 Mo producers for nonproliferation reason. These days, worldwide 99 Mo supply is not only insufficient but also unstable. Because, most of the main 99 Mo production reactors are about 50 years old and suffered from frequent and unscheduled shutdown. Planned weekly productivity of 2000 Ci fission 99 Mo, in a 6-day reference, will cover 100% domestic demand of Korea, as well as 20% of international market. It is expected to replace 4.3 million USD ($800/Ci) of 99 Mo import for domestic market while exporting 82.8 million USD for world market, annually

  6. Mullite/Mo interfaces formed by Intrusion bonding

    Energy Technology Data Exchange (ETDEWEB)

    Bartolome, Jose F.; Diaz, Marcos; Moya, Jose S.; Saiz, Eduardo; Tomsia, Antoni P.

    2003-04-30

    The microstructure and strength of Mo/mullite interfaces formed by diffusion bonding at 1650 C has been analyzed. Interfacial metal-ceramic interlocking contributes to flexural strength of approx. 140 MPa as measured by 3 point bending. Saturation of mullite with MoO2 does not affect the interfacial strength.

  7. Mo-Si-B-Based Coatings for Ceramic Base Substrates

    Science.gov (United States)

    Perepezko, John Harry (Inventor); Sakidja, Ridwan (Inventor); Ritt, Patrick (Inventor)

    2015-01-01

    Alumina-containing coatings based on molybdenum (Mo), silicon (Si), and boron (B) ("MoSiB coatings") that form protective, oxidation-resistant scales on ceramic substrate at high temperatures are provided. The protective scales comprise an aluminoborosilicate glass, and may additionally contain molybdenum. Two-stage deposition methods for forming the coatings are also provided.

  8. Preparation of a gel of zirconium molybdate for use in the generators of 99 Mo - 99m Tc prepared with 99 Mo produced by the 98 Mo(n,γ)99 Mo reaction

    International Nuclear Information System (INIS)

    Osso Junior, Joao A.; Lima, Ana Lucia V.P.; Silva, Nestor C. da; Nieto, Renata C.; Velosa, Adriana C. de

    1998-01-01

    IPEN develops a project concerning the preparation of a gel of Zirconium Molybdate for use in the generators of 99 Mo- 99m Tc . 99m Tc is the most used radioisotope in nuclear medicine diagnosis procedures and nowadays the generators are being prepared with imported 99 Mo, produced by 235 U fission. The production of 99 Mo by the 98 Mo(n, γ) 99 Mo reaction is now possible because of the power upgrade of IPEN's IEA-R1 reactor, from 2 to 5 MW. This work describes the preparation method of Zirconium Molybdate gel that will be used in the 99 Mo- 99m Tc generators. The gel is prepared by the chemical reaction between Mo, in Mo O 3 form, and Zr, in Zr O Cl 2 .8H 2 O form. After the reaction, the gel is filtered, dried and cracked with saline solution. The product is then loaded into glass columns for use as 99m Tc generator. The results showed the good quality of the gel prepared at laboratory level and of the generators evaluated. (author)

  9. Mullite/Mo interfaces formed by Intrusion bonding

    OpenAIRE

    Bartolome, Jose F.; Diaz, Marcos; Moya, Jose S.; Saiz, Eduardo; Tomsia, Antoni P.

    2003-01-01

    The microstructure and strength of Mo/mullite interfaces formed by diffusion bonding at 1650oC has been analyzed. Interfacial metal-ceramic interlocking contributes to flexural strength of approx. 140 MPa as measured by 3 point bending. Saturation of mullite with MoO2 does not affect the interfacial strength.

  10. Ammonia treated Mo/AC catalysts for CO hydrogenation with ...

    Indian Academy of Sciences (India)

    SHARIF F ZAMAN

    the influence of acid treated AC as a support with K-Ni-. Mo active ... K-Ni-Mo/AC catalyst was more selective to oxygenates. (>40% ... mineral impurities (K, Si, Sn and Fe) <1%. ...... edge technical support with thanks Science and Technology.

  11. Development of Fission Mo-99 Process for LEU Dispersion Target

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seung Kon; Lee, Su Seung; Hong, Soon Bog; Jang, Kyung Duk; Park, Ul Jae; Lee, Jun Sig [KAERI, Daejeon (Korea, Republic of)

    2016-05-15

    KAERI (Korea Atomic Energy Research Institute) is developing LEU-based fission {sup 99}Mo production process which is connected to the new research reactor (Kijang New Research Reactor, KJRR), which is being constructed in Gijang, Busan, Korea. Historically, the most fission {sup 99}Mo producers have been used highly enriched uranium (HEU) targets so far. However, to reduce the use of HEU in private sector for non-proliferation, {sup 99}Mo producers are forced to convert their HEU-based process to use low enriched uranium (LEU) targets. Economic impact of a target conversion from HEU to LEU is significant. Overall cost for the production of the fission {sup 99}Mo increases significantly with the conversion of fission {sup 99}Mo targets from HEU to LEU. It is not only because the yield of LEU is only 50% of HEU, but also because radioactive waste production increases 200%. On the basis, worldwide efforts on the development of {sup 99}Mo production process that is optimized for the LEU target become an important issue. In this study, fission {sup 99}Mo process with non-irradiated LEU targets was presented except separation and purification steps. Pre- and post-irradiation tests of the fission {sup 99}Mo target will be done in 4th quarter of 2016.

  12. Toroidal deuteron accelerator for Mo-98 neutron activation

    International Nuclear Information System (INIS)

    Araujo, Wagner L.; Campos, Tarcisio P.R. Universidade Federal de Minas Gerais

    2017-01-01

    The radionuclide Tc- 99m is the most useful radioisotope in nuclear medicine. It can be produced by the Mo-99 beta minus decay. Mo-99 has often been produced in a high- flux nuclear reactor through radioactive neutron capture reactions on Mo-98. The present paper provides a preliminary design of a toroidal transmutation system (TTS) based on a toroidal compact deuteron accelerator, which can provide the Mo-98 transmutation into Mo-99. This system is essentially composed of a multi-aperture plasma electrode and a target, submitted to 180 kV, where a positive deuteron beam is accelerated toward a titanium-target loaded with deuterium in which nuclear d-d fusion reactions are induced. The Particle Studio package of the Computer Simulation Technology (CST) software was applied to design, simulate and optimize the deuteron beam on the target. MCNP code provided to neutronic analysis. Based on electromagnetic and neutronic simulations, the neutron yield and reaction rates were estimated. The simulated data allowed appraising the Mo-99 activity. A TTS, in a specific configuration, could produce a total deuterium current of 1.6 A at the target and a neutron yield of 10 13 n.s -1 . In a arrangement of 30 column samples, TTS provides 230 mCi s -1 Mo 99 in each column, which represents 80% of Tc-99m in secular equilibrium. As conclusion, the system holds potential for generating Mo-99 and Tc-99m in a suitable activity in secular equilibrium. (author)

  13. Development of Fission Mo-99 Process for LEU Dispersion Target

    International Nuclear Information System (INIS)

    Lee, Seung Kon; Lee, Su Seung; Hong, Soon Bog; Jang, Kyung Duk; Park, Ul Jae; Lee, Jun Sig

    2016-01-01

    KAERI (Korea Atomic Energy Research Institute) is developing LEU-based fission 99 Mo production process which is connected to the new research reactor (Kijang New Research Reactor, KJRR), which is being constructed in Gijang, Busan, Korea. Historically, the most fission 99 Mo producers have been used highly enriched uranium (HEU) targets so far. However, to reduce the use of HEU in private sector for non-proliferation, 99 Mo producers are forced to convert their HEU-based process to use low enriched uranium (LEU) targets. Economic impact of a target conversion from HEU to LEU is significant. Overall cost for the production of the fission 99 Mo increases significantly with the conversion of fission 99 Mo targets from HEU to LEU. It is not only because the yield of LEU is only 50% of HEU, but also because radioactive waste production increases 200%. On the basis, worldwide efforts on the development of 99 Mo production process that is optimized for the LEU target become an important issue. In this study, fission 99 Mo process with non-irradiated LEU targets was presented except separation and purification steps. Pre- and post-irradiation tests of the fission 99 Mo target will be done in 4th quarter of 2016

  14. 77 FR 29875 - Establishment of Class E Airspace; Houston, MO

    Science.gov (United States)

    2012-05-21

    ...-0903; Airspace Docket No. 11-ACE-20] Establishment of Class E Airspace; Houston, MO AGENCY: Federal... at Houston, MO. Controlled airspace is necessary to accommodate new Area Navigation (RNAV) Standard Instrument Approach Procedures at Houston Memorial Airport. The FAA is taking this action to enhance the...

