Risk estimates for lung tumours from inhaled 239PuO2, 238PuO2, and 239Pu(NO3)4 in beagle dogs

International Nuclear Information System (INIS)

Dagle, G.E.; Park, J.F.; Gilbert, E.S.; Weller, R.E.

1989-01-01

Lung cancer risks are being studied in beagle dogs given single exposures to aerosols of 239 PuO 2 , 238 PuO 2 , or 239 Pu(NO 3 ) 4 . A major objective of these studies is to examine the risk of lung cancer relative to the specific activity of the radionuclide, rate of dose accumulation due to differences in solubilities of the radionuclides, and the presence of competing risk from extrapulmonary lesions. Dose-response relationships were studied for the three groups of dogs, with analyses specifically designed to evaluate differences in response. Based on estimated cumulative dose to the lung, risks were found to differ significantly among the radionuclides; they were highest for 239 Pu(NO 3 ) 4 and lowest for 238 PuO 2 . A model in which the risk was assumed to be a pure quadratic function of dose fitted the data much better than a pure linear model. Currently, all three groups of dogs can be compared only to 10 years after exposure. However, it is apparent that the average cumulative dose to the lung may not be an adequate predictor of lung cancer risk for different isotopic and physicochemical forms of plutonium. (author)

Carbonyl[4-(2,3-dimethylphenylaminopent-3-en-2-onato-κ2N,O](triphenylphosphine-κPrhodium(I

Directory of Open Access Journals (Sweden)

Gertruida J. S. Venter

2009-11-01

Full Text Available In the title compound, [Rh(C13H16NO(C18H15P(CO], the coordination geometry of the RhI atom is square-planar, formed by the coordinating N and O atoms of the bidentate enaminoketonate ligand, one C atom from the carbonyl group and a P atom from triphenylphosphine. The complex displays a 0.591 (3:0.409 (3 ratio disorder of the phenyl unit of the monoanionic N,O-bidentate ligand. Intramolecular hydrogen bonding is observed between a C—H group of the triphenylphosphine unit and the O atom of the enaminoketonate ligand.

32 CFR 644.532 - Reporting accidents.

Science.gov (United States)

2010-07-01

... 32 National Defense 4 2010-07-01 2010-07-01 true Reporting accidents. 644.532 Section 644.532... and Improvements § 644.532 Reporting accidents. Immediately upon receipt of information of an accident... that an accident has occurred, the former using command should be requested to send qualified explosive...

Risk estimates for lung tumors from inhaled 239PuO2, 238PuO2, and /sup 239Pu/(NO3)4 in beagle dogs

International Nuclear Information System (INIS)

Dagle, G.E.; Park, J.F.; Gilbert, E.S.; Weller, R.E.

1988-06-01

Lung-cancer risks are being studied in beagle dogs given single exposures to aerosols of 239 PuO 2 , 238 PuO 2 , or 239 Pu(NO 3 ) 4 . A major objective of these studies is to examine the risk of lung cancer relative to the specific activity of the radionuclide, rate of dose accumulation due to differences in solubilities of the radionuclides, and the presence of competing risk from extrapulmonary lesions. Dose-response relationships were studied for the three groups of dogs, with analyses specifically designed to evaluate differences in response. Based on estimated cumulative dose to the lung, risks were found to differ significantly among the radionuclides; they were highest for 239 Pu(NO 3 ) 4 and lowest for 238 PuO 2 . A model in which the risk was assumed to be a pure quadratic function of dose fit the data much better than a pure linear model. Currently, all three groups of dogs can be compared only to 10 years after exposure. However, it is apparent that the average cumulative dose to the lung may not be an adequate predictor of lung-cancer risk for different isotopic and physicochemical forms of plutonium. 13 refs., 2 tabs

Faster dissolution of PuO2 in nitrous media by means of electrolytic oxidation

International Nuclear Information System (INIS)

Baumgaertner, F.; Kim, J.I.; Luckner, N.; Brueckl, N.; Lieberer, E.

1984-03-01

The contribution shows that the dissolution of PuO 2 in HNO 3 can be accelerated considerably by means of electrolytic oxidation. A glass apparatus has been developed which uses platinum electrodes providing for sufficient contact between electrodes and solids. Increase of temperature, acid concentration, and electrode current density, and a good contact between electrode and metal oxide will improve the dissolution kinetics. The reaction could be made even faster by addition of Ce 4+ . (orig.) [de

Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures.

Science.gov (United States)

Zhao, Hai-Qian; Wang, Zhong-Hua; Gao, Xing-Cun; Liu, Cheng-Hao; Qi, Han-Bing

2018-01-01

H2O2 was adopted to oxidize NO in simulated flue gas at 100-500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300-500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption.

27 CFR 5.32 - Mandatory label information.

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2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Mandatory label information. 5.32 Section 5.32 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS LABELING AND ADVERTISING OF DISTILLED SPIRITS Labeling Requirements for...

Chlorination of UO2, PuO2, and rare-earth oxides using ZrCl4

International Nuclear Information System (INIS)

Sakamura, Yoshiharu; Inoue, Tadashi; Iwai, Takashi; Moriyama, Hirotake

2001-01-01

A new chlorination method using ZrCl 4 , which has a high reactivity with oxygen, has been investigated for more efficient oxide treatment. After actinide oxides are chlorinated and dissolved in a molten salt bath, actinide metals can be selectively collected using the electrorefining process. This process is well suited for pyrochemical reprocessing of metallic fuels. In LiCl-KCI eutectic melts, rare-earth oxides (Y 2 O 3 , La 2 O 3 , CeO 2 , and Nd 2 O 3 ) and actinide oxides (UO 2 and PuO 2 ) were chlorinated by adding ZrCl 4 . As a result, rare-earth and actinide elements were dissolved into the salt as trivalent ions and ZrO 2 was precipitated. When an excess of ZrCI 4 was added, oxides in powder form were completely chlorinated in five hours. It was demonstrated that the ZrCI 4 chlorination method, free from corrosive gas such as chlorine, was very simple and useful. (author)

Volume properties and refraction of aqueous solutions of bisadducts of light fullerene C60 and essential amino acids lysine, threonine, and oxyproline (C60(C6H13N2O2)2, C60(C4H8NO3)2, and C60(C5H9NO2)2) at 25°C

Science.gov (United States)

Semenov, K. N.; Ivanova, N. M.; Charykov, N. A.; Keskinov, V. A.; Kalacheva, S. S.; Duryagina, N. N.; Garamova, P. V.; Kulenova, N. A.; Nabieva, A.

2017-02-01

Concentration dependences of the density of aqueous solutions of bisadducts of light fullerene C60 and essential amino acids are studied by pycnometry. Concentration dependences of the average molar volumes and partial volumes of components (H2O and corresponding bisadducts) are calculated for C60(C6H13N2O2)2-H2O, C60(C4H8NO3)2-H2O, and C60(C5H9NO2)2-H2O binary systems at 25°C. Concentration dependences of the indices of refraction of C60(C6H13N2O2)2-H2O, C60(C4H8NO3)2-H2O, and C60(C5H9NO2)2-H2O binary systems are determined at 25°C. The concentration dependences of specific refraction and molar refraction of bisadducts and aqueous solutions of them are calculated.

Synthesis of bis(3-{[2-(allyloxyethoxy]methyl}-2,4,6-trimethylbenzoyl(phenylphosphine oxide – a tailor-made photoinitiator for dental adhesives

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Norbert Moszner

2010-03-01

Full Text Available Because of the poor solubility of the commercially available bisacylphosphine oxides in dental acidic aqueous primer formulations, bis(3-{[2-(allyloxyethoxy]methyl}-2,4,6-trimethylbenzoyl(phenylphosphine oxide (WBAPO was synthesized starting from 3-(chloromethyl-2,4,6-trimethylbenzoic acid by the dichlorophosphine route. The substituent was introduced by etherification with 2-(allyloxyethanol. In the second step, 3-{[2-(allyloxyethoxy]methyl}-2,4,6-trimethylbenzoic acid was chlorinated. The formed acid chloride showed an unexpected low thermal stability. Its thermal rearrangement at 180 °C resulted in a fast formation of 3-(chloromethyl-2,4,6-trimethylbenzoic acid 2-(allyloxyethyl ester. In the third step, the acid chloride was reacted with phenylphosphine dilithium with the formation of bis(3-{[2-(allyloxyethoxy]methyl}-2,4,6-trimethylbenzoyl(phenylphosphine, which was oxidized to WBAPO. The structure of WBAPO was confirmed by 1H NMR, 13C NMR, 31P NMR, and IR spectroscopy, as well as elemental analysis. WBAPO, a yellow liquid, possesses improved solubility in polar solvents and shows UV–vis absorption, and a high photoreactivity comparable with the commercially available bisacylphosphine oxides. A sufficient storage stability was found in dental acidic aqueous primer formulations.

Varying the Lewis base coordination of the Y2N2 core in the reduced dinitrogen complexes {[(Me3Si)2N]2(L)Y}2(μ-η2:η2-N2) (L = benzonitrile, pyridines, triphenylphosphine oxide, and trimethylamine N-oxide).

Science.gov (United States)

Corbey, Jordan F; Farnaby, Joy H; Bates, Jefferson E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2012-07-16

The effect of the neutral donor ligand, L, on the Ln(2)N(2) core in the (N═N)(2-) complexes, [A(2)(L)Ln](2)(μ-η(2):η(2)-N(2)) (Ln = Sc, Y, lanthanide; A = monoanion; L = neutral ligand), is unknown since all of the crystallographically characterized examples were obtained with L = tetrahydrofuran (THF). To explore variation in L, displacement reactions between {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2)), 1, and benzonitrile, pyridine (py), 4-dimethylaminopyridine (DMAP), triphenylphosphine oxide, and trimethylamine N-oxide were investigated. THF is displaced by all of these ligands to form {[(Me(3)Si)(2)N](2)(L)Y}(2)(μ-η(2):η(2)-N(2)) complexes (L = PhCN, 2; py, 3; DMAP, 4; Ph(3)PO, 5; Me(3)NO, 6) that were fully characterized by analytical, spectroscopic, density functional theory, and X-ray crystallographic methods. The crystal structures of the Y(2)N(2) cores in 2-5 are similar to that in 1 with N-N bond distances between 1.255(3) Å and 1.274(3) Å, but X-ray analysis of the N-N distance in 6 shows it to be shorter: 1.198(3) Å.

Effect of microdose distribution on chromosome aberration frequency in liver cells of the Chinese hamster following exposure to 239PuO2 or 238PuO2 particles

International Nuclear Information System (INIS)

Brooks, A.L.; Peters, R.F.; Retherford, J.C.

1974-01-01

Chinese hamsters were injected intravenously with 239 PuO 2 or 238 PuO 2 particles of known size or with 238 Pu citrate to determine the effect of particle size and specific activity on the frequency and distribution of chromosome damage in the liver. Three particle sizes were used in the 239 PuO 2 experiment: 0.15, 0.44, and 0.89 μm, and all animals were injected with a constant activity, 5 x 10 -4 muCi 239 Pu/gm body weight. The 238 PuO 2 was injected in three particle sizes, 0.17, 0.41, and 1.1 μm and at three activity levels. The 238 Pu citrate was injected at 5 x 10 -3 muCi 238 Pu/gm body weight. Hamsters injected with 239 PuO 2 were sacrificed at 15, 42, and 122 days after injection and those injected with either 238 PuO 2 or 238 Pu citrate were sacrificed 12 days after injection. The number of alpha tracks/star increased as a function of the particle size injected. A change in particle size with time was noted as smaller particles were aggregated into larger ones by the phagocytic action of Kupffer cells. Injection of 239 PuO 2 and 238 PuO 2 produced a distribution of chromosome damage which was non-poison in nature. 239 PuO 2 produced increased damage with increasing average dose with some cells containing a large number of aberrations, but there was relatively little particle size effect. Conversely, aberration frequencies after 238 PuO 2 injection were inversely related to particle size and no cells were seen with large amounts of damage. The 238 Pu citrate produced 6 x 10 -3 aberrations/cell/rad which was a higher rate than observed for 238 Pu particles. Risk for the production of cellular damage in the liver was greater per μCi following injection of either 238 Pu or 239 Pu citrate than it was following deposition of the same amount of 239 PuO 2 or 238 PuO 2 particles. (U.S.)

Critical sizes of light-water moderated UO2 and PuO2-UO2 lattices

International Nuclear Information System (INIS)

Tsuruta, Harumichi; Kobayashi, Iwao; Suzuki, Takenori; Ohno, Akio; Murakami, Kiyonobu

1978-02-01

Experimental critical sizes are presented for a total of about 250 lattices with 2.6 w/o UO 2 and 3.0 w/o PuO 2 -natural UO 2 fuel rods. The moderator was H 2 O and water-to-fuel volume ratios in the lattice cells ranged from 1.50 to 3.00 in the UO 2 lattices and from 2.42 to 5.55 in the PuO 2 -UO 2 lattices. The critical sizes were determined with the number of the fuel rods and a water level which were required to make the lattice critical in the shape of a rectangular parallelepiped over the temperature range from room temperature to 80 0 C. Reactivity variations of the PuO 2 -UO 2 lattices due to decaying of 241 Pu to 241 Am were traced during 3 years. Some critical sizes of the UO 2 and PuO 2 -UO 2 lattices with a water gap and of the UO 2 lattices with liquid poison in the moderator are also reported. Some physics parameters, such as the temperature coefficient of reactivity, the water-level worth, the reflector saving, the ratio between a migration area and an infinite multiplication factor and the critical buckling, are shown in relation to the critical sizes of the unperturbed lattices without the water gap and liquid poison. (auth.)

A theoretical study of hydrogen atoms adsorption and diffusion on PuO_2 (110) surface

International Nuclear Information System (INIS)

Yu, H.L.; Tang, T.; Zheng, S.T.; Shi, Y.; Qiu, R.Z.; Luo, W.H.; Meng, D.Q.

2016-01-01

The mechanisms of adsorption and diffusion of hydrogen atoms on the PuO_2 (110) surface are investigated by density functional theory corrected for onsite Coulombic interactions (GGA + U). In order to find out the energetically more favorable adsorption site and optimum diffusion path, adsorption energy of atomic H on various sites and the diffusion energy barrier are derived and compared. Our results show that both chemisorption and physisorption exist for H atoms adsorption configurations on PuO_2 (110) surface. Two processes for H diffusion are investigated using the climbing nudged-elastic-band (cNEB) approach. We have identified two diffusion mechanisms, leading to migration of atomic H on the surface and diffusion from surface to subsurface. The energy barriers indicate that it is energetically more favorable for H atom to be on the surface. Hydrogen permeation through purity PuO_2 surface is mainly inhibited from hydrogen atom diffusion from surface to subsurface. - Highlights: • H atoms adsorption on PuO_2 (110) surface are investigated by GGA + U. • Both chemisorption and physisorption exist for H atoms adsorption configurations. • H atoms migration into PuO_2 (100) surface are inhibited with the barrier of 2.15 eV. • H atoms diffusion on PuO_2 (110) surface are difficult at room temperature.

Solubility Modeling of the Binary Systems Fe(NO3)3–H2O, Co(NO3)2–H2O and the Ternary System Fe(NO3)3–Co(NO3)2–H2O with the Extended Universal Quasichemical (UNIQUAC) Model

DEFF Research Database (Denmark)

Arrad, Mouad; Kaddami, Mohammed; Goundali, Bahija El

2016-01-01

Solubility modeling in the binary system Fe(NO3)3–H2O, Co(NO3)2–H2O and the ternary system Fe(NO3)3–Co(NO3)2–H2O is presented. The extended UNIQUAC model was applied to the thermodynamic assessment of the investigated systems. The model parameters obtained were regressed simultaneously using...... the available databank but with more experimental points, recently published in the open literature. A revision of previously published parameters for the cobalt ion and new parameters for the iron(III) nitrate system are presented. Based on this set of parameters, the equilibrium constants of hydrates...

Abscisic Acid-Induced H2O2 Accumulation Enhances Antioxidant Capacity in Pumpkin-Grafted Cucumber Leaves under Ca(NO3)2 Stress

Science.gov (United States)

Shu, Sheng; Gao, Pan; Li, Lin; Yuan, Yinghui; Sun, Jin; Guo, Shirong

2016-01-01

With the aim to clarifying the role of the ABA/H2O2 signaling cascade in the regulating the antioxidant capacity of grafted cucumber plants in response to Ca(NO3)2 stress, we investigated the relationship between ABA-mediated H2O2 production and the activities of antioxidant enzymes in the leaves of pumpkin-grafted cucumber seedlings. The results showed that both ABA and H2O2 were detected in pumpkin-grafted cucumber seedlings in response to Ca(NO3)2 treatment within 0.5 h in the leaves and peaked at 3 and 6 h after Ca(NO3)2 treatment, respectively, compared to the levels under control conditions. The activities of superoxide dismutase (SOD), ascorbate peroxidase (APX), and peroxidase (POD) in pumpkin-grafted cucumber leaves gradually increased over time and peaked at 12 h of Ca(NO3)2 stress. Furthermore, in the leaves of pumpkin-grafted cucumber seedlings, the H2O2 generation, the antioxidant enzyme activities and the expression of SOD, POD and cAPX were strongly blocked by an inhibitor of ABA under Ca(NO3)2 stress, but this effect was eliminated by the addition of exogenous ABA. Moreover, the activities and gene expressions of these antioxidant enzymes in pumpkin-grafted leaves were almost inhibited under Ca(NO3)2 stress by pretreatment with ROS scavengers. These results suggest that the pumpkin grafting-induced ABA accumulation mediated H2O2 generation, resulting in the induction of antioxidant defense systems in leaves exposed to Ca(NO3)2 stress in the ABA/H2O2 signaling pathway. PMID:27746808

Gas chromatography of adducts of rare earth dipivaloylmethanates with triphenylphosphine oxide

International Nuclear Information System (INIS)

Magazeeva, N.V.; Martynenko, L.I.; Murav'eva, I.A.; Spitsyn, V.I.

1987-01-01

A gas chromatographic method for determination of stability provisional constants of dipivaloylmethanates of REE with triphenylphosphine oxide is suggested, and ML 3 xTPPO adduct stability is shown to decrease in Ho-Lu series. ML 3 chromatographing at the presence of TPPO is stated to increase the coefficients of REE separation

Calculations of thermodynamic properties of PuO2 by the first-principles and lattice vibration

International Nuclear Information System (INIS)

Minamoto, Satoshi; Kato, Masato; Konashi, Kenji; Kawazoe, Yoshiyuki

2009-01-01

Plutonium dioxide (PuO 2 ) is a key compound of mixed oxide fuel (MOX fuel). To predict the thermal properties of PuO 2 at high temperature, it is important to understand the properties of MOX fuel. In this study, thermodynamic properties of PuO 2 were evaluated by coupling of first-principles and lattice dynamics calculation. Cohesive energy was estimated from first-principles calculations, and the contribution of lattice vibration to total energy was evaluated by phonon calculations. Thermodynamic properties such as volume thermal expansion, bulk modulus and specific heat of PuO 2 were investigated up to 1500 K

27 CFR 5.32a - Voluntary disclosure of major food allergens.

Science.gov (United States)

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Voluntary disclosure of major food allergens. 5.32a Section 5.32a Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX... Labeling Requirements for Distilled Spirits § 5.32a Voluntary disclosure of major food allergens. (a...

Effect of triphenylphosphine, triphenylphosphine sulphide and bis-(diphenylphosphino) methane on the redox behaviour of lithium iodide: a cyclic voltammetric study

International Nuclear Information System (INIS)

Lobana, T.S.; Gratzel, M.; Vlachopolous, N.

1994-01-01

The effect of a series of tertiary phosphine Lewis bases, namely, triphenylphosphine, triphenylphosphine sulphide and bis(diphenyl-phosphino) methane on the redox behaviour of lithium iodide in acetonitrile is studied using cyclic voltammetry. Whereas triphenyl-phosphine sulphide causes practically no change on the redox peaks of lithium iodide observed at E 1/2 , 0.150V and 0.570V, both the other phosphines cause significant effects. The redox peak at E 1/2 , 0.570V disappears, while that at Ev 1/2 , 0.150V undergoes shifts to lower E 1/2 values. (author). 5 refs., 1 fig

Magnetic susceptibility of sodium disilicate glasses containing PuO2

International Nuclear Information System (INIS)

Aldred, A.T.

1979-01-01

A solubility limit of approx. 6 mol % PuO 2 in sodium disilicate (Na 2 O.2SiO 2 ) glass has been determined. Magnetic susceptibility measurements on these glasses yield approximate Curie-Weiss behavior, in contrast to the temperature-independent susceptibility of crystalline PuO 2 . This result is interpreted to indicate that the local site symmetry around the Pu ion in the sodium disilicate glass is much different than in crystalline PuO 2 . The effective paramagnetic moments determined from the temperature dependence of the susceptibility are found to be consistent with calculated free-ion values based on the most likely 5f electron configurations

Determination of nitrogen in PuO2-UO2 mixed oxide with fusion-TCD method

International Nuclear Information System (INIS)

Hiyama, Toshiaki; Takahashi, Toshio; Ohuchi, Yoshiro; Suzuki, Takeshi; Kaya, Akira

1983-01-01

Nitrogen in plutonium and uranium mixed oxide has been determined by several different methods. In the classical Dumas method, nitrogen is measured volumetrically. Other procedures are modifications of the Kjeldahl method in which nitrogen is converted to ammonia. All these methods are accompanied with the same problems in which the analysis takes usually 2 or 3 days with waste solutions generated. So far, the authors have tried to determine nitrogen in PuO 2 -UO 2 mixed oxide with an improved dry process, in which an impulse furnace is used to heat the sample in a graphite crucible under a helium atmosphere. Nitrogen released from the sample were separated from other gases (i.e., a large amount of carbon monoxide, very small amount of hydrogen etc.) by a combination of original two moleculer sieve columns and pre-cut system. Separated nitrogen was then detected on the basis of thermal conductivities. (author)

Photochemical reduction of uranyl ion with triphenylphosphine

International Nuclear Information System (INIS)

Brar, A.S.; Sidhu, M.S.; Sandhu, S.S.

1981-01-01

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

Roles of free radicals in NO oxidation by Fenton system and the enhancement on NO oxidation and H2O2 utilization efficiency.

Science.gov (United States)

Zhao, Haiqian; Dong, Ming; Wang, Zhonghua; Wang, Huaiyuan; Qi, Hanbing

2018-06-20

Low H 2 O 2 utilization efficiency is the main problem when Fenton system was used to oxidize NO in flue gas. To understand the behavior of the free radicals during NO oxidation process in Fenton system is crucial to solving this problem. The oxidation capacity of ·OH and HO 2 · on NO in Fenton system was compared and the useless consumption path of ·OH and HO 2 · that caused the low utilization efficiency of H 2 O 2 were studied. A method to enhance the oxidation ability and H 2 O 2 utilization efficiency by adding reducing additives in Fenton system was proposed. The results showed that both of ·OH and HO 2 · were active substances that oxidize NO. However, the oxidation ability of ·OH radicals was stronger. The vast majority of ·OH and HO 2 · was consumed by rapid reaction ·OH+HO 2 ·→H 2 O+O 2 , which was the primary reason for the low utilization efficiency of H 2 O 2 in Fenton system. Hydroxylamine hydrochloride and ascorbic acid could accelerate the conversion of Fe 3+ to Fe 2+ , thereby increase the generation rate of ·OH and decrease the generation rate of HO 2 ·. As a result, the oxidation ability and H 2 O 2 utilization efficiency were enhanced.

Synthesis and reactions of 4-(p-methoxybenzyl-6-[5,6,7,8-tetrahydro-2-naphthyl]-pyridazin-3(2H-one

Directory of Open Access Journals (Sweden)

NAGWA M.S. EL-DIN HARB

1999-11-01

Full Text Available The condensation of 4-(p-methoxybenzyl-6-[5,6,7,8-tetrahydro-2-naphthyl]-pyridazin-3(2H-one (3, prepared by the reaction of 6-[5,6,7,8-tetrahydro-2-naphthyl]-4,5-dihydropyridazin-3(2H-one (1 and anisaldehyde, with dimethyl sulphate, formaldehyde and acrylonitrile, and also the formation of the Mannich base, proceeded smoothly at the 2-position to give compounds 4,5,6,7, respectively. 4-p-Methoxybenzyl-3-chloro-6-[5,6,7,8-tetrahydro-2-naphthyl]-pyridazine (9 was prepared in law yield by the action of phosphorus oxychloride on 3. The reaction of 9 with benzylamine, aniline and piperidine gave 10a,b,c, respectively. 4-p-Methoxybenzyl-6-[5,6,7,8-tetrahydro-2-napthyl]pyridazine-3(2H-thione (12 was prepared either by the action of thiourea on 9, or by the reaction of 3 with phosphorus pentasulphide. The reaction of these thiones with acrylonitrile, morpholine and piperidine to give 13 and 14 a,b, respectively, were also investigated.

Gallium Content in PuO2 Using Laser Induced Breakdown Spectroscopy (LIBS)

International Nuclear Information System (INIS)

Smith, C.A.; Martinez, M.A.; Veirs, D.K.

1999-01-01

Laser Induced Breakdown Spectroscopy (LIBS) has been applied to the semi-quantitative analysis of gallium in plutonium oxide at the Los Alamos Plutonium Facility. The oxide samples were generated by the Thermally Induced Gallium Removal (TIGR) process, a pretreatment step prior to MOX fuel processing. The TIGR process uses PuO 2 containing 1 wt% gallium (nominal) as feed material. Following the TIGR process, gallium content was analyzed by LIBS and also by conventional wet chemical analysis (ICP-MS). Although the data range was insufficient to obtain an adequate calibration, general agreement between the two techniques was good. LIBS was found to have a useful analytical range of 34-400 ppm for Ga in PuO 2

Investigation on the immobilisation of carbon in OPC-BFS and OPC-PFA systems

International Nuclear Information System (INIS)

Kinoshita, H.; Borges, P. H. R.; Utton, C. A.; Milestone, N. B.; Lynsdale, C.

2008-01-01

The reaction of CO 2 gas with OPC, OPC-BFS and OPC-PFA composite cement systems were studied using XRD, SEM and TG to investigate the applicability of these materials to immobilise carbon arising from graphite waste. XRD results suggested that calcite formed in OPC system after the carbonation reaction, whereas calcite and vaterite were observed in OPC-BFS and OPC-PFA systems. In OPC system, nearly half of Ca(OH) 2 was consumed to form CaCO 3 . In OPC-BFS and OPC-PFA systems, the amount of CaCO 3 formed, corresponded to the consumption of greater than 100% of Ca(OH) 2 initially present, suggesting that other hydration products e.g. C-S-H were also consumed, either directly or indirectly during the carbonation process. The OPC-BFS system became more porous after carbonation. OPC-PFA system indicated a high efficiency on the conversion of Ca in the system into CaCO 3 . (authors)

Nqrs Data for C6H7F7N2OSb2 (Subst. No. 0880)

Science.gov (United States)

Chihara, H.; Nakamura, N.

This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C6H7F7N2OSb2 (Subst. No. 0880)

Oligomeric proanthocyanidins (OPCs) modulating radiation-induced oxidative stress on functional and structural performance of eye in male rats

International Nuclear Information System (INIS)

Said, U.Z.; Soliman, S.M.; Azab, Kh.Sh.; El-Tahawy, N.A.

2005-01-01

Eye oxidative stress may play a major role in the etiology and pathogenesis of eye disorders such as macular degeneration and photic injury of retinal degeneration that lead to vision loss. Proanthocyanidins derived from pine bark and from grape seeds have various anti pathophysiological functions. This study was performed to evaluate the role of oligomeric proanthocyanidins (OPCs) on the radiation-induced changes in rat eye tissues. OPCs were supplemented to rats (100 mg /kg body weight/ day) for 14 successive days before and 7 successive days after exposure to 7 Gy (single dose) of whole body gamma irradiation. The results revealed radiation-induced depletion in the activities of eye endogenous antioxidant enzymes and rise in pro-oxidant levels. Supplementation of OPCs pre- and post-irradiation has significantly reduced the levels of thiobarbituric acid reactive substances, xanthine oxidase, and significantly ameliorated the activities of xanthine dehydrogenase and reactive oxygen scavenging enzymes such as superoxide dismutase, glutathione peroxidase and catalase activities in eye tissues. OPCs significantly ameliorated the radiation-induced changes in levels of insulin and glucose in the serum. The oxidative stress induced cellular damage as indicated by retardation in the responses of eye to photo stimulation as well as histopathological changes in the eye tissues. Severe intra-retinal hemorrhages, cornea swelling, disruption of photoreceptor layer of the retina and epithelial necrosis were seen. The eye tissues of rats that received OPCs supplement showed significant less severe histological damage and remarkable improvement in photo stimulation responses when compared to irradiated rats on the 7 T h and 21 s t days after exposure to gamma irradiation. According to the results obtained, it could be concluded that OPCs might protect the eye tissues from the oxidative stress possibly by virtue of its anti oxidative activity through augmentation of antioxidant

Oxidant effect of La(NO{sub 3}){sub 3}·6H{sub 2}O solution on the crystalline characteristics of nanocrystalline ZrO{sub 2} films grown by atomic layer deposition

Energy Technology Data Exchange (ETDEWEB)

Oh, Nam Khen [Graduate School of Energy Science and Technology, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon 34134 (Korea, Republic of); Vacuum Center, Korea Research Institute of Standards and Science (KRISS), 267 Gajeong-ro, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Kim, Jin-Tae [Vacuum Center, Korea Research Institute of Standards and Science (KRISS), 267 Gajeong-ro, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Department of Nanomaterials Science and Engineering, University of Science and Technology, 217 Gajeong-ro, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Kang, Goru; An, Jong-Ki; Nam, Minwoo [Vacuum Center, Korea Research Institute of Standards and Science (KRISS), 267 Gajeong-ro, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Kim, So Yeon [Graduate School of Energy Science and Technology, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon 34134 (Korea, Republic of); Park, In-Sung, E-mail: parkis77@hanyang.ac.kr [Institute of Nano Science and Technology, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 04763 (Korea, Republic of); Yun, Ju-Young, E-mail: jyun@kriss.re.kr [Vacuum Center, Korea Research Institute of Standards and Science (KRISS), 267 Gajeong-ro, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Department of Nanomaterials Science and Engineering, University of Science and Technology, 217 Gajeong-ro, Yuseong-gu, Daejeon 34113 (Korea, Republic of)

2017-02-01

Highlights: • The La(NO{sub 3}){sub 3}·6H{sub 2}O aqua solution is introduced as an oxidant in ALD process. • The H{sub 2}O and La(NO{sub 3}){sub 3}·6H{sub 2}O lead different crystalline properties of ZrO{sub 2} films. • Concentration of La(NO{sub 3}){sub 3}·6H{sub 2}O solution minimally influences crystalline status. - Abstract: Nanocrystalline ZrO{sub 2} films were synthesized by atomic layer deposition method using CpZr[N(CH{sub 3}){sub 2}]{sub 3} (Cp = C{sub 5}H{sub 5}) as the metal precursor and La(NO{sub 3}){sub 3}·6H{sub 2}O solution as the oxygen source. La element in the deposited ZrO{sub 2} films could not be detected as its content was below the resolution limit of the X-ray photoelectron spectroscopy. The alternative introduction of La(NO{sub 3}){sub 3}·6H{sub 2}O solution to conventionally used H{sub 2}O as the oxidant effectively altered the crystalline structure, grain size, and surface roughness of the grown ZrO{sub 2} films. Specifically, the crystalline structure of the ZrO{sub 2} film changed from a mixture of tetragonal and monoclinic phases to monoclinic phase. The average grain size also increased, and the resulting film surface became rougher. The average grain sizes of the ZrO{sub 2} films prepared from La(NO{sub 3}){sub 3}·6H{sub 2}O solution at concentrations of 10, 20, 30, and 40% were 280, 256, 208, and 200 nm, respectively, whereas that prepared using H{sub 2}O oxidant was 142 nm. However, the concentration of La(NO{sub 3}){sub 3}·6H{sub 2}O solution minimally influenced the crystalline characteristics of the nanocrystalline ZrO{sub 2} films i.e., the crystalline structure, grain size, and surface roughness except for crystallite size.

High pressure oxidation of C2H4/NO mixtures

DEFF Research Database (Denmark)

Giménez-López, J.; Alzueta, M.U.; Rasmussen, C.T.

2011-01-01

An experimental and kinetic modeling study of the interaction between C2H4 and NO has been performed under flow reactor conditions in the intermediate temperature range (600–900K), high pressure (60bar), and for stoichiometries ranging from reducing to oxidizing conditions. The main reaction...... pathways of the C2H4/O2/NOx conversion, the capacity of C2H4 to remove NO, and the influence of the presence of NOx on the C2H4 oxidation are analyzed. Compared to the C2H4/O2 system, the presence of NOx shifts the onset of reaction 75–150K to lower temperatures. The mechanism of sensitization involves...... the reaction HOCH2CH2OO+NO→CH2OH+CH2O+NO2, which pushes a complex system of partial equilibria towards products. This is a confirmation of the findings of Doughty et al. [3] for a similar system at atmospheric pressure. Under reducing conditions and temperatures above 700K, a significant fraction of the NOx...

Predictions of PuO2 and tracer compound release from ISV melts

International Nuclear Information System (INIS)

Cronenberg, A.W.; Callow, R.A.

1992-04-01

Two field tests were conducted at the Idaho National Engineering Laboratory (INEL) to assess in situ vitrification (ISV) suitability for long-term stabilization of buried radioactive waste. Both tests contained rare-earth oxide tracers (DY 2 O 3 , Yb 2 O 3 , and Tb 4 O 7 ) to simulate the presence of plutonium in the form of PuO 2 . In the first test, Intermediate Field Test (IFT)-l, approximately 4-% release of tracer material occurred during soil melting and associated off-gassing, while essentially nil release was observed for the second experiment (IFT-2) for which off-gassing was much reduced. This report presents an evaluation of the IFT test data in terms of governing release processes. Prediction of tracer release during ISV melting centered on an assessment of three potential transport mechanisms, (a) tracer diffusion through stagnant pool, (b) tracer transport by convective currents, and (c) tracer carry-off by escaping gas bubbles. Analysis indicates that tracer release by escaping gas is the dominant release mechanism, which is consistent with video records of gas bubble escape from the ISV melt surface. Quantitative mass transport predictions were also made for the IFT-I test conditions, indicating similarity between the 4-% release data and calculational results at viscosities of ∼ poise and tracer diffusivities of ∼10 -6 CM 2 /s. Since PuO 2 has similar chemical and transport (diffusivity) properties as the rare-earth tracers used in the rare earth tracers used in the IFT experiments, release of PuO 2 is predicted for similar off-gassing conditions. Reduced off-gassing during ISV would thus be expected to improve the overall retention of heavy-oxides within vitrified soil

Synthesis and characterisation of sulphonated poly(arylene sulphone) terpolymers with triphenylphosphine oxide moieties for proton exchange membrane fuel cells

Energy Technology Data Exchange (ETDEWEB)

Titvinidze, G.; Kaltbeitzel, A.; Manhart, A.; Meyer, W.H. [Max Planck Institute for Polymer Research, Mainz (Germany)

2010-06-15

For application in fuel cells, a series of sulphonated poly(phenylene sulphone) terpolymers with triphenylphosphine oxide moieties as constitutional units in the polymer backbone have been prepared. The synthesis of the terpolymers represents a two-step process including: (i) an aromatic nucleophilic substitution polycondensation of three difluoro monomers with varying ratios, i.e. 3,3'-disulphonate-4,4'-difluorodiphenylsulphone, 4,4'-difluorodiphenylsulphone and bis(4-fluorophenyl)phenyl phosphine oxide (BFPPO), with 4,4'-thiobisbenzenethiol yielding sulphonated poly(phenylene sulphide) terpolymers (sPPSPO) and (ii) their following oxidation with hydrogen peroxide in acidic solution to yield sulphonated poly(phenylene sulphone) terpolymers (sPPSO2PO). The structures and molecular compositions were confirmed by {sup 1}H and {sup 13}C NMR spectroscopy. The ion exchange capacity (IEC) was adjusted at will choosing the appropriate ratio of sulphonated and unsulphonated monomers. Terpolymers with 1.72 {<=} IEC {<=} 2.32 have been obtained. Sulphonated poly(arylene) ionomers containing only sulphone (-SO{sub 2}-) linkages and phosphine oxide (-PO-) units rather than ether or sulphide in the backbone reveal a high thermal and oxidative stability. Membranes were cast either from dimethylformamide (DMF) or from dimethyl sulphoxide (DMSO) solutions. For all terpolymers some general characteristic trends were observed, such as an increase of the proton conductivity with increasing IEC, water uptake and temperature. The series of sPPSO2PO membranes offered high conductivities at high humidification, however, their performance strongly depends on the relative humidity. The mechanical properties of sulphonated poly(phenylene sulphone)s have been considerably improved by means of terpolymerisation with phenylene oxide moieties. Even under high humidification the terpolymers form clear, flexible membranes the stress at break of some membranes exceeds that of

Mechanical properties of 238PuO2

International Nuclear Information System (INIS)

Petrovic, J.J.; Hecker, S.S.; Land, C.C.; Rohr, D.L.

1977-04-01

The mechanical properties of 238 PuO 2 have been examined in the Los Alamos Scientific Laboratory mechanical test facility built to handle α-radioactive materials. Compression tests were conducted as a function of temperature, strain rate, grain size, density, and storage time. At temperatures less than or equal to 1400 0 C, test specimens of 238 PuO 2 exhibit pseudobrittle behavior due to internal cracks. Plastic deformation is ''localized'' at the crack tips. Generalized plastic deformation is observed at 1500 0 C. Ultimate stress values decrease markedly with increasing temperature and decreasing strain rate, and decrease less with decreasing density, increasing storage time, and increasing grain size. Room temperature fracture is transgranular, whereas intergranular fracture predominates at elevated temperatures. Crack-free specimens of 239 PuO 2 exhibit extensive plastic deformation at 1000 0 C and above. The relationship of these test results to the impact properties of 238 PuO 2 fuel in radioisotope thermoelectric generators is discussed

Highly efficient extraction and oxidative desulfurization system using Na7H2LaW10O36⋅32 H2O in [bmim]BF4 at room temperature.

Science.gov (United States)

Xu, Junhua; Zhao, Shen; Chen, Wei; Wang, Miao; Song, Yu-Fei

2012-04-10

Highly efficient, deep desulfurization of model oil containing dibenzothiophene (DBT), benzothiophene (BT), or 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been achieved under mild conditions by using an extraction and catalytic oxidative desulfurization system (ECODS) in which a lanthanide-containing polyoxometalate Na(7)H(2)LnW(10)O(36)⋅32 H(2)O (LnW(10); Ln = Eu, La) acts as catalyst, [bmim]BF(4) (bmim = 1-butyl-3-methylimidazolium) as extractant, and H(2)O(2) as oxidant. Sulfur removal follows the order DBT>4,6-DMDBT>BT at 30 °C. DBT can be completely oxidized to the corresponding sulfone in 25 min under mild conditions, and the LaW(10)/[bmim]BF(4) system could be recycled for ten times with only slight decrease in activity. Thus, LaW(10) in [bmim]BF(4) is one of the most efficient systems for desulfurization using ionic liquids as extractant reported so far. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structurally characterized 1,1,3,3-tetramethylguanidine solvated magnesium aryloxide complexes: [Mg(mu-OEt)(DBP)(H-TMG)]2, [Mg(mu-OBc)(DBP)(H-TMG)]2, [Mg(mu-TMBA)(DBP)(H-TMG)]2, [Mg(mu-DPP)(DBP)(H-TMG)]2, [Mg(BMP)2(H-TMG)2], [Mg(O-2,6-Ph2C6H3)2 (H-TMG)2].

Science.gov (United States)

Monegan, Jessie D; Bunge, Scott D

2009-04-06

The synthesis and structural characterization of several 1,1,3,3-tetramethylguanidine (H-TMG) solvated magnesium aryloxide complexes are reported. Bu(2)Mg was successfully reacted with H-TMG, HOC(6)H(3)(CMe(3))(2)-2,6 (H-DBP), and either ethanol, a carboxylic acid, or diphenyl phosphate in a 1:1 ratio to yield the corresponding [Mg(mu-L)(DBP)(H-TMG)](2) where L = OCH(2)CH(3) (OEt, 1), O(2)CC(CH(3))(3) (OBc, 2), O(2)C(C(6)H(2)-2,4,6-(CH(3))(3)) (TMBA, 3), or O(2)P(OC(6)H(5))(2) (DPP, 4). Bu(2)Mg was also reacted with two equivalents of H-TMG and HOC(6)H(3)(CMe(3))-2-(CH(3))-6 (BMP) or HO-2,6-Ph(2)C(6)H(3) to yield [Mg(BMP)(2)(H-TMG)(2)] (5) and [Mg(O-2,6-Ph(2)C(6)H(3))(2)(H-TMG)(2)] (6). Compounds 1-6 were characterized by single-crystal X-ray diffraction. Polymerization of l- and rac-lactide with 1 was found to generate polylactide (PLA). A discussion concerning the relevance of compounds 2 - 4 to the structure of Mg-activated phosphatase enzymes is also provided. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, and (1)H, (13)C and (31)P NMR studies.

New metal-organic frameworks of [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La, Ce) and [Ce2(C2O4)(C6H6O7)2] . 4H2O

International Nuclear Information System (INIS)

Weng Shengfeng; Wang, Yun-Hsin; Lee, Chi-Shen

2012-01-01

Two novel materials, [M(C 6 H 5 O 7 )(C 6 H 6 O 7 )(C 6 H 7 O 7 )(H 2 O)] . H 2 O (M=La(1a), Ce(1b)) and [Ce 2 (C 2 O 4 )(C 6 H 6 O 7 ) 2 ] . 4H 2 O (2), with a metal-organic framework (MOF) were prepared with hydrothermal reactions and characterized with photoluminescence, magnetic susceptibility, thermogravimetric analysis and X-ray powder diffraction in situ. The crystal structures were determined by single-crystal X-ray diffraction. Compound 1 crystallized in triclinic space group P1-bar (No. 2); compound 2 crystallized in monoclinic space group P2 1 /c (No. 14). The structure of 1 is built from a 1D MOF, composed of deprotonated citric ligands of three kinds. Compound 2 contains a 2D MOF structure consisting of citrate and oxalate ligands; the oxalate ligand arose from the decomposition in situ of citric acid in the presence of Cu II ions. Photoluminescence spectra of compounds 1b and 2 revealed transitions between the 5d 1 excited state and two levels of the 4f 1 ground state ( 2 F 5/2 and 2 F 7/2 ). Compounds 1b and 2 containing Ce III ion exhibit a paramagnetic property with weak antiferromagnetic interactions between the two adjacent magnetic centers. - Graphical Abstract: [M(C 6 H 5 O 7 )(C 6 H 6 O 7 )(C 6 H 7 O 7 )(H 2 O)] . H 2 O (M=La(1a), Ce(1b)) and [Ce 2 (C 2 O 4 )(C 6 H 6 O 7 ) 2 ] . 4H 2 O (2)—with 1D and 2D structures were synthesized and characterized. Highlights: ► Two MOF – [M(C 6 H 5 O 7 )(C 6 H 6 O 7 )(C 6 H 7 O 7 )(H 2 O)] . H 2 O (M=La(1a), Ce(1b)) and [Ce 2 (C 2 O 4 )(C 6 H 6 O 7 ) 2 ] . 4H 2 O (2) – with 1D and 2D structures. ► The adjacent chains of the 1D framework were correlated with each other through an oxalate ligand to form a 2D layer structure. ► The source of the oxalate ligand was the decomposition in situ of citric acid oxidized in the presence of Cu II ions.

Ultra-small plutonium oxide nanocrystals: an innovative material in plutonium science.

Science.gov (United States)

Hudry, Damien; Apostolidis, Christos; Walter, Olaf; Janssen, Arne; Manara, Dario; Griveau, Jean-Christophe; Colineau, Eric; Vitova, Tonya; Prüssmann, Tim; Wang, Di; Kübel, Christian; Meyer, Daniel

2014-08-11

Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non-conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium-based nanomaterials. Here we show that ultra-small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2 ) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2 (NO3 )2 ]⋅3 H2 O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X-ray diffraction (PXRD), X-ray absorption fine structure (XAFS), X-ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chlorido(1,3-dimethylthiourea-κSbis(triphenylphosphine-κPcopper(I acetonitrile hemisolvate

Directory of Open Access Journals (Sweden)

Brian W. Skelton

2009-08-01

Full Text Available The title compound, [CuCl(C3H8N2S(C18H15P2]·0.5CH3CN, was prepared by the reaction of copper(I chloride with 1,3-dimethylthiourea (dmtu and triphenylphosphine (PPh3 in acetonitrile. The CuI atom has a distorted tetrahedral environment formed by two P atoms from triphenylphosphine, one S atom from the dmtu ligand and one Cl atom. In addition, the molecules exhibit intra- and intermolecular N—H...Cl interactions.

Durability of low-pH cementitious materials based on OPC or CAC

International Nuclear Information System (INIS)

Garcia Calvo, J.L.; Sanchez, M.; Alonso, M.C.; Fernandez Luco, L.

2015-01-01

Low pH cementitious materials are considered to be used in underground repositories for high level waste but there are still some characteristics related to their long-term durability that must be analyzed in depth. In this sense, different shrinkage tests have been made using low-pH cement formulations based on Ordinary Portland Cement (OPC) or Calcium Aluminate Cement (CAC), on mortar and concrete specimens. The obtained results show that, regarding the autogenous shrinkage, low-pH cementitious materials show similar values than those observed in the reference samples. In fact, the main shrinkage problems in the low-pH materials are related with those based on OPC with high silica fume contents in drying conditions. Besides, as the use of reinforced concrete can be required in underground repositories, the susceptibility of reinforcements to corrosion when using low-pH cementitious materials based on OPC was analyzed, using two different reinforcements: carbon steel and galvanized steel. The lower pore solution pH of the low-pH OPC based materials generates the corrosion of the carbon steel reinforcement. However, when galvanized steels are used, any corrosion problem is detected regardless of the cement formulation. (authors)

Fission and explosive energy releases of PuO2, PuO2--UO2, UO2, and UO3 assemblies

International Nuclear Information System (INIS)

Koelling, J.J.; Hansen, G.E.; Byers, C.C.

1977-01-01

The critical masses and fission and explosive energy releases of PuO 2 , PuO 2 --UO 2 , UO 2 , and UO 3 assemblies have been calculated. The parameters selected for the model are conservative. They were chosen after review of appropriate plants that have been and are proposed for construction in the future. The resulting data envelopes are intended to include any conceivable set of circumstances that could ultimately lead to a nuclear incident. All energy release analysis was performed for initial fission spikes only: recriticality mechanisms were not considered

Nqrs Data for C6H7F4N2OSb (Subst. No. 0879)

Science.gov (United States)

Chihara, H.; Nakamura, N.

This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C6H7F4N2OSb (Subst. No. 0879)

Measurements of thermal disadvantage factors in light-water moderated PuO2-UO2 and UO2 lattices

International Nuclear Information System (INIS)

Ohno, Akio; Kobayashi, Iwao; Tsuruta, Harumichi; Hashimoto, Masao; Suzaki, Takenori

1980-01-01

The disadvantage factor for thermal neutrons in light-water moderated PuO 2 -UO 2 and UO 2 square lattices were obtained from measurements of thermal neutron density distributions in a unit lattice cell, measured with Dy-Al wire detectors. The lattices consisted of 3.4 w/o PuO 2 .UO 2 and 2.6 w/o UO 2 fuel rods, and the water-to-fuel volume ratio within the unit cell was parametrically changed. The PuO 2 .UO 2 and UO 2 fuel rods were designed to realize equal fissile atomic number density. The disadvantage factors thus measured were 1.36 +- 0.07, 1.37 +- 0.08, 1.40 +- 0.06 and 1.38 +- 0.06 in the PuO 2 .UO 2 fuel lattices, and 1.30 +- 0.06, 1.31 +- 0.08, 1.30 +- 0.08 and 1.33 +- 0.06 in the UO 2 , for water-to-fuel volume ratios, of 1.76, 2.00, 2.38 and 2.95, respectively. This difference in disadvantage factor between PuO 2 .UO 2 and UO 2 fuel lattices corresponds to about 8%. Calculated results obtained by multigroup transport code LASER agreed well with the measured ones. (author)

Post-irradiation examination of CANDU fuel bundles fuelled with (Th, Pu)O2

International Nuclear Information System (INIS)

Karam, M.; Dimayuga, F.C.; Montin, J.

2010-01-01

AECL has extensive experience with thoria-based fuel irradiations as part of an ongoing R&D program on thorium within the Advanced Fuel Cycles Program. The BDL-422 experiment was one component of the thorium program that involved the fabrication and irradiation testing of six Bruce-type bundles fuelled with (Th, Pu)O 2 pellets. The fuel was manufactured in the Recycle Fuel Fabrication Laboratories (RFFL) at Chalk River allowing AECL to gain valuable experience in fabrication and handling of thoria fuel. The fuel pellets contained 86.05 wt.% Th and 1.53 wt.% Pu in (Th, Pu)O 2 . The objectives of the BDL-422 experiment were to demonstrate the ability of 37-element geometry (Th, Pu)O 2 fuel bundles to operate to high burnups up to 1000 MWh/kgHE (42 MWd/kgHE), and to examine the (Th, Pu)O 2 fuel performance. This paper describes the post-irradiation examination (PIE) results of BDL-422 fuel bundles irradiated to burnups up to 856 MWh/kgHE (36 MWd/kgHE), with power ratings ranging from 52 to 67 kW/m. PIE results for the high burnup bundles (>1000 MWh/kgHE) are being analyzed and will be reported at a later date. The (Th, Pu)O 2 fuel performance characteristics were superior to UO 2 fuel irradiated under similar conditions. Minimal grain growth was observed and was accompanied by benign fission gas release and sheath strain. Other fuel performance parameters, such as sheath oxidation and hydrogen distribution, are also discussed. (author)

Cation interdiffusion in the UO2 - (U, Pu)O2 and UO2 - PuO2 systems

International Nuclear Information System (INIS)

Leme, D.G.

1985-01-01

The interdiffusion of U and Pu ions in UO sub(2 +- x) - (U sub(0,83) Pu sub(0,17))O sub(2 + - x) and UO sub(2 + - x) -PuO sub(2 - x) sintered pellets and UO sub(2 +- x) -(U sub(0,82) Pu sub(0,18))O sub(2 + - x) single crystals has been studied as a function of the oxygen potential ΔG sup(-) (O 2 ) or the stoichiometric ratio O/M. The diffusion profiles of UO 2 /(U,Pu)O 2 and UO 2 /PuO 2 couples of different O/M ratios have been measured using high resolution α-spectrometer and microprobe. Thermal annealing of the specimens was performed in controlled atmospheres using either CO-CO 2 gas mixtures for constant O/M ratios or purified argon. The interdiffusion profiles have been analysed by means of the Boltzmann-Matano and Hall methods. The interdiffusion coefficient D sus(approx.) increases with increasing Pu content in sintered pellets (up to 17 wt. %PuO 2 ) showing a strong dependence of D sup(approx.) on the O/M ratio. The micropobe results show that the interdiffusion along grain boundaries is the main diffusion mechanism in the pellets. Experiments have also been carried out in single cristals to measure just the bulk-interdiffusion and avoiding effects due to grain boundaries. A marked dependence of D sup(approx.) on O/M ratio or on oxygen potential ΔG sup(-) (O 2 ), similar to the dependence already reported for self diffusion by means of radioactive tracers, has also been observed. (Author) [pt

Results of the irradiation of mixed UO2 - PuO2 oxide fuel elements

International Nuclear Information System (INIS)

Mikailoff, H.; Mustelier, J.P.; Bloch, J.; Ezran, L.; Hayet, L.

1966-01-01

In order to study the behaviour of fuel elements used for the first charge of the reactor Rapsodie, a first batch of eleven needles was irradiated in the reactor EL3 and then examined. These needles (having a shape very similar lo that of the actual needles to be used) were made up of a stack of sintered mixed-oxide pellets: UO 2 containing about 10 per cent of PuO 2 . The density was 85 to 97 per cent of the theoretical, value. The diametral gap between the oxide and the stainless steel can was between 0,06 and 0,27 mm. The specific powers varied from 1230 to 2700 W/cm 3 and the can temperature was between 450 and 630 C. The maximum burn-up attained was 22000 MW days/tonne. Examination of the needles (metrology, radiography and γ-spectrography) revealed certain macroscopic changes, and the evolution of the fuel was shown by micrographic studies. These observations were used, together with flux measurements results, to calculate the temperature distribution inside the fuel. The volume of the fission gas produced was measured in some of the samples; the results are interpreted taking into account the temperature distribution in the oxide and the burn-up attained. Finally a study was made both of the behaviour of a fuel element whose central part was molten during irradiation, and of the effect of sodium which had penetrated into some of the samples following can rupture. (author) [fr

A multinuclear solid-state magnetic resonance study of silver nitrate triphenylphosphine

International Nuclear Information System (INIS)

Oh, S.-W.; Bernard, G.M.; Wasylishen, R.E.; McDonald, R.; Ferguson, M.J.

2005-01-01

Variable-temperature solid-state 31 P, 15 N, and 2 H NMR spectroscopy, X-ray diffraction, and differential scanning calorimetry studies of the 1:1 adduct of silver nitrate and triphenylphosphine (AgNO 3 ·PPh 3 ) reveal a solid-solid phase transition at 300 K. The principal components of the phosphorus and nitrogen chemical shift tensors for both phases are determined from NMR spectra of MAS and stationary samples. In addition, the indirect spin-spin coupling between phosphorus and the naturally occurring isotopes of silver ( 107 Ag and 109 Ag) are resolved. Experimental 2 H NMR line shapes for silver nitrate perdeuterated triphenylphosphine are those characteristic of rigid phenyl groups at temperatures above and below the phase-transition temperature. Powder and single-crystal X-ray diffraction data for AgNO 3 ·PPh 3 obtained at 193, 295, and 313 K are reported; data obtained at 193 and 295 K are almost identical, but are significantly different from those obtained at 313 K and from an earlier single-crystal X-ray diffraction investigation performed at 298 K. All X-ray studies found that AgNO 3 ·PPh 3 crystallizes in the monoclinic form, space group P2 1 lc. (author)

Preparation, microstructures, and properties of PuO2

International Nuclear Information System (INIS)

Bickford, D.F.; Rankin, D.T.; Smith, P.K.

1976-01-01

PuO 2 pellets with controlled microstructures were fabricated to meet operational requirements for packaged heat sources. Size distributions, morphologies (forms and structures), and packing densities were measured on calcined and milled powders, slugged compacts, and presintered granules. These variables influence microstructure, porosity distribution, and fracture behavior of hot-pressed and sintered PuO 2

Hematological responses after inhaling 238PuO2: An extrapolation from beagle dogs to humans

International Nuclear Information System (INIS)

Scott, B.R.; Muggenburg, B.A.; Welsh, C.A.; Angerstein, D.A.

1994-01-01

The alpha emitter plutonium-238 ( 238 Pu), which is produced in uranium-fueled, light-water reactors, is used as a thermoelectric power source for space applications. Inhalation of a mixed oxide form of Pu is the most likely mode of exposure of workers and the general public. Occupational exposures to 238 PuO 2 have occurred in association with the fabrication of radioisotope thermoelectric generators. Organs and tissue at risk for deterministic and stochastic effects of 238 Pu-alpha irradiation include the lung, liver, skeleton, and lymphatic tissue. Little has been reported about the effects of inhaled 238 PuO 2 on peripheral blood cell counts in humans. The purpose of this study was to investigate hematological responses after a single inhalation exposure of Beagle dogs to alpha-emitting 238 PuO 2 particles and to extrapolate results to humans

Csbnd H⋯Ni and Csbnd H⋯π(chelate) interactions in nickel(II) complexes involving functionalized dithiocarbamates and triphenylphosphine

Science.gov (United States)

Sathiyaraj, E.; Thirumaran, S.; Selvanayagam, S.; Sridhar, B.; Ciattini, Samuele

2018-05-01

New bis(N-benzyl-N-substituted benzyldithiocarbamato-S,S‧)nickel(II) (1-3) and (N-benzyl-N-substituted benzyldithiocarbamato-S,S‧)(isothiocyanato-N)- (triphenylphosphane)nickel(II) (4-6) [where substituted benzyl = 2-HOsbnd C6H4sbnd CH2sbnd (1,4), 3-HOsbnd C6H4sbnd CH2sbnd (2,5), 4-Fsbnd C6H4sbnd CH2sbnd (3,6)] were synthesized and characterized using IR, electronic, and NMR (1H and 13C) spectra. X-ray structural analysis of homoleptic complex (1) and heteroleptic complexes (5 and 6) confirmed the presence of four coordinated nickel in a distorted square planar arrangement with NiS4 and NiS2PN chromophores, respectively. The νC-S stretching vibrations are observed around 990 cm-1 without any splitting supporting the bidentate coordination of the dithiocarbamate ligand. Electronic spectral studies of all the complexes (1-6) indicate that the geometry of the nickel atom is probably square planar. NMR spectra of all homoleptic and heteroleptic complexes (1-6) reveal a weak signal associated with the backbone carbon (N13CS2) in the region 204.0-210.0 ppm with a weak intensity characteristic of the quaternary carbon signals. The greater trans influence of triphenylphosphine in complexes 5 and 6 is supported by the long Nisbnd S distance compared to other Nisbnd S distance which is opposite to the NCS- ligand. In the structure of complex 5, C-H⋯π(chelate) interactions results in polymeric chain. Both structures show intramolecular Ni⋯H interactions but that on 6 is the strongest. C-H⋯π interactions are also found in 1, 5 and 6. Hirshfeld surface analysis and the associated 2D fingerprint plots of 1, 5 and 6 have been studied to evaluate intermolecular interactions. The molecular geometries of complexes 1, 5 and 6 have been optimized by abinitio HF method using LANL2DZ program.

Synthesis and X-ray Crystallography of [Mg(H2O)6][AnO2(C2H5COO)3]2 (An = U, Np, or Pu).

Science.gov (United States)

Serezhkin, Viktor N; Grigoriev, Mikhail S; Abdulmyanov, Aleksey R; Fedoseev, Aleksandr M; Savchenkov, Anton V; Serezhkina, Larisa B

2016-08-01

Synthesis and X-ray crystallography of single crystals of [Mg(H2O)6][AnO2(C2H5COO)3]2, where An = U (I), Np (II), or Pu (III), are reported. Compounds I-III are isostructural and crystallize in the trigonal crystal system. The structures of I-III are built of hydrated magnesium cations [Mg(H2O)6](2+) and mononuclear [AnO2(C2H5COO)3](-) complexes, which belong to the AB(01)3 crystallochemical group of uranyl complexes (A = AnO2(2+), B(01) = C2H5COO(-)). Peculiarities of intermolecular interactions in the structures of [Mg(H2O)6][UO2(L)3]2 complexes depending on the carboxylate ion L (acetate, propionate, or n-butyrate) are investigated using the method of molecular Voronoi-Dirichlet polyhedra. Actinide contraction in the series of U(VI)-Np(VI)-Pu(VI) in compounds I-III is reflected in a decrease in the mean An═O bond lengths and in the volume and sphericity degree of Voronoi-Dirichlet polyhedra of An atoms.

Moisture corrections in neutron coincidence counting of PuO2

International Nuclear Information System (INIS)

Stewart, J.E.; Menlove, H.O.

1987-01-01

Passive neutron coincidence counting is capable of 1% assay accuracy for pure, well-characterized PuO 2 samples that contain plutonium masses from a few tens of grams to several kilograms. Moisture in the sample can significantly bias the assay high by changing the (α,n) neutron production, the sample multiplication, and the detection efficiency. Monte Carlo calculations and an analytical model of coincidence counting have been used to quantify the individual and cumulative effects of moisture biases for two PuO 2 sample sizes and a range of moisture levels from 0 to 9 wt %. Results of the calculations suggest a simple correction procedure for moisture bias that is effective from 0 to 3 wt % H 2 O. The procedure requires that the moisture level in the sample be known before the coincidence measurement

Dosimetry and response in rat pulmonary epithelium following inhalation of 239PuO2

International Nuclear Information System (INIS)

Rhoads, K.; Mahaffey, J.A.; Sanders, C.L.

1983-01-01

The distribution of inhaled 239 PuO 2 and pathologic changes have been studied in the lung of rats. The clearance of inhaled 237 239 PuO 2 from the lung is a function of the amount of deposited Pu with a decrease in early alveolar clearance with increasing lung burden. With increasing time post-exposure there is a greater concentration of PuO 2 and an increased aggregation of PuO 2 particles in subpleural regions of the lung. Fibrotic and metaplastic lesions in the lung were usually focal, being found in subpleural regions associated with aggregates of PuO 2 . An average of 12 +- 6 percent of the lung volume was fibrotic at 530 days after an initial alveolar deposition of 180 nCi 239 Pu. Lung tumors occupied 4 +- 6 percent and epithelial metaplasias less than 1 percent of the lung volume at this time. Cell proliferation as assayed by tritiated thymidine autoradiography was greater in fibrotic, metaplastic and neoplastic regions than in areas of normal alveolar-bronchiolar epithelium. Turnover times ranged from about 6 days for fibrotic lesions to 1 to 3 days for metaplastic and neoplastic lesions. The lung tumor doubling times were 57 to 116 days due to tumor cell necrosis and other factors that limit tumor cell survival. Cell proliferation rates for adenomatous metaplasia were similar to those for adenocarcinoma while those for squamous cell metaplasia were similar to those for squamous cell carcinoma. Squamous lesions exhibited a more rapid growth than did adenomatous lesions

27 CFR 5.32b - Petitions for exemption from major food allergen labeling.

Science.gov (United States)

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Petitions for exemption from major food allergen labeling. 5.32b Section 5.32b Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS LABELING AND ADVERTISING OF...

Crystal and molecular structure of 2,2’-(quinoxaline-2,3-diyl)dipyridinium dinitrate (H_2L)(NO_3)_2

International Nuclear Information System (INIS)

Egorova, O. A.; Polyakova, I. N.; Sergienko, V. S.; Davydov, V. V.