  15. Mo-99 production by fission and future projections

    International Nuclear Information System (INIS)

    Carranza, E.C.; Novello, A.; Bronca, M.; Cestau, D.; Bavaro, R.; Centurion, R.; Bravo, C.; Bronca, P.; Gualda, E.; Fraguas, F.; Giomi, A.; Ivaldi, L.

    2012-01-01

    Description of the I-131 and Mo-99 production process: The process starts with the irradiation of uranium-aluminum mini plates in the RA-3, Argentinean Reactor No.3, Ezeiza Atomic Center. In a nuclear reactor there is a constant flow of neutrons and when a neutron with proper energy impacts on a nucleus of U-235, it is absorbed at the same time generate an unstable configuration nuclear. For this reason, the nucleus formed is fission, getting two different atoms. Approximately 6% of the fissions produce Mo-99 and 3% produce I-131; the percentage remaining corresponds to formation of atoms without interest for use in medicine. In conclusion, the objective of the process developed in the Fission Plant, is starting from uranium mini plates, separate the Mo-99 and I-131 generated, the remaining elements formed. - Evolution of Mo-99 Production in the last 10 years: The Fission Mo-99 Plant Production begins routine production of Mo-99 in 1985, using targets made of uranium enriched at 90% U-235. In the 1990s, global concern regarding the use of highly enriched uranium, due to non-proliferation issues, caused the interruption of supply of nuclear material (HEU enriched at 90% of U-235). Following this, Argentina developed target based on low-enriched uranium (less than 20% U-235), becoming in 2002 the first country in the world to produce Mo-99 with LEU targets. From 2002 to date, the activity produced of Mo-99 has been tripled annually (author)

  16. A review on the process technology for Mo-99 production

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jin Hoh; Yoo, Jae Hyung; Jung, Won Myung; Lee, Kyoo Il; Woo, Moon Sik; Hwang, Doo Sung; Kim, Yun Koo [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    1994-07-01

    Tc-99m is most frequently used in nuclear medical diagnostics because of its favourable nuclear properties and reasonable prices, and the demand of Tc-99m, is on the increase recently. Mo-99, the parent radionuclide of Tc-99m, is the only source of Tc-99m. This review described overall aspects of process technologies for Mo-99 production. Firstly, the chemical, physical and radioactive properties of Tc-99m, Mo-99 were examined to understand Mo-99 separation process. Also, the technology for Mo-99 production with both the neutron capture and nuclear fission method were examined. But the neutron capture method was scarcely used for large production of Mo-99 because of its low specific activity and high production cost. This review also described mainly process technologies in the nuclear fission method, fabrication and condition for irradiation of targets, transport and dissolution of targets irradiated, separation and purification of Mo-99, etc. Especially, for Mo-99 separation and purification process, the characteristics, merits and demerits of various processes, which have been developed in a few countries, were examined and analyzed. 30 figs., 16 tabs., 60 refs. (Author).

  17. Highly flexible, conductive and transparent MoO3/Ag/MoO3 multilayer electrode for organic photovoltaic cells

    International Nuclear Information System (INIS)

    Abachi, T.; Cattin, L.; Louarn, G.; Lare, Y.; Bou, A.; Makha, M.; Torchio, P.

    2013-01-01

    MoO 3 /Ag/MoO 3 (MAM) multilayer structures were deposited by vacuum evaporation on polyethylene terephthalate (PET) substrate. We demonstrate that, as in the case of glass substrate, the sheet resistance of such structures depends significantly on the Ag film deposition rate. When it is deposited between 0.2 and 0.4 nm/s, an Ag thickness of 11 nm allows achieving sheet resistance of 13 Ω/sq and an averaged transmission of 74%. A study of the influence of the PET substrate on the optimum MoO 3 thicknesses was done. A good qualitative agreement between the theoretical calculations of the variation of the optical transmittance of the MoO 3 /Ag/MoO 3 structures is obtained. The optimum MAM structures MoO 3 (17.5 nm)/Ag (11 nm)/MoO 3 (35 nm) has a factor of merit F M = 4.21 10 −3 (Ω/sq) −1 . Proven by the scotch test the MAM structures exhibit a good adhesion to the PET substrates. The MAM structures were also submitted to bending tests. For outer bending, the samples exhibit no variation of their resistance value, while for inner bending there is a small increase of the resistance of the MAM structures. However this increasing is smaller than that exhibited by Indium Tin Oxide. When the PET/MAM structures are used as anode in organic photovoltaic cells, it is shown that the need to use thicker Ag films inside the multilayer and to cover the MAM with Au to obtain promising Current density vs Voltage characteristics is due to the heating of the PET substrate during the deposition process. - Highlights: • MoO 3 /Ag/MoO 3 structures deposited on polyethylene terephthalate substrate. • MoO 3 /Ag/MoO 3 structures deposited by vacuum evaporation. • The Ag deposition rate influences the properties of the structures. • The MoO 3 /Ag/MoO 3 optimum structure has a factor of merit F M = 4.21 10 −3 (Ω/sq) −1 . • The MoO 3 /Ag/MoO 3 structures exhibit a high flexibility

  18. Electrodeposition of CoNiMo thin films using glycine as additive: anomalous and induced codeposition

    International Nuclear Information System (INIS)

    Esteves, Marcos C.; Sumodjo, Paulo T.A.; Podlaha, Elizabeth J.

    2011-01-01

    Highlights: → Mixed/induced codeposition of CoNiMo from a glycine containing bath. → Deposition in a rotating cylinder Hull cell. → The mechanism is explained in term of the complex species that can be formed. - Abstract: The present study focuses on the behavior of the CoNiMo mixed anomalous/induced codeposition process, using glycine as a probe to influence the coverage of adsorbed intermediates. In order to facilitate the investigation of a wide variation of parameters the electrodeposition of the alloy films was performed using a rotating cylinder Hull cell. Alloy composition, current efficiency and partial currents of each metal were analyzed. The partial current densities and hence alloy composition was affected by the amount of glycine in the electrolyte: increasing glycine enhanced both cobalt and molybdenum deposition rates and hindered nickel deposition. It is suggested that the glycine facilitates the adsorption of M(I) adsorbed intermediates that control the anomalous and induced codeposition behavior. The current efficiency ranged from 30 up to 75% and was only slightly affected by glycine at high applied current densities. Films with a tridimensional porous structure were obtained applying current densities higher than 200 mA cm -2 , formed as a consequence of the large hydrogen evolution side reaction, presenting conditions for a novel Mo-alloy electrode structure.

  19. [Herbal textual research of common Mongolian medicine "Du Ge Mo Nong"].

    Science.gov (United States)

    Xi, Jie; Zhong, Hua-Rong; Wucharila-Tu; Buhe Bater; Li, Hui-Hu; Zhong, Guo-Yue

    2016-11-01

    This study is aimed to provide the source for clinical medication by clarifing the common base of Mongolia medicinal materials "Du Ge Mo Nong". In this paper literature research and plant taxonomy method were adopted combined with investigation of the markets and clinical use status to clarify the origin of common traditional Mongolian medicine "Du Ge Mo Nong". The results showed that the Mongolian medicine "Du Ge Mo Nong" and Tibetan medicine "Du Mu Niu" were the same crude drug and originated from the seeds of Holarrhena antidysenteriaca of family Apocynaceae in earliest time. In Mongolian medicine clinic, the seed of Cynanchum thesioides of family Asclepiadaceae and the fruit of Forsythia suspense of family Oleaceae was used respectively about 18 century and recent time, as the substitutes of H. antidysenteriaca. In present standards on Mongolian material medicine, C. thesioides is including only, and H. antidysenterica is not used almost. In Tibetan medicine clinic, H. antidysenterica is being used so far. But there are various substitutes including the seeds, fruits or grass of many species classified to family Apocynaceae, Asclepiadaceae and Onagraceae from ancient time to the present, and C. forrestii and C. komarovii may be used at present. It's necessary to strengthen the arrangement on Mongolian medicine's varieties by the multidisciplinary methods including literature research, investigation of resources and the use state, and comparison of active substances and biological activities between the different substitutes,and so on. Copyright© by the Chinese Pharmaceutical Association.

  20. Electrical transport properties of MoO3 thin films prepared by laser assisted evaporation

    International Nuclear Information System (INIS)

    Lopez-Carreno, L.D.; Pardo, A.; Zuluaga, M.; Torres, J.; Alfonso, J.E.; Cortes-Bracho, O.L.