2016-01-01

The crystal structure of 2,2’-(quinoxaline-2,3-diyl)dipyridinium dinitrate (H_2L)(NO_3)_2 is studied by X-ray diffraction (T = 150 K, R1 = 0.0467). The H_2L"2"+ cation is located on the twofold rotation axis and connected with two NO_3"− anions by strong N–H···O hydrogen bonds. Planar quinoxaline fragments of cations form stacks with the interplanar spacing of 3.308 Å. The structure of the diprotonated H_2L"2"+ cation is compared with those of the monoprotonated H_2L"2"+ cation and neutral L molecule.

Aerosol Physics Considerations for Using Cerium Oxide CeO₂ as a Surrogate for Plutonium Oxide PuO₂ in Airborne Release Fraction Measurements for Storage Container Investigations

Energy Technology Data Exchange (ETDEWEB)

Moore, Murray E. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Tao, Yong [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2017-02-16

Cerium oxide (CeO2) dust is recommended as a surrogate for plutonium oxide (PuO2) in airborne release fraction experiments. The total range of applicable particle sizes for PuO2 extends from 0.0032 μm (the diameter of a single PuO2 molecule) to 10 μm (the defined upper boundary for respirable particles). For particulates with a physical particle diameter of 1.0 μm, the corresponding aerodynamic diameters for CeO2 and PuO2 are 2.7 μm and 3.4 μm, respectively. Cascade impactor air samplers are capable of measuring the size distributions of CeO2 or PuO2 particulates. In this document, the aerodynamic diameters for CeO2 and PuO2 were calculated for seven different physical diameters (0.0032, 0.02, 0.11, 0.27, 1.0, 3.2, and 10 μm). For cascade impactor measurements, CeO2 and PuO2 particulates with the same physical diameter would be collected onto the same or adjacent collection substrates. The difference between the aerodynamic diameter of CeO2 and PuO2 particles (that have the same physical diameter) is 39% of the resolution of a twelve-stage MSP Inc. 125 cascade impactor, and 34% for an eight-stage Andersen impactor. An approach is given to calculate the committed effective dose (CED) coefficient for PuO2 aerosol particles, compared to a corresponding aerodynamic diameter of CeO2 particles. With this approach, use of CeO2 as a surrogate for PuO2 material would follow a direct conversion based on a molar equivalent. In addition to the analytical information developed for this document, several US national labs have published articles about the use of CeO2 as a PuO2 surrogate. Different physical and chemical aspects were considered by these investigators, including thermal properties, ceramic formulations, cold pressing, sintering, molecular reactions, and mass loss in high temperature gas flows. All of those US national lab studies recommended the use of CeO2 as a surrogate material for PuO2.

Pyrochemical processes for the recovery of weapons grade plutonium either as a metal or as PuO2 for use in mixed oxide reactor fuel pellets

International Nuclear Information System (INIS)

Colmenares, C.A.; Ebbinghaus, B.B.; Bronson, M.C.

1995-01-01

The authors have developed two processes for the recovery of weapons grade Pu, as either Pu metal or PuO 2 , that are strictly pyrochemical and do not produce any liquid waste. Large amounts of Pu metal (up to 4 kg.), in various geometric shapes, have been recovered by a hydride/dehydride/casting process (HYDEC) to produce metal ingots of any desired shape. The three processing steps are carried out in a single compact apparatus. The experimental technique and results obtained will be described. The authors have prepared PuO 2 powders from weapons grade Pu by a process that hydrides the Pu metal followed by the oxidation of the hydride (HYDOX process). Experimental details of the best way to carry out this process will be presented, as well as the characterization of both hydride and oxide powders produced

The Raman fingerprint of plutonium dioxide: Some example applications for the detection of PuO2 in host matrices

Science.gov (United States)

Manara, D.; Naji, M.; Mastromarino, S.; Elorrieta, J. M.; Magnani, N.; Martel, L.; Colle, J.-Y.

2018-02-01

Some example applications are presented, in which the peculiar Raman fingerprint of PuO2 can be used for the detection of crystalline Pu4+ with cubic symmetry in an oxide environment in various host materials, like mixed oxide fuels, inert matrices and corium sub-systems. The PuO2 Raman fingerprint was previously observed to consist of one main T2g vibrational mode at 478 cm-1 and two crystal electric field transition lines at 2130 cm-1 and 2610 cm-1. This particular use of Raman spectroscopy is promising for applications in nuclear waste management, safety and safeguard.

Chronic cigarette smoke exposure increases the pulmonary retention and radiation dose of 239Pu inhaled as 239PuO2 by F344 rats

International Nuclear Information System (INIS)

Finch, G.L.; Lundgren, D.L.; Barr, E.B.; Chen, B.T.; Griffith, W.C.; Hobbs, C.H.; Hoover, M.D.; Nikula, K.J.; Mauderly, J.L.

1998-01-01

As a portion of a study to examine how chronic cigarette smoke exposure might alter the risk of lung tumors from inhaled 239 PuO 2 in rats, the effects of smoke exposure on alpha-particle lung dosimetry over the life-span of exposed rats were determined. Male and female rats were exposed to inhaled 239 PuO 2 alone or in combination with cigarette smoke. Animals exposed to filtered air along served as controls for the smoke exposure. Whole-body exposure to mainstream smoke diluted to concentrations of either 100 or 250 mg total particulate matter m -3 began at 6 wk of age and continued for 6 h d -1 , 5 d wk -1 , for 30 mo. A single, pernasal, acute exposure to 239 PuO 2 was given to all rats at 12 wk of age. Exposure to cigarette smoke caused decreased body weight gains in a concentration dependent manner. Lung-to-body weight ratios were increased in smoke-exposed rats. Rats exposed to cigarette smoke before the 239 PuO 2 exposure deposited less 239 Pu in the lung than did controls. Except for male rats exposed to LCS, exposure to smoke retarded the clearance of 239 Pu from the lung compared to control rats through study termination at 870 d after 239 PuO 2 exposure. Radiation doses to lungs were calculated by sex and by exposure group for rats on study for at least 360 d using modeled body weight changes, lung-to-body weight ratios, and standard dosimetric calculations. For both sexes, estimated lifetime radiation doses from the time of 239 PuO 2 exposure to death were 3.8 Gy, 4.4 Gy, or 6.7 Gy for the control, LCS, or HCS exposure groups, respectively. Assuming an approximately linear dose-response relationship between radiation dose and lung neoplasm incidence, approximate increases of 20% or 80% in tumor incidence over controls would be expected in rats exposed to 239 PuO 2 and LCS or 239 PuO 2 and HCS, respectively

A multinuclear solid-state magnetic resonance study of silver nitrate triphenylphosphine

Energy Technology Data Exchange (ETDEWEB)

Oh, S.-W.; Bernard, G.M.; Wasylishen, R.E. [Univ. of Alberta, Dept. of Chemistry, Gunning/Lemieux Chemistry Centre, Edmonton, Alberta (Canada)]. E-mail: roderick.wasylishen@ualberta.ca; McDonald, R.; Ferguson, M.J. [Univ. of Alberta, Dept. of Chemistry, X-Ray Crystallography Lab., Edmonton, Alberta (Canada)

2005-10-15

Variable-temperature solid-state {sup 31}P, {sup 15}N, and {sup 2}H NMR spectroscopy, X-ray diffraction, and differential scanning calorimetry studies of the 1:1 adduct of silver nitrate and triphenylphosphine (AgNO{sub 3}{center_dot}PPh{sub 3}) reveal a solid-solid phase transition at 300 K. The principal components of the phosphorus and nitrogen chemical shift tensors for both phases are determined from NMR spectra of MAS and stationary samples. In addition, the indirect spin-spin coupling between phosphorus and the naturally occurring isotopes of silver ({sup 107}Ag and {sup 109}Ag) are resolved. Experimental {sup 2}H NMR line shapes for silver nitrate perdeuterated triphenylphosphine are those characteristic of rigid phenyl groups at temperatures above and below the phase-transition temperature. Powder and single-crystal X-ray diffraction data for AgNO{sub 3}{center_dot}PPh{sub 3} obtained at 193, 295, and 313 K are reported; data obtained at 193 and 295 K are almost identical, but are significantly different from those obtained at 313 K and from an earlier single-crystal X-ray diffraction investigation performed at 298 K. All X-ray studies found that AgNO{sub 3}{center_dot}PPh{sub 3} crystallizes in the monoclinic form, space group P2{sub 1}lc. (author)

Low-level 239PuO2 lifespan studies

International Nuclear Information System (INIS)

Sanders, C.L.

1985-01-01

This project will produce data to generate a dose-response curve (and to evaluate other statistical methods that also incorporate survival time) for lung-tumor incidence in Wistar rats following inhalation of 239 PuO 2 at levels producing lifetime radiation doses to the lung of 2000 rad. The lung clearance of 239 Pu is best represented by a two-exponential equation, with 78% of the initial alveolar depositions (IAD) cleared with a half-time of 19 days and 22% cleared with a half-time of 180 days. A total of 593 of 2134 exposed and 242 of 1058 sham-exposed rats have died. Among the dead rats, the percent with primary lung tumors was 71% for the 150-nCi group, 70% for the 82-nCi group, and 23% for the 32-nCi group. No lung tumors have been found in controls, and only three have been found at an IAD of < 7.5 nCi. 1 figure, 3 tables

Computational study on the mechanisms and energetics of trimethylindium reactions with H2O and H2S.

Science.gov (United States)

Raghunath, P; Lin, M C

2007-07-19

The reactions of trimethylindium (TMIn) with H2O and H2S are relevant to the chemical vapor deposition of indium oxide and indium sulfide thin films. The mechanisms and energetics of these reactions in the gas phase have been investigated by density functional theory and ab initio calculations using the CCSD(T)/[6-31G(d,p)+Lanl2dz]//B3LYP/[6-31G(d,p)+Lanl2dz] and CCSD(T)/[6-31G(d,p)+Lanl2dz] //MP2/[6-31G(d,p)+Lanl2dz] methods. The results of both methods are in good agreement for the optimized geometries and relative energies. When TMIn reacts with H2O and H2S, initial molecular complexes [(CH3)3In:OH2 (R1)] and [(CH3)3In:SH2 (R2)] are formed with 12.6 and 3.9 kcal/mol binding energies. Elimination of a CH4 molecule from each complex occurs with a similar energy barrier at TS1 (19.9 kcal/mol) and at TS3 (22.1 kcal/mol), respectively, giving stable intermediates (CH3)2InOH and (CH3)2InSH. The elimination of the second CH4 molecule from these intermediate products, however, has to overcome very high and much different barriers of 66.1 and 53.2 kcal/mol, respectively. In the case of DMIn with H2O and H2S reactions, formation of both InO and InS is exothermic by 3.1 and 30.8 kcal/mol respectively. On the basis of the predicted heats of formation of R1 and R2 at 0 K and -20.1 and 43.6 kcal/mol, the heats of formation of (CH3)2InOH, (CH3)2InSH, CH3InO, CH3InS, InO, and InS are estimated to be -20.6, 31.8, and 29.0 and 48.4, 35.5, and 58.5 kcal/mol, respectively. The values for InO and InS are in good agreement with available experimental data. A similar study on the reactions of (CH3)2In with H2O and H2S has been carried out; in these reactions CH3InOH and CH3InSH were found to be the key intermediate products.

Effects of CO, O2, NO, H2O, and irradiation temperature on the radiation-induced oxidation of SO2

International Nuclear Information System (INIS)

Tokunaga, Okihiro; Nishimura, Koichi; Suzuki, Nobutake; Washino, Masamitsu

1977-01-01

When a SO 2 -H 2 O-O 2 -N 2 gaseous mixture was irradiated by electron beams of 1.5 MeV, SO 2 was easily oxidized to H 2 SO 4 . Effects of CO, O 2 , NO, H 2 O, and irradiation temperature on the radiation-induced oxidation of SO 2 were studied by measuring the SO 2 concentration gas chromatographically. The G(-SO 2 ) increased greatly at the addition of a small amount of O 2 , and then decreased gradually with an increase in the O 2 concentration, i.e., the G(-SO 2 ) values were 0.9, 8.0, and 5.3 for the 0, 0.1, and 20% O 2 concentrations at 100 0 C, respectively (Fig.4). The G(-SO 2 ) was independent of the H 2 O concentration in the range of 0.84 to 8.4% (Fig.5). The G(-SO 2 ) decreased with a rise in the irradiation temperature (Fig.6) and an apparent activation energy of the oxidation reaction of SO 2 obtained was -4.2 kcal.mol -1 . The effects of CO, NO, and O 2 on the G(-SO 2 ) showed that SO 2 was mainly oxidized by OH and O and that the contribution of OH to the oxidation of SO 2 increased with an increase in the O 2 concentration (Table 1). The rate constants for the reactions of SO 2 with OH and O, obtained from competitive reactions of SO 2 with CO and O 2 , were 5.4 x 10 11 cm 3 .mol -1 .sec -1 and 5.0 x 10 11 cm 3 .mol -1 .sec -1 , respectively. (auth.)

7-[3-(4-[2,3-dimethylphenyl]piperazinyl)propoxy]-2 (1H)-quinolinone (OPC-4392), a presynaptic dopamine autoreceptor agonist and postsynaptic D2 receptor antagonist

International Nuclear Information System (INIS)

Yasuda, Y.; Kikuchi, T.; Suzuki, S.; Tsutsui, M.; Yamada, K.; Hiyama, T.

1988-01-01

The assertion that OPC-4392 acts as an agonist at presynaptic dopamine autoreceptors is supported by the following behavioral and biochemical observations: OPC-4392, 3-PPP and apomorphine inhibited the reserpine-induced increase in DOPA accumulation in the forebrain of mice and in the frontal cortex, limbic forebrain and striatum of rats. In addition, the gamma-butyrolactone (GBL)-induced increase in DOPA accumulation in the mouse forebrain was also inhibited by OPC-4392, 3-PPP and apomorphine. The inhibitory effect of OPC-4392 on GBL-induced DOPA accumulation lasted for at least 8 hours after oral administration to mice, while that of 3-PPP and apomorphine disappeared in 4 hours after subcutaneous injection. OPC-4392 failed to increase spontaneous motor activity in reserpinized mice, enhance spontaneous ipsilateral rotation in rats with unilateral striatal kainic acid (KA) lesions, induce contralateral rotation in rats with unilateral striatal 6-hydroxydopamine (6-OHDA) lesions and inhibit 14 C-acetylcholine (Ach) release stimulated by 20 mM KCl in rat striatal slices

High temperature investigation of the solid/liquid transition in the PuO2-UO2-ZrO2 system

Science.gov (United States)

Quaini, A.; Guéneau, C.; Gossé, S.; Sundman, B.; Manara, D.; Smith, A. L.; Bottomley, D.; Lajarge, P.; Ernstberger, M.; Hodaj, F.

2015-12-01

The solid/liquid transitions in the quaternary U-Pu-Zr-O system are of great interest for the analysis of core meltdown accidents in Pressurised Water Reactors (PWR) fuelled with uranium-dioxide and MOX. During a severe accident the Zr-based cladding can become completely oxidised due to the interaction with the oxide fuel and the water coolant. In this framework, the present analysis is focused on the pseudo-ternary system UO2-PuO2-ZrO2. The melting/solidification behaviour of five pseudo-ternary and one pseudo-binary ((PuO2)0.50(ZrO2)0.50) compositions have been investigated experimentally by a laser heating method under pre-set atmospheres. The effects of an oxidising or reducing atmosphere on the observed melting/freezing temperatures, as well as the amount of UO2 in the sample, have been clearly identified for the different compositions. The oxygen-to-metal ratio is a key parameter affecting the melting/freezing temperature because of incongruent vaporisation effects. In parallel, a detailed thermodynamic model for the UO2-PuO2-ZrO2 system has been developed using the CALPHAD method, and thermodynamic calculations have been performed to interpret the present laser heating results, as well as the high temperature behaviour of the cubic (Pu,U,Zr)O2±x-c mixed oxide phase. A good agreement was obtained between the calculated and experimental data points. This work enables an improved understanding of the major factors relevant to severe accident in nuclear reactors.

Low-Temperature Oxidation of H2/CH4/C2H6/Ethanol/DME: Experiments and Modelling at High Pressures

DEFF Research Database (Denmark)

Hashemi, Hamid; Christensen, Jakob M.; Glarborg, Peter

2015-01-01

The main aim of this work was to measure the oxidation characteristics of H2, CH4, C2H6, DME,and ethanol at high pressures (20—100 bar) and low to intermediate temperatures (450—900K) in a laminar flow reactor. Furthermore, a detailed chemical kinetic model was sought to address the oxidation of ...

NO accumulation alleviates H2 O2 -dependent oxidative damage induced by Ca(NO3 )2 stress in the leaves of pumpkin-grafted cucumber seedlings.

Science.gov (United States)

Li, Lin; Shu, Sheng; Xu, Qing; An, Ya-Hong; Sun, Jin; Guo, Shi-Rong

2017-05-01

Nitric oxide (NO) and hydrogen peroxide (H 2 O 2 ), two important signaling molecules, are stimulated in plants by abiotic stresses. In this study, we investigated the role of NO and its interplay with H 2 O 2 in the response of self-grafted (S-G) and salt-tolerant pumpkin-grafted (Cucurbita maxima × C. moschata) cucumber seedlings to 80 mM Ca(NO 3 ) 2 stress. Endogenous NO and H 2 O 2 production in S-G seedlings increased in a time-dependent manner, reaching maximum levels after 24 h of Ca(NO 3 ) 2 stress. In contrast, a transient increase in NO production, accompanied by H 2 O 2 accumulation, was observed at 2 h in rootstock-grafted plants. N w -Nitro-l-Arg methyl ester hydrochloride (l-NAME), an inhibitor of nitric oxide synthase (NOS), tungstate, an inhibitor of nitrate reductase (NR), and 2-(4-carboxyphenyl)-4,4,5,5-tetramethy-limidazoline-1-oxyl-3-oxide (cPTIO), a scavenger of NO, were found to significantly inhibit NO accumulation induced by salt stress in rootstock-grafted seedlings. H 2 O 2 production was unaffected by these stress conditions. Ca(NO 3 ) 2 stress-induced NO accumulation was blocked by pretreatment with an H 2 O 2 scavenger (dimethylthiourea, DMTU) and an inhibitor of NADPH oxidase (diphenyleneiodonium, DPI). In addition, maximum quantum yield of PSII (Fv/Fm), as well as the activities and transcript levels of antioxidant enzymes, were significantly decreased by salt stress in rootstock grafted seedlings after pretreatment with these above inhibitors; antioxidant enzyme transcript levels and activities were higher in rootstock-grafted seedlings compared with S-G seedlings. These results suggest that rootstock grafting could alleviate the oxidative damage induced by Ca(NO 3 ) 2 stress in cucumber seedlings, an effect that may be attributable to the involvement of NO in H 2 O 2 -dependent antioxidative metabolism. © 2016 Scandinavian Plant Physiology Society.

Phase equilibrium of PuO2-x - Pu2O3 based on first-principles calculations and configurational entropy change

International Nuclear Information System (INIS)

Minamoto, Satoshi; Kato, Masato; Konashi, Kenji

2011-01-01

Combination of an oxygen vacancy formation energy calculated using first-principles approach and the configurational entropy change treated within the framework of statistical mechanics gives an expression of the Gibbs free energy at large deviation from stoichiometry of plutonium oxide PuO 2 . An oxygen vacancy formation energy 4.20 eV derived from our previously first-principles calculation was used to evaluate the Gibbs free energy change due to oxygen vacancies in the crystal. The oxygen partial pressures then can be evaluated from the change of the free energy with two fitting parameters (a vacancy-vacancy interaction energy and vibration entropy change due to induced vacancies). Derived thermodynamic expression for the free energy based on the SGTE thermodynamic data for the stoichiometric PuO 2 and the Pu 2 O 3 compounds was further incorporated into the CALPHAD modeling, then phase equilibrium between the stoichiometric Pu 2 O 3 and non-stoichiometric PuO 2-x were reproduced.

Nido-Carborane building-block reagents. 2. Bulky-substituent (alkyl)2C2B4H6 derivatives and (C6H5)2C2B4H6: synthesis and properties

International Nuclear Information System (INIS)

Boyter, H.A. Jr.; Grimes, R.N.

1988-01-01

The preparation and chemistry of nido-2,3-R 2 C 2 C 2 B 4 H 6 carboranes in which R is n-butyl, isopentyl, n-hexyl, and phenyl was investigated in order to further assess the steric and electronic influence of the R groups on the properties of the nido-C 2 B 4 cage, especially with respect to metal complexation at the C 2 B 3 face and metal-promoted oxidative fusion. The three dialkyl derivatives were prepared from the corresponding dialkylacetylenes via reaction with B 5 H 9 and triethylamine, but the diphenyl compound could not be prepared in this manner and was obtained instead in a thermal reaction of B 5 H 9 with diphenylacetylene in the absence of amine. All four carboranes are readily bridge-deprotonated by NaH in THF, and the anions of the dialkyl species, on treatment with FeCl 2 and air oxidation, generate the respective R 4 C 4 B 8 H 8 carborane fusion products were R = n-C 4 H 9 , i-C 5 H 11 or n-C 6 H 13 . The diphenylcarborane anion Ph 2 C 2 B 4 H 5 - did not form detectable metal complexes with Fe 2+ , Co 2+ , or Ni 2+ , and no evidence of a Ph 4 C 4 B 8 H 8 fusion product has been found. Treatment of Ph 2 C 2 B 4 H 6 with Cr(CO) 6 did not lead to metal coordination of the phenyl rings, unlike (PhCH 2 ) 2 C 2 B 4 H 6 , which had previously been shown to form mono- and bis(tricarbonylchromium) complexes. However, the reaction of Ph 2 C 2 B 4 H 5 - , CoCl 2 , and (PhPCH 2 ) 2 did give 1,1-(Ph 2 PCH 2 ) 2 -1-Cl-1,2,3-Co(Ph 2 C 2 B 4 H 4 ), the only case in which metal complexation of the diphenylcarborane was observed. 14 references, 3 figures, 3 tables

Toxicity of inhaled 239PuO2 in Fischer 344 rats

International Nuclear Information System (INIS)

Redman, H.C.; Boecker, B.B.; Muggenburg, B.A.; Griffith, W.C.; Guilmette, R.A.; Mewhinney, J.A.; Scott, B.R.

1979-01-01

Studies on the biological effects of inhaled particles of 239 PuO 2 have been initiated in the Fischer 344 rat. To obtain information on the importance of homogeneity or nonhomogeneity of radiation dose to the lung, young adult (84 +- 7 days) animals have been exposed to monodisperse aerosols (sigma/sub g/ 239 PuO 2 of 1.0 and 2.8 μm aerodynamic diameter (AD). To determine the effects of age at exposure, aged rats (600 to 660 days) have been exposed to monodisperse aerosols of 239 PuO 2 of 1.0 μm aerodynamic diameter. To date, 480 young adult rats have been exposed to 239 PuO 2 : 240 rats to 1.0 μm AD particles and 240 rats to 2.85 μm AD particles. The projected exposure level ranged from 0.012 to 0.115 μCi/kg body weight. One hundred sixty rats were sham-exposed and maintained as controls. Also, 240 aged rats have been exposed to date to 1.0 μm AD particles of 239 PuO 2 . The projected activity level ranged from 0.012 to 0.115 μCi/kg body weight. Eighty rats were sham-exposed and maintained as controls. In addition, a serial sacrifice study to determine radiation-dose pattern in rats resulting from the inhalation of these monodisperse aerosols of 239 PuO 2 has been initiated in the young adult rat

Direct fabrication of 238PuO2 fuel forms

International Nuclear Information System (INIS)

Burney, G.A.; Congdon, J.W.

1982-07-01

The current process for the fabrication of 238 PuO 2 heat sources includes precipitation of small particle plutonium oxalate crystals (4 to 6 μm diameter), a calcination to PuO 2 , ball milling, cold pressing, granulation (60 to 125 μm), and granule sintering prior to hot pressing the fuel pellet. A new two-step direct-strike Pu(III) oxalate precipitation method which yields mainly large well-developed rosettes (50 to 100 μm diameter) has been demonstrated in the laboratory and in the plant. These large rosettes are formed by agglomeration of small (2 to 4 μm) crystals, and after calcining and sintering, were directly hot pressed into fuel forms, thus eliminating several of the powder conditioning steps. Conditions for direct hot pressing of the large heat-treated rosettes were determined and a full-scale General Purpose Heat Source pellet was fabricated. The pellet had the desired granule-type microstructure to provide dimensional stability at high temperature. 27 figures

Semiconducting perovskites (2-XC6H4C2H4NH3)2SnI4 (X = F, Cl, Br): steric interaction between the organic and inorganic layers.

Science.gov (United States)

Xu, Zhengtao; Mitzi, David B; Dimitrakopoulos, Christos D; Maxcy, Karen R

2003-03-24

Two new semiconducting hybrid perovskites based on 2-substituted phenethylammonium cations, (2-XC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) (X = Br, Cl), are characterized and compared with the previously reported X = F compound, with a focus on the steric interaction between the organic and inorganic components. The crystal structure of (2-ClC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) is solved in a disordered subcell [C2/m, a = 33.781(7) A, b = 6.178(1) A, c = 6.190(1) A, beta = 90.42(3)(o), and Z = 2]. The structure is similar to the known (2-FC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) structure with regard to both the conformation of the organic cations and the bonding features of the inorganic sheet. The (2-BrC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) system adopts a fully ordered monoclinic cell [P2(1)/c, a = 18.540(2) A, b = 8.3443(7) A, c = 8.7795(7) A, beta = 93.039(1)(o), and Z = 2]. The organic cation adopts the anti conformation, instead of the gauche conformation observed in the X = F and Cl compounds, apparently because of the need to accommodate the additional volume of the bromo group. The steric effect of the bromo group also impacts the perovskite sheet, causing notable distortions, such as a compressed Sn-I-Sn bond angle (148.7(o), as compared with the average values of 153.3 and 154.8(o) for the fluoro and chloro compounds, respectively). The optical absorption features a substantial blue shift (lowest exciton peak: 557 nm, 2.23 eV) relative to the spectra of the fluoro and chloro compounds (588 and 586 nm, respectively). Also presented are transport properties for thin-film field-effect transistors (TFTs) based on spin-coated films of the two hybrid semiconductors.

Insights into the degradation of (CF3)2CHOCH3 and its oxidative product (CF3)2CHOCHO & the formation and catalytic degradation of organic nitrates

Science.gov (United States)

Bai, Feng-Yang; Jia, Zi-Man; Pan, Xiu-Mei

2018-06-01

In this work, a systematic investigation of the atmospheric oxidation mechanism of (CF3)2CXOCH3 and their oxidative products (CF3)2CXOCHO (X = H, F) initiated by OH radical or Cl atom is performed by density functional theory. This study reveals that the introduction of NO and O2 promotes the formation of organic nitrates, which are hygroscopic and are inclined to form secondary organic aerosols (SOA) and can affect the air quality. The rate constants of the individual reactions are found to be in agreement with the experimental results. One of the intriguing findings of this work is that the peroxynitrite of (CF3)2CHOCH2OONO formed from the subsequent reactions of (CF3)2CHOCH3 is more favorable to isomerize to organic nitrate (CF3)2CHOCH2ONO2 than to dissociate into alkoxy radical (CF3)2CHOCH2O and NO2 because of the lower energy barrier of isomerization. The second significant observation is that the organic nitrate can be degraded more favorably with the presence of NH3, CH3NH2, and CH3NHCH3 than its naked decomposition reaction (CF3)2CHOCH2ONO2→(CF3)2CHOCHO + HONO. The ammonium salt, a vital part of haze, is harmful to human health and can be formed in the existence of the NH3, CH3NH2, and CH3NHCH3. In addition, the toxic substance of peroxyalkyl nitrate (CF3)2CHOC(O)ONO2 which can reduce the visibility of the atmosphere is produced as the primary subsequent oxidation product of (CF3)2CHOCHO in a NO-rich environment. The main species detected experimentally are confirmed by this study. The computational results are crucial to risk assessment and pollution prevention of the volatile organic compounds (VOCs).

Conformational isomerism in mixed-ligand complexes of 2,2'-bipyridine and triphenylphosphine with copper(I) halides

International Nuclear Information System (INIS)

Barron, P.F.; Engelhardt, L.M.; Healy, P.C.; Kildea, J.D.; White, A.H.

1988-01-01

Mixed-ligand complexes of triphenylphosphine and 2,2'-bipyridine and copper(I) halides have been synthesized. The 31 P NMR spectra of the complexes were measured and are reported along with data for complete structural characterization of the complexes. The results indicate a novel dichotomy of conformational isomers to be present in the chloride lattice. The Cu-P bond length was found to not vary with different halides. 8 refs., 4 figs., 6 tabs

Glucose-6-phosphate dehydrogenase deficiency does not increase the susceptibility of sperm to oxidative stress induced by H2O2.

Science.gov (United States)

Roshankhah, Shiva; Rostami-Far, Zahra; Shaveisi-Zadeh, Farhad; Movafagh, Abolfazl; Bakhtiari, Mitra; Shaveisi-Zadeh, Jila

2016-12-01

Glucose-6-phosphate dehydrogenase (G6PD) deficiency is the most common human enzyme defect. G6PD plays a key role in the pentose phosphate pathway, which is a major source of nicotinamide adenine dinucleotide phosphate (NADPH). NADPH provides the reducing equivalents for oxidation-reduction reductions involved in protecting against the toxicity of reactive oxygen species such as H 2 O 2 . We hypothesized that G6PD deficiency may reduce the amount of NADPH in sperms, thereby inhibiting the detoxification of H 2 O 2 , which could potentially affect their motility and viability, resulting in an increased susceptibility to infertility. Semen samples were obtained from four males with G6PD deficiency and eight healthy males as a control. In both groups, motile sperms were isolated from the seminal fluid and incubated with 0, 10, 20, 40, 60, 80, and 120 µM concentrations of H 2 O 2 . After 1 hour incubation at 37℃, sperms were evaluated for motility and viability. Incubation of sperms with 10 and 20 µM H 2 O 2 led to very little decrease in motility and viability, but motility decreased notably in both groups in 40, 60, and 80 µM H 2 O 2 , and viability decreased in both groups in 40, 60, 80, and 120 µM H 2 O 2 . However, no statistically significant differences were found between the G6PD-deficient group and controls. G6PD deficiency does not increase the susceptibility of sperm to oxidative stress induced by H 2 O 2 , and the reducing equivalents necessary for protection against H 2 O 2 are most likely produced by other pathways. Therefore, G6PD deficiency cannot be considered as major risk factor for male infertility.

Progesterone amplifies oxidative stress signal and promotes NO production via H2O2 in mouse kidney arterial endothelial cells.