    2007-01-01

    In the present paper the growth of MoO 3 thin films on common glass substrates are described. The films were prepared by evaporation of a MoO 3 target with a CO 2 laser (10.6 μm), operating in the continuous wave mode. The effect of substrate temperature on the crystallographic structure and electrical properties of MoO 3 thin films was studied. The chemical composition of the different species formed on the films surface was obtained by X-ray photoelectron spectroscopy (XPS) and the crystalline structure was studied with X-ray diffraction (XRD). The electrical conductivity of the films was determined using the standard four-points method. Conductivity of the films varied from de 10 -9 to 10 -5 (Ωcm) -1 in the 300-600 K temperature range. Arrhenius-type plots for the electrical conductivity indicate the presence of at least two different conduction mechanisms. The I-V characteristic curve shows an ohmic behavior only in the 4.5-60 V range. Outside this interval the I-V curve has a behavior described by a power law. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  1. Electrical transport properties of MoO{sub 3} thin films prepared by laser assisted evaporation

    Energy Technology Data Exchange (ETDEWEB)

    Lopez-Carreno, L.D.; Pardo, A.; Zuluaga, M.; Torres, J.; Alfonso, J.E. [Group of Materials with Technological Applications, GMAT, Physics Department, Universidad Nacional de Colombia, Bogota (Colombia); Cortes-Bracho, O.L. [Group of Materials with Technological Applications, GMAT, Physics Department, Universidad Nacional de Colombia, Bogota (Colombia); Electronic Engineering Department, Universidad Nacional de Colombia, Bogota (Colombia)

    2007-07-01

    In the present paper the growth of MoO{sub 3} thin films on common glass substrates are described. The films were prepared by evaporation of a MoO{sub 3} target with a CO{sub 2} laser (10.6 {mu}m), operating in the continuous wave mode. The effect of substrate temperature on the crystallographic structure and electrical properties of MoO{sub 3} thin films was studied. The chemical composition of the different species formed on the films surface was obtained by X-ray photoelectron spectroscopy (XPS) and the crystalline structure was studied with X-ray diffraction (XRD). The electrical conductivity of the films was determined using the standard four-points method. Conductivity of the films varied from de 10{sup -9} to 10{sup -5} ({omega}cm){sup -1} in the 300-600 K temperature range. Arrhenius-type plots for the electrical conductivity indicate the presence of at least two different conduction mechanisms. The I-V characteristic curve shows an ohmic behavior only in the 4.5-60 V range. Outside this interval the I-V curve has a behavior described by a power law. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  2. Formation, properties, and ion irradiation effects of hexagonal structure MoN thin films

    International Nuclear Information System (INIS)

    Christen, D.K.; Sekula, S.T.; Ellis, J.T.; Lewis, J.D.; Williams, J.M.

    1986-09-01

    Thin films (100-120 nm) of hexagonal structures MoN have been fabricated by reaction of Mo films in an NH 3 atmosphere. The as-formed films possessed superconducting transition temperatures T/sub c/ ≅ 13 0 K, with resistance ratios r = R(296K)/R(T/sub c/) in the range 5 to 10, low-temperature normal state resistivities rho 0 = 4 to 10 μΩ-cm, and extrapolated upper critical fields H/sub c2/(0) = 4.0 to 5.0 T. Thin film x-ray diffraction patterns revealed no visible second phase, with measured lattice parameters close to literature values. The effects of lattice disorder on the superconducting and electronic properties were investigated by irradiation with nitrogen ions of energy 45 and 340 keV, resulting in a nearly uniform damage profile without the introduction of any new chemical species. The results indicate that ordered hexagonal MoN shows some of the unusual properties characteristic of moderate-to-high T/sub c/ transition metal compounds, but is relatively insensitive to degradation of the superconducting properties by lattice disorder. For ion fluences PHI up to 2 x 10 16 N-ions/cm 2 , T/sub c/ is found to decrease monotonically and saturate at 9.5 0 K, almost 3/4 the initial value, while H/sub c2/(0) undergoes a gradual increase to 11T

  3. ¿Cómo salir del liberalismo?

    Directory of Open Access Journals (Sweden)

    Lenin Flórez

    2001-01-01

    Full Text Available Alain Touraine ¿Cómo salir del Liberalismo? Piadós, Bacelona, 1999, 123 páginas. El libro parece circunscribirse al actual contexto político de Francia, que el autor considera como una coyuntura de salida del liberalismo. Su tema central gira alrededor de entender la democracia en este periodo y un proyecto político de más largo alcance. Sin embargo, sabemos que tiene serias investigaciones sobre la realidad latinoamericana, lo que nos indica que su temática rebasa el mundo europeo. Sin duda, el texto que reseñamos tiene un carácter crítico y sus planteamientos suscitan la controversia teórica.

  4. The Mo/Ta (100) interface

    International Nuclear Information System (INIS)

    Quintanar, C.; Velasco, V.R.; Garcia-Moliner, F.

    1990-12-01

    We have calculated the interface local density of states (ILDOS) formed by the transition metals Mo/Ta using a tight-binding Slater-Koster description and the Green Function matching method together with quickly converging algorithms to compute the transfer matrices. We obtain the surface LDOS as a byproduct. Our result is a useful tool to analyze experimental results and to check models as a function of the value of the tight-binding parameters either of the bulk or at the interface itself. We consider the (100) direction. We compare the interface to the bulk and to the surface and comment on some recently found experimental results for this interface. (author). 17 refs, 2 figs

  5. Chemical sensitivity of Mo gate Mos capacitors

    Energy Technology Data Exchange (ETDEWEB)

    Lombardi, R.M.; Aragon, R. [Laboratorio de Peliculas delgadas, Facultad de Ingenieria, Paseo Colon 850, 1063, Buenos Aires (Argentina)

    2006-07-01

    Mo gate Mos capacitors exhibit a negative shift of their C-V characteristic by up to 240 mV, at 125 C, in response to 1000 ppm hydrogen, in controlled nitrogen atmospheres. The experimental methods for obtaining capacitance and conductance, as a function of polarisation voltage, as well as the relevant equivalent circuits are reviewed. The single-state interface state density, at the semiconductor-dielectric interface, decreases from 2.66 x 10{sup 11} cm{sup -2} e-v{sup -1}, in pure nitrogen, to 2.5 x 10{sup 11} cm{sup -2} e-v{sup -1} in 1000 ppm hydrogen in nitrogen mixtures, at this temperature. (Author)

  6. Plasmons on the edge of MoS2 nanostructures

    DEFF Research Database (Denmark)

    Andersen, Kirsten; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer

    2014-01-01

    Using ab initio calculations we predict the existence of one-dimensional (1D), atomically confined plasmons at the edges of a zigzag MoS2 nanoribbon. The strongest plasmon originates from a metallic edge state localized on the sulfur dimers decorating the Mo edge of the ribbon. A detailed analysis...... of the dielectric function reveals that the observed deviations from the ideal 1D plasmon behavior result from single-particle transitions between the metallic edge state and the valence and conduction bands of the MoS2 sheet. The Mo and S edges of the ribbon are clearly distinguishable in calculated spatially...... resolved electron energy loss spectrum owing to the different plasmonic properties of the two edges. The edge plasmons could potentially be utilized for tuning the photocatalytic activity of MoS2 nanoparticles....

  7. Phase transformation in a Ni-Mo-Cr alloy

    International Nuclear Information System (INIS)

    Dymek, S.; Wrobel, M.; Blicharski, M.; Dollar, M.

    2001-01-01

    The paper gives a characteristic of a nickel-based superalloy containing 25 wt.% Mo and 8 wt.% Cr with particular attention to the influence of a thermochemical and heat treatment on phase transformations. The applied heat treatments are comprised of soaking temperature 1100 o C followed by aging at 650 o C at three conditions: conventional aging for 72 hours, prolonged aging for 4000 hours and prolonged aging for 4000 hours followed by cold working and subsequent aging for 1000 hours. The conventional aging led to the formation of lenticular precipitates of the dispersed metastable Ni 2 (Mo,Cr) phase. The aging for 4000 hours brought about coarsening of the ordered domains without changing their crystallographic and ordering characteristics. The plastic deformation preceded the further aging for 1000 hours accelerated the decomposition of the Ni 2 (Mo,Cr) phase on the mixture of the Ni 3 Mo and Ni 4 Mo-based phases. (author)

  8. Fission induced swelling of U–Mo/Al dispersion fuel

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yeon Soo, E-mail: yskim@anl.gov [Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Jeong, G.Y. [Ulsan National Institute of Science and Technology, 50 UNIST-gil, Eonyang-eup, Uljoo-gun, Ulsan 689-798 (Korea, Republic of); Park, J.M. [Korea Atomic Energy Research Institute, 989-111 Daedeok-daero, Yuseong-gu, Daejeon 305-353 (Korea, Republic of); Robinson, A.B. [Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415-6188 (United States)

    2015-10-15

    Fission-induced swelling of U–Mo/Al dispersion fuel meat was measured using microscopy images obtained from post-irradiation examination. The data of reduced-size plate-type test samples and rod-type test samples were employed for this work. A model to predict the meat swelling of U–Mo/Al dispersion fuel was developed. This model is composed of several submodels including a model for interaction layer (IL) growth between U–Mo and Al matrix, a model for IL thickness to IL volume conversion, a correlation for the fission-induced swelling of U–Mo alloy particles, a correlation for the fission-induced swelling of IL, and models of U–Mo and Al consumption by IL growth. The model was validated using full-size plate data that were not included in the model development.