Science.gov (United States)

Yuan, Xiao-Hua; Fan, Yang-Yang; Yang, Chun-Rong; Gao, Xiao-Rui; Zhang, Li-Li; Hu, Ying; Wang, Ya-Qin; Jun, Hu

2016-01-01

The role of progesterone on the cardiovascular system is controversial. Our present research is to specify the effect of progesterone on arterial endothelial cells in response to oxidative stress. Our result showed that H2O2 (150 μM and 300 μM) induced cellular antioxidant response. Glutathione (GSH) production and the activity of Glutathione peroxidase (GPx) were increased in H2O2-treated group. The expression of glutamate cysteine ligase catalytic subunit (GCLC) and modifier subunit (GCLM) was induced in response to H2O2. However, progesterone absolutely abolished the antioxidant response through increasing ROS level, inhibiting the activity of Glutathione peroxidase (GPx), decreasing GSH level and reducing expression of GClC and GCLM. In our study, H2O2 induced nitrogen monoxide (NO) production and endothelial nitric oxide synthase (eNOS) expression, and progesterone promoted H2O2-induced NO production. Progesterone increased H2O2-induced expression of hypoxia inducible factor-α (HIFα) which in turn regulated eNOS expression and NO synthesis. Further study demonstrated that progesterone increased H2O2 concentration of culture medium which may contribute to NO synthesis. Exogenous GSH decreased the content of H2O2 of culture medium pretreated by progesterone combined with H2O2 or progesterone alone. GSH also inhibited expression of HIFα and eNOS, and abolished NO synthesis. Collectively, our study demonstrated for the first time that progesterone inhibited cellular antioxidant effect and increased oxidative stress, promoted NO production of arterial endothelial cells, which may be due to the increasing H2O2 concentration and amplified oxidative stress signal. Copyright © 2015. Published by Elsevier Ltd.

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

Science.gov (United States)

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

2016-08-01

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

On silvation and thermal transformations of B10H12(PPh3)2

International Nuclear Information System (INIS)

Il'inchik, E.A.; Dunaev, S.T.; Myakishev, K.G.; Asanov, I.P.

1994-01-01

It is shown, that exchange reaction between B 10 H 12 (SMe 2 ) 2 and triphenylphospohine is benzene leads to formation of B 10 H 12 (PPh 3 ) 2 xPh solvate during B 10 H 12 (PPh 3 ) 2 synthesis. B 10 H 12 (PPh 3 ) 2 x0.7CHCl 3 is prepared by recrystallization of the latest solvate from chloroform, B 10 H 12 (PPh 3 ) 2 - from acetone. The composition is fixed after vacuum drying (1.3 Pa; 60 deg). In all cases, prepared crystals are amorphous ones. Pyrolysis of B 10 H 12 (PPh 3 ) 2 at 250 deg is accompained by the loss of 4 hydrogen and 0.05 triphenylphosphine moles. Besides hydrogen, benzene and methane are determined in gaseous phase. Formation of boron carbide and phosphide in solid phase at 750 deg isn't observed

Electronic and electrochemical properties of platinum(II) and platinum-mercury-carboxylato complexes containing 2-Me2NCH2C6H4, 2,6-(Me2NCH2)2C6H3- and 2-Me2NC6H4CH2 - ligands

NARCIS (Netherlands)

Koten, G. van; Ploeg, A.F.M.J. van der; Schmitz, J.E.J.; Linden, J.G.M. van der

1982-01-01

The organoplatinum(II) compounds [{2, 6-(Me{2}NCH{2}){2}C{6}H{3}}PtBr] and cis-[(C-N){2}Pt] (C-N = 2-Me{2}NCH{2}C{6}H{4}, 2-Me{2}NC{6}H{4}CH{2}) can be chemically irreversibly oxidized in the potential range 1.00 to 1.35 V vs. an Ag/AgCl electrode, whereas the organoplatinum@?mercury complexes

Thermal durability of OPC pastes admixed with nano iron oxide

Directory of Open Access Journals (Sweden)

Ahmed A. Amer

2015-08-01

Full Text Available Nanotechnology helps in producing materials with prospective properties, for each field of science (physics, chemistry, bio-science as well as construction materials. Nanoparticles belong to the materials in the field of civil engineering which have a high surface area to provide high chemical reactivity. Some researchers have employed nanoparticles into cementitious materials based on ordinary Portland cement to modify the properties of this system. They have important advantages for the hydration and microstructure of cement paste to increase the rate of hydration and the amount of formed CSH gel. The aim of this work is to investigate the influence of NF on the fire resistance of OPC pastes. The NF was synthesized by thermal decomposition of basic ferric acetate fired at 275, 600 and 800 °C. The crystal size of the prepared NF as previously determined was 14.6, 16.98 and 18.68 nm, respectively. OPC admixed with 1 wt% NF prepared at 275 °C gives the higher fire resistance than those admixed with 2 or 3 wt%. It shows the higher bulk density, compressive strength and lower porosity up to 450 °C than the blank OPC. As the firing temperature of NF increases the fire resistance diminishes.

Inhaled 239PuO2 in rats with pulmonary emphysema. II

International Nuclear Information System (INIS)

Lundgren, D.L.; Mauderly, J.L.; Carlton, W.W.; Hahn, F.F.

1988-01-01

The modifying effects of pre-existing pulmonary emphysema on deposition, distribution, retention, and effects of inhaled 239 PuO 2 in the rat were investigated. The presence of emphysema in the rats tested was indicated by respiratory function measurements and confirmed microscopically. Initial lung burdens of 239 Pu per kg body weight were less in rats with emphysema than in control rats; however, the retention of 239 Pu was similar in emphysematous and control rats. Survival and lung tumor occurrence were similar in emphysematous and control rats exposed to 239 PuO 2 . We concluded that rats with pre-existing pulmonary emphysema were not more sensitive to the effects of inhaled 239 PuO 2 than control rats. (author)

Plutonium oxide dissolution

International Nuclear Information System (INIS)

Gray, J.H.

1992-01-01

Several processing options for dissolving plutonium oxide (PuO 2 ) from high-fired materials have been studied. The scoping studies performed on these options were focused on PuO 2 typically generated by burning plutonium metal and PuO 2 produced during incineration of alpha contaminated waste. At least two processing options remain applicable for dissolving high-fired PuO 2 in canyon dissolvers. The options involve solid solution formation of PuO 2 With uranium oxide (UO 2 ) and alloying incinerator ash with aluminum. An oxidative dissolution process involving nitric acid solutions containing a strong oxidizing agent, such as cerium (IV), was neither proven nor rejected. This uncertainty was due to difficulty in regenerating cerium (IV) ions during dissolution. However, recent work on silver-catalyzed dissolution of PuO 2 with persulfate has demonstrated that persulfate ions regenerate silver (II). Use of persulfate to regenerate cerium (IV) or bismuth (V) ions during dissolution of PuO 2 materials may warrant further study

The transportation of PuO2 and MOX fuel and management of irradiated MOX fuel

International Nuclear Information System (INIS)

Dyck, H.P.; Rawl, R.; Durpel, L. van den

2000-01-01

Information is given on the transportation of PuO 2 and mixed-oxide (MOX) fuel, the regulatory requirements for transportation, the packages used and the security provisions for transports. The experience with and management of irradiated MOX fuel and the reprocessing of MOX fuel are described. Information on the amount of MOX fuel irradiated is provided. (author)

Nqrs Data for C3H2Cl10N2PSb[C3HCl4N2P·Cl6HSb](Subst. No. 0601)

Science.gov (United States)

Chihara, H.; Nakamura, N.

This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C3H2Cl10N2PSb [C3HCl4N2P·Cl6HSb] (Subst. No. 0601)

Shrinkage behaviour and related corrosion performance of low-pH cementitious materials based on OPC or CAC

Directory of Open Access Journals (Sweden)

García-Calvo, J. L.

2016-03-01

Full Text Available Prior to using low-pH cementitious materials in underground repositories for high level waste, the characteristics determining their long-term durability must be analysed in depth. In this sense, different shrinkage tests have been made on mortar and concrete specimens using low-pH cement formulations based on ordinary portland cement (OPC or calcium aluminate cement (CAC, with high mineral admixtures contents. They showed similar autogenous shrinkage than samples without mineral admixtures but higher drying shrinkage when materials based on OPC with high silica fume contents were considered. Besides, as the use of reinforced concrete could be required in underground repositories, the susceptibility of reinforcement to corrosion when using low-pH cementitious materials based on OPC was analyzed, considering carbon steel and galvanized steel. In the formers corrosion was detected due to the low pore solution pH but any problem was detected when galvanized reinforcement were used.Previo al empleo de materiales con cementos de bajo pH en almacenamientos geológicos profundos (AGP de residuos radiactivos de alta actividad, características relacionadas con su durabilidad a largo plazo deben ser verificadas. Así, su estabilidad volumétrica se ha analizado en morteros y hormigones de bajo pH basados en OPC o CAC, con elevados contenidos de adiciones minerales. Estos presentaron retracciones autógenas similares a las medidas en materiales convencionales, pero retracciones por secado mayores en los basados en OPC y altos contenidos de humo de sílice. Dado que en zonas de los AGP podría emplearse hormigón armado, también se evaluó la susceptibilidad a la corrosión de aceros al carbono y aceros galvanizados en materiales de bajo pH basados en OPC. Se detectó un inicio temprano de corrosión en los primeros debido al bajo pH presente en el fluido de los poros de estos materiales, sin detectarse problemas al emplear aceros galvanizados.

Optical spectroscopy of two-dimensional layered (C(6)H(5)C(2)H(4)-NH(3))(2)-PbI(4) perovskite.

Science.gov (United States)

Gauthron, K; Lauret, J-S; Doyennette, L; Lanty, G; Al Choueiry, A; Zhang, S J; Brehier, A; Largeau, L; Mauguin, O; Bloch, J; Deleporte, E

2010-03-15

We report on optical spectroscopy (photoluminescence and photoluminescence excitation) on two-dimensional self-organized layers of (C(6)H(5)C(2)H(4)-NH(3))(2)-PbI(4) perovskite. Temperature and excitation power dependance of the optical spectra gives a new insight into the excitonic and the phononic properties of this hybrid organic/inorganic semiconductor. In particular, exciton-phonon interaction is found to be more than one order of magnitude higher than in GaAs QWs. As a result, photoluminescence emission lines have to be interpreted in the framework of a polaron model.

Finite element analysis of local overheating within plutonium enriched UO2 fuel rods caused by PuO2 islands

International Nuclear Information System (INIS)

Sarmiento, G.S.

1980-01-01

Within natural UO 2 fuel elements enriched with plutonium, this last material should form PuO 2 solid solutions inside the UO 2 pellets, in a wide range of concentrations. If the solutions are obtained by mechanical mixing of the oxides, PuO 2 islands are formed in the UO 2 matrix. These islands may be the source of several problems in the fuel behaviour, the most important being the overheating of the matrix in the neighbourhood of the particles. It is caused by the large fission cross section of plutonium compared with that of uranium. A detailed study of the thermal effects produced by PuO 2 particles in the UO 2 matrix and the cladding is then important for the specification of their permissible size. A portion of the fuel rods with spherical particles in the most significant places was studied. In order to obtain the dimensionless overheating of the fuel and cladding produced by the presence of those particles, the spatial distribution of temperature was calculated, solving the stationary and linear bidimensional equation of heat conducting using a finite element code. Several geometrical variables and material properties have been taken as dimensionless parameters. A satisfactory convergence of the numerical results to an asymptotic limit with a well-known exact solution, has been obtained. (orig.)

Antiviral activity of 3(2H- and 6-chloro-3(2H-isoflavenes against highly diverged, neurovirulent vaccine-derived, type2 poliovirus sewage isolates.

Directory of Open Access Journals (Sweden)

Lester M Shulman

Full Text Available BACKGROUND: Substituted flavanoids interfere with uncoating of Enteroviruses including Sabin-2 polio vaccine strains. However flavanoid resistant and dependent, type-2 polio vaccine strains (minimally-diverged, emerged during in vitro infections. Between 1998-2009, highly-diverged (8 to >15% type-2, aVDPV(2s, from two unrelated persistent infections were periodically isolated from Israeli sewage. AIM: To determine whether highly evolved aVDPV(2s derived from persistent infections retained sensitivity to isoflavenes. METHODS: Sabin-2 and ten aVDPV(2 isolates from two independent Israeli sources were titered on HEp2C cells in the presence and absence of 3(2H- Isoflavene and 6-chloro-3(2H-Isoflavene. Neurovirulence of nine aVDPV(2s was measured in PVR-Tg-21 transgenic mice. Differences were related to unique amino acid substitutions within capsid proteins. PRINCIPAL FINDINGS: The presence of either flavanoid inhibited viral titers of Sabin-2 and nine of ten aVDPV(2s by one to two log(10. The tenth aVDPV(2, which had unique amino acid substitution distant from the isoflavene-binding pocket but clustered at the three- and five-fold axies of symmetry between capsomeres, was unaffected by both flavanoids. Genotypic neurovirulence attenuation sites in the 5'UTR and VP1 reverted in all aVDPV(2s and all reacquired a full neurovirulent phenotype except one with amino acid substitutions flanking the VP1 site. CONCLUSION: Both isoflavenes worked equally well against Sabin 2 and most of the highly-diverged, Israeli, aVDPV(2s isolates. Thus, functionality of the hydrophobic pocket may be unaffected by selective pressures exerted during persistent poliovirus infections. Amino acid substitutions at sites remote from the drug-binding pocket and adjacent to a neurovirulence attenuation site may influence flavanoid antiviral activity, and neurovirulence, respectively.

Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

Directory of Open Access Journals (Sweden)

J. N. Crowley

2012-01-01

Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

Frequency analysis of pulmonary tumors occurrence at the rat after exposure to actinide oxide aerosols. Risk factors identification by comparing NpO2 and PuO2

International Nuclear Information System (INIS)

Dudoignon, N.

2001-07-01

Inhalation of actinide oxide particles is potentially one route of contamination of workers, which might induce pulmonary tumours due to aerosol generation during nuclear fuel fabrication process. Dose-effect relationships for lung tumour induction have been well established from epidemiological and experimental studies. However, they do not take into account specific parameters of exposure. The aim of this study was to compare cancer incidence among groups of rats exposed either to NpO 2 or to PuO 2 , two actinide oxides with different specific activity, but with similar aerosol granulometry. During the rat life-span, lung tumour development could occur and the individual follow-up allowed the determination of lung dose at death. Although aerosol particle sizes were similar, the mean number of particles per unit of activity was 2400 times higher for NpO 2 as compared to PuO 2 . This range of variation appeared higher than the variation of specific activity (450). Initial distribution of aerosol was then much more homogeneous for neptunium. In the range of initial lung deposits studied, the only physiological changes observed concerned lung clearance and rat life- span after exposure to the highest levels of Np activity. Pathological examination performed at death showed that carcinogenic power of neptunium was 2 to 3 times higher than that of plutonium. Dose-effect relationships appeared linear and when compared to previous studies, showed an increase of lung cancer risk as the specific activity of the inhaled actinide oxide decreases. The range of risk variation can reach a factor of 10, revealing that the consideration of lung dose at death solely might not be sufficient for an accurate estimate of risk and that specific parameters of exposure, such as nature and granulometry of aerosols, should also be taken into account. (author)

[(H2O)(terpy)Mn(μ-O)2Mn(terpy)(OH2)](NO3)3 (terpy = 2,2′:6,2″-terpyridine) and its relevance to the oxygen-evolving complex of photosystem II examined through pH dependent cyclic voltametry

Science.gov (United States)

Cady, Clyde W.; Shinopoulos, Katherine E.; Crabtree, Robert H.; Brudvig, Gary W.

2010-01-01

Photosynthetic water oxidation occurs naturally at a tetranuclear manganese center in the photosystem II protein complex. Synthetically mimicking this tetramanganese center, known as the oxygen-evolving complex (OEC), has been an ongoing challenge of bioinorganic chemistry. Most past efforts have centered on water-oxidation catalysis using chemical oxidants. However, solar energy applications have drawn attention to electrochemical methods. In this paper, we examine the electrochemical behavior of the biomimetic water-oxidation catalyst [(H2O)(terpy)Mn(μ-O)2Mn(terpy)(H2O)](NO3)3 [terpy = 2,2′:6′,2″-terpyridine] (1) in water under a variety of pH and buffered conditions and in the presence of acetate that binds to 1 in place of one of the terminal water ligands. These experiments will show that 1 not only exhibits proton-coupled electron-transfer reactivity analogous to the OEC, but also may be capable of electrochemical oxidation of water to oxygen. PMID:20372724

Density functional study on the heterogeneous oxidation of NO over α-Fe_2O_3 catalyst by H_2O_2: Effect of oxygen vacancy

International Nuclear Information System (INIS)

Song, Zijian; Wang, Ben; Yu, Jie; Ma, Chuan; Zhou, Changsong; Chen, Tao; Yan, Qianqian; Wang, Ke; Sun, Lushi

2017-01-01

Highlights: • NO and H_2O_2 adsorption on perfect and oxygen defect α-Fe_2O_3 (0 0 1) surface were studied by DFT calculations. • H_2O_2 shows high chemical reactivity for its adsorption on oxygen defect α-Fe_2O_3 (0 0 1) surface. • Oxygen vacancy plays an important role of the catalytic oxidation of NO by H_2O_2 over the α-Fe_2O_3 catalyst surfaces. • Mechanism of NO oxidation over α-Fe_2O_3 (0 0 1) surface by H_2O_2 was explained. - Abstract: Catalytic oxidation with H_2O_2 is a promising method for NOx emission control in coal-fired power plants. Hematite-based catalysts are attracting increased attention because of their surface redox reactivity. To elucidate the NO oxidation mechanism on α-Fe_2O_3 surfaces, density functional theory (DFT) calculations were conducted by investigating the adsorption characteristics of nitric oxide (NO) and hydrogen peroxide (H_2O_2) on perfect and oxygen defect α-Fe_2O_3 (0 0 1) surfaces. Results show that NO was molecularly adsorbed on two kinds of surfaces. H_2O_2 adsorption on perfect surface was also in a molecular form; however, H_2O_2 dissociation occurred on oxygen defect α-Fe_2O_3 (0 0 1) surface. The adsorption intensities of the two gas molecules in perfect α-Fe_2O_3 (0 0 1) surface followed the order NO > H_2O_2, and the opposite was true for the oxygen defect α-Fe_2O_3 (0 0 1). Oxygen vacancy remarkably enhanced the adsorption intensities of NO and H_2O_2 and promoted H_2O_2 decomposition on catalyst surface. As an oxidative product of NO, HNO_2 was synthesized when NO and H_2O_2 co-adsorbed on the oxygen defect α-Fe_2O_3 (0 0 1) surface. Analyses of Mulliken population, electron density difference, and partial density of states showed that H_2O_2 decomposition followed the Haber–Weiss mechanism. The trends of equilibrium constants suggested that NO adsorption on α-Fe_2O_3 (0 0 1) surface was more favorable at low than at high temperatures, whereas H_2O_2 adsorption was favorable between 375 and

NDA PDP Program PuO2 increased particle size specification and design

International Nuclear Information System (INIS)

Marshall, R.S.; Taggart, D.P.; Becker, G.K.; Woon, W.Y.

1996-01-01

Provisions in the National TRU Program Quality Assurance Program Plan require an assessment of performance for nondestructive waste assay (NDA) systems employed in the program. This requirement is in part fulfilled through the use of Performance Demonstration programs. In order to optimize the quality and quantity of information acquired during a given Performance Demonstration Program cycle, the assessment employed is to be carefully specified and designed. The assessment must yield measurement system performance data meaningful with respect to NDA system capability to accommodate attributes of interest known to occur in actual waste forms. The design and specification of the increased particle size PuO 2 PDP working reference materials (WRMs) is directed at providing a straightforward mechanism to assess waste NDA system capability to account for biases introduced by large PuO 2 particles. The increased particle size PuO 2 PDP WRM design addresses actual waste form attributes associated with PuO 2 particle size and distributions thereof, the issue of a known and stable WRM configuration and equally important appropriate certification and tractability considerations

Bone tumors induced by inhalation of 238PuO2 in dogs

International Nuclear Information System (INIS)

Park, J.F.; Lund, J.E.; Ragan, H.A.; Hackett, P.L.; Frazier, M.E.

1976-01-01

Plutonium-238, an alpha-emitting radionuclide, is used as a heat source in thermoelectric power generators such as have been employed on lunar expeditions of communications satellites and in cardiac pacemakers. It has an 86.4 year half-life and emits 5.5 MeV alpha particles. Beagle dogs were given single 10 to 30 minute exposures to 238 PuO 2 aerosols to study the long-term translocation of plutonium and biologicl effects. Dogs with a terminal body burden ranging from 7 to 260 MuCi were euthanized due to respiratory insufficiency related to plutonium-induced pneumonitis during the first 3 years after exposure. Nine of the 11 dogs euthanized during the 4 to 6 year postexposure period had osteosarcomas. The terminal plutonium body burden in the tumor-bearing dogs ranged from 0.5 to 2.6 muCi with 30 to 55 percent of the plutonium in the skeleton. Experiments are in progress to further define the dose-effect relationship of inhaled 238 PuO 2 and investigate the mechanisms of plutonium-induced neoplasia

Toxicity of inhaled 238PuO2 I

International Nuclear Information System (INIS)

Diel, J.H.; Mewhinney, J.A.

1980-01-01

The deposition, retention, translocation and microscopic distribution of inhaled 238 PuO 2 particles were studied to better define the organs at risk and uniformity of dose and cell types or structures at risk in the lung. Beagle dogs were exposed once by inhalation to an aerosol of 238 PuO 2 with particle aerodynamic diameters of 0.7, 1.4, or 2.7 μm (+-10%). Initial burdens averaged about 700 nCi, a level not expected to induce life-shortening effects in Beagle dogs. Animals were sacrificed at times from 4 hours to 2 years after exposure. Whole body retention of plutonium and its distribution among organs in the sacrificed animals was determined by radiochemical analysis for plutonium content of excreta and tissue samples. The distribution of particles in lung was determined using autoradiographs of lung tissue sections and computer-assisted data collection and analysis. Soon after exposure, PuO 2 was relatively insoluble in lung with individual particles being randomly distributed throughout the lung. A distinct change in the rate of dissolution from lung occurred at about 100 days after exposure resulting in decreased pulmonary retention and increased uptake by liver and skeleton. Particle breakup was observed in autoradiographs for time periods in excess of 128 days after exposure. Broken up particles dissolved rapidly leaving little residue in the lung. The remaining particles were randomly distributed in the lung. These results are discussed in relation to current radiation protection guides for plutonium radionuclides. (author)

In Vitro and In Vivo Antibacterial Activities of OPC-20011, a Novel Parenteral Broad-Spectrum 2-Oxaisocephem Antibiotic

Science.gov (United States)

Matsumoto, Makoto; Tamaoka, Hisashi; Ishikawa, Hiroshi; Kikuchi, Mikio

1998-01-01

OPC-20011, a new parenteral 2-oxaisocephem antibiotic, has an oxygen atom at the 2- position of the cephalosporin frame. OPC-20011 had the best antibacterial activities against gram-positive bacteria, including methicillin-resistant Staphylococcus aureus (MRSA), Enterococcus faecalis, and penicillin-resistant Streptococcus pneumoniae: MICs at which 90% of the isolates were inhibited were 6.25, 6.25, and 0.05 μg/ml, respectively. Its activity is due to a high affinity of the penicillin-binding protein 2′ in MRSA, an affinity which was approximately 1,050 times as high as that for flomoxef. Against gram-negative bacteria, OPC-20011 also showed antibacterial activities similar to those of ceftazidime. The in vivo activities of OPC-20011 were comparable to or greater than those of reference compounds in murine models of systemic infection caused by gram-positive and -negative pathogens. OPC-20011 was up to 10 times as effective as vancomycin against MRSA infections in mice. This better in vivo efficacy is probably due to the bactericidal activity of OPC-20011, while vancomycin showed bacteriostatic activity against MRSA. OPC-20011 produced a significant decrease of viable counts in lung tissue at a dose of 2.5 mg/kg of body weight, an efficacy similar to that of ampicillin at a dose of 10 to 20 mg/kg on an experimental murine model of respiratory tract infection caused by non-ampicillin-susceptible S. pneumoniae T-0005. The better therapeutic efficacy of OPC-20011 was considered to be due to its potent antibacterial activity and low affinity for serum proteins of experimental animals (29% in mice and 6.4% in rats). PMID:9797230

Crystal structure of Sm(NO3)3x6H2O

International Nuclear Information System (INIS)

Espenbetov, A.A.; Gerr, R.G.; Struchkov, Yu.T.; Sal'nikova, N.A.; Akimov, V.M.; Odinets, Z.K.

1985-01-01

X-ray diffraction study of a salt, prepared when mixing concentrated nitric acid solutions of NaNO 3 and Sm(NO 3 ) 3 , has been carried out. It is established, that the salt is a concretion of two crystals: NaNO 3 and Sm(NO 3 ) 3 x6H 2 O (1). X-ray diffraction study of 1 is carried out (lambda Mo, diffractometer, 1511 reflections, the method of heavy atom, the least square method in anisotropic approximation up to R=0.0348). The crystals of 1 are triclinic: a=6.755, b=9.168, c=11.684 A, α=69.93, β=88.86, γ=69.28, Z=2, Fedorov group P anti 1. Symmetery of 10-vertex coordination polyhedron (CP) of Sm atom is close to Csub(s). Sm atom coordination can be described as 4;5:1. Four H 2 O molecules are included into CP, at the expense of two remaining H 2 O molecules CP are bound with each other

Nano crystalline ZnO catalyzed one pot three-component synthesis of 7-alkyl-6H,7H- naphtho[1',2':5,6]pyrano[3,2-c] chromen-6-ones under solvent-free conditions

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M. J. Piltan

2016-08-01

Full Text Available In the present paper, an efficient one-pot synthesis of 7-alkyl-6H,7H-naphtho[1',2':5,6]pyrano[3,2-c]chromen-6-ones is described by three-component reaction of β-naphthol, aromatic aldehydes and 4-hydroxycoumarin using ZnO nanoparticles under solvent-free conditions. The present method provides a novel and efficient procedure for the synthesis of chromene derivatives with some advantageous such as short reaction times, easy workup, high yields, wide range of products, reusability of the catalyst, little catalyst loading and green conditions in the presence of ZnO nanoparticles (7 mol% at 110 ºC.

Mobile Column Measurements of HCHO, NO2, NH3, and C2H6 in Colorado during FRAPPE

Science.gov (United States)

Kille, N.; Volkamer, R. M.; Baidar, S.; Ortega, I.; Sinreich, R.; Hannigan, J. W.; Cooper, O. R.; Nussbaumer, E.; Pfister, G.

2015-12-01

Gases from anthropogenic sources have the potential to have a profound impact on air quality. Emissions from large cattle feedlots and ONG (Oil and Natural Gas) sites are comprised of NH3 (ammonia) and C2H6 (ethane) as pollutants. C2H6 contributes to photochemical ozone (O3) production and oxidation production of HCHO (formaldehyde). NH3 is a major source for reactive nitrogen to form particulate matter 2.5, which negatively affects human health. NO2 (nitrogen dioxide), emitted during combustion, is considered a large-scale pollutant and contributes to the formation of O3. Deploying an innovative suite of remote sensing instruments in a mobile laboratory, a Multi Axis Differential Optical Absorption Spectrometer (MAX-DOAS), a UV-Vis Spectrometer, and a Fourier Transform Infrared Spectrometer, we obtain mobile column measurements at high spatial and temporal resolution, 2 seconds for the UV-Vis and IR spectrometers and 20 seconds for the MAX-DOAS. Within the scope of the Front Range Air Pollution and Photochemistry Experiment (FRAPPE) we measure total columns of HCHO, NO2, NH3, and C2H6 using the University of Colorado mobile laboratory. Emissions of urban areas, agriculture, and ONG sites were studied. For the measurement of total columns the solar occultation flux method has been applied. We measured significant variability in the columns. The measurement of total columns allows one to determine the emission flux and source strength when driving a closed box around or upwind and downwind of a source with the mobile laboratory. We present results from select research drives.

Structuring effects of [Ln6O(OH)8(NO3)6(H2O)12]2+ entities

International Nuclear Information System (INIS)

Guillou, O.; Daiguebonne, C.; Calvez, G.; Le Dret, F.; Car, P.-E.

2008-01-01

In order to obtain highly porous lanthanide-based coordination polymers we are currently investigating reactions between [Ln 6 O(OH) 8 (NO 3 ) 6 (H 2 O) 12 ] 2+ di-cationic hexanuclear entities and sodium salts of benzene-poly-carboxylic acids. Two new coordination polymers obtained during this study are reported here. In both cases, the hexanuclear entity has been destroyed during the reaction. However the resulting compounds are original thanks to a structuring effect of the poly-metallic complex. The first compound of chemical formula [Y 2 (C 8 H 4 O 4 ) 3 (DMF)(H 2 O)],2DMF crystallizes in the monoclinic system, space group P121/n (n o 14) with a = 16.0975(3) A, b = 14.4605(3) A, c = 17.7197(4) A, β = 92.8504(9) o and Z = 4. The second compound of chemical formula Y 2 (NO 3 ) 2 (C 10 H 2 O 8 )(DMF) 4 crystallizes in the triclinic system, space group P-1 (n o 2) with a = 7.5312(3) A, b = 9.0288(3) A, c = 13.1144(6) A, α = 92.6008(14) o , β = 94.9180(14) o , γ = 112.1824(16) o and Z = 2. Both crystal structures are 2D. Both crystal structures are described and the original structural features are highlighted and related to a potential structuring effect of the hexanuclear precursor

Rapid generation of OPC-like cells from human pluripotent stem cells for treating spinal cord injury.

Science.gov (United States)

Kim, Dae-Sung; Jung, Se Jung; Lee, Jae Souk; Lim, Bo Young; Kim, Hyun Ah; Yoo, Jeong-Eun; Kim, Dong-Wook; Leem, Joong Woo

2017-07-28

Remyelination via the transplantation of oligodendrocyte precursor cells (OPCs) has been considered as a strategy to improve the locomotor deficits caused by traumatic spinal cord injury (SCI). To date, enormous efforts have been made to derive OPCs from human pluripotent stem cells (hPSCs), and significant progress in the transplantation of such cells in SCI animal models has been reported. The current methods generally require a long period of time (>2 months) to obtain transplantable OPCs, which hampers their clinical utility for patients with SCI. Here we demonstrate a rapid and efficient method to differentiate hPSCs into neural progenitors that retain the features of OPCs (referred to as OPC-like cells). We used cell sorting to select A2B5-positive cells from hPSC-derived neural rosettes and cultured the selected cells in the presence of signaling cues, including sonic hedgehog, PDGF and insulin-like growth factor-1. This method robustly generated neural cells positive for platelet-derived growth factor receptor-α (PDGFRα) and NG2 (~90%) after 4 weeks of differentiation. Behavioral tests revealed that the transplantation of the OPC-like cells into the spinal cords of rats with contusive SCI at the thoracic level significantly improved hindlimb locomotor function. Electrophysiological assessment revealed enhanced neural conduction through the injury site. Histological examination showed increased numbers of axon with myelination at the injury site and graft-derived myelin formation with no evidence of tumor formation. Our method provides a cell source from hPSCs that has the potential to recover motor function following SCI.

Interactions of Plutonium Dioxide with Water and Oxygen-Hydrogen Mixtures

International Nuclear Information System (INIS)

Haschke, J.M.; Allen, T.H.

1999-01-01

Pressure-volume-temperature data and mass spectrometric results obtained during exposure of PuO 2 to D 2 O show that the dioxide reacts with water at room temperature to produce a higher oxide (PuO 2+x )and H 2 . Results demonstrate that PuO 2+x is the thermodynamically stable oxide in air. The absence of O 2 at detectable levels in the gas phase implies that radiolytic decomposition of water to the elements is not a significant reaction. The rate of the PuO 2 +H 2 O reaction is 6±4 nmol H 2 /m 2 day, a value that is independent of the H 2 O concentration on the oxide over a range that extends from fractional monolayer coverage to saturation by liquid water. Evaluation of literature data shows that oxide compositions in excess of PuO 2.25 are attained, but the maximum value of x is unknown. During exposure of PuO 2 to a 2:1 D 2 :O 2 mixture at room temperature, the elements combine by a process consistent with a surface-catalyzed reaction. Water is simultaneously formed by the H 2 +O 2 reaction and consumed by the PuO 2 + H 2 O reaction and accumulates until the opposing rates are equal. Thereafter, PuO 2+x is formed at a constant rate by the water-catalyzed PuO 2 + O 2 reaction. The failure of earlier attempts to prepare higher oxides of plutonium is discussed and the catalytic cycle that promotes the reaction of PuO 2 with O 2 is described. Implications of the results for extended storage and environmental chemistry of oxide are examined. Moisture-catalyzed oxidation of PuO 2 accounts for observation of both pressure increases and decreases in oxide storage containers with air atmospheres. Application of the experimental rate results indicates that the reaction of a typical oxide with 0.5 mass % of adsorbed water maybe complete after 25 to 50 years at room temperature

Synthesis and reactions of triphenylphosphine-O-benzophenonimine and derivatives

International Nuclear Information System (INIS)

Elamin, Manahil Babiker

1999-08-01

O-Amino benzophenone and its para and meta isomers were prepared using Friedl-Craft benzoylation. Their azides were also prepared via their diazonium salts. The azide of o-amino benzophenone in its reduced form (o-benzylaniline) and its cyclic ketal were synthesised. All azides thus formed were reacted separately with triphenylphosphine to give the corresponding phosphinimines, the Wittig reagents nitrogen analog. The reactivity of the phosphorous bond. (P=N) in the different phosphoranes were studied by two types of reactions: (1) the Wittig type of reaction using benzaldehyde and its into derivatives with each of the above prepared phosphinimines. While triphenylphosphine-m-benzophenonimine (ii) and the triphenylphosphine benzophenonimine ethylene acetal (v) and it's reduced form triphenylphosphine-o-benzophenonimine (iv) react giving the corresponding schiffis bases. However, the ortho (i) and the para (iii) isomers failed to react. This lack of reactivity is presumably due to their great stability which came about through the extensive resonance that reduced the nucleophilicity of the nitrogen nucleophiles. (2) The phophinimines each was irradiated using Hanovia medium pressure UV lamp. Also the ortho and para isomers were not affected while others reacted giving the corresponding azo-compound and triphenylphosphine. they were separated and detected by chromatography.(Author)

Three new d10 transition metal selenites containing PO4 tetrahedron: Cd7(HPO4)2(PO4)2(SeO3)2, Cd6(PO4)1.34(SeO3)4.66 and Zn3(HPO4)(SeO3)2(H2O)

Science.gov (United States)

Ma, Yun-Xiang; Gong, Ya-Ping; Hu, Chun-li; Mao, Jiang-Gao; Kong, Fang

2018-06-01

Three new d10 transition metal selenites containing PO4 tetrahedron, namely, Cd7(HPO4)2(PO4)2(SeO3)2 (1), Cd6(PO4)1.34(SeO3)4.66 (2) and Zn3(HPO4)(SeO3)2(H2O) (3), have been synthesized by hydrothermal reaction. They feature three different structural types. Compound 1 exhibits a novel 3D network composed of 3D cadmium selenite open framework with phosphate groups filled in the 1D helical tunnels. The structure of compound 2 displays a new 3D framework consisted of 2D cadmium oxide layers bridged by SeO3 and PO4 groups. Compound 3 is isostructural with the reported solids of Co3(SeO3)3-x(PO3OH)x(H2O) when x is equal to 1.0. Its structure could be viewed as a 3D zinc oxide open skeleton with SeO3 and HPO4 polyhedra attached on the wall of the tunnels. They represent the only examples in metal selenite phosphates in addition to the above cobalt compounds. Optical diffuse reflectance spectra revealed that these solids are insulators, which are consistent with the results of band structure computations based on DFT algorithm.

Interface Trap Profiles in 4H- and 6H-SiC MOS Capacitors with Nitrogen- and Phosphorus-Doped Gate Oxides

Science.gov (United States)

Jiao, C.; Ahyi, A. C.; Dhar, S.; Morisette, D.; Myers-Ward, R.

2017-04-01

We report results on the interface trap density ( D it) of 4H- and 6H-SiC metal-oxide-semiconductor (MOS) capacitors with different interface chemistries. In addition to pure dry oxidation, we studied interfaces formed by annealing thermal oxides in NO or POCl3. The D it profiles, determined by the C- ψ s method, show that, although the as-oxidized 4H-SiC/SiO2 interface has a much higher D it profile than 6H-SiC/SiO2, after postoxidation annealing (POA), both polytypes maintain comparable D it near the conduction band edge for the gate oxides incorporated with nitrogen or phosphorus. Unlike most conventional C- V- or G- ω-based methods, the C- ψ s method is not limited by the maximum probe frequency, therefore taking into account the "fast traps" detected in previous work on 4H-SiC. The results indicate that such fast traps exist near the band edge of 6H-SiC also. For both polytypes, we show that the total interface trap density ( N it) integrated from the C- ψ s method is several times that obtained from the high-low method. The results suggest that the detected fast traps have a detrimental effect on electron transport in metal-oxide-semiconductor field-effect transistor (MOSFET) channels.

Microspheres of UO2, ThO2 and PuO2 for the high temperature reactor

International Nuclear Information System (INIS)

Brandau, E.

2002-01-01

The production of high temperature reactor fuel, so called pebble fuel, was done in the eighties by a special vibrational dropping process to obtain as sintered UO 2 - or ThO 2 -microspheres, so called 'Kernels', with a diameter size of about 300 μm. These microspheres have been coated and embedded in carbon balls to get the pebble fuel. Since the early nineties BRACE is developing the processings of microspheres starting with sols and suspensions to produce Al 2 O 3 , ZrO 2 , HfO 2 and Actinide oxide microspheres. Two main developments have been made: 1) the preparation of the feed solution (sol, suspension) and the solidification processing, and 2) the equipment, design, and electronic control have been completely changed. A newly developed suspension process for actinide oxides and for metal oxides e.g. Al 2 O 3 , TiO 2 , SiO 2 , ZrO 2 , HfO 2 , CeO 2 , ThO 2 , UO 2 , PuO 2 leads to cheaper production of as sintered microspheres. The processing and the installations will be described and the experience of production will be shown. (author)

Reaction of cyclic epoxide compounds with triphenylphosphine

International Nuclear Information System (INIS)

Kas'yan, L.I.; Stepanova, N.V.; Galafeeva, M.F.; Boldeskul, I.E.; Trachevskii, V.V.; Zefirov, N.S.

1987-01-01

Significant differences were found in the reactivity of a series of epoxides of cycloalkenes and methylenecycloalkanes and diepoxides in reaction with triphenylphosphine, depending both on the steric effects of the cyclic fragments and on their strain. The level of the strain can be judged indirectly from the chemical shifts of the 1 H and 13 C nuclei and the spin-spin coupling constants of the C-H bonds in the epoxide ring

Irradiation experiments of recycled PuO2-UO2 fuels by SAXTON reactor, (1)

International Nuclear Information System (INIS)

Yumoto, Ryozo; Akutsu, Hideo

1975-01-01

Seventy two mixed oxide fuel rods made by PNC were irradiated in Saxton Core 3. This paper generally describes the fuel specifications, the power history of the fuel and the post-irradiation examination of the PNC fuel. The specifications of the 4.0 w/o and 5.0 w/o enriched PuO 2 fuel rods with zircaloy-4 cladding are presented in a table and a figure. The positions of PNC fuel rods in the Saxton reactor are shown in a figure. Sixty eight 5.0 w/o PuO 2 -UO 2 fuel rods were assembled in a 9 x 9 rod array together with zircaloy-4 bars, a flux thimble, and a Sb-Be source. The power history of the Saxton Core 3 and the irradiation history of the PNC fuel rods are summarized in tables. The peak power and burnup of each fuel rod and the axial power profile are also presented. The maximum linear power rate and burnup attained were 512W/cm and 8700 MWD/T, respectively. As for the post irradiation examination, the items of nondestructive test, destructive test, and cladding test are presented together with the working flow diagram of the examination. It is concluded that the performance of all fuel rods was safe and satisfactory throughout the power history. (Aoki, K.)

Hydrothermal synthesis and characterization of the praseodymium borate-nitrate Pr[B{sub 5}O{sub 8}(OH)(H{sub 2}O){sub 0.87}]NO{sub 3}.2H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Ortner, Teresa S.; Huppertz, Hubert [Innsbruck Univ. (Austria). Inst. fuer Allgemeine, Anorganische und Theoretische Chemie

2017-10-01

The praseodymium borate-nitrate Pr[B{sub 5}O{sub 8}(OH)(H{sub 2}O){sub 0.87}]NO{sub 3}.2H{sub 2}O was obtained in a hydrothermal synthesis. It crystallizes monoclinically in the space group P2{sub 1}/n (no. 14) with four formula units (Z=4) and unit cell parameters of a=641.9(3), b=1551.8(7), c=1068.4(5) pm, with β=90.54(2) yielding V=1.0643(8) nm{sup 3}. The defect variant constitutes the missing member in the series of isostructural, early rare earth borate-nitrates of the composition RE[B{sub 5}O{sub 8}(OH)(H{sub 2}O){sub x}]NO{sub 3}.2H{sub 2}O [RE=La (x=0; 1), Ce (x=1), Nd (x=0.85), Sm (x=0)]. In addition to powder and single-crystal X-ray diffraction data, the novel borate-nitrate was characterized through IR and Raman spectroscopy.

Density study of the ternary mixture Mg(NO3)2-HNO3-H2O

International Nuclear Information System (INIS)

Jubin, R.T.; Marley, J.L.; Counce, R.M.

1985-06-01

Densities for the Mg(NO 3 ) 2 -HNO 3 -H 2 O system have been experimentally measured; more than 140 measurements were made covering ranges of 30 to 70 wt % Mg(NO 3 ) 2 , 0 to 40 wt % HNO 3 , and temperatures of 50 to 145 0 C. A mathematical model for the observed density relationships has been developed. 6 refs., 3 figs., 8 tabs

Ceramic grade (U,Pu)O2 powder fabrication

International Nuclear Information System (INIS)

Cristallini, O.A.; Villegas de Maroto, Marina; De Pino, J.I.; Osuna, H.A.

1980-01-01

Ceramic grade UO 2 powder was obtained by the homogeneous precipitation method. This procedure was afterwards applied to the fabrication of ceramic grade (U,Pu)O 2 powders, and mixed oxide powders with Pu content ranging from 0.7 to 16% were obtained. The obtainment of mixed ceramic oxides as well as the recuperation of fabrication scraps were developed in three steps: 1)study of the process of homogeneous precipitation of ammonium diuranate (ADU); 2) co-precipitation of ADU/PuO 2 .H 2 O for Pu concentrations of 0.6 and 6.8; 3) the thermal conditioning to mixed oxide (U,Pu)O 2 powders. The experimental procedure involves the following steps: preparation of the PuO 2 (NO 3 ) 4 solution; co-precipitation of the PuO 2 (NO 3 ) 2 solution with an UO 2 (NO 3 ) 2 solution; filtration and drying of the precipitate, thermal treatment and finally, mixing, pressing and sintering of the (U,Pu)O 2 and Nukem UO 2 powder with a 0. of zinc stearate. Different controls were made by means of physical, chemical and ceramographic tests. This method can be used for the fabrication of fast reactor fuels or, previous mechanical dispersion in UO 2 powder, for the fabrication of thermal reactors fuels. (M.E.L.) [es

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

Science.gov (United States)

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

2016-08-01

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

Toxicity of 239PuO2 inhaled by aged Beagle dogs. X

International Nuclear Information System (INIS)

Muggenburg, B.A.; Hahn, F.F.; Gillett, N.A.; Guilmette, R.A.; Boecker, B.B.; McClellan, R.O.

1988-01-01

The influence of age at exposure on the metabolism, dosimetry, and biological effects of inhaled 239 PuO 2 particles is being studied in aged Beagle dogs (8.0-10.5 yr of age at exposure). Forty-eight dogs inhaled 239 PuO 2 particles with an activity median aerodynamic diameter of 1.5 mm to achieve graded levels of initial pulmonary burdens (IPB) ranging from 0.02-0.66 μCi 239 Pu/kg body weight (0.75-24 kBq/kg). Twelve other dogs were exposed to the aerosol diluent only. All forty-eight exposed dogs have died, including two in the past year. The twelve control dogs have also died, including one in the past year. Radiation pneumonitis and pulmonary fibrosis have been the primary causes of death in these aged dogs exposed to 239 PuO 2 . (author)

Kinetics of the high temperature oxygen exchange reaction on 238PuO2 powder

International Nuclear Information System (INIS)

Whiting, Christofer E.; Du, Miting; Felker, L. Kevin; Wham, Robert M.; Barklay, Chadwick D.; Kramer, Daniel P.

2015-01-01

Oxygen exchange reactions performed on PuO 2 suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO 2 . Previous CeO 2 surrogate studies exhibit similar behavior, confirming that CeO 2 is a good qualitative surrogate for PuO 2 , in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO 2 oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO 2 Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

Toxicity of inhaled 239PuO2 in immature Beagle dogs. VII

International Nuclear Information System (INIS)

Guilmette, R.A.; Muggenburg, B.A.; Hahn, F.F.; Mauderly, J.L.; Boecker, B.B.; McClellan, R.O.

1985-01-01

Immature Beagle dogs have been exposed by inhalation to a monodisperse aerosol of 239 PuO 2 (1.5 μm AMAD) to compare the biological effects with those observed in dogs exposed to a similar aerosol as young or aged adults. The study includes 96 dogs exposed to 239 PuO 2 and 12 controls. The lung burdens of the plutonium-exposed dogs ranged from 0.00030 to 0.80 μCi/kg body weight (0.011-30 kBq/kg). No dogs died during this year. Seven dogs were diagnosed as having developing lung disease, mainly fibrosis, and one had a developing lung tumor. With 20 dogs having estimated cumulative radiation doses in excess of 1000 rad (10 Gy), the biological response of the dogs exposed as juveniles appears to be less than that seen in mature dogs. However, major uncertainties still exist in the current estimations of radiation dose, particularly regarding the local distribution of alpha radiation dose. 1 reference, 4 figures, 1 table

In Vitro Antiplasmodial Activity and Cytotoxic Effect of (Z-2-Benzylidene-4, 6-Dimethoxybenzofuran-3(2H-One Derivatives

Directory of Open Access Journals (Sweden)

Ali RAMAZANI

2016-10-01

Full Text Available Background: Aurones are naturally occurring compounds that belong to flavenoids family and have antiplasmodial effects. This study investigated some new aurones derivatives against chloroquine sensitive Plasmodium falciparum. Here we report the synthesis, in vitro antiplasmodial activity and cytotoxic evaluation of 11 compound from derivatives of (Z-2- benzylidene-4, 6-dimethoxybenzofuran-3(2H-one.Methods: The cytotoxic evaluations of active compounds were performed with MTT (3-[4, 5-dimethylthiazol-2-yl]-2, 5 diphenyltetrazolium bromide assay on human breast cancer cell lines; MCF7 and T47D.Results: From 11 compounds M3, M6 and M7 compounds showed good antiplasmodial effect against chloroquine-sensitive 3D strain of P. falciparum with IC50 (50% inhibitory concentration values of 7.82, 7.27 and 2.3 µM respectively. No noticeable toxicity was‌ observed with these compounds when tested against tested cell lines. Conclusion: The replacement of the 4 and 5 positions at ring B of aurone derivatives, with propoxy and bromide (Br respectively was revealed highly advantageous for their antiplasmodial effect.

Standard test methods for chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade mixed oxides ((U, Pu)O2)

CERN Document Server

American Society for Testing and Materials. Philadelphia

2010-01-01

1.1 These test methods cover procedures for the chemical, mass spectrometric, and spectrochemical analysis of nuclear-grade mixed oxides, (U, Pu)O2, powders and pellets to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Uranium in the Presence of Pu by Potentiometric Titration Plutonium by Controlled-Potential Coulometry Plutonium by Amperometric Titration with Iron (II) Nitrogen by Distillation Spectrophotometry Using Nessler Reagent 7 to 14 Carbon (Total) by Direct Combustion-Thermal Conductivity 15 to 26 Total Chlorine and Fluorine by Pyrohydrolysis 27 to 34 Sulfur by Distillation-Spectrophotometry 35 to 43 Moisture by the Coulometric, Electrolytic Moisture Analyzer 44 to 51 Isotopic Composition by Mass Spectrometry Rare Earths by Copper Spark Spectroscopy 52 to 59 Trace Impurities by Carrier Distillation Spectroscopy 60 to 69 Impurities by Spark-Source Mass Spectrography 70 to 76 Total Gas in Reactor-Grade Mixed Dioxide P...

Supramolecular interactions between triphenylphosphine oxide and benzamide evaluated by positron annihilation lifetime spectroscopy

Science.gov (United States)

Oliveira, F. C.; Denadai, A. M. L.; Fulgêncio, F.; Oliveira, A. M.; Andrade, A. C. A.; Melo, A. C. A.; Yoshida, M. I.; Windmöller, D.; Magalhães, W. F.

2017-04-01

In the present work, intermolecular interactions between triphenylphosphine oxide (TPPO) and benzamide (BZM) has been studied in solid state by Positron Annihilation Lifetime Spectroscopy (PALS) and supported by several analytical techniques (in solid state and in solution) and by computational modeling (in gaseous phase). Isothermal Titration Calorimetry (ITC) in ethyl acetate solvent showed that complexation is a stepwise process, with 2:1 and 1:1 TPPO/BZM stoichiometries, both driven by entropy. HPLC analysis of isolated single crystal confirmed the existence of a 2:1 TPPO/BZM crystalline complex in solid state. The results of thermal analysis (TGA, DTA and DSC) and FTIR spectroscopy showed that the interactions in the complexes are relatively weaker than those found in pure precursors. Finally, PALS showed higher positronium formation probability (I3) at [TPPO0.62·BZM0.38] and [TPPO0.25·BZM0.75] molar fractions, corroborating the existence of two stoichiometries for the TPPO/BZM system and suggesting greater electronic availability of n- and π-electrons in heterosynton complexes, as resulting of interactions, bring forward new evidences of the participation of electronic excited states on the positronium formation mechanism.

Kinetic Investigation of Homogeneous H(2)-D(2) Equilibration Catalyzed by Pt-Au Cluster Compounds. Characterization of the Cluster [(H)Pt(AuPPh(3))(9)](NO(3))(2).

Science.gov (United States)

Rubinstein, Leon I.; Pignolet, Louis H.

1996-11-06

The new Pt-Au hydrido cluster compound [(H)Pt(AuPPh(3))(9)](NO(3))(2) (3) has been synthesized and characterized by NMR, FABMS, and single-crystal X-ray diffraction [triclinic, P&onemacr;, a = 17.0452(1) Å, b = 17.4045(2) Å, c = 55.2353(1) Å, alpha = 89.891(1) degrees, beta = 85.287(1) degrees, gamma = 75.173(1) degrees, V = 15784.0(2) Å(3), Z = 4 (two molecules in asymmetric unit), residual R = 0.089 for 45 929 observed reflections and 3367 variables, Mo Kalpha radiation]. The Pt(AuP)(9) core geometry is a distorted icosahedron with three vertices vacant. The Pt-Au, Au-Au, and Au-P distances are within the normal ranges observed in other Pt-Au clusters. This cluster is a catalyst for H(2)-D(2) equilibration in homogeneous solution phase and has been used in a general mechanistic study of this reaction catalyzed by Pt-Au clusters. We previously proposed that a key step in the mechanism for catalytic H(2)-D(2) equilibration is the dissociation of a PPh(3) ligand to give a cluster with an open Au site for bonding of H(2) or D(2). This was based on qualitative observations that PPh(3) inhibited the rate of HD production with [Pt(AuPPh(3))(8)](NO(3))(2) (1) as catalyst. In order to test this hypothesis, phosphine inhibition (on the rate of HD production) and phosphine ligand exchange kinetic experiments were carried out with [(H)(PPh(3))Pt(AuPPh(3))(7)](NO(3))(2) (2) and 3. In this paper we show that the rate constant for phosphine dissociation determined from the PPh(3) inhibition rate study of H(2)-D(2) equilibration with cluster 2 is nearly identical to the rate constant for dissociative phosphine ligand exchange. The slower rate for H(2)-D(2) equilibration observed with 3 compared with 2 (5.5 x 10(-3) vs 7.7 x 10(-2) turnover s(-1)) is explained by its smaller rate constant for phosphine dissociation (2.8 x 10(-5) vs 2.9 x 10(-4) s(-1)). The fact that clusters 2 and 3 show similar kinetic behaviors suggests that the PPh(3) dissociation step in the catalytic H(2

Experimental research on influencing factors of wet removal of NO from coal-fired flue gas by UV/H2O2 advanced oxidation process

Institute of Scientific and Technical Information of China (English)

无

2010-01-01

Wet removal of NO from coal-fired flue gas by UV/H2O2 Advanced Oxidation Process (AOP) were investigated in a self-designed UV-bubble reactor. Several main influencing factors (UV intensity, H2O2 initial concentration, initial pH value, solution temperature, NO initial concentration, liquid-gas ratio and O2 percentage content) on the NO removal efficiency were studied. The results showed that UV intensity, H2O2 initial concentration, NO initial concentration and liquid-gas ratio are the main influencing factors. In the best conditions, the highest NO removal efficiency by UV/H2O2 advanced oxidation process could reach 82.9%. Based on the experimental study, the influencing mechanism of the relevant influencing factors were discussed in depth.

Sources of superoxide/H2O2 during mitochondrial proline oxidation

Directory of Open Access Journals (Sweden)

Renata L.S. Goncalves

2014-01-01

Full Text Available p53 Inducible gene 6 (PIG6 encodes mitochondrial proline dehydrogenase (PRODH and is up-regulated several fold upon p53 activation. Proline dehydrogenase is proposed to generate radicals that contribute to cancer cell apoptosis. However, there are at least 10 mitochondrial sites that can produce superoxide and/or H2O2, and it is unclear whether proline dehydrogenase generates these species directly, or instead drives production by other sites. Amongst six cancer cell lines, ZR75-30 human breast cancer cells had the highest basal proline dehydrogenase levels, and mitochondria isolated from ZR75-30 cells consumed oxygen and produced H2O2 with proline as sole substrate. Insects use proline oxidation to fuel flight, and mitochondria isolated from Drosophila melanogaster were even more active with proline as sole substrate than ZR75-30 mitochondria. Using mitochondria from these two models we identified the sites involved in formation of superoxide/H2O2 during proline oxidation. In mitochondria from Drosophila the main sites were respiratory complexes I and II. In mitochondria from ZR75-30 breast cancer cells the main sites were complex I and the oxoglutarate dehydrogenase complex. Even with combinations of substrates and respiratory chain inhibitors designed to minimize the contributions of other sites and maximize any superoxide/H2O2 production from proline dehydrogenase itself, there was no significant direct contribution of proline dehydrogenase to the observed H2O2 production. Thus proline oxidation by proline dehydrogenase drives superoxide/H2O2 production, but it does so mainly or exclusively by providing anaplerotic carbon for other mitochondrial dehydrogenases and not by producing superoxide/H2O2 directly.

Positronium formation studies in crystalline molecular complexes: Triphenylphosphine oxide - Acetanilide

Science.gov (United States)

Oliveira, F. C.; Denadai, A. M. L.; Guerra, L. D. L.; Fulgêncio, F. H.; Windmöller, D.; Santos, G. C.; Fernandes, N. G.; Yoshida, M. I.; Donnici, C. L.; Magalhães, W. F.; Machado, J. C.

2013-04-01

Hydrogen bond formation in the triphenylphosphine oxide (TPPO), acetanilide (ACN) supramolecular heterosynton system, named [TPPO0.5·ACN0.5], has been studied by Positron Annihilation Lifetime Spectroscopy (PALS) and supported by several analytical techniques. In toluene solution, Isothermal Titration Calorimetry (ITC) presented a 1:1 stoichiometry and indicated that the complexation process is driven by entropy, with low enthalpy contribution. X-ray structure determination showed the existence of a three-dimensional network of hydrogen bonds, allowing also the confirmation of the existence of a 1:1 crystalline molecular complex in solid state. The results of thermal analysis (TGA, DTA and DSC) and FTIR spectroscopy showed that the interactions in the complex are relatively weaker than those found in pure precursors, leading to a higher positronium formation probability at [TPPO0.5·ACN0.5]. These weak interactions in the complex enhance the possibility of the n- and π-electrons to interact with positrons and consequently, the probability of positronium formation is higher. Through the present work is shown that PALS is a sensible powerful tool to investigate intermolecular interactions in solid heterosynton supramolecular systems.

Ferrous ion oxidations by ·H, ·OH and H2O2 in aerated FBX dosimetry system

International Nuclear Information System (INIS)

Gupta, B.L.; Nilekani, S.R.

1998-01-01

In the ferrous ion, benzoic acid and xylenol orange (FBX) dosimetric system, benzoic acid (BA) increases the G(Fe 3+ ) value. Xylenol orange (XO) controls the BA sensitized chain reaction as well as forms a complex with Fe 3+ . In the aerated FBX system each ·H, ·OH and H 2 O 2 oxidizes 8.5, 6.6 and 7.6 Fe 2+ ions, respectively; and these values respectively increase to 11.3, 7.6 and 8.6 in oxygenated solution. About 8% ·OH reacts with XO and the remaining with BA. The above fractional values are due to this competition. This ·OH reaction with XO oxidizes 1.8% and 2.1% ferrous ions only in aerated and oxygenated solutions, respectively. There is a competition between ·H reactions with O 2 and with BA, but both lead to the production of H 2 O 2 . The oxidation of Fe 2+ by ·OH reactions at different concentrations of H 2 O 2 is linear with absorbed dose while the ·H reactions make the oxidation of Fe 2+ non-linear with dose. This is due to competition reaction of H-adduct of BA between O 2 and Fe 3+

Synthesis, spectroscopic, structural and thermal characterizations of [(C7H6NO42TeBr6·4H2O

Directory of Open Access Journals (Sweden)

S. Smaoui

2018-02-01

Full Text Available Tellurium (IV complexes with pyridine-2,6-dicarboxylate ligand were synthesized by slow evaporation from aqueous solutions yielding a new compound: [(C7H6NO42TeBr6·4H2O]. The structure of this compound was solved and refined by single-crystal X-ray diffraction. The compound is centrosymmetric P21/c (N°: 14 with the parameters a = 8.875(5 Å, b = 15.174(5 Å, c = 10.199(5 Å, β = 94.271° (5 and Z = 2. The structure consists of isolated H2O, isolated [TeBr6]2− octahedral anions and (pyridine-2,6-dicarboxylate [C7H6NO4]+ cations. The stability of the structure was ensured by ionic and hydrogen bonding contacts (N–H⋯Br and O–H⋯Br and Van-Der Walls interaction. The thermal decomposition of the compound was studied by thermogravimetric analysis (TGA and differential scanning calorimetry (DSC. The FTIR and Raman spectroscopy at different temperatures confirm the existence of vibrational modes that correspond to the organic, inorganic and water molecular groups. Additionally, the UV–Vis diffuse reflectance spectrum was recorded in order to investigate the band gap nature. The measurements show that this compound exhibits a semiconducting behavior with an optical band gap of 2.66 eV.

Toxicity of inhaled 238PuO2 II

International Nuclear Information System (INIS)

Muggenburg, B.A.; Mewhinney, J.A.; Merickel, B.S.; Boecker, B.B.; Hahn, F.F.; Guilmette, R.A.; Mauderly, J.L.; McClellan, R.O.

1980-01-01

Studies are in progress to determine dose-response relationships for inhaled 238 PuO 2 . Beagle dogs were given a single, brief, nose-only inhalation exposure to aerosols of monodisperse particles of 238 PuO 2 . Aerosols of two sizes were used, 1.5 μm aerodynamic diameter (AD) and 3.0 μm AD. Dogs were exposed to achieve initial lung burdens of 0.56, 0.28, 0.14, 0.07, 0.03 or 0.01 μCi 238 PuO 2 /kg body weight. Twelve dogs were exposed at each activity level to each aerosol particle size. The local dose around each 3.0 μm AD particle was 10 times higher than the local dose around 1.5 μm AD particles, but the dose averaged over the whole lung was the same at each activity level for both particle sizes. The lung retention of 238 Pu was divided into two phases of clearance. During the first 100 days after exposure, the average retention half-time for 238 Pu in the lung was 310 days. When the solubility changed due to particle breakup, the retention half-time decreased to 180 days during the period from 1OO to 1,500 days after exposure. The first biological effects observed were lymphopenia and neutropenia in peripheral blood. To date, 28 Beagle dogs have died at times from 536 to 1683 days after exposure. Initial lung burdens for the dead dogs ranged from 0.18 to 2.2 μCi 238 Pu/kg body weight. Nine died with radiation pneumonitis and pulmonary fibrosis, 10 died with lung tumors and 19 dogs died with bone tumors. There are 116 exposed and 22 control dogs surviving and under observation. Current patterns of dose versus response are discussed. (author)

Studies on the experimental variables effects on rhodium catalyzed hydroformylation of unsaturated fatty esters and comparison of [RhH(CO)(PPh3)3] and [RhCl3.3H2O] as starting catalytic precursors

International Nuclear Information System (INIS)

Mendes, Ana N.F.; Gregorio, Jose R.; Rosa, Ricardo G. da

2005-01-01

Hydroformylation experiments were performed with technical-grade methyl oleate (MO) and soybean oil (SO) using [RhH(CO)(PPh 3 ) 3 ] and [RhCl 3 .3H 2 O] (double bond/Rh = 745) as catalyst precursors modified or not by triphenylphosphine. [RhH(CO)(PPh 3 ) 3 ] shows 100% conversion and 80-91% selectivity to aldehydes in only 4h for both substrates under mild conditions (100 deg C, 40 bar, CO/H 2 = 2:1, ligand/Rh = 10:1). Despite the rapid isomerization of the soybean oil, producing trans isomers and conjugated dienes, no effects were observed on its further conversion to aldehydes. The reaction of soybean oil conducted with pure [RhCl 3 .3H 2 O] produced only conjugated dienes, and when this precursor was modified with triphenylphosphine (ligand/Rh = 10:1) no reaction was observed at all. Curiously, yellow crystals corresponding to the complex [Rh(Cl)(CO)(PPh 3 ) 2 ] were quantitatively isolated at the end of the reaction. (author)

OPC unified architecture

CERN Document Server

Mahnke, Wolfgang; Damm, Matthias

2009-01-01

The OPC Foundation defines standards for online data exchange between automation systems. They address access to current data (OPC DA), alarms and events (OPC A&E) and historical data (OPC HDA). This book presents an introduction into OPC UA and explains the concepts of the standard and other topics that are not directly addressed by the standard.