  9. Signatures of Low-Mo Ancient Ocean May be Preserved in Cyanobacterial Genomes

    Science.gov (United States)

    Glass, J. B.; Wolfe-Simon, F. L.; Poret-Peterson, A. T.; Anbar, A. D.

    2010-04-01

    Before 800 million years ago, Mo was scarce in the ocean. We present evidence that primitive cyanobacteria store Mo using a protein called "Mop." Mop genes preserved in modern genomes may be signatures of the imprint of ancient Mo limitation.

  10. Rocking disc electro-deposition of copper films on Mo/MoSe{sub 2} substrates

    Energy Technology Data Exchange (ETDEWEB)

    Cummings, Charles Y.; Frith, Paul E. [Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Zoppi, Guillaume; Forbes, Ian [Northumbria Photovoltaics Applications Centre, Northumbria University, NE1 8ST (United Kingdom); Rogers, Keith D. [Cranfield Health, Cranfield University, Shrivenham Campus, Swindon, SN6 8LA (United Kingdom); Lane, David W. [Department of Applied Science, Security and Resilience, Cranfield University, Shrivenham, Swindon, SN6 8LA (United Kingdom); Marken, Frank, E-mail: F.Marken@bath.ac.uk [Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom)

    2011-08-31

    A novel electro-deposition method based on a rocking disc system with {pi}/3 amplitude and variable frequency is introduced. Uniform copper films were deposited from a 0.1 M CuSO{sub 4}/3.0 M NaOH/0.2 M sorbitol bath directly onto 12.1 cm{sup 2} Mo/MoSe{sub 2} substrates with X-ray diffraction showing a thickness variation of {+-}5% over this area. Investigation of the mass transport conditions suggests (i) uniform diffusion over the sample, (ii) a rate of mass transport proportional to the square root of the rocking rate, and (iii) turbulent conditions, which are able to dislodge gas bubbles during electro-deposition.

  11. Light-Induced Activation of a Molybdenum Oxotransferase Model within a Ru(II)-Mo(VI) Dyad.

    Science.gov (United States)

    Ducrot, Aurélien B; Coulson, Ben A; Perutz, Robin N; Duhme-Klair, Anne-Kathrin

    2016-12-19

    Nature uses molybdenum-containing enzymes to catalyze oxygen atom transfer (OAT) from water to organic substrates. In these enzymes, the two electrons that are released during the reaction are rapidly removed, one at a time, by spatially separated electron transfer units. Inspired by this design, a Ru(II)-Mo(VI) dyad was synthesized and characterized, with the aim of accelerating the rate-determining step in the cis-dioxo molybdenum-catalyzed OAT cycle, the transfer of an oxo ligand to triphenyl phosphine, via a photo-oxidation process. The dyad consists of a photoactive bis(bipyridyl)-phenanthroline ruthenium moiety that is covalently linked to a bioinspired cis-dioxo molybdenum thiosemicarbazone complex. The quantum yield and luminescence lifetimes of the dyad [Ru(bpy) 2 (L 2 )MoO 2 (solv)] 2+ were determined. The major component of the luminescence decay in MeCN solution (τ = 1149 ± 2 ns, 67%) corresponds closely to the lifetime of excited [Ru(bpy) 2 (phen-NH 2 )] 2+ , while the minor component (τ = 320 ± 1 ns, 31%) matches that of [Ru(bpy) 2 (H 2 -L 2 )] 2+ . In addition, the (spectro)electrochemical properties of the system were investigated. Catalytic tests showed that the dyad-catalyzed OAT from dimethyl sulfoxide to triphenyl phosphine proceeds significantly faster upon irradiation with visible light than in the dark. Methylviologen acts as a mediator in the photoredox cycle, but it is regenerated and hence only required in stoichiometric amounts with respect to the catalyst rather than sacrificial amounts. It is proposed that oxidative quenching of the photoexcited Ru unit, followed by intramolecular electron transfer, leads to the production of a reactive one-electron oxidized catalyst, which is not accessible by electrochemical methods. A significant, but less pronounced, rate enhancement was observed when an analogous bimolecular system was tested, indicating that intramolecular electron transfer between the photosensitizer and the catalytic center

  12. Determination of Mo- and Ca-isotope ratios in Ca100MoO4 crystal for AMoRE-I experiment

    Science.gov (United States)

    Karki, S.; Aryal, P.; Kim, H. J.; Kim, Y. D.; Park, H. K.

    2018-01-01

    The first phase of the AMoRE (Advanced Mo-based Rare process Experiment) is to search for neutrinoless double-beta decay of 100Mo with calcium molybdate (Ca100MoO4) crystals enriched in 100Mo and depleted in 48Ca using a cryogenic technique at Yangyang underground laboratory in Korea. It is important to know 100Mo- and 48Ca-isotope ratios in Ca100MoO4 crystal to estimate half-life of 100Mo decays and to 2 νββ background from 48Ca. We employed the ICP-MS (Inductive Coupled Plasma Mass Spectrometer) to measure 100Mo- and 48Ca-isotope ratios in Ca100MoO4 crystal. The measured results for 100Mo- and 48Ca-isotope ratios in the crystal are (94 . 6 ± 2 . 8) % and (0 . 00211 ± 0 . 00006) %, respectively, where errors are included both statistical and systematic uncertainties.

  13. Intercalation of Si between MoS2 layers

    Directory of Open Access Journals (Sweden)

    Rik van Bremen

    2017-09-01

    Full Text Available We report a combined experimental and theoretical study of the growth of sub-monolayer amounts of silicon (Si on molybdenum disulfide (MoS2. At room temperature and low deposition rates we have found compelling evidence that the deposited Si atoms intercalate between the MoS2 layers. Our evidence relies on several experimental observations: (1 Upon the deposition of Si on pristine MoS2 the morphology of the surface transforms from a smooth surface to a hill-and-valley surface. The lattice constant of the hill-and-valley structure amounts to 3.16 Å, which is exactly the lattice constant of pristine MoS2. (2 The transitions from hills to valleys are not abrupt, as one would expect for epitaxial islands growing on-top of a substrate, but very gradual. (3 I(V scanning tunneling spectroscopy spectra recorded at the hills and valleys reveal no noteworthy differences. (4 Spatial maps of dI/dz reveal that the surface exhibits a uniform work function and a lattice constant of 3.16 Å. (5 X-ray photo-electron spectroscopy measurements reveal that sputtering of the MoS2/Si substrate does not lead to a decrease, but an increase of the relative Si signal. Based on these experimental observations we have to conclude that deposited Si atoms do not reside on the MoS2 surface, but rather intercalate between the MoS2 layers. Our conclusion that Si intercalates upon the deposition on MoS2 is at variance with the interpretation by Chiappe et al. (Adv. Mater. 2014, 26, 2096–2101 that silicon forms a highly strained epitaxial layer on MoS2. Finally, density functional theory calculations indicate that silicene clusters encapsulated by MoS2 are stable.

  14. Final report of MoReMO 2011-2012. Modelling resilience for maintenance and outage

    International Nuclear Information System (INIS)

    Gotcheva, N.; Macchi, L.; Oedewald, P.; Eitrheim, M.H.R.; Axelsson, C.; Reiman, T.; Pietikaeinen, E.