Photocrystallographic structure determination of a new geometric isomer of [Ru(NH3)4(H2O)(eta1-OSO)][MeC6H4SO3]2.

Science.gov (United States)

Bowes, Katharine F; Cole, Jacqueline M; Husheer, Shamus L G; Raithby, Paul R; Savarese, Teresa L; Sparkes, Hazel A; Teat, Simon J; Warren, John E

2006-06-21

The structure of a new metastable geometric isomer of [Ru(NH3)4(H2O)(SO2)][MeC6H4SO3]2 in which the SO2 group is coordinated through a single oxygen in an eta1-OSO bonding mode has been determined at 13 K; the new isomer was obtained as a 36% component of the structure within a single crystal upon irradiation using a tungsten lamp.

Hierarchical Cr_2O_3@OPC composites with octahedral shape for rechargeable nonaqueous lithium-oxygen batteries

International Nuclear Information System (INIS)

Gan, Yongqing; Lai, Yanqing; Zhang, Zhian; Chen, Wei; Du, Ke; Li, Jie

2016-01-01

The development of catalyst materials is the most significant issue that hinders the practical applications of Li-O_2 batteries. Herein we show the design and synthesis of the hierarchical chromic oxide-octahedral porous carbon (Cr_2O_3@OPC) composites catalyst with octahedral shape that derived from Cr-based metal-organic frameworks (MIL-101(Cr)) precursor. When applied as cathode catalysts in rechargeable Li-O_2 batteries, the electrode with Cr_2O_3@OPC composites catalyst exhibits a low charge and discharge over-potential, high discharge capacity and excellent cycling stability. What's more, the electrode with Cr_2O_3@OPC composite shows a discharge capacity up to ∼4800 mAh g_(_c_a_t_a_l_y_s_t _+ _c_a_r_b_o_n_)"−"1 at a current density of 0.1 mA cm"−"2, and exhibits a very stable discharge voltage plateau of 2.7 V and a charge voltage plateau of ∼3.9 V. With the addition of Cr_2O_3@OPC composite, the Li-O_2 batteries can obtain good cycle performance over 50 cycles at a fixed capacity of 800 mAh g_(_c_a_t_a_l_y_s_t _+ _c_a_r_b_o_n_)"−"1. These results indicating that the Cr_2O_3@OPC composite derived from MIL-101(Cr) would be a promising catalyst for Li-O_2 batteries. - Highlights: • The Cr_2O_3@C composites were prepared by the pyrolysis of Cr-MIL-101. • The Cr_2O_3@C composites possess octahedral shape consisted of Cr_2O_3@C nanoparticle. • The Cr_2O_3@C composites have mesoporous structure with large specific area. • The Cr_2O_3@C composites have an excellent intrinsic electrocatalytic activity. • The Cr_2O_3@C electrode exhibits great cycling performance.

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

Science.gov (United States)

Odoh, Samuel O; Schreckenbach, Georg

2013-05-06

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

Measurement of oxygen chemical diffusion in PuO2-x and analysis of oxygen diffusion in PuO2-x and (Pu,U)O2-x

International Nuclear Information System (INIS)

Kato, Masato; Uchida, Teppei; Sunaoshi, Takeo

2013-01-01

Oxygen chemical diffusion in PuO 2-x was investigated in the temperature range of 1473-1873 K by thermogravimetry as functions of oxygen-to-metal (O/M) ratios and temperatures. The oxygen chemical diffusion coefficients, D were determined assuming that the reduction curves were dominated by a diffusion process. The O/M ratio and Pu content dependence on the chemical diffusion coefficients were evaluated. The chemical diffusion coefficient had its minimum value at around O/M=1.98 and decreased with increasing Pu content in (U,Pu)O 2-x . The self-diffusion coefficients were evaluated. A model for describing the relationship among O/M ratio, oxygen chemical diffusion, and self-diffusion was proposed based on defect chemistry. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Fabrication of ThO2, UO2, and PuO2-UO2 pellets

International Nuclear Information System (INIS)

Rasmussen, D.E.; Jentzen, W.R.; McCord, R.B.

1978-01-01

Fabrication of ThO pellets for EBR-II irradiation testing and fabrication of UO 2 and PuO 2 -UO 2 pellets for United Kingdom Prototype Fast Reactor (PFR) irradiation testing is discussed. Effect of process parameters on density and microstructure of pellets fabricated by the cold press and sinter technique is reviewed

Fabrication of 0.5-inch diameter FBR mixed oxide fuel pellets

International Nuclear Information System (INIS)

Rasmussen, D.E.; Benecke, M.W.; McCord, R.B.

1979-01-01

Large diameter (0.535 inch) mixed oxide fuel pellets for Fast Breeder Reactor application were successfully fabricated by the cold-press-and-sinter technique. Enriched UO 2 , PuO 2 -UO 2 , and PuO 2 -ThO 2 compositions were fabricated into nominally 90% theoretical density pellets for the UO 2 and PuO 2 -UO 2 compositions, and 88% and 93% T.D. for the PuO 2 -ThO 2 compositions. Some processing adjustments were required to achieve satisfactory pellet quality and density. Furnace heating rate was reduced from 200 to 50 0 C/h for the organic binder burnout cycle for the large, 0.535-inch diameter pellets to eliminate pellet cracking during sintering. Additional preslugging steps and die wall lubrication during pressing were used to eliminate pressing cracks in the PuO 2 -ThO 2 pellets

Syntheses of [5-2H]-uracil, [5-2H]-cytosine, [6-2H]-uracil and [6-2H]-cytosine

International Nuclear Information System (INIS)

Kiritani, Reiko; Asano, Takeyoshi; Fujita, Shin-ichi; Dohmaru, Takaaki; Kawanishi, Tetsuro

1986-01-01

Syntheses of [5- 2 H]-, [6- 2 H]-uracil and [5- 2 H]-, [6- 2 H]-cytosine were investigated. The catalytic reaction of uracil or cytosine with 2 H 2 gas in alkaline media gave rise to [6- 2 H]-compounds almost exclusively. On the other hand, the reaction of 5-bromouracil or 5-bromocytosine with 2 H 2 gas gave rise to a mixture of [5- 2 H]-, [6- 2 H]- and [5- 2 H, 6- 2 H]-compounds depending on the experimental conditions. By controlling the temperature, the pressure of 2 H 2 gas and the amount of catalyst, [5- 2 H]-uracil and [5- 2 H]-cytosine were obtained. The isotopic distribution in each product was measured by 1 H NMR spectroscopy combined with an HPLC method. (author)

In vitro dose-response of macrophages to 239PuO2 and 241AmO2

International Nuclear Information System (INIS)

Schneider, R.P.; Robinson, A.V.

1979-01-01

As part of a study designed to examine various means of solubilizing actinide particles within macrophages, we have measured the in vitro effects of 241 AmO 2 and 239 PuO 2 on these cells. Dose distribution within the cell population was estimated by autoradiography and compared to cell detachment as a function of time. The 241 AmO 2 and 239 PuO 2 were toxic in proportion to their radioactivity rather than their mass. Approximately 385 intracellular disintegrations are required from either radionuclide to cause cells to detach from the flask surface

Construction of New Coordination Polymers from 4’-(2,4-disulfophenyl)- 3,2’:6’3”-terpyridine: Polymorphism, pH-dependent syntheses, structures, and properties

Energy Technology Data Exchange (ETDEWEB)

Zhang, Li; Li, Chao-Jie; He, Jia-En; Chen, Yin-Yu [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Zheng, Sheng-Run, E-mail: zhengsr@scnu.edu.cn [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, Guangzhou, 510006 (China); Fan, Jun [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Zhang, Wei-Guang, E-mail: wgzhang@scnu.edu.cn [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, Guangzhou, 510006 (China)

2016-01-15

Nine new coordination compounds, namely, [Co(HDSPTP){sub 2}(H{sub 2}O){sub 4}]·4H{sub 2}O (H{sub 2}DSPTP=4’-(2,4-disulfophenyl)-3,2’:6’3”-terpyridine, 1 and 2), {[Ni(DSPTP)(H_2O)_4]·3H_2O}{sub n} (3), {[Cu(HDSPTP)_2(H_2O)_3]·8H_2O}{sub n} (4), {[Cu(HDSPTP)_2(H_2O)_3]·6H_2O}{sub n} (5), {[Cu(DSPTP)(H_2O)_2]·H_2O}{sub n} (6), {[Zn(DSPTP)(H_2O)_2]·2H_2O}{sub n} (7), {[Cd(DSPTP)(H_2O)_2]·2H_2O}{sub n} (8), and [Ag{sub 2}(DSPTP)(H{sub 2}O)]{sub n} (9), were constructed based on a new ligand containing both terpyridyl and sulfo groups. The reactions of H{sub 2}DSPTP with Co(NO{sub 3}){sub 2}.6H{sub 2}O resulted in two mononuclear complexes (compounds 1 and 2). They are polymorphisms that display different hydrogen bonding networks. They are selectively synthesized by altering the added alkalis. The reaction of H{sub 2}DSPTP with Ni(NO{sub 3}){sub 2}·6H{sub 2}O resulted in a 1D “S-shaped” coordination chain (compound 3). The reactions of Cu(II) with H{sub 2}DSPTP at different pH value resulted in the following three compounds: two kinds of 1D chains obtained at pH 3.0 and 4.0 for compounds 4 and 5, respectively, and a 3D framework based on binuclear ring units with 4-connected sra topology (Compound 6). The reactions of H{sub 2}DSPTP with ds-block ions resulted in the following three compounds: a Zn(II) (compound 7) and a Cd(II) (compound 8) 3D frameworks with structures similar to that in compound 6, and a 3D framework based on tetranuclear Ag(I) SBUs with binodal (4,8)-connected flu type 3D framework topology. The structural diversity is mainly attributed to the rich coordination modes (from monodentate to µ{sub 7}-mode) and conformations (cis–cis and cis–trans) of HDSPTP{sup −}/DSPTP{sup 2−} ligands and the metal center and can be controllable synthesized by altering the alkalis, and pH value. Thermal stability of all compounds was performed, and the thermal behaviors of compounds 6 and 8 were further explored by PXRD. Compound 6 exhibits

Local and Nanoscale Structure and Speciation in the PuO{sub 2+x-y}(OH){sub 2y} {center_dot}zH{sub 2}O System

Energy Technology Data Exchange (ETDEWEB)

Conradson, Steven D.; Begg, Bruce D.; Clark, David L.; Den Auwer, Christophe J.; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Haire, Richard G.; Hess, Nancy J.; Hess, Ryan F.; Keogh, D. Webster; Morales, Luis A.; Neu, Mary P.; Paviet-Hartmann, Patricia; Runde, Wolfgang; Tait, C DREW.; Veirs, D. Kirk; Villella, Phillip M.

2004-09-26

Pu L3 X-ray absorption fine structure spectra from 24 samples of PuO{sub 2+x} (and two related Pu substituted oxides), prepared by a variety of methods, demonstrate that (1) although the Pu sublattice remains the ordered part of the Pu distribution, the nearest-neighbor O atoms even at x = 0 are found in a multisite distribution with Pu-O distances consistent with the stable incorporation of OH{sup -} (and possibly H{sub 2}O and H{sup +}) into the PuO{sub 2} lattice; (2) the excess O from oxidation is found at Pu-O distances <1.9 {angstrom}, consistent with the multiply bound ''oxo''-type ligands found in molecular complexes of Pu(V) and Pu(VI); (3) the Pu associated with these oxo groups is most likely Pu(V), so that the excess O probably occurs as PuO{sub 2}{sup +} moieties that are aperiodically distributed through the lattice; and (4) the collective interactions between these defect sites most likely cause them to cluster so as give nanoscale heterogeneity in the form of domains that may have unusual reactivity, observed as sequential oxidation by H{sub 2}O at ambient conditions. The most accurate description of PuO{sub 2} is therefore actually PuO{sub 2+x-y}(OH){sub 2y} {center_dot} zH{sub 2}O, with pure, ordered, homogeneous PuO{sub 2} attained only when H{sub 2}O is rigorously excluded and the O activity is relatively low.

PHASE CHANGES ON 4H AND 6H SIC AT HIGH TEMPERATURE OXIDATION

Directory of Open Access Journals (Sweden)

Jan Setiawan

2016-10-01

Full Text Available ABSTRACT PHASE CHANGES ON 4H AND 6H SIC AT HIGH TEMPERATURE OXIDATION. The oxidation on two silicon carbide contain 6H phase and contains 6H and 4H phases has been done.  Silicon carbide is ceramic non-oxide with excellent properties that potentially used in industry.  Silicon carbide is used in nuclear industry as structure material that developed as light water reactor (LWR fuel cladding and as a coating layer in the high temperature gas-cooled reactor (HTGR fuel.  In this study silicon carbide oxidation simulation take place in case the accident in primary cooling pipe is ruptured.  Sample silicon carbide made of powder that pressed into pellet with diameter 12.7 mm and thickness 1.0 mm, then oxidized at temperature 1000 oC, 1200 oC dan 1400 oC for 1 hour.  The samples were weighted before and after oxidized.  X-ray diffraction con-ducted to the samples using Panalytical Empyrean diffractometer with Cu as X-ray source.  Diffraction pattern analysis has been done using General Structure Analysis System (GSAS software. This software was resulting the lattice parameter changes and content of SiC phases.  The result showed all of the oxidation samples undergoes weight gain.  The 6S samples showed the highest weight change at oxidation temperature 1200 oC, for the 46S samples showed increasing tendency with the oxidation temperature.  X-ray diffraction pattern analysis showed the 6S samples contain dominan phase 6H-SiC that matched to ICSD 98-001-5325 card.  Diffraction pattern on 6S showed lattice parameter, composition and crystallite size changes.  Lattice parameters changes had smaller tendency from the model and before oxidation.  However, the lowest silicon carbide composition or the highest converted into other phases up to 66.85 %, occurred at oxidation temperature 1200 oC.  The 46S samples contains two polytypes silicon car-bide.  The 6H-SiC phases matched by ICSD 98-016-4972 card and 4H-SiC phase matched by ICSD 98

Design improvements for gloveboxes used [in] 238PuO2 process operations

International Nuclear Information System (INIS)

George, T.G.

1997-01-01

238 PuO 2 process operations are housed in a complex of 76 gloveboxes and introductory hoods connected by means of an overhead trolley housed in a tunnel. Because a significant number of the gloveboxes used for 238 PuO 2 processing were installed before the original startup of the facility in 1978, they have been in service for nearly 20 years. During a recent heat source production campaign, numerous contamination releases in the 238 PuO 2 processing area were traced to degraded elastomer gaskets used for glovebox connections, and attachment of feed-throughs, service panels, and windows. Evaluation of the degraded gaskets revealed that a combination of radiolytic degradation related to the high specific activity of 238 Pu, and extended service at high altitude in a low (to extremely low) humidity environment had resulted in accelerated gasket aging. However, it was also apparent that gasket design was the most important factor in actual contamination release. All of the contamination releases that were traced to degraded gaskets occurred in variations of a design that used a spline to expand an elastomeric gasket into the space between a connecting flange, window, or service panel, and a glovebox opening. No contamination releases were traced to the gasket design that employed bolted clamps to compress the gasket between a connecting flange, window, or panel, and the exterior surface of a glovebox opening. As a result of these findings, the Actinide Ceramics group at LANL (NMT-9) has initiated a routine replacement and upgrade program to replace aging gloveboxes. All of the new gloveboxes will utilize the preferred gasket design, which is expected to reduce the number and frequency of contamination releases

1,5-Dimethyl-2-phenyl-1H-pyrazol-3(2H-one–4,4′-(propane-2,2-diylbis[1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H-one] (1/1

Directory of Open Access Journals (Sweden)

Krzysztof Lyczko

2013-01-01

Full Text Available The asymmetric unit of the title compound, C11H12N2O·C25H28N4O2, contains two different molecules. The smaller is known as antipyrine [systematic name: 1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H-one] and the larger is built up from two antypirine molecules which are connected through a C atom of the pyrazolone ring to a central propanyl part [systematic name: 4,4′-(propane-2,2-diylbis[1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H-one]. Intramolecular C—H...O hydrogen bonds occur in the latter molecule. In the crystal, C—H...O hydrogen bonds link the molecules into a two-dimensional network parallel to (001.

Influence of process parameters on the fabrication of UO2-PuO2 pellets using the granulation technique

International Nuclear Information System (INIS)

Vollath, D.; Wedemeyer, H.

1982-01-01

The preparation of UO 2 -PuO 2 fuel pellets from ground and granulated powders results in the formation of mixed oxide solid solutions which is decisive for the solubility of the fuel. Compared with granulated powders made from sintered and ground material, the compaction of green powders leads to much lower compaction densities at the same compaction pressure. Discontinuities of the porosity of sintered pellets made from long-time ground powders probably reflect the rupture of the granulate structure during compaction. Unusual high values of contact numbers obtained by gas effusion measurements indicate a network of cracks in the sintered material. (orig.)

Density functional study on the heterogeneous oxidation of NO over α-Fe{sub 2}O{sub 3} catalyst by H{sub 2}O{sub 2}: Effect of oxygen vacancy

Energy Technology Data Exchange (ETDEWEB)

Song, Zijian, E-mail: szj22zc15@163.com [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Wang, Ben, E-mail: benwang@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Yu, Jie, E-mail: yujie@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Ma, Chuan, E-mail: machuan628@163.com [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Zhou, Changsong, E-mail: zhouchangsong@hust.edu.cn [School of Energy and Mechanical Engineering, Nanjing Normal University, 210042, Nanjing (China); Chen, Tao, E-mail: chentao_hust@foxmail.com [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Yan, Qianqian [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Wang, Ke, E-mail: m201570959@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Sun, Lushi, E-mail: sunlushi@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China)

2017-08-15

Highlights: • NO and H{sub 2}O{sub 2} adsorption on perfect and oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface were studied by DFT calculations. • H{sub 2}O{sub 2} shows high chemical reactivity for its adsorption on oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface. • Oxygen vacancy plays an important role of the catalytic oxidation of NO by H{sub 2}O{sub 2} over the α-Fe{sub 2}O{sub 3} catalyst surfaces. • Mechanism of NO oxidation over α-Fe{sub 2}O{sub 3} (0 0 1) surface by H{sub 2}O{sub 2} was explained. - Abstract: Catalytic oxidation with H{sub 2}O{sub 2} is a promising method for NOx emission control in coal-fired power plants. Hematite-based catalysts are attracting increased attention because of their surface redox reactivity. To elucidate the NO oxidation mechanism on α-Fe{sub 2}O{sub 3} surfaces, density functional theory (DFT) calculations were conducted by investigating the adsorption characteristics of nitric oxide (NO) and hydrogen peroxide (H{sub 2}O{sub 2}) on perfect and oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surfaces. Results show that NO was molecularly adsorbed on two kinds of surfaces. H{sub 2}O{sub 2} adsorption on perfect surface was also in a molecular form; however, H{sub 2}O{sub 2} dissociation occurred on oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface. The adsorption intensities of the two gas molecules in perfect α-Fe{sub 2}O{sub 3} (0 0 1) surface followed the order NO > H{sub 2}O{sub 2}, and the opposite was true for the oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1). Oxygen vacancy remarkably enhanced the adsorption intensities of NO and H{sub 2}O{sub 2} and promoted H{sub 2}O{sub 2} decomposition on catalyst surface. As an oxidative product of NO, HNO{sub 2} was synthesized when NO and H{sub 2}O{sub 2} co-adsorbed on the oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface. Analyses of Mulliken population, electron density difference, and partial density of states showed that H{sub 2}O{sub 2} decomposition

Carbonato-bridged Ni(II)2Ln(III)2 (Ln(III) = Gd(III), Tb(III), Dy(III)) complexes generated by atmospheric CO2 fixation and their single-molecule-magnet behavior: [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH or H2O)Ln(III)(NO3)}2]·solvent [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato].

Science.gov (United States)

Sakamoto, Soichiro; Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Re, Nazzareno

2013-06-17

Atmospheric CO2 fixation of [Ni(II)(3-MeOsaltn)(H2O)2]·2.5H2O [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato], Ln(III)(NO3)3·6H2O, and triethylamine occurred in methanol/acetone, giving a first series of carbonato-bridged Ni(II)2Ln(III)2 complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH)Ln(III)(NO3)}2] (1Gd, 1Tb, and 1Dy). When the reaction was carried out in acetonitrile/water, it gave a second series of complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(H2O)Ln(III)(NO3)}2]·2CH3CN·2H2O (2Gd, 2Tb, and 2Dy). For both series, each Ni(II)2Ln(III)2 structure can be described as two di-μ-phenoxo-bridged Ni(II)Ln(III) binuclear units bridged by two carbonato CO3(2-) units to form a carbonato-bridged (μ4-CO3)2{Ni(II)2Ln(III)2} structure. The high-spin Ni(II) ion has octahedral coordination geometry, and the Ln(III) ion is coordinated by O9 donor atoms from Ni(II)(3-MeOsaltn), bidentate NO3(-), and one and two oxygen atoms of two CO3(2-) ions. The NO3(-) ion for the first series roughly lie on Ln-O(methoxy) bonds and are tilted toward the outside, while for the second series, the two oxygen atoms roughly lie on one of the Ln-O(phenoxy) bonds due to the intramolecular hydrogen bond. The temperature-dependent magnetic susceptibilities indicated a ferromagnetic interaction between the Ni(II) and Ln(III) ions (Ln(III) = Gd(III), Tb(III), Dy(III)) for all of the complexes, with a distinctly different magnetic behavior between the two series in the lowest-temperature region due to the Ln(III)-Ln(III) magnetic interaction and/or different magnetic anisotropies of the Tb(III) or Dy(III) ion. Alternating-current susceptibility measurements under the 0 and 1000 Oe direct-current (dc) bias fields showed no magnetic relaxation for the Ni(II)2Gd(III)2 complexes but exhibited an out-of-phase signal for Ni(II)2Tb(III)2 and Ni(II)2Dy(III)2, indicative of slow relaxation of magnetization. The energy barriers, Δ/kB, for the spin flipping were estimated from the Arrhenius

[KDy(Hptc3(H3ptc]n·2n(Hbipy·5n(H2O, a Layered Coordination Polymer Containing DyO6N3 Tri-Capped Trigonal Prisms (H3ptc = Pyridine 2,4,6-Tricarboxylic Acid, C8H5NO6; Bipy = 2,2'-Bipyridine, C10H8N2

Directory of Open Access Journals (Sweden)

Shoaib Anwar

2012-08-01

Full Text Available The synthesis, structure and properties of the bimetallic layered coordination polymer, [KDy(C8H3NO63(C8H5NO6]n·2n(C10H9N2·5n(H2O = [KDy(Hptc3(H3ptc]n·2n(Hbipy·5n(H2O, are described. The Dy3+ ion is coordinated by three O,N,O-tridentate doubly-deprotonated pyridine tri-carboxylate (Hptc ligands to generate a fairly regular DyO6N3 tri-capped trigonal prism, with the N atoms acting as the caps. The potassium ion is coordinated by an O,N,O-tridentate H3ptc molecule as well as monodentate and bidentate Hptc ligands to result in an irregular KNO9 coordination geometry. The ligands bridge the metal-atom nodes into a bimetallic, layered, coordination polymer, which extends as corrugated layers in the (010 plane, with the mono-protonated bipyridine cations and water molecules occupying the inter-layer regions: Unlike related structures, there are no dysprosium–water bonds. Many O–HLO and N–HLO hydrogen bonds consolidate the structure. Characterization and bioactivity data are described. Crystal data: C52H42DyKN8O29, Mr = 1444.54, triclinic,  (No. 2, Z = 2, a = 9.188(2 Å, b = 15.7332(17 Å, c = 19.1664(19 Å, α = 92.797(6°, β = 92.319(7°, γ = 91.273(9°, V = 2764.3(7 Å3, R(F = 0.029, wR(F2 = 0.084.

Synthesis, crystal structure and DFT studies of a novel dinuclear copper(I) complex with triphenylphosphine and 2-mercaptonicotinic acid

Science.gov (United States)

Ahmad, Tayyaba; Mahmood, Rashid; Georgieva, Ivelina; Zahariev, Tsvetan; Tahir, Muhammad Nawaz; Shaheen, Muhammad Ashraf; Gilani, Mazhar Amjad; Ahmad, Saeed

2018-02-01

A novel dinuclear copper(I) complex, {[Cu2(Mnt)2(PPh3)2Cl2].2H2O.CH3CN}2 (1) (Mnt = Mercaptonicotinic acid, PPh3 = triphenylphosphine) was prepared and its structure was determined by X-ray crystallography. The complex 1 consists of two dinuclear molecules and in each molecule, the two copper atoms are bridged by S atoms of N-protonated mercaptonicotinic acid forming a four-membered ring. The planar Cu2S2 core is characterized by significant cuprophilic interactions (Cusbnd Cu distance = 2.7671(8), 2.8471(8) Å). Each copper atom in 1 is coordinated by two sulfur atoms of Mnt, one phosphorus atom of PPh3 and a chloride ion adopting a tetrahedral geometry. The calculated Gibbs energies for reaction in CH3CN supported the experimental structure and predicted more favorable formation of dinuclear Cu(I) complex as compared to the mononuclear Cu(I) complex. The dinuclear complex is stabilized by 65.98 kJ mol-1 by coupling of two mononuclear Cu(I) complexes. The IR spectra of 1 and Mnt ligand were reliably interpreted and the Mnt vibrations, which are sensitive to the ligand coordination to Cu(I) ion in 1 were selected with the help of DFT/ωB97XD calculations.

UO2-PuO2 fuel pin capsule-irradiations of the test series FR 2-5a

International Nuclear Information System (INIS)

Dienst, W.; Goetzmann, O.; Schulz, B.

1975-06-01

In the capsule-irradiation test series FR 2-5a, short UO 2 -PuO 2 fuel pins (80 mm fuel length) of 7 mm diameter were irradiated in a thermal neutron flux at mean rod powers of 400 - 450 W/cm and mean cladding surface temperatures of 500 - 550 0 C to burnups of 0.6, 1.8 and 5.0 at% (U + Pu). Void volume redistribution in the fuel pins was examined in micrographs of cross-sections by measuring crack widths, central void diameters, and fuel porosity. The width of the radial cracks at the outer fuel rim was taken as a basis for measuring the irradiation-induced densification of the UO 2 -PuO 2 fuel. The result was that the final fuel density after irradiation-induced densification amounted to 92 - 94% TD and had already been reached after 0.6 at% burnup. The porosity measurement on fuel cross-sections was to show a possible dependence of the radial porosity redistribution on the initial sintered density. Examining the fuel pin diameters after irradiation showed permanent cladding strains after 5 at% burnup, which must be due to mechanical interaction with the fuel. To judge if the chemical compatibility between the fuel and the cladding of Cr-Ni-stainless steel 1.4988, the depths of chemical attack on the cladding inside was measured by micrographs of fuel pin cross-sections. (orig./GSC) [de

[Effect of germacrone in alleviating HUVECs damaged by H2O2-induced oxidative stress].

Science.gov (United States)

Chen, Qiong-Fang; Wang, Gang; Tang, Li-Qing; Yu, Xian-Wen; Li, Zhao-Fei; Yang, Xiu-Fen

2017-09-01

This study focuses on the protective effect of germacrone on human umbilical vein endothelial cells(HUVECs) damaged by H2O2-induced oxidative stress and its possible mechanisms. The oxidative damage model was established by using 500 μmol•L⁻¹ H2O2 to treat HUVECs for 3 hours, and then protected with different concentrations of germacrone for 24 hours. The effect of germacrone on cell viability of HUVECs damaged by H2O2 was detected by MTT. The contents of PGI2, TXB2, ET-1, t-PA, PAI-1, TNF-α and IL-6 were detected by ELISA. The content of NO was detected by using nitrate reductase method. Colorimetry was used to detect NOS and GSH-Px. The contents of MDA, SOD and LDH were detected by TBA, WST-1 and microplate respectively. Apoptosis was observed by Hoechst 33258 fluorescent staining. The mRNA expressions of Bax, Bcl-2 and Caspase-3 in cells were detected by RT-PCR. The results showed that the cell damage rate was 52% after treated with 500 μmol•L⁻¹ H2O2 for 3 hours. The cell activity was increasing with the rise of germacrone concentration within the range of 20-200 mol•L⁻¹. Compared with normal group, the contents of PGI2, NO, T-NOS, t-PA, SOD, GSH-Px and Bcl-2 mRNA expressions were lower after damaged with H2O2. The contents of PAI-1, ET-1, IL-6, TNF-α, TXB2, LDH, MDA, Bax mRNA and Caspase-3 mRNA expressions were increased. Compared with model group, the contents of PGI2, NO, T-NOS, t-PA, SOD, GSH-Px and Bcl-2 mRNA expressions were increased after treated with germacrone. The contents of PAI-1, ET-1, IL-6, TNF-α, TXB2, LDH, MDA, Bax mRNA and Caspase-3 mRNA expressions were lower after treated with germacrone. According to Hoechst 33258 fluorescence staining, compared with normal group, the cell membrane and the nucleus showed strong dense blue fluorescence, and the number of cells significantly decreased in model group. Compared with model group, blue fluorescence intensity decreased in drug group. The above findings demonstrate that

Sr{sub 2}CoMoO{sub 6} anode for solid oxide fuel cell running on H{sub 2} and CH{sub 4} fuels

Energy Technology Data Exchange (ETDEWEB)

Zhang, Ping [Engineering Research Center of Nano-GEO Materials of Education Ministry, China University of Geosciences, Wuhan 430074 (China); Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); Huang, Yun-Hui [Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); State Key Laboratory of Materials Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan 430074 (China); Cheng, Jin-Guang; Goodenough, John B. [Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); Mao, Zong-Qiang [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China)

2011-02-15

The double perovskite Sr{sub 2}CoMoO{sub 6-{delta}} was investigated as a candidate anode for a solid oxide fuel cell (SOFC). Thermogravimetric analysis (TGA) and powder X-ray diffraction (XRD) showed that the cation array is retained to 800 C in H{sub 2} atmosphere with the introduction of a limited concentration of oxide-ion vacancies. Stoichiometric Sr{sub 2}CoMoO{sub 6} has an antiferromagnetic Neel temperature T{sub N} {approx} 37 K, but after reduction in H{sub 2} at 800 C for 10 h, long-range magnetic order appears to set in above 300 K. In H{sub 2}, the electronic conductivity increases sharply with temperature in the interval 400 C < T < 500 C due to the onset of a loss of oxygen to make Sr{sub 2}CoMoO{sub 6-{delta}} a good mixed oxide-ion/electronic conductor (MIEC). With a 300-{mu}m-thick La{sub 0.8}Sr{sub 0.12}Ga{sub 0.83}Mg{sub 0.17}O{sub 2.815} (LSGM) as oxide-ion electrolyte and SrCo{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} as the cathode, the Sr{sub 2}CoMoO{sub 6-{delta}} anode gave a maximum power density of 1017 mW cm{sup -2} in H{sub 2} and 634 mW cm{sup -2} in wet CH{sub 4}. A degradation of power in CH{sub 4} was observed, which could be attributed to coke build up observed by energy dispersive spectroscopy (EDS). (author)

Study of the kinetics and mechanism of the dissolution of PUO2 by Cr(II) ion in acidic medium

International Nuclear Information System (INIS)

Machuron-Mandard, X.