    2013-04-01

    The project Modelling Resilience for Maintenance and Outage (MoReMO) represents a two-year joint effort by VTT Technical Research Centre of Finland, Institute for Energy Technology (IFE, Norway) and Vattenfall (Sweden) to develop and test new approaches for safety management. The overall goal of the project was to present concepts on how resilience can be operationalized and built in a safety critical and socio-technical context. Furthermore, the project also aimed at providing guidance for other organizations that strive to develop and improve their safety performance in a business driven industry. We have applied four approaches in different case studies: Organisational Core Task modelling (OCT), Functional Resonance Analysis Method (FRAM), Efficiency Thoroughness Trade-Off (ETTO) analysis, and Work Practice and Culture Characterisation. During 2011 and 2012 the MoReMO project team has collected data through field observations, interviews, workshops, and document analysis on the work practices and adjustments in maintenance and outage in Nordic NPPs. The project consisted of two sub-studies, one focused on identifying and assessing adjustments and supporting resilient work practices in maintenance activities, while the other focused on handling performance trade-offs in maintenance and outage, as follows: A. Adjustments in maintenance work in Nordic nuclear power plants (VTT and Vattenfall). B. Handling performance trade-offs - the support of adaptive capacities (IFE and Vattenfall). The historical perspective of maintenance and outage management (Chapter 1.1) was provided by Vattenfall. Together, the two sub-studies have provided valuable insights for understanding the rationale behind work practices and adjustments, their effects on resilience, promoting flexibility and balancing between flexibility and reliability. (Author)

  15. Final report of MoReMO 2011-2012. Modelling resilience for maintenance and outage

    Energy Technology Data Exchange (ETDEWEB)

    Gotcheva, N.; Macchi, L.; Oedewald, P. [Technical Research Centre of Finland (VTT), Espoo (Finland); Eitrheim, M.H.R. [Institute for Energy Technology (IFE) (Norway); Axelsson, C.; Reiman, T.; Pietikaeinen, E. [Ringhals AB (NPP), Vattenfall AB (Sweden)

    2013-04-15

    The project Modelling Resilience for Maintenance and Outage (MoReMO) represents a two-year joint effort by VTT Technical Research Centre of Finland, Institute for Energy Technology (IFE, Norway) and Vattenfall (Sweden) to develop and test new approaches for safety management. The overall goal of the project was to present concepts on how resilience can be operationalized and built in a safety critical and socio-technical context. Furthermore, the project also aimed at providing guidance for other organizations that strive to develop and improve their safety performance in a business driven industry. We have applied four approaches in different case studies: Organisational Core Task modelling (OCT), Functional Resonance Analysis Method (FRAM), Efficiency Thoroughness Trade-Off (ETTO) analysis, and Work Practice and Culture Characterisation. During 2011 and 2012 the MoReMO project team has collected data through field observations, interviews, workshops, and document analysis on the work practices and adjustments in maintenance and outage in Nordic NPPs. The project consisted of two sub-studies, one focused on identifying and assessing adjustments and supporting resilient work practices in maintenance activities, while the other focused on handling performance trade-offs in maintenance and outage, as follows: A. Adjustments in maintenance work in Nordic nuclear power plants (VTT and Vattenfall). B. Handling performance trade-offs - the support of adaptive capacities (IFE and Vattenfall). The historical perspective of maintenance and outage management (Chapter 1.1) was provided by Vattenfall. Together, the two sub-studies have provided valuable insights for understanding the rationale behind work practices and adjustments, their effects on resilience, promoting flexibility and balancing between flexibility and reliability. (Author)

  16. Benchmark experiment for the cross section of the 100Mo(p,2n)99mTc and 100Mo(p,pn)99Mo reactions

    Science.gov (United States)

    Takács, S.; Ditrói, F.; Aikawa, M.; Haba, H.; Otuka, N.

    2016-05-01

    As nuclear medicine community has shown an increasing interest in accelerator produced 99mTc radionuclide, the possible alternative direct production routes for producing 99mTc were investigated intensively. One of these accelerator production routes is based on the 100Mo(p,2n)99mTc reaction. The cross section of this nuclear reaction was studied by several laboratories earlier but the available data-sets are not in good agreement. For large scale accelerator production of 99mTc based on the 100Mo(p,2n)99mTc reaction, a well-defined excitation function is required to optimise the production process effectively. One of our recent publications pointed out that most of the available experimental excitation functions for the 100Mo(p,2n)99mTc reaction have the same general shape while their amplitudes are different. To confirm the proper amplitude of the excitation function, results of three independent experiments were presented (Takács et al., 2015). In this work we present results of a thick target count rate measurement of the Eγ = 140.5 keV gamma-line from molybdenum irradiated by Ep = 17.9 MeV proton beam, as an integral benchmark experiment, to prove the cross section data reported for the 100Mo(p,2n)99mTc and 100Mo(p,pn)99Mo reactions in Takács et al. (2015).

  17. Carbon and Mo transformations during the synthesis of mesoporous Mo2C/carbon catalysts by carbothermal hydrogen reduction

    Science.gov (United States)

    Wang, Haiyan; Liu, Shida; Liu, Bing; Montes, Vicente; Hill, Josephine M.; Smith, Kevin J.

    2018-02-01

    The synthesis of mesoporous Mo2C/carbon catalysts by carbothermal hydrogen reduction is reported. Petroleum coke (petcoke) was activated with KOH at 800 °C to obtain high surface area microporous activated petcoke (APC; 2000 m2/g). The APC was wet impregnated with ammonium heptamolybdate (AHM: 10 wt% Mo), dried and reduced in H2 at temperatures from 400 to 800 °C, to yield Mo2C/APC catalysts. Increased reduction temperature increased the Mo2C yield and the mesoporous volume of the Mo2C/APC. At a reduction temperature of 750 °C the mesopore volume of the catalyst doubled compared to the APC support and accounted for 37% of the total pore volume. Maintaining the final CHR temperature for 90 min further increased the Mo2C yield and mesoporosity of the catalyst. The role of Mo2C in the catalytic hydrogenation of the APC and mesopore generation is demonstrated. The activity of the Mo2C/carbon catalysts in the hydrodeoxygenation of 4-methyl phenol increased with increased CHR temperature and catalyst mesoporosity.

  18. Theoretical prediction of high electron mobility in multilayer MoS2 heterostructured with MoSe2

    Science.gov (United States)

    Ji, Liping; Shi, Juan; Zhang, Z. Y.; Wang, Jun; Zhang, Jiachi; Tao, Chunlan; Cao, Haining

    2018-01-01

    Two-dimensional (2D) MoS2 has been considered to be one of the most promising semiconducting materials with the potential to be used in novel nanoelectronic devices. High carrier mobility in the semiconductor is necessary to guarantee a low power dissipation and a high switch speed of the corresponding electronic device. Strain engineering in 2D materials acts as an important approach to tailor and design their electronic and carrier transport properties. In this work, strain is introduced to MoS2 through perpendicularly building van der Waals heterostructures MoSe2-MoS2. Our first-principles calculations demonstrate that acoustic-phonon-limited electron mobility can be significantly enhanced in the heterostructures compared with that in pure multilayer MoS2. It is found that the effective electron mass and the deformation potential constant are relatively smaller in the heterostructures, which is responsible for the enhancement in the electron mobility. Overall, the electron mobility in the heterostructures is about 1.5 times or more of that in pure multilayer MoS2 with the same number of layers for the studied structures. These results indicate that MoSe2 is an excellent material to be heterostructured with multilayer MoS2 to improve the charge transport property.

  19. Coke formation during the hydrotreatment of bio-oil using NiMo and CoMo catalysts

    NARCIS (Netherlands)

    Kadarwati, Sri; Hu, Xun; Gunawan, Richard; Westerhof, Roel; Gholizadeh, Mortaza; Hasan, M. D.Mahmudul; Li, Chun-Zhu

    2017-01-01

    This study aims to investigate the coke formation during the hydrotreatment of bio-oil at low temperature. The catalytic hydrotreatment of bio-oil produced from the pyrolysis of mallee wood was carried out using pre-sulphided NiMo and CoMo catalysts at a temperature range of 150–300 °C. Our results

  20. Effect of Mo addition on the electrocatalytic activity of Pt-Sn-Mo/C for direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Lee, Eungje; Murthy, Arun; Manthiram, Arumugam

    2011-01-01

    Carbon-supported Pt-Sn-Mo electrocatalysts have been synthesized by a polyol reduction method and characterized for ethanol electro-oxidation reaction (EOR). While the percent loading of the synthesized nanoparticles on the carbon support is higher than 35%, energy dispersive spectroscopy (EDS) reveals that the Mo contents in the nanoparticle catalysts are lower than the nominal value, indicating incomplete reduction of the Mo precursor. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analyses reveal that the Sn and Mo exist as oxide phases at the surface layers of the nanoparticles and the degree of alloying is very low. The electrochemical properties of the electrocatalysts have been evaluated by cyclic voltammetry (CV) and chronoamperometry. The catalytic activity for EOR decreases in the order PtSnMo 0.6 /C > PtSnMo 0.4 /C > PtSn/C. Single cell direct ethanol fuel cell (DEFC) tests also confirm that the PtSnMo 0.6 /C anode catalyst exhibit better performance than the PtSn/C anode catalyst. An analysis of the electrochemical data suggests that the incorporation of Mo to Pt-Sn enhances further the catalytic activity for EOR.

  1. Novel Mechanism of Fatty Acid Sensing in Enteroendocrine Cells: Specific Structures in Oxo-Fatty Acids Produced by Gut Bacteria are Responsible for CCK Secretion in STC-1 Cells via GPR40.

    Science.gov (United States)

    Hira, Tohru; Ogasawara, Shono; Yahagi, Asuka; Kamachi, Minami; Li, Jiaxin; Nishimura, Saki; Sakaino, Masayoshi; Yamashita, Takatoshi; Kishino, Shigenobu; Ogawa, Jun; Hara, Hiroshi

    2018-06-25

    The secretion of gut hormones, such as cholecystokinin (CCK) is stimulated by fatty acids. Although a chain length-dependent mechanism has been proposed, other structural relationships to releasing activity remain unclear. We aimed to elucidate specific structures in fatty acids that are responsible for their CCK-releasing activity, and related sensing mechanisms in enteroendocrine cells. We examined CCK secretory activities in a murine CCK-producing cell line STC-1 by exposing the cells to various modified fatty acids produced by gut lactic acid bacteria. The effects of fatty acids on gastric emptying rate as a CCK-mediated function were examined using acetaminophen- and phenol red-methods in rats. Out of more than thirty octadecanoic (C18)-derived fatty acids tested, five oxo-fatty acids potently stimulated CCK secretion without cytotoxic effects in STC-1 cells. Three fatty acids had a distinct specific structure containing one double-bond, whereas the other two had two double-bonds, nearby an oxo residue. CCK secretion induced by representative fatty acids (10-oxo-trans-11-18:1 and 13-oxo-cis-9,cis-15-18:2) was attenuated by a fatty acid-receptor GPR40 antagonist. Oral administration of 13-oxo-cis-9,cis-15-18:2 lowered the gastric emptying rate in rats in a dose- and structure-dependent manner. These results revealed a novel fatty acid-sensing mechanism in enteroendocrine cells. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  2. Thermodynamic calculation and an experimental study of the combustion synthesis of (Mo{sub 1−x}Nb{sub x})Si{sub 2} (0 ⩽ x ⩽ 1)

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaohong, E-mail: matinbow@163.com; Lu, Qiong; Wu, Guangzhi; Shi, Jialing; Sun, Zhi

    2015-08-25

    Highlights: • (Mo{sub 1−x}Nb{sub x})Si{sub 2} alloys were synthesized by a simple and energy-saving process of SHS. • Theoretical adiabatic temperature of (Mo{sub 1−x}Nb{sub x})Si{sub 2} was calculated for the first time. • The variation of the actual temperature is consistent with theoretical temperature. - Abstract: The theoretical adiabatic temperature of (Mo{sub 1−x}Nb{sub x})Si{sub 2} (0 ⩽ x ⩽ 1) is calculated. The results indicate that the theoretical adiabatic temperature of (Mo{sub 1−x}Nb{sub x})Si{sub 2} increases with an increasing Nb content when (Mo{sub 1−x}Nb{sub x})Si{sub 2} is of a single-phase structure, but decreases with an increasing Nb content when (Mo{sub 1−x}Nb{sub x})Si{sub 2} is of a double-phase structure. All of the temperatures are higher than 1800 K, indicating that (Mo{sub 1−x}Nb{sub x})Si{sub 2} (0 ⩽ x ⩽ 1) can be prepared by the combustion synthesis method. In this work, (Mo{sub 1−x}Nb{sub x})Si{sub 2} (0 ⩽ x ⩽ 1) alloys are successfully synthesized by the combustion synthesis process from elemental powders of Mo, Nb, and Si. The highest combustion temperature and combustion product structure are studied. The results confirm that the variation of the experimental maximum combustion temperature of (Mo{sub 1−x}Nb{sub x})Si{sub 2} is consistent with that of the theoretical adiabatic temperature. The combustion products are non-equilibrium species, and a supersaturated solid solution of C11{sub b} type (Mo{sub 1−x}Nb{sub x})Si{sub 2} forms during combustion synthesis.

  3. Studies of the effect of irradiation in a nuclear reactor, of targets containing Mo used for the preparation of 99Mo gel, material that constitutes the 99Mo - 99mTc generators

    International Nuclear Information System (INIS)

    Nieto, Renata Correa

    2004-01-01

    The most used radioisotope in Nuclear Medicine is 99m Tc, obtained in the 99 Mo - 99m Tc generator form. 99 Mo can be produced by several nuclear reactions in Cyclotron and Reactor. The production in Cyclotron is not technically and commercially feasible. The production in Nuclear Reactor can be made in two ways: 235 U fission and 99 Mo (n,γ) 99 Mo reaction. A project aiming the production of 99 Mo by activation of Mo is under way at IPEN, producing a gel type MoZr generator. There are two ways of preparing the gel and the generators: by irradiating MoO 3 and preparing the gel or by the preparation of the gel and further irradiation. This work consists in the study of the irradiation effects in several targets containing Mo for the production of 99 Mo by the 98 Mo (n,γ) 99 Mo reaction and further preparation of the gel for use as a gel type 99 Mo - 99m Tc generator. Three rinds of gel were studied: zirconium, titanium and cerium molybdate, and their morphology, infrared structure and elution yield of 99m Tc were analysed. The best results were achieved with the generators prepared with MoZr post formed gel, with amorphous structure and better elution yields. The pre formed gel induced crystallinity and worst performance of the generators. (author)

  4. Geochronology of the Thompson Creek Mo Deposit: Evidence for the Formation of Arc-related Mo Deposits

    Science.gov (United States)

    Lawrence, C. D.; Coleman, D. S.; Stein, H. J.

    2016-12-01

    The Thompson Creek Mo deposit in central ID, has been categorized as an arc-related Mo deposit due to the location, grade of Mo, and relative lack of enrichments in F, Rb, and Nb, compared to the Climax-type Mo deposits. Geochronology from this arc-related deposit provides an opportunity to compare and contrast magmatism, and mineralization to that in Climax-type deposits. Distinct pulses of magmatism were required to form the Thompson Creek Mo deposit, which is consistent with recent geochronology from Climax-type deposits. Molybdenite Re-Os geochronology from five veins requires at least three pulses of magmatism and mineralization between 89.39 +/- 0.37 and 88.47 +/- 0.16 Ma. Zircon U-Pb ages from these mineralized samples overlap with molybdenite mineralization, but show a much wider range (91.01 +/- 0.37 to 87.27 +/- 0.69). Previous work from Climax-type Mo deposits suggest a correlation between a super eruption, and the subsequent rapid (<1 Ma) onset, and completion of Mo mineralizing intrusions. The longer life (3-4 Ma) for the Thompson Creek Mo deposit suggests that the mineralizing intrusions for arc-related Mo deposits may not need to have as high [Mo] as the Climax-type deposits. This study also finds a shift in the source of magmatism from the pre- to syn-mineralizing intrusions. Zircons from pre-mineralizing intrusions have much higher (15-60 pg) concentrations of radiogenic Pb than zircons from mineralized intrusions, which all have less than 15 pg, though whole rock [U] are similar.

  5. Microwave-Assisted Synthesis and Crystal Structure of Oxo(diperoxo(4,4'-di-tert-butyl-2,2'-bipyridine-molybdenum(VI

    Directory of Open Access Journals (Sweden)

    Alírio E. Rodrigues

    2009-09-01

    Full Text Available The oxodiperoxo complex MoO(O22(tbbpy (tbbpy = 4,4'-di-tert-butyl-2,2'- bipyridine was isolated from the reaction of MoO2Cl2(tbbpy in water under microwaveassisted heating at 120 ºC for 4 h. The structure of the oxodiperoxo complex was determined by single crystal X-ray diffraction. The MoVI centre is seven-coordinated with a geometry which strongly resembles a highly distorted bipyramid. Individual MoO(O22(tbbpy complexes are interdigitated along the [010] direction to form a column. The crystal structure is formed by the close packing of the columnar-stacked complexes. Interactions between neighbouring columns are essentially of van der Waals type mediated by the need to effectively fill the available space.

  6. A new species of electric ray of the genus Narcine Henle, 1834 from ...

    African Journals Online (AJOL)

    A new species of electric ray of the genus Narcine Henle, 1834 is described from seven specimens collected from two localities off the western coast of Madagascar, in the Moçambique Channel. Narcine insolita, sp. nov. is distinguished from all other species of the genus by the unique presence of a very prominent first ...

  7. Radioiodination and biodistribution of NBNPQD ( 2-benzyl-1-oxo-1-2-dihydropyrido (4,3-b) quinoxaline 5,10- dioxide) in tumor bearing mice

    International Nuclear Information System (INIS)

    Ibrahim, I. T.; Habib, S. A.; Wally, H. A.; El-Shishtawy, M. M.