1991-11-01

The study of the dissolution of actinides oxides is a topic of particular importance in nuclear energy production. The present study deals with the understanding of the reductive dissolution of PuO 2 in sulfuric acid media under the action of Cr 2+ aq ion. In the first chapter of the document, crystallographic and electronic properties of PuO 2 are described, followed by informations related to its dissolution in acidic media. The second chapter concerns the presentation of the different theories usable to interpret the kinetics of heterogeneous reaction and those for the understanding of electronic transfer applied to semi-conductors. With the help of the above mathematical tools an empirical law rate is established and a reactional model proposed. It appears that the electronic transfer is purely of the heterogenous nature and that the limiting step of the overall process corresponds certainly to the rupture of plutonium oxygen bond [fr

Bluish-white-light-emitting diodes based on two-dimensional lead halide perovskite (C6H5C2H4NH3)2PbCl2Br2

Science.gov (United States)

Cai, Peiqing; Wang, Xiangfu; Seo, Hyo Jin; Yan, Xiaohong

2018-04-01

Bluish-white-light-emitting diodes (BWLEDs) are designed based on the two-dimensional mixed halide perovskite (C6H5C2H4NH3)2PbCl2Br2 at room temperature. Bluish-white electroluminescence devices were fabricated by a spin-coating method. The BWLEDs can be turned on at 4.9 V and depict a maximum luminance of ˜70 cd/m2 at 7 V. Low and room temperature photoluminescence spectra show the coexistence of free exciton and self-trapped exciton luminescence in a deformable lattice. The strategy of achieving white electroluminescence (EL) from mixed halide perovskite reported here can be applied to other two-dimensional perovskites to increase the optoelectronic efficiency of the device in the future.

[Mechanism and performance of styrene oxidation by O3/H2O2].

Science.gov (United States)

He, Jue-Cong; Huang, Qian-Ru; Ye, Qi-Hong; Luo, Yu-Wei; Zhang, Zai-Li; Fan, Qing-Juan; Wei, Zai-Shan

2013-10-01

It can produce a large number of free radicals in O3/H2O2, system, ozone and free radical coupling oxidation can improve the styrene removal efficiency. Styrene oxidation by O3/H2O2 was investigated. Ozone dosage, residence time, H2o2 volume fraction, spray density and molar ratio of O3/C8H8 on styrene removal were evaluated. The experimental results showed that styrene removal efficiency achieved 85.7%. The optimal residence time, H2O2, volume fraction, spray density and O3/C8H8 molar ratio were 20. 6 s, 10% , 1.72 m3.(m2.h)-1 and 0.46, respectively. The gas-phase degradation intermediate products were benzaldehyde(C6H5CHO) and benzoic acid (C6H5 COOH) , which were identified by means of gas chromatography-mass spectrometry(GC-MS). The degradation mechanism of styrene is presented.

Pulmonary distribution of inhaled 239PuO2 in dogs

International Nuclear Information System (INIS)

McShane, J.F.; Dagle, G.E.; Park, J.F.; Catt, D.L.

1980-01-01

Dogs exposed to 239 PuO 2 by inhalation were killed from 1 to 69 mo postexposure. The distribution of plutonium in the lungs, which was studied by analyzing autoradiographs, changed relative to time postexposure. This study investigates methods of measuring these changes

Tamarix gallica phenolics protect IEC-6 cells against H2O2 induced stress by restricting oxidative injuries and MAPKs signaling pathways.

Science.gov (United States)

Bettaib, Jamila; Talarmin, Hélène; Droguet, Mickaël; Magné, Christian; Boulaaba, Mondher; Giroux-Metges, Marie-Agnès; Ksouri, Riadh

2017-05-01

Polyphenolic compounds gained interest in the pharmaceutical research area due to their beneficial properties. Herein, antioxidant and cytoprotective capacities of T. gallica extract on H 2 O 2 -challenged rat small intestine epithelial cells were investigated. To set stress conditions, IEC-6 cultures were challenged with numerous H 2 O 2 doses and durations. Then, 40μM H 2 O 2 during 4h were selected to assess the cytoprotective effect of different T. gallica extract concentrations. Oxidative parameters, measured through CAT and SOD activities as well as MDA quantification were assessed. In addition, the expression of possibly involved MAPKs was also valued. Main results reported that T. gallica was rich in polyphenols and exhibited an important antioxidant activity (DPPH Assay, IC 50 =6μgmL -1 ; ABTS + test, IC 50 =50μgmL -1 ; Fe-reducing power, EC 50 =100μgmL -1 ). The exposure of IEC-6 cultures to 40μM H 2 O 2 during 4h caused oxidative stress manifested by (i) over 70% cell mortality, (ii) over-activity of CAT (246%), (iii) excess in MDA content (18.4nmolmg -1 ) and (iiii) a trigger of JNK phosphorylation. Pretreatment with T. gallica extract, especially when used at 0.25μgmL -1 , restored cell viability to 122%, and normal cell morphology in H 2 O 2 -chalenged cells. In addition, this extract normalized CAT activity and MDA content (100% and 14.7nmolmg -1 , respectively) to their basal levels as compared to control cells. Furthermore, stopping cell death seems to be due to dephosphorylated JNK MAPK exerted by T. gallica bioactive compounds. In all, T. gallica components provided a cross-talk between regulatory pathways leading to an efficient cytoprotection against harmful oxidative stimulus. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Thiolato-technetium complexes. 5. Synthesis, characterization, and electrochemical properties of bis(o-phenylenebis(dimethylarsine))technetium(II) and -technetium(III) complexes with thiolato ligands. Single-crystal structural analyses of trans-[Tc(SCH3)2(DIARS)2]PF6 and trans-[Tc(SC6H5)2(DIARS)2]0

International Nuclear Information System (INIS)

Konno, Takumi; Heineman, W.R.; Deutsch, E.; Kirchhoff, J.R.; Heeg, M.J.; Stuckey, J.A.

1992-01-01

Three different thiols have been brought into reaction with trans-[Tc(OH)(O)(DIARS) 2 ] 2+ to produce initially the Tc(II) complex, [Tc(SR) 2 (DIARS) 2 ] 0 , which can be oxidized to the Tc(III) complex, [Tc(SR) 2 (DIARS) 2 ] + (DIARS = o-phenylenebis(dimethylarsine)). In the case of SR = SCH 3 and SCH 2 C 6 H 5 , the Tc(II) and Tc(III) products were found to be in the trans geometry, while for SR = SC 6 H 5 , both cis and trans isomers were generated. Two of the complexes were structurally characterized by X-ray diffraction. trans-[Tc(SCH 3 ) 2 (DIARS) 2 ]PF 6 , chemical formula TcAs 4 S 2 PF 6 C 22 H 38 , crystallizes in the monoclinic space group. The Tc atom occupies an inversion center. Representative elemental analyses, FAB mass spectra, and visible-UV spectra are reported. Electrochemical and spectroelectrochemical measurements were taken on trans-[Tc(SCH 3 ) 2 (DIARS) 2 ] + , trans-[Tc(SCH 2 C 6 H 5 ) 2 (DIARS) 2 ] + , and cis-[Tc(SC 6 H 5 ) 2 (DIARS) 2 ] + , which exhibit a reversible Tc(III/II) redox couple in the range -0.32 to -0.47 V vs. Ag/AgCl. Another redox couple is present in the range -1.22 to -1.70 V; this is ascribed to Tc(II/I) and is reversible only for SR = SCH 2 C 6 H 5 at 20C. At room temperature, chemically irreversible couples are exhibited at ca. +1.0 V for Tc(IV/III)

Polysaccharide from Angelica sinensis protects H9c2 cells against oxidative injury and endoplasmic reticulum stress by activating the ATF6 pathway.

Science.gov (United States)

Niu, Xiaowei; Zhang, Jingjing; Ling, Chun; Bai, Ming; Peng, Yu; Sun, Shaobo; Li, Yingdong; Zhang, Zheng

2018-01-01

Objectives Angelica sinensis exerts various pharmacological effects, such as antioxidant and anti-apoptotic activity. This study aimed to investigate the active ingredients in A. sinensis with antioxidant properties and whether A. sinensis polysaccharide (ASP) protects H9c2 cells against oxidative and endoplasmic reticulum (ER) stress. Methods The ingredients of A. sinensis and their targets and related pathways were determined using web-based databases. Markers of oxidative stress, cell viability, apoptosis, and ER stress-related signalling pathways were measured in H9c2 cells treated with hydrogen peroxide (H 2 O 2 ) and ASP. Results The ingredient-pathway-disease network showed that A. sinensis exerted protective effects against oxidative injury through its various active ingredients on regulation of multiple pathways. Subsequent experiments showed that ASP pretreatment significantly decreased H 2 O 2 -induced cytotoxicity and apoptosis in H9c2 cells. ASP pretreatment inhibited H 2 O 2 -induced reactive oxygen species generation, lactic dehydrogenase release, and malondialdehyde production. ASP exerted beneficial effects by inducing activating transcription factor 6 (ATF6) and increasing ATF6 target protein levels, which in turn attenuated ER stress and increased antioxidant activity. Conclusions Our findings indicate that ASP, a major water-soluble component of A. sinensis, exerts protective effects against H 2 O 2 -induced injury in H9c2 cells by activating the ATF6 pathway, thus ameliorating ER and oxidative stress.

Reaction of plutonium with water kinetic and equilibrium behavior of binary and ternary phases in the Pu + O + H system

International Nuclear Information System (INIS)

Haschke, J.M.; Hodges, A.E. III; Bixby, G.E.; Lucas, R.L.

1983-01-01

The kinetic and equilibrium behavior of the Pu + O + H system has been studied by measuring the production of hydrogen gas formed by a sequence of hydrolysis reactions. The kinetic dependence of the Pu + H 2 O reaction on salt concentration and temperature has been defined. The metal is quantitatively converted to a fine black powder which has been identified as plutonium monoxide monohydride, PuOH. Other hydrolysis products formed in aqueous media include a second oxide hydride, Pu 7 O 9 H 3 , and the oxides Pu 2 O 3 , Pu 7 O 12 , Pu 9 O 16 , Pu 10 O 18 , Pu 12 O 22 , and PuO 2 . Thermal decomposition products of PuOH include Pu 2 O 2 H and PuO. A tentative phase diagram for Pu + O + H is presented and structural relationships of the oxide hydrides and oxides are discussed. 10 figures, 5 tables

Hierarchical Cr{sub 2}O{sub 3}@OPC composites with octahedral shape for rechargeable nonaqueous lithium-oxygen batteries

Energy Technology Data Exchange (ETDEWEB)

Gan, Yongqing; Lai, Yanqing; Zhang, Zhian, E-mail: zhangzhian@csu.edu.cn; Chen, Wei; Du, Ke; Li, Jie

2016-04-25

The development of catalyst materials is the most significant issue that hinders the practical applications of Li-O{sub 2} batteries. Herein we show the design and synthesis of the hierarchical chromic oxide-octahedral porous carbon (Cr{sub 2}O{sub 3}@OPC) composites catalyst with octahedral shape that derived from Cr-based metal-organic frameworks (MIL-101(Cr)) precursor. When applied as cathode catalysts in rechargeable Li-O{sub 2} batteries, the electrode with Cr{sub 2}O{sub 3}@OPC composites catalyst exhibits a low charge and discharge over-potential, high discharge capacity and excellent cycling stability. What's more, the electrode with Cr{sub 2}O{sub 3}@OPC composite shows a discharge capacity up to ∼4800 mAh g{sub (catalyst} {sub +} {sub carbon)}{sup −1} at a current density of 0.1 mA cm{sup −2}, and exhibits a very stable discharge voltage plateau of 2.7 V and a charge voltage plateau of ∼3.9 V. With the addition of Cr{sub 2}O{sub 3}@OPC composite, the Li-O{sub 2} batteries can obtain good cycle performance over 50 cycles at a fixed capacity of 800 mAh g{sub (catalyst} {sub +} {sub carbon)}{sup −1}. These results indicating that the Cr{sub 2}O{sub 3}@OPC composite derived from MIL-101(Cr) would be a promising catalyst for Li-O{sub 2} batteries. - Highlights: • The Cr{sub 2}O{sub 3}@C composites were prepared by the pyrolysis of Cr-MIL-101. • The Cr{sub 2}O{sub 3}@C composites possess octahedral shape consisted of Cr{sub 2}O{sub 3}@C nanoparticle. • The Cr{sub 2}O{sub 3}@C composites have mesoporous structure with large specific area. • The Cr{sub 2}O{sub 3}@C composites have an excellent intrinsic electrocatalytic activity. • The Cr{sub 2}O{sub 3}@C electrode exhibits great cycling performance.

Electrochemical, H2O2-Boosted Catalytic Oxidation System

Science.gov (United States)

Akse, James R.; Thompson, John O.; Schussel, Leonard J.

2004-01-01

An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

Analysis of safety margins for PuO2 containers

International Nuclear Information System (INIS)

Hubert, P.; Tomachevsky, E.

1987-11-01

In the regular manner the containers for PuO 2 transport are type B(U) and give satisfaction to the AIEA proofs. However the vigour of this conception's containers and the analysis of other radioactive containers permit to think that large safety margins exist. In this paper, the importance and the kind of these margins are studied [fr

Synthesis, crystal structures, and characterization of double complex salts [Au(en)2][Rh(NO2)6]·2H2O and [Au(en)2][Rh(NO2)6

Science.gov (United States)

Plyusnin, Pavel E.; Makotchenko, Evgenia V.; Shubin, Yury V.; Baidina, Iraida A.; Korolkov, Ilya V.; Sheludyakova, Liliya A.; Korenev, Sergey V.

2015-11-01

Double complex salts of rhodium(III) and gold(III) of the composition [Au(en)2][Rh(NO2)6]·2H2O (1) and [Au(en)2][Rh(NO2)6] (2) have been prepared. Crystal structures of the compounds have been determined by single crystal X-ray diffraction. The compounds have been characterized by PXRD, IR, far-IR, CHN and DTA. The complexes have a layered structures. The presence of water in 1 makes the structure of the hydrated DCS less dense as compared to the anhydrous one. The environment of the cation and the anion in the two structures is the same, oxygen atoms of the nitro groups are involved in hydrogen bonds N-H⋯O, N⋯O distances being approximately the same. The structures of 1 and 2 are notable in having shortened contacts between the gold atoms and the oxygen atoms of the nitro groups of the neighboring complex anions. The thermal behavior of the complexes in a hydrogen atmosphere was investigated. The final product of thermolysis prepared at the temperature 600°C is a two-phase mixture of pure metallic gold and the solid solution Rh0.93Au0.07.

Oxidation Properties of Nitrogen-Doped Silicon Films Deposited from Si2H6 and NH3

Science.gov (United States)

Scheid, Emmanuel; Boyer, Pierre; Samitier, Josep; Hassani, Ahmed

1994-03-01

Si2H6/NH3 gas mixture was employed to obtain, by low-pressure chemical vapor deposition (LPCVD) at low temperature, nitrogen-doped silicon (NIDOS) films with various N/Si ratios. Thermal oxide was grown in dry oxygen at 900°C and 1100°C on NIDOS films. The result indicates that the nitrogen content of NIDOS films, assessed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR), greatly influences their oxidation rate.

Kinetics and Thermochemistry of the Br((sup 2)P3/2) + NO2 Association Reaction

Science.gov (United States)

Kreutter, K. D.; Nicovich, J. M.; Wine, P. H.

1997-01-01

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Br((sup 2)P3/2) + NO2 association reaction as a function of temperature (259-432 K) pressure (12.5 - 700 Torr), and buffer gas identity (He, Ar, H2, N2, CO2, CF4, SF6). The reaction is found to be in the falloff regime between third and second order over the entire range of conditions investigated. At temperatures below 350 K, the association reaction is found to be irreversible on the time scale of the experiment (approximately 30 ms). At higher temperatures reversible addition is observed, allowing equilibrium constants for BrNO2 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data are in only fair agreement and lead to the following thermochemical parameters for the association reaction: Delta-H(298) = 19.6 +/- 1.7 kcal/mol, Delta-H(0) = -18.6 +/- 2.0 kcal/mol, Delta-S(298) = 29.3 +/- 4.2 cal/mol/K, Delta-H(sub f)(sub 298)(BrNO2) = 17.0 +/-1.8 kcal/mol(uncertainties are 2 sigma estimates of absolute accuracy). The value for Delta-H(0) determined in this study has been employed to calculate k(sub 0)(sup SC), the low-pressure third-order rate coefficient in the strong collision limit, by using the method of Troe; calculated values of k(sub 0)(sup SC) are inconsistent with experimental results unless Delta-H(0) is assigned a value near the lower limit derived from analysis of the high-temperature approach to equilibrium data, i.e. delta-H(0) approximately equals -16.6 kcal/mol. A potential source of systematic error in the calculation of both k(sub 0)(sup SC) and the absolute entropy of BrNO2 results from the complete lack of knowledge of the energies and degeneracies of the electronic states of BrNO3. The procedure developed by Troe and co-workers has been employed to extrapolate experimental falloff curves to the low- and high-pressure limits. Derived values for k(sub 0)(M,298K) in units of 10(exp -31) cm(exp 6

Study of phase equilibrium of Pu2O3-PuO2 system by the first-principles calculation and CALPHAD approach

International Nuclear Information System (INIS)

Minamoto, Satoshi; Kato, Masato; Konashi, Kenji

2010-01-01

A combination of a first-principles calculation, lattice dynamics and CALPHAD (CALculation of PHAse Diagrams) modeling is proven as a powerful tool so as to evaluate the Gibbs free energy and a phase equilibrium between compounds including large amount of vacancies. In this work, non-stoichiometric PuO 2-x (dioxide) and Pu 2 O 3 (sesquioxide) has been studied. An electron cohesive energy was evaluated from a first-principles calculations to estimate total energy of the compounds and a vacancy formation energy, and the theory of statistical mechanics was applied to evaluate enthalpy/entropy change due to oxygen vacancies for the non-stoichiometry of the PuO 2 (i.e. PuO 2-x ). Then a vacancy-vacancy interaction energy was determined by fitting to the experimental data of a quantity of non-stoichiometry of the PuO 2 compounds as a function of oxygen potentials at large deviation from stoichiometry. The resulting Gibbs free energy yields phase boundary between the phases with good agreement with to the experimental data.

Microprobe analysis of PuO2--UO2 nuclear fuel

International Nuclear Information System (INIS)

Clark, W.I.; Rasmussen, D.E.; Carlson, R.L.; Highley, D.M.

1977-01-01

For the preirradiation characterization of FFTF UO 2 --PuO 2 fuel, a program was developed to determine the preirradiation porosity, grain structure, and microcomposition of the fuel. Two computer programs, MITRAN and MERIT, were developed to evaluate the homogeneity of the fuel. These programs use elemental composition data generated by the electron microprobe. MITRAN determines information on the size and frequency of individual regions, whereas MERIT provides an index of the thermal performance of the fuel and calculated statistical data for comparison to other fuel batches

Effects of inhaled insoluble 239PuO2 on immune responses following lung immunization

International Nuclear Information System (INIS)

Bice, D.E.; Harris, D.L.; Brooks, A.L.; Mewhinney, J.A.

1978-01-01

To determine if inhaled 239 PuO 2 suppresses immunity in lung-associated lymph nodes, Chinese hamsters were exposed to a polydisperse aerosol of 239 PuO 2 produced at 1150 0 C. The mean lung burden of these animals was estimated to be 10 nCi at 8 days after exposure. At 128, 256 and 400 days after exposure, sham exposed controls and experimental animals were immunized by intratracheal instillation of 1 x 10 8 sheep red blood cells (SRBC). Six days later, they were sacrificed and the number of antibody forming cells (AFC) in lung-associated lymph nodes, spleen and cervical lymph nodes was evaluated. Results of these studies indicated that the number of AFC in lung-associated lymph modes was significantly lower in animals exposed to 239 PuO 2 . Only a few AFC were found in spleen and cervical lymph nodes after intratracheal immunization and the number in exposed animals was not significantly different than in the controls. These data indicate that even though the 239 PuO 2 exposure had suppressed immune responses in lung-associated lymph nodes, their filtering capacity was unaffected and antigen did not translocate to the spleen. We conclude that, at the sacrifice intervals evaluated, the immune function of lung-associated lymph nodes was suppressed and that distant lymphoid tissue (e.g., spleen and cervical lymph nodes) did not replace the immune function of the lung-associated lymph nodes

Dose-response study in F344 rats exposed to (U,Pu)O2 or PuO2

International Nuclear Information System (INIS)

Mewhinney, J.A.; Eidson, A.F.; Hahn, F.F.; Scott, B.R.; Seiler, F.A.; Boecker, B.B.

1987-01-01

The relationship of radiation dose to lung and the biological effect observed was investigated following inhalation of two types of plutonium-containing particulate materials in rats. Bulk powder samples of the two materials were obtained from within gloveboxes used in the routine manufacture of mixed plutonium and uranium oxide nuclear fuel. The materials were a solid solution of uranium and plutonium treated at 1750 0 C and a PuO 2 feedstock. Groups of rats received a single inhalation exposure to a material to achieve one of three levels of initial pulmonary burden. Rats were maintained for their lifespan to observe the biological effects produced. These effects were observed in the lungs of rats exposed to either type of particle. The same types of lung cancer were produced by both particulate materials. The incidences of cancers were also similar at comparable levels of initial pulmonary burden for the two materials. The crude incidence of lung cancers for rats exposed to these materials was not different than those reported for similar studies that used laboratory-produced aerosols of PuO 2 . Using a linear dose-effect model, the relative risk of lung cancer for rats exposed to these industrial materials was 2.3 +- 1.0 (SE) at a lung dose of 100 rad. The doubling dose for lung cancers was 78 +- 63 rad to lung to median life span. 21 refs., 9 figs., 10 tabs

Mixed oxide fuel pellet and manufacturing method thereof

International Nuclear Information System (INIS)

Yuda, Ryoichi; Ito, Ken-ichi; Masuda, Hiroshi.

1993-01-01

In a method of manufacturing nuclear fuel pellets which comprises compression molding a mixed oxide powder containing UO 2 and PuO 2 followed by sintering, a sintering agent having a composition comprising about 40 to 80 wt% of SiO 2 and the balance of Al 2 O 3 is mixed to a mixed oxide at a ratio of about 40ppm to about 0.5 wt% based on the total amount of the mixed oxide and the sintering agent, to prepare a mixture. The mixture is molded into a compression product and then sintered at a weakly acidic atmosphere at a temperature of about 1500degC to 1800degC. With such procedures, the sintering agent forms an eutectic product of a single liquid phase, PuO 2 is dispersed over the entire region of the pellet by way of the liquid phase, formation of a solid solution phase is promoted to annihilate a free PuO 2 phase. Further, growth of crystal grains is promoted. Accordingly, since the MOX fuel pellets prepared according to the present invention have a uniform solid solution state, and no free PuO 2 phase remains, increase of FP gas emission due to local nuclear fission of Pu can be avoided. (T.M.)

Synthesis, structural approach and electronic properties of V{sub 18}O{sub 45}, (N{sub 2}C{sub 6}H{sub 14}){sub 6}: a new organically templated vanadium oxide exhibiting V{sub 2}O{sub 5} layer topology

Energy Technology Data Exchange (ETDEWEB)

Sicard, M.; Maignan, A. [Laboratoire Crismat-ISMRa UMR 6508, 14 - Caen (France); Riou, D. [Universite de Versailles St Quentin, Institut Lavoisier UMR CNRS 8637, 78 - Versailles (France)

2002-02-01

V{sub 18}O{sub 45}, (N{sub 2}C{sub 6}H{sub 14}){sub 6} was hydrothermally synthesized in the form of thin platelets. Its structural approach was investigated by single crystal X-ray diffraction (non-centrosymmetric P2{sub 1} (No 4) monoclinic space group with a 10.7713(3) Angstrom, b = 11.2697(3) Angstrom, c = 29.7630(9) Angstrom, {beta} = 93.924(1) deg., V = 3604.4(2) Angstrom{sup 3}, Z = 2). V{sub 18}O{sub 45}, (N{sub 2}C{sub 6}H{sub 14}){sub 6} exhibits a lamellar structure built up from the stacking of vanadium oxide slabs between which the di-protonated 1,4-di-aza-bi-cyclo[2.2.2]octane organic cations are intercalated. The oxide layers are topologically similar to those encountered in the parent vanadium penta-oxide V{sub 2}O{sub 5} but exhibiting here a mixed valence V{sup IV}/V{sup V} with a ratio equal to 2. The electronic conductivity measurements performed on the crystals show that the resistivity curves are described by an Arrhenius law with an activation energy of 0.16 eV. (authors)

Microscopic dose distribution around PuO2 particles in lungs of hamsters, rats and dogs

International Nuclear Information System (INIS)

Diel, J.H.; Mewhinney, J.A.; Guilmette, R.A.

1982-01-01

Syrian hamsters, Fischer-344 rats and Beagle dogs inhaled monodisperse aerosols of PuO 2 and were sacrificed 1 to 16 days after exposure. The microscopic distribution of dose and tissue-at-risk around individual particles in lung was studied using autoradiographs of the lungs. The dose pattern in dogs and rats was more diffuse than in hamsters, resulting in a calculation of about twice the tumor incidence in rats and dogs as in hamsters on the basis of dose pattern using the same dose-effect model for all three species. The tumorigenic effect of inhaled insoluble PuO 2 particles depends on the species inhaling the material; Syrian hamsters are much less susceptible than are rats or dogs. It has been suggested that a difference in dose distribution resulting from differences in particle distributions in the two species may contribute to the differences in susceptibility in Syrian hamsters and rats. The role of dose distribution in lung cancer production is explored in this study by measuring microscopic dose patterns in regions surrounding single PuO 2 particles in lung. The alveolar structures of the dog and rat are different than those of the hamster. Based on these measurements, particles of PuO 2 in lung are more likely to cause lung cancer in dogs and rats than in hamsters

Interaction of 238PuO2 heat sources with terrestrial and aquatic environments

International Nuclear Information System (INIS)

Patterson, J.H.; Nelson, G.B.; Matlack, G.M.; Waterbury, G.R.

1975-01-01

Radioisotope thermoelectric generators used in space missions are designed with a great factor of safety to ensure that they will withstand reentry from orbit and impact with the earth, and safely contain the nuclear fuel until it is recovered. Existing designs, utilizing 238 PuO 2 fuel, have proved more than adequately safe. More data about the interaction of this material with terrestrial and aquatic environments is continually being sought to predict the behavior of these heat sources in the extremely unlikely contact of these materials with the land or ocean. Terrestrial environments are simulated with large environmental chambers that permit control of temperature, humidity, and rainfall using different kinds of soils. Rain falling on thermally hot chunks of 238 PuO 2 causes the spallation of the surface of the fuel into extremely fine particles, as small as 50 nm, that are later transported downward through the soil. Some of the plutonia particles become agglomerated with soil particles. Plutonium transport is more significant during winter than during summer because evaporation losses from the soil are less in winter. Aquatic environments are simulated with large aquaria that provide temperature and aeration control. Earlier fuel designs that employed a plutonia-molybdenum cermet showed plutonium release rates of about 10 μCi/m 2 - s, referred to the total surface area of the cermet. Present advanced fuels, employing pure plutonium oxide, show release rates of about 20 nCi/m 2 - s in seawater and about 150 nCi/m 2 - s in freshwater. The temperature of these more advanced heat sources does not seem to affect the release rate in seawater. (auth)

Evaluation of a low-cost optical particle counter (Alphasense OPC-N2) for ambient air monitoring

Science.gov (United States)

Crilley, Leigh R.; Shaw, Marvin; Pound, Ryan; Kramer, Louisa J.; Price, Robin; Young, Stuart; Lewis, Alastair C.; Pope, Francis D.

2018-02-01

A fast-growing area of research is the development of low-cost sensors for measuring air pollutants. The affordability and size of low-cost particle sensors makes them an attractive option for use in experiments requiring a number of instruments such as high-density spatial mapping. However, for these low-cost sensors to be useful for these types of studies their accuracy and precision need to be quantified. We evaluated the Alphasense OPC-N2, a promising low-cost miniature optical particle counter, for monitoring ambient airborne particles at typical urban background sites in the UK. The precision of the OPC-N2 was assessed by co-locating 14 instruments at a site to investigate the variation in measured concentrations. Comparison to two different reference optical particle counters as well as a TEOM-FDMS enabled the accuracy of the OPC-N2 to be evaluated. Comparison of the OPC-N2 to the reference optical instruments shows some limitations for measuring mass concentrations of PM1, PM2.5 and PM10. The OPC-N2 demonstrated a significant positive artefact in measured particle mass during times of high ambient RH (> 85 %) and a calibration factor was developed based upon κ-Köhler theory, using average bulk particle aerosol hygroscopicity. Application of this RH correction factor resulted in the OPC-N2 measurements being within 33 % of the TEOM-FDMS, comparable to the agreement between a reference optical particle counter and the TEOM-FDMS (20 %). Inter-unit precision for the 14 OPC-N2 sensors of 22 ± 13 % for PM10 mass concentrations was observed. Overall, the OPC-N2 was found to accurately measure ambient airborne particle mass concentration provided they are (i) correctly calibrated and (ii) corrected for ambient RH. The level of precision demonstrated between multiple OPC-N2s suggests that they would be suitable devices for applications where the spatial variability in particle concentration was to be determined.

NO2-initiated multiphase oxidation of SO2 by O2 on CaCO3 particles

Science.gov (United States)

Yu, Ting; Zhao, Defeng; Song, Xiaojuan; Zhu, Tong

2018-05-01

The reaction of SO2 with NO2 on the surface of aerosol particles has been suggested to be important in sulfate formation during severe air pollution episodes in China. However, we found that the direct oxidation of SO2 by NO2 was slow and might not be the main reason for sulfate formation in ambient air. In this study, we investigated the multiphase reaction of SO2 with an O2 / NO2 mixture on single CaCO3 particles using Micro-Raman spectroscopy. The reaction converted the CaCO3 particle to a Ca(NO3)2 droplet, with CaSO4 ⚫ 2H2O solid particles embedded in it, which constituted a significant fraction of the droplet volume at the end of the reaction. The reactive uptake coefficient of SO2 for sulfate formation was on the order of 10-5, which was higher than that for the multiphase reaction of SO2 directly with NO2 by 2-3 orders of magnitude. According to our observations and the literature, we found that in the multiphase reaction of SO2 with the O2 / NO2 mixture, O2 was the main oxidant of SO2 and was necessary for radical chain propagation. NO2 acted as the initiator of radical formation, but not as the main oxidant. The synergy of NO2 and O2 resulted in much faster sulfate formation than the sum of the reaction rates with NO2 and with O2 alone. We estimated that the multiphase oxidation of SO2 by O2 initiated by NO2 could be an important source of sulfate and a sink of SO2, based on the calculated lifetime of SO2 regarding the loss through the multiphase reaction versus the loss through the gas-phase reaction with OH radicals. Parameterization of the reactive uptake coefficient of the reaction observed in our laboratory for further model simulation is needed, as well as an integrated assessment based on field observations, laboratory study results, and model simulations to evaluate the importance of the reaction in ambient air during severe air pollution episodes, especially in China.