    2012-12-01

    NBNPQD (2-benzyl-1-oxo-1,2 dihydropyrido (quinoxaline 5,10-dioxide) is a new synthesized quinoxaline derivative. It could be labeled with Auger emitter iodine-125 successfully with yield about 90%. The labeled product was evaluated by electrophoresis and studied. 1 23I - NBNPQD was stable up to 48 h post labeling. Biodistribution study of 1 23I - NBNPQD in normal and tumor bearing mice was also conducted. The biodistribution data revealed that 1 23I -NBNPQD diffused rapidly to tumor sites in to both ascites and solid tumor bearing mice. 1 23I -NBNPQD was decline rapidly from most of organs but slowly from tumor sites. In-vitro radiotoxicity of 1 23I - NBNPQD increased with the increase of its radioactivity. This study encourages the possible use of 1 23I - NBNPQD in tumor imaging and treatment. It also encourages further studies on the chemotherapeutic activity of NBNPQD hoping to get a new potent antitumor agent. (Author)

  8. Synthesis, characterization, and crystal structure of 2-amino-7-methyl-5-oxo-4-phenyl-4,5-dihydropyrano[3,2-c] pyran-3-carbonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, S. [University of Jammu, X-ray Crystallography Laboratory, Post-Graduate Department of Physics and Electronics (India); Banerjee, B.; Brahmachari, G. [Visva-Bharati (a Central University), Laboratory of Natural Products & Organic Synthesis, Department of Chemistry (India); Kant, Rajni; Gupta, V. K., E-mail: vivek-gupta2k2@hotmail.com [University of Jammu, X-ray Crystallography Laboratory, Post-Graduate Department of Physics and Electronics (India)

    2015-12-15

    2-Amino-7-methyl-5-oxo-4-phenyl-4,5-dihydropyrano[3,2-c] pyran-3-carbonitrile, C{sub 16}H{sub 12}N{sub 2}O{sub 3} is synthesized via one-pot multi-component reaction at room temperature using commercially available urea as inexpensive and environmentally benign organo-catalyst. Its structure is determined by single-crystal X-ray diffraction technique The crystals are monoclinic, a = 10.7357(12), b = 8.7774(8), c = 15.0759(16) Å, β = 103.575(11)°, Z = 4, sp. gr. P2{sub 1}/n, R = 0.0551 for 1696 observed reflections. The crystal structure is stabilized by N–H···N, C–H···O, and C–H···π interactions.

  9. Synthesis and dynamic NMR study of ketenimines derived from tert-butyl isocyanide, alkyl 2-arylamino-2-oxo-acetates, and dialkyl acetylenedicarboxylates.

    Science.gov (United States)

    Yavari, Issa; Nasiri, Farough; Djahaniani, Horieh

    2004-01-01

    The adduct produced in the reaction between tert-butyl isocyanide and dialkyl acetylenedicarboxylates was trapped by alkyl 2-arylamino-2-oxo-acetates. When the aryl group is 2-methyl-6-nitrophenyl or 2,6-di-isopropylphenyl, the product exists as two stable rotamers at room temperature as a result of restricted rotation around the Ar-N single bond. When the aryl group is 1-naphthyl or 8-quinolinyl, dynamic NMR effects are observed in the 1H NMR spectra. The calculated free-energy of activation for interconversion of the rotational isomers in 1-naphthyl and 8-quinolinyl derivatives amounts to about 99+/-2 and 68.5+/-2 kJ mol(-1), respectively.

  10. 4-Acyloxy-2,5-diphenyl-3-oxo-2,3-dihydrothiophene 1,1-dioxides as acylating agents in the Friedel-Crafts reaction

    International Nuclear Information System (INIS)

    Van Ree, T.

    1989-01-01

    The 'activated esters', 4-acyloxy-2,5-diphenyl-3-oxo-2,3-dihydrothiophene 1,1-dioxides, easily accessible from 4,6-diphenylthieno[3,4-d][1,3]dioxol-2-one 5,5-dioxide, have been found to be excellent acylating agents in the Friedel-Crafts reaction with olefins and activated aromatic compounds. In the case of the olefins, product mixtures containing β-chloroketones were treated with 1,8-diazabicyclo[5.4.0]undex-7-ene to afford the corresponding unsaturated ketones in 30 - 73% yields, whereas aromatic ketones were obtained in high yields. The activated esters react slightly faster than the corresponding alkanoyl chlorides, and form fewer by-products

  11. Aminothiols linked to quinoline and acridine chromophores efficiently decrease 7,8-dihydro-8-oxo-2'-deoxyguanosine formation in γ-irradiated DNA

    International Nuclear Information System (INIS)

    Laayoun, A.; Coulombeau, C.; Constant, J.F.; Lhomme, J.; Berger, M.; Cadet, J.

    1994-01-01

    In a search for more active radioprotective compounds, we have prepared and examined a series of model molecules in which the radioprotective β-aminothiol unit (free or derivatized as acetate or phosphorothioate) is tethered to the DNA-binding chromophores quinoline and acridine through links of variable length. The modifying activity of these 'hybrid' molecules was estimated by measuring the formation of 8-oxo-2'-deoxyguanosine (8-oxodGuo) in double-strand DNA upon exposure to γ-rays in oxygen-free solution in the presence of the drugs. We show that all hybrid molecules protect the guanine moiety from oxidation more efficiently than the parent β-aminothiol units. The degree of protection is the highest for the molecules in which the thiol is linked to the strong binding intercalator acridine through a long polyaminochain. (author)

  12. Solvent influence on the photophysical properties of 4-(2-Oxo-2H-benzo[h]chromen-4-ylmethoxy)-benzaldehyde

    Science.gov (United States)

    Pramod, A. G.; Renuka, C. G.; Shivashankar, K.; Boregowda, P.; Nadaf, Y. F.

    2018-05-01

    Steady-state absorption and the fluorescence properties of the synthesized Benzofuran derivatives were studied. Absorption and fluorescence spectra of 4-(2-Oxo-2H-benzo[h]chromen-4-ylm ethoxy)-benzaldehyde (4-OBCM) have been recorded at room temperature in extensive variety of solvents of various polarities. 4-OBCM Fluorescence band maxima of the solvents are small amount spectral shifted to hypsochromic when the solvent polarity will increase, compared to absorption band under the identical circumstance. This suggests an increase in dipole moment of excited state compared to ground state. The ground-state dipole moment of 4-OBCM was found from quantum mechanical methods and the excited state dipole moment of 4-OBCM was evaluated from Lippert-Mataga Bakhshiev's, Kawski-Chamma-Viallet's and Reichardt conditions by methods for solvatochromic shift. Kamlet-Taft coefficients which affect this absorption profiles.

  13. Discovery of new nanomolar inhibitors of GPa: Extension of 2-oxo-1,2-dihydropyridinyl-3-yl amide-based GPa inhibitors.

    Science.gov (United States)

    Loughlin, Wendy A; Jenkins, Ian D; Karis, N David; Healy, Peter C

    2017-02-15

    Glycogen Phosphorylase (GP) is a functionally active dimeric enzyme, which is a target for inhibition of the conversion of glycogen to glucose-1-phosphate. In this study we report the design and synthesis of 14 new pyridone derivatives, and seek to extend the SAR analysis of these compounds. The SAR revealed the minor influence of the amide group, importance of the pyridone ring both spatially around the pyridine ring and for possible π-stacking, and confirmed a preference for inclusion of 3,4-dichlorobenzyl moieties, as bookends to the pyridone scaffold. Upon exploring a dimer strategy as part of the SAR analysis, the first extended 2-oxo-dihydropyridinyl-3-yl amide nanomolar based inhibitors of GPa (IC 50  = 230 and 260 nM) were identified. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  14. Binding events of (S )-N -(3-oxo-octanoyl)-homoserine lactone with agrobacterium tumefaciens mutant cells studied by saturation transfer difference NMR

    Energy Technology Data Exchange (ETDEWEB)

    Cabeca, Luis Fernando; Pomini, Armando Mateus; Cruz, Pedro Luiz R.; Marsaioli, Anita J. [University of Campinas (UNICAMP), SP (Brazil). Chemistry Inst.

    2011-07-01

    Quorum-sensing is a widely studied communication phenomenon in bacteria, which involves the production and detection of signaling substances in relation with cell density and colony behavior. Herein, the membrane binding interactions of the signal (S)-N-(3-oxo-octanoyl)-HSL with A. tumefaciens NTL4(pZLR4) cells were studied using saturation transfer difference NMR spectroscopy (STD-NMR). The substance epitope map was obtained showing that the hydrophobic acyl chain is the most important interacting site for the signal and the cell membrane. Results were interpreted upon comparisons with a simpler system, using liposomes as membrane models. Some insights on the use of b-cyclodextrin as acyl-HSL carrier were also provided. (author)

  15. 10-oxo-12(Z)-octadecenoic acid, a linoleic acid metabolite produced by gut lactic acid bacteria, potently activates PPARγ and stimulates adipogenesis.

    Science.gov (United States)

    Goto, Tsuyoshi; Kim, Young-Il; Furuzono, Tomoya; Takahashi, Nobuyuki; Yamakuni, Kanae; Yang, Ha-Eun; Li, Yongjia; Ohue, Ryuji; Nomura, Wataru; Sugawara, Tatsuya; Yu, Rina; Kitamura, Nahoko; Park, Si-Bum; Kishino, Shigenobu; Ogawa, Jun; Kawada, Teruo

    2015-04-17

    Our previous study has shown that gut lactic acid bacteria generate various kinds of fatty acids from polyunsaturated fatty acids such as linoleic acid (LA). In this study, we investigated the effects of LA and LA-derived fatty acids on the activation of peroxisome proliferator-activated receptors (PPARs) which regulate whole-body energy metabolism. None of the fatty acids activated PPARδ, whereas almost all activated PPARα in luciferase assays. Two fatty acids potently activated PPARγ, a master regulator of adipocyte differentiation, with 10-oxo-12(Z)-octadecenoic acid (KetoA) having the most potency. In 3T3-L1 cells, KetoA induced adipocyte differentiation via the activation of PPARγ, and increased adiponectin production and insulin-stimulated glucose uptake. These findings suggest that fatty acids, including KetoA, generated in gut by lactic acid bacteria may be involved in the regulation of host energy metabolism. Copyright © 2015 Elsevier Inc. All rights reserved.

  16. Toward consensus in the analysis of urinary 8-oxo-7,8-dihydro-2'-deoxyguanosine as a noninvasive biomarker of oxidative stress

    DEFF Research Database (Denmark)

    Urinary (DNA) Lesion Analysis, European Standards Committee on; Evans, Mark D; Olinski, Ryszard

    2010-01-01

    Of the DNA-derived biomarkers of oxidative stress, urinary 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) is the most frequently measured. However, there is significant discrepancy between chromatographic and immunoassay approaches, and intratechnique agreement among all available chromatography...... as mass spectrometric (MS), electrochemical detection (EC), or enzyme-linked immunosorbant assay (ELISA). Overall, there was good within-technique agreement, with the majority of laboratories' results lying within 1 sd of their consensus mean. However, ELISA showed more within-technique variation than did...... the chromatographic techniques and, for the urine samples, reported higher values. Bland-Altman plots revealed good agreement between MS and EC methods but concentration-dependent deviation for ELISA. All methods ranked urine samples according to concentration similarly. Creatinine levels are routinely used...

  17. A novel three dimensional semimetallic MoS{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Zhen-Kun [Beijing Computational Science Research Center, Beijing 100084 (China); Departments of Physics and Electronics, Hengyang Normal University, Hengyang 421008 (China); Zhang, Hui; Liu, Li-Min, E-mail: limin.liu@csrc.ac.cn [Beijing Computational Science Research Center, Beijing 100084 (China); Liu, Hao [Chengdu Green Energy and Green Manufacturing Technology R and D Center, Chengdu, Sichuan 610207 (China); Lau, Woon-Ming [Beijing Computational Science Research Center, Beijing 100084 (China); Chengdu Green Energy and Green Manufacturing Technology R and D Center, Chengdu, Sichuan 610207 (China)

    2014-05-28

    Transition metal dichalcogenides (TMDs) have many potential applications, while the performances of TMDs are generally limited by the less surface active sites and the poor electron transport efficiency. Here, a novel three-dimensional (3D) structure of molybdenum disulfide (MoS{sub 2}) with larger surface area was proposed based on first-principle calculations. 3D layered MoS{sub 2} structure contains the basal surface and joint zone between the different nanoribbons, which is thermodynamically stable at room temperature, as confirmed by first principles molecular dynamics calculations. Compared the two-dimensional layered structures, the 3D MoS{sub 2} not only owns the large surface areas but also can effectively avoid the aggregation. Interestingly, although the basal surface remains the property of the intrinsic semiconductor as the bulk MoS{sub 2}, the joint zone of 3D MoS{sub 2} exhibits semimetallic, which is derived from degenerate 3d orbitals of the Mo atoms. The high stability, large surface area, and high conductivity make 3D MoS{sub 2} have great potentials as high performance catalyst.

  18. Using molybdenum depleted in 95Mo in UMo fuel

    International Nuclear Information System (INIS)

    Bakker, K.; Wijtsma, F.; Bos, A.; Mol, C.; Rakhorst, H.; Bretscher, M.; Hofman, G.; Snelgrove, J.

    2002-01-01

    In recent years significant interest was gained in UMo fuel to be used in Material Test Reactors. This interest was induced by the fact that UMo fuel is mechanically stable, even at high uranium concentrations and high U-burnup. These properties are required in order to use Low Enriched Uranium (LEU) and still be able to achieve high flux and burnup values and, thus, to facilitate the conversion from High Enriched Uranium (HEU) to LEU. Neutronics computations have shown that, although the Mo concentration in UMo fuel is not very high (about 5 - 10w%), the neutron absorption cross sections of natural Mo are sufficiently high to have a considerable negative impact on the reactivity of this UMo fuel. In the present research the neutron absorption cross sections of natural Mo are discussed and the option to reduce the cross section of molybdenum by depleting the Mo in 95 Mo is described. Finally the economic consequences of using Mo depleted in 95 Mo are briefly discussed

  19. Homogenization of compacted blends of Ni and Mo powders

    International Nuclear Information System (INIS)

    Lanam, R.D.; Yeh, F.C.H.; Rovsek, J.E.; Smith, D.W.; Heckel, R.W.

    1975-01-01

    The homogenization behavior of compacted blends of Ni and Mo powders was studied primarily as a function of temperature, mean compact composition, and Mo powder particle size. All compact compositions were in the Ni-rich terminal solid-solution range; temperatures were between 950 and 1200 0 C (in the region of the phase diagram where only the Mo--Ni intermediate phase forms); average Mo particle sizes ranged from 8.4 mu m to 48 mu m. Homogenization was characterized in terms of the rate of decrease of the amounts of the Mo-rich terminal solid-solution phase and the Mo--Ni intermediate phase. The experimental results were compared to predictions based upon the three-phase, concentric-sphere homogenization model. In general, agreement between experimental data and model predictions was fairly good for high-temperature treatments and for compact compositions which were not close to the solubility limit of Mo in Ni. Departures from the model are discussed in terms of surface diffusion contributions to homogenization and non-uniform mixing effects. (U.S.)

  20. Studies on {sup 99}Mo-{sup 99m}Tc adsorption and elution behaviors using the inorganic sorbent ceric tungstate and conventional organic resins

    Energy Technology Data Exchange (ETDEWEB)

    El-Sweify, Fatma H.; Fattah, Alaa El-Din A. Abdel; Aly, Shorouk M.; Ghamry, Mohamed A. [Atomic Energy Authority, Cairo (Egypt). Hot Laboratories Center; El-Sheikh, Ragaa [Zagazig Univ. (Egypt). Chemistry Dept.

    2017-09-01

    Adsorption behavior of {sup 99}Mo(VI) and {sup 99m}Tc(VII) was studied on ceric tungstate (CeW) and compared with the adsorption on the conventional cation and anion exchangers Dowex-50X8 and AG-2X8, respectively. The studies were carried out under static and dynamic conditions. The effect of contact time and pH on the adsorption was investigated under static conditions. High K{sub d}-values for sorption of {sup 99}Mo(VI) on (CeW) were obtained over the investigated pH range. {sup 99m}Tc was adsorbed with much lower K{sub d}-values. The K{sub d}-values were pH dependent. K{sub d}-values of {sup 99}Mo-adsorption on AG-2X8 were lower than those on (CeW) and vice versa for {sup 99m}Tc. Ionic species of both elements were not adsorbed on Dowex-50X8, indicating the absence of cationic species and the adsorption of both elements on AG-2X8 and (CeW) as anionic species. The loading and elution behaviors of {sup 99}Mo and {sup 99m}Tc on (CeW) were studied using different eluents. {sup 99}Mo remained strongly adsorbed under all conditions whereas {sup 99m}Tc was easily eluted. Adsorption of some fission products, i.e. {sup 95}Zr(IV) and {sup 95}Nb(V), in addition to {sup 123m}Te(IV) and {sup 75}Se(IV), as representatives of their corresponding fission product isotopes, as well as {sup 181}Hf, as probable radioactive contaminant was also studied. Solutions of the ionic species of those metals were loaded in mixtures together with {sup 99}Mo on (CeW) columns. Strong adsorption of those ionic species and {sup 99}Mo on (CeW) was found whereas {sup 99m}Tc was easily eluted. Different eluents were investigated for eluting {sup 99m}Tc from {sup 99}Mo-adsorbed on (CeW).