Low-level inhaled-239PuO2 life-span studies in rats

International Nuclear Information System (INIS)

Sanders, C.L.; McDonald, K.E.; Killand, B.W.; Mahaffey, J.A.; Cannon, W.C.

1986-01-01

This study determined the dose-response curve for lung tumor incidence in rats after inhalation of high-fired 239 PuO 2 , which gave radiation doses to the lung of from ∼5 to >1000 rads. Exposed rats were given a single, nose-only, inhalation exposure to 169 Yb- 239 PuO 2 aerosol (AMAD, 1.6 +- 0.11 μm). The effective half-time for 169 Yb in the lung was 14 days, whereas ∼76% of 239 Pu was cleared with a half-time of 20 days and 24%, with a half-time of 180 days. Whole-body counting for 169 Yb at 14 days after exposure was an accurate method for determining 239 Pu IAD in individual rats, even at IAD's as low as 0.60 nCi of 239 Pu. The 239 Pu lung-clearance curve and an equation describing changes in lung weight with body weight and age were used to determine lung radiation doses. The IAD's of exposure groups were 0.60 +- 0.15 nCi of 239 Pu (1000 rats), 0.98 +- 0.25 (531 rats), 2.4 +- 0.69 (209 rats), 5.7 +- 1.2 (98 rats), and 7.5 +- 2.0 to 150 +- 37 nCi (300 rats); corresponding radiation doses to the lung estimated at 3 years after exposure were 8.3, 14, 33, 79, and 100 to 2100 rads, respectively. 71 refs., 5 figs., 4 tabs

Crystal and molecular structure of the coordination compounds of Er3+ with 1-(methoxydiphenylphosphoryl)-2-diphenylphosphorylbenzene [ErL21(NO3)2]2[Er(NO3)2(H2O)5]0.333(NO3)2.333 · 2.833H2O and its ethyl substituted derivative [ErL22(NO3)2][Er(NO3)5]0.5 · 0.5H2O

International Nuclear Information System (INIS)

Polyakova, I. N.; Baulin, V. E.; Ivanova, I. S.; Pyatova, E. N.; Sergienko, V. S.; Tsivadze, A. Yu.

2015-01-01

The coordination compounds of Er 3+ with 1-(methoxydiphenylphosphoryl)-2-diphenylphosphorylbenzene [ErL 2 1 (NO 3 ) 2 ] 2 [Er(NO 3 ) 2 (H 2 O) 5 ] 0.333 (NO 3 ) 2.333 · 2.833H 2 O (I) and its ethyl substituted derivative [ErL 2 2 (NO 3 ) 2 ][Er(NO 3 ) 5 ] 0.5 · 0.5H 2 O (II) are synthesized and their crystal structures are studied. I and II contain [ErL 2 (NO 3 ) 2 ] + complex cations of identical composition and close structure. The eight-vertex polyhedron of the Er atom in the shape of a distorted octahedron with two split trans vertices is formed by the O atoms of the phosphoryl groups of L ligands and nitrate anions. L ligands close nine-membered metallocycles. The structures contain spacious channels which are populated differently, namely, by disordered [Er(NO 3 ) 2 (H 2 O) 5 ] + complex cations, NO 3 − anions, and crystallization water molecules in I and disordered [Er(NO 3 ) 5 ] 2− complex anions and crystallization water molecules in II. The IR spectra of I and II are studied

Disagregation of (U, Pu)O2 fuels in molten sodium nitrate and oxides system

International Nuclear Information System (INIS)

Chou, T.S.

1976-01-01

An oxidation process based on the use of an alkali-nitrate melt has been considered as a possible head end step for the reprocessing of FBR spent fuels. The total alkali solubility in the nitrate melt was examined. It is influenced by the temperature. At 500 degC the alkali solubility in the sodium nitrate melt is about 17 mol %. Examining solidified mixture of sodium and nitrate or sodium oxides and nitrite by X-ray diffraction has revealed five unknown lattices. NaNO 3 .xNa 2 O 2 is cubic (a=8.71A), NaNO 2 .xNa 2 O 2 is tetragonal (a=5.939A, c=9.997A), NaNO 2 .xNa 2 O is cubic (a=10.586A). The structure of NaNO 3 .xNa 2 O and NaNO 3 .xNaO 2 could not be determined. The solubility of barium and ruthenium was briefly investigated. The reaction (U,Pu)O 2 with the alkaline sodium nitrate melt proceeds along the grain boundaries of the solid solution. Two steps have been recognized. First (U,Pu)O 2 is oxidized to (U,Pu)Osub(2+x) and in a subsequent step (U,Pu)Osub(2+x) reacts with sodium peroxide to form (U,Pu) 2 O 5 .xNa 2 O 2 . Disaggregation efficiency is a function of temperature, alkali concentration and physical properties of the pellets. High temperature and low alkali concentration lead to high efficiency. The structure of the reaction products (U,Pu)O 2 with alkaline NaNO 3 melt was shown to depend mainly on the alkali concentration. As the alkali concentration is lower than 2 mole % (U,Pu) 2 O 5 . Na 2 O 2 is the dominate phase. (U,Pu) 2 O 5 .3Na 2 O 2 corresponds to 6 mole % and over 11 mole % alkali, (U,Pu) 2 O 5 .xNa 2 O 2 becomes the main product. The solubility of the fuel (U,Pu) in the alkali sodium nitrate melt increases with the alkali concentration up to 6000-8000 ppm for uranium and 1200-1700 ppm for plutonium at 500 degC with only 5 mole % alkali. As a result of high losses of fissile material in the salt bath molten salt process must regarded as uneligible for a general head end step in fuel reprocessing. Nevertheless its application can still be

Biochemical effects of inhaled 239PuO2 on lung lipids

International Nuclear Information System (INIS)

Tombropoulos, E.G.; Hadley, J.G.; Thomas, J.M.; Craig, D.K.

1977-01-01

Results of experiments carried out to assess the effect of 239 Pu α irradiation on lung lipid biosynthesis and to determine the lungs ability to incorporate palmitate into lavage lecithin and its turnover are reported. The experiments were carried out on rats which had inhaled 239 PuO 2 particles. The study of palmitate incorporation into lipids shows conclusively that for medium (23 to 42 nCi) or high (more than 100 nCi) lung depositions the incorporation by isolated mitochondria is significantly (P 239 PuO 2 were positive, with respect to controls in 8 of 10 instances, when measured following the label of palmitate in lung lavage lecithin. The interpretation of the significant result (P < 0.05) is that: (1) initial and/or final lecithin pool sizes were different, (2) transfer rates were affected between blood and lung, or (3) rates of degradation of lung lavage lecithin were affected. (U.K.)

Toxicity of inhaled 239PuO2 in aged beagle dogs

International Nuclear Information System (INIS)

Muggenburg, B.A.; Hahn, F.F.; Guilmette, R.A.; Boecker, B.B.; McClellan, R.O.

1980-01-01

Studies to determine the effects of age at exposure on metabolism, dosimetry and biological effects of inhaled particles of 239 PuO 2 have been initiated in aged beagle dogs (8.0 to 10.5 years of age at exposure). Beagle dogs have been exposed to 1.5 μm AD particles of 239 PuO 2 resulting in initial lung burdens ranging from 0.03 to 0.76 μCi/kg body weight. Dogs exposed to the aerosol diluent serve as controls. There were four blocks exposed in the past year, one of males and three of female dogs. Nine dogs died during the year. Seven of these had radiation pneumonitis and two died of nonradiation induced diseases. The surviving dogs are as long as 538 days after exposure. There are three blocks of male dogs planned for exposure in the next 12 months

Neutron Flux Depression in the UO2-PuO2 (15 to 30%) Fuel Rods from IVO-FR2-Vg7-Irradiation Experiment

International Nuclear Information System (INIS)

Lopez Jimenez, J.; Fernandez Marron, J.L.

1983-01-01

The thermal-neutron flux depression within a fuel rod has a great influence in the radial temperature profile of the rod, especially for high enrichment fuel. For this reason, a study was made about the UO 2 -PUO 2 (15 to 30% PUO 2 ) fuel pins for the KfK-JEN joint irradiation program IVO, in the FR2 reactor. Different methods (diffusion, Bonalumi, successive generations) were compared and a new approach (parabolic approximation) was developed. (Author) 22 refs

Neutron flux depression in the UO2-PuO2 (15 to 30%) fuel rods from IVO-FR2-Vg7-Irradiation experiment

International Nuclear Information System (INIS)

Lopez Jimenez, J.; Fernandez Marron, J.L.

1983-01-01

The thermal-neutron flux depression within a fuel rod has a great influence on the radial temperature profile of the rod, especially for high enrichment fuel. For this reason, a study was made about the UO 2 -PuO 2 (15 to 30% PuO 2 ) fuel pins for the KfK-JEN joint irradiation program IVO, in the FR2 reactor. Different methods (diffusion, Bonalumi, successive generations) were compared and a new approach (parabolic approximation) was developed. (author)

Insertion and C-H bond activation of unsaturated substrates by bis(benzamidinato)yttrium alkyl, [PhC(NSiMe(3))(2)](2)YR (R=CH(2)Ph center dot THF,CH(SiMe(3))(2)), and hydride, {[PhC(NSiMe(3))(2)]Y-2(mu-H)}(2), compounds

NARCIS (Netherlands)

Duchateau, R; vanWee, CT; Teuben, JH

1996-01-01

The reactivity of benzamidinate-stabilized yttrium complexes [PhC(NSiMe(3))(2)](2)YR (R = CH(2)Ph . THF, CH(SiMe(3))(2) and {[PhC(NSiMe(3))(2)]Y-2(mu-H)}(2) have been investigated. The complexes are thermally stable showing no sign of decomposition, ligand or solvent metalation or H/D exchange after

Poly[(6-carboxypicolinato-κ3O2,N,O6(μ3-pyridine-2,6-dicarboxylato-κ5O2,N,O6:O2′:O6′dysprosium(III

Directory of Open Access Journals (Sweden)

Xu Li

2009-11-01

Full Text Available In the title complex, [Dy(C7H3NO4(C7H4NO4]n, one of the ligands is fully deprotonated while the second has lost only one H atom. Each DyIII ion is coordinated by six O atoms and two N atoms from two pyridine-2,6-dicarboxylate and two 6-carboxypicolinate ligands, displaying a bicapped trigonal-prismatic geometry. The average Dy—O bond distance is 2.40 Å, some 0.1Å longer than the corresponding Ho—O distance in the isotypic holmium complex. Adjacent DyIII ions are linked by the pyridine-2,6-dicarboxylate ligands, forming a layer in (100. These layers are further connected by π–π stacking interactions between neighboring pyridyl rings [centroid–centroid distance = 3.827 (3 Å] and C—H...O hydrogen-bonding interactions, assembling a three-dimensional supramolecular network. Within each layer, there are other π–π stacking interactions between neighboring pyridyl rings [centroid–centroid distance = 3.501 (2 Å] and O—H...O and C—H...O hydrogen-bonding interactions, which further stabilize the structure.

New data on the toxicity and translocation of inhaled 239PuO2 in baboons

International Nuclear Information System (INIS)

Metivier, H.; Masse, R.; Rateau, G.; Nolibe, D.; Lafuma, J.

1989-01-01

In 1973-1974, baboons were exposed to a polydispersed aerosol of 239 PuO 2 , prepared at 1000 0 C, at the Commissariat a l'Energie Atomique in France. The data published in 1978 for these baboons were used by Bair et al (1980), for comparison with those obtained in beagles exposed to 239 PuO 2 at the Pacific Northwest Laboratory, USA. Since our 1978 publication, 8 baboons have died or were killed by euthanasia when moribund, and 11 were still alive when the present report was drafted. Two of the eight baboons died of lung squamous cell carcinoma at 2171 and 2528 days respectively. The remaining 6 died of fibrosis, interstitial pneumonia or diseases unrelated to Pu toxicity. The relationship observed in the eight baboons between initial lung burden and survival time shows that their lifespan was longer than expected from the data curve based on the findings for the first 1000 days. However, this increased survival time was not observed if the lifespan was expressed as a function of the average lung burden. (author)

Highly efficient alkane oxidation catalyzed by [Mn(V)(N)(CN)4](2-). Evidence for [Mn(VII)(N)(O)(CN)4](2-) as an active intermediate.

Science.gov (United States)

Ma, Li; Pan, Yi; Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Chen, Gui; Lau, Kai-Chung; Lau, Tai-Chu

2014-05-28

The oxidation of various alkanes catalyzed by [Mn(V)(N)(CN)4](2-) using various terminal oxidants at room temperature has been investigated. Excellent yields of alcohols and ketones (>95%) are obtained using H2O2 as oxidant and CF3CH2OH as solvent. Good yields (>80%) are also obtained using (NH4)2[Ce(NO3)6] in CF3CH2OH/H2O. Kinetic isotope effects (KIEs) are determined by using an equimolar mixture of cyclohexane (c-C6H12) and cyclohexane-d12 (c-C6D12) as substrate. The KIEs are 3.1 ± 0.3 and 3.6 ± 0.2 for oxidation by H2O2 and Ce(IV), respectively. On the other hand, the rate constants for the formation of products using c-C6H12 or c-C6D12 as single substrate are the same. These results are consistent with initial rate-limiting formation of an active intermediate between [Mn(N)(CN)4](2-) and H2O2 or Ce(IV), followed by H-atom abstraction from cyclohexane by the active intermediate. When PhCH2C(CH3)2OOH (MPPH) is used as oxidant for the oxidation of c-C6H12, the major products are c-C6H11OH, c-C6H10O, and PhCH2C(CH3)2OH (MPPOH), suggesting heterolytic cleavage of MPPH to generate a Mn═O intermediate. In the reaction of H2O2 with [Mn(N)(CN)4](2-) in CF3CH2OH, a peak at m/z 628.1 was observed in the electrospray ionization mass spectrometry, which is assigned to the solvated manganese nitrido oxo species, (PPh4)[Mn(N)(O)(CN)4](-)·CF3CH2OH. On the basis of the experimental results the proposed mechanism for catalytic alkane oxidation by [Mn(V)(N)(CN)4](2-)/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4](2-) to generate a manganese(VII) nitrido oxo active species, [Mn(VII)(N)(O)(CN)4](2-), which then oxidizes alkanes (R'H) via a H-atom abstraction/O-rebound mechanism. The proposed mechanism is also supported by density functional theory calculations.

Catalytic oxidation of NO to NO2 on activated carbon

International Nuclear Information System (INIS)

Zhancheng Guo; Yusheng Xie

2001-01-01

Catalytic oxidation of NO to NO 2 over activated carbons PAN-ACF, pitch-ACF and coconut-AC at room temperature (30 o C) were studied to develop a method based on oxidative removal of NO from flue gases. For a dry gas, under the conditions of a gas space flow rate 1500 h -1 in the presence of oxygen of 2-20% in volume concentration, the activated coconut carbon with a surface area 1200 m 2 /g converted about 81-94% of NO with increasing oxygen concentration, the pitch based activated carbon fiber with a surface area 1000 m 2 /g about 44-75%, and the polyacrylonitrile-based activated carbon fiber with a surface area 1810 m 2 /g about 25-68%. The order of activity of the activated carbons was PAN-ACF c P NO P O2 β (F/W), where β is 0.042, 0.16, 0.31 for the coconut-AC, the pitch-ACF and the PAN-ACF respectively, and k c is 0.94 at 30 o C. (author)

Tribromoisocyanuric acid/triphenylphosphine: a new system for conversion of alcohols into alkyl bromides

Energy Technology Data Exchange (ETDEWEB)

Andrade, Vitor S.C. de; Mattos, Marcio C.S. de, E-mail: mmattos@iq.ufrj.br [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Departamento de Quimica Organica

2014-05-15

An efficient and facile method has been developed for the conversion of alcohols into alkyl bromides under neutral conditions using tribromoisocyanuric acid and triphenylphosphine (molar ratio 1.0:0.7:2.0, alcohol/tribromoisocyanuric acid/triphenylphosphine) in dichloromethane at room temperature. This method can be applied for the conversion of primary, secondary, benzilic and allylic alcohols, and their corresponding bromides are obtained in 67-82 % yield. Tertiary alcohols do not react under these conditions. (author)

Tribromoisocyanuric acid/triphenylphosphine: a new system for conversion of alcohols into alkyl bromides

International Nuclear Information System (INIS)

Andrade, Vitor S.C. de; Mattos, Marcio C.S. de

2014-01-01

An efficient and facile method has been developed for the conversion of alcohols into alkyl bromides under neutral conditions using tribromoisocyanuric acid and triphenylphosphine (molar ratio 1.0:0.7:2.0, alcohol/tribromoisocyanuric acid/triphenylphosphine) in dichloromethane at room temperature. This method can be applied for the conversion of primary, secondary, benzilic and allylic alcohols, and their corresponding bromides are obtained in 67-82 % yield. Tertiary alcohols do not react under these conditions. (author)

Toxicity of 239PuO2 in immature Beagle dogs. VIII

International Nuclear Information System (INIS)

Guilmette, R.A.; Muggenburg, B.A.; Hahn, F.F.; Boecker, B.B.; McClellan, R.O.

1986-01-01

Immature Beagle dogs have been exposed by inhalation to a monodisperse aerosol of 239 PuO 2 (1.5 μm AMAD) to compare the biological effects with those observed in dogs exposed to a similar aerosol as young or aged adults. The study includes 96 dogs exposed to 239 PuO 2 and 12 controls. The lung burdens of the plutonium-exposed dogs ranged from 0.00030 to 0.80 μCi/kg body weight (0.011-30 kBq/kg). A total of 82 experimental and 11 control dogs are still alive. Seven dogs died this year. Of these, six died of radiation-induced lung disease; the other of a nonradiation cause. As is the case for dogs exposed as young adult animals, the primary causes of death have been lung carcinomas and radiation pneumonitis and fibrosis. However, it is premature to compare the dose-response relationships for the two age groups. 4 figures

Synthesis and investigation of aluminium uranium-containing compounds of Al[B5UO6]2[OH]·nH2O (B5=P, As) composition

International Nuclear Information System (INIS)

Chernorukov, N.G.; Sulejmanov, E.V.; Barch, S.V.

2001-01-01

The technique of synthesis of hydroxyuranophosphate and hydroxyuranoarsenate of aluminium is developed. Hydroxyuranophosphates and hydroxyuranoarsenates of aluminium are prepared by reaction of interaction of aqueous solutions of orthophosphoric (orthoarsenic) acid (0.05 mol/l), uranyl nitrate (0.05 mol/l) and aluminium nitrate (0.1 mol/l) at 20 Deg C. Peculiarities of the structure and thermal degradation reactions are studied by the methods of x-ray diffraction, IR spectroscopy, thermography. It is shown that in dependence on outer conditions in the systems Al[PUO 6 ] 2 ·[OH]·nH 2 O and Al[AsUO 6 ] 2 ·[OH]·nH 2 O crystal hydrates with hydrate numbers n=3-11(13) and anhydrous compounds form. The compounds have laminated type of lattice. Two-dimensional layers of [P(As)UO 6 ] ∞ n- are the basis of anion sublattice of these compounds. Aluminium in coordination surrounding of hydroxy groups and water molecules forms cationic sublattice [ru

Homogenization in powder compacts of UO2-PuO2

International Nuclear Information System (INIS)

Verma, R.

1979-01-01

The homogenization kinetics in mixed UO 2 -PuO 2 compacts have been studied by adopting a concentric core-shell model of diffusion. An equation relating the extent of homogenization expressed in terms of the fraction of UO 2 remaining undissolved and the time of annealing has been derived. From the equation, the periods required at different annealing temperatures to attain a specified level of homogenization have been calculated. These calculated homogenization times have been found to be in fair agreement with the experimentally observed homogenization times. The derived relationship has also been shown to satisfactorily predict homogenization in Cu-Ni powder compacts. (Auth.)

Oxygen potential of a prototypic Mo-cermet fuel containing plutonium oxide

International Nuclear Information System (INIS)

Miwa, Shuhei; Osaka, Masahiko; Nozaki, Takahiro; Arima, Tatsumi; Idemitsu, Kazuya

2015-01-01

Oxygen potential of a prototypic Mo-cermet fuel containing 50 vol.% PuO_2_−_x were investigated by the thermogravimetric analysis in the temperature range from 1273 K to 1473 K. It was shown that the oxygen potential and oxidation rate of the Mo-cermet were the same as those of pure PuO_2_−_x below the oxygen potential of Mo/MoO_2 oxidation reaction. The same features of the Mo-cermet sample containing 50 vol.% PuO_2_−_x with those of pure PuO_2_−_x were discussed in terms of the microstructure. - Highlights: • Oxygen potential of Mo-cermet fuel was investigated by thermogravimetric analysis. • It was the same as that of pure PuO_2_−_x below the oxygen potential for Mo/MoO_2. • Gradual oxidation of Mo matrix occurred only above the oxygen potential for Mo/MoO_2. • Mo matrix and PuO_2_−_x in Mo-cermet fuel can thus be thermochemically individual.

Natural 4-Hydroxy-2,5-dimethyl-3(2H)-furanone (Furaneol®)

OpenAIRE

Wilfried Schwab

2013-01-01

4-Hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF, furaneol®) and its methyl ether 2,5-dimethyl-4-methoxy-3(2H)-furanone (DMMF) are import aroma chemicals and are considered key flavor compounds in many fruit. Due to their attractive sensory properties they are highly appreciated by the food industry. In fruits 2,5-dimethyl-3(2H)-furanones are synthesized by a series of enzymatic steps whereas HDMF is also a product of the Maillard reaction. Numerous methods for the synthetic preparation of these c...

On chlorization of uranium and plutonium oxides in NaCl-KCl-MgCl2 molten eutectic

International Nuclear Information System (INIS)

Vorobej, M.P.; Desyatnik, V.N.; Pirogov, S.M.

1978-01-01

The chlorination process of U 3 O 8 , UO 2 , and PuO 2 in a melt of anhydrous NaCl-KCl-MgCl 2 with gaseous chlorine and carbon tetrachloride has been studied. The chlorination rate of uranium oxides has been studied within a temperature range 500-800 deg C at a chlorine feeding rate of 10 ml/min. Thermoqravimetric and X-ray analyses have shown that K 2 UO 2 Cl 4 compound is the final product of chlorination of uranium oxides. The mechanism of chlorination has been proposed. THe rate of PuO 2 chlorination has been studied within the same temperature range. It has been established that PuO 2 is readily chlorinated with CCl 4 vapours at a feeding rate of 10 ml/min. In contrast to uranium, chloride forms of plutonium in a highest oxidized state are unstable and are reduced in the melt to Pu(3) and Pu(4). The oxygen being released is retained by CCl 4 and by the products of CCl 4 pyrolysis

Instrumentation and procedures for moisture corrections to passive neutron coincidence counting assays of bulk PuO2 and MOX powders

International Nuclear Information System (INIS)

Stewart, J.E.; Menlove, H.O.; Ferran, R.R.; Aparo, M.; Zeppa, P.; Troiani, F.

1993-05-01

For passive neutron-coincidence-counting verification measurements of PuO 2 and MOX powder, assay biases have been observed that result from moisture entrained in the sample. This report describes a unique set of experiments in which MOX samples, with a range of moisture concentrations, were produced and used to calibrate and evaluate two prototype moisture monitors. A new procedure for moisture corrections to PuO 2 and MOX verification measurements yields MOX assays accurate to 1.5% (1σ) for 0.6- and 1.1-kg samples. Monte Carlo simulations were used to extend the measured moisture calibration data to higher sample masses. A conceptual design for a high-efficiency neutron coincidence counter with improved sensitivity to moisture is also presented

No-carrier-added (NCA) synthesis of 6-[18F]fluoro-L-DOPA using 3,5,6,7,8,8a-hexahydro-7,7,8a-trimethyl-[6S-(6α, 8α, 8αβ)]-6,8-methano-2H-1,4-benzoxazin-2-one

International Nuclear Information System (INIS)

Horti, A.; Yale Univ., West Haven, CT; Redmond, D.E. Jr.; Soufer, R.

1995-01-01

3,5,6,7,8,8a-Hexahydro-7,7,8a-trimethyl-[6S-(6α,8α , 8αβ)]-6,8-methano-2H-1,4-benzoxazino-2-one (2) was investigated as chiral auxiliary for asymmetric NCA nucleophilic synthesis of 6-[ 18 F]Fluoro-L-DOPA. Direct condensation of 3,4-dimethoxy-2-[ 18 F]fluorobenzaldehyde (1a) or 6-[ 18 F]fluoro-piperonal (1b) in the presence of NaH with 2 gave the corresponding [ 18 F]-3-[(2-fluorophenyl)methylene]-3,5,6,7,8,8a-hexahydro-7,7,8 a-trimethyl-[6S-(3Z,3α,6α,8α,8αβ)]-6, 8-methano-2H-1,4-benzoxazin-2-one derivative 3a or 3b as a single stereoisomer. L-Selectride promoted hydrogenation of the olefinic double bond of these derivatives, in presence of tertbutyl alcohol, afforded the corresponding [ 18 F]-3-[(2-fluorophenyl) methyl]-3,5,6,7,8,8a-hexahydro-7,7,8a-trimethyl-[3S-(3α, 6α, 8α8αβ)]-6,8-methano-2H-1,4-benzoxazin-2-one derivatives (4a,b) without affecting the orientation of diasterofacial discrimination. Deprotection of the derivatives 4a,b yielded 6-[ 18 F]fluoro-L-DOPA (e.e. >90%, 3% radiochemical yield (EOB), total synthesis time 125 min, specific activity >2000 mCi/μmol). Direct deprotection/reduction of the compounds 3a,b provides the enantiomeric mixture of 6-[ 18 F]fluoro-D,L-DOPA (10-12% radiochemical yield) and, after chiral separation, 6-[ 18 F]fluoro-L-DOPA (e.e. 98%, 4-5% radiochemical yield). (author)

Noninvasive monitoring of moisture uptake in Ca(NO3)2 -polluted calcareous stones by 1H-NMR relaxometry.

Science.gov (United States)

Casieri, Cinzia; Terenzi, Camilla; De Luca, Francesco

2015-01-01

NMR transverse relaxation time (T(2)) distribution of (1)H nuclei of water has been used to monitor the moisture condensation kinetics in Ca(NO(3))(2)  · (4)H(2)O-polluted Lecce stone, a calcareous stone with highly regular porous structure often utilized as basic material in Baroque buildings. Polluted samples have been exposed to water vapor adsorption at controlled relative humidity to mimic environmental conditions. In presence of pollutants, the T(2) distributions of water in stone exhibit a range of relaxation time values and amplitudes not observed in the unpolluted case. These characteristics could be exploited for in situ noninvasive detection of salt pollution in Lecce stone or as damage precursors in architectural buildings of cultural heritage interest. Copyright © 2014 John Wiley & Sons, Ltd.

Rhodium(III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes through C(sp²)-H/alkene functionalization.

Science.gov (United States)

Zhou, Ming-Bo; Pi, Rui; Hu, Ming; Yang, Yuan; Song, Ren-Jie; Xia, Yuanzhi; Li, Jin-Heng

2014-10-13

This study describes a new rhodium(III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes using a Cu(OAc)2 oxidant for building a spirocyclic ring system, which includes the functionalization of an aryl C(sp(2))-H bond and addition/protonolysis of an alkene C=C bond. This method is applicable to a wide range of 5-aryl-2,3-dihydro-1H-pyrroles and internal alkynes, and results in the assembly of the spiro[indene-1,2'-pyrrolidine] architectures in good yields with excellent regioselectivities. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dissolution of mixed oxide fuel as a function of fabrication variables

International Nuclear Information System (INIS)

Lerch, R.E.

1979-08-01

Dissolution properties of mechanically blended mixed oxide fuel were very dependent on the six fuel fabrication variables studied. Fuel sintering temperature, source of PuO 2 and PuO 2 content of the fuel had major effects: (1) as the sintering temperature was increased from 1400 to 1700 0 C, pellet dissolution was more complete; (2) pellets made from burned metal derived PuO 2 were more completely dissolved than pellets made from calcined nitrate derived PuO 2 which in turn were more completely dissolved than pellets made from calcined nitrate derived PuO 2 ; (3) as the PuO 2 content decreased from 25 to 15 wt % PuO 2 , pellet dissolution was more complete. Preferential dissolution of uranium occurred in all the mechanically blended mixed oxide. Unirradiated mixed oxide fuel pellets made by the Sol Gel process were generally quite soluble in nitric acid. Unirradiated mixed oxide fuel pellets made by the coprecipitation process dissolved completely and rapidly in nitric acid. Fuel made by the coprecipitation process was more completely dissolved than fuel made by the Sol Gel process which, in turn, was more completely dissolved than fuel made by mechanically blending UO 2 and PuO 2 as shown below. Addition of uncomplexed fluoride to nitric acid during fuel dissolution generally rendered all fuel samples completely dissolvable. In boiling 12M nitric acid, 95 to 99% of the plutonium which was going to dissolve did so in the first hour. Irradiated mechanically blended mixed oxide fuel with known fuel fabrication conditions was also subjected to fuel dissolution tests. While irradiation was shown to increase completeness of plutonium dissolution, poor dissolubility due to adverse fabrication conditions (e.g., low sintering temperature) remained after irradiation

Maximum likelihood analysis of bioassay data from long-term follow-up of two refractory PuO2 inhalation cases.

Science.gov (United States)

Avtandilashvili, Maia; Brey, Richard; James, Anthony C

2012-07-01

The U.S. Transuranium and Uranium Registries' tissue donors 0202 and 0407 are the two most highly exposed of the 18 registrants who were involved in the 1965 plutonium fire accident at a defense nuclear facility. Material released during the fire was well characterized as "high fired" refractory plutonium dioxide with 0.32-μm mass median diameter. The extensive bioassay data from long-term follow-up of these two cases were used to evaluate the applicability of the Human Respiratory Tract Model presented by International Commission on Radiological Protection in Publication 66 and its revision proposed by Gregoratto et al. in order to account for the observed long-term retention of insoluble material in the lungs. The maximum likelihood method was used to calculate the point estimates of intake and tissue doses and to examine the effect of different lung clearance, blood absorption, and systemic models on the goodness-of-fit and estimated dose values. With appropriate adjustments, Gregoratto et al. particle transport model coupled with the customized blood absorption parameters yielded a credible fit to the bioassay data for both cases and predicted the Case 0202 liver and skeletal activities measured postmortem. PuO2 particles produced by the plutonium fire are extremely insoluble. About 1% of this material is absorbed from the respiratory tract relatively rapidly, at a rate of about 1 to 2 d (half-time about 8 to 16 h). The remainder (99%) is absorbed extremely slowly, at a rate of about 5 × 10(-6) d (half-time about 400 y). When considering this situation, it appears that doses to other body organs are negligible in comparison to those to tissues of the respiratory tract. About 96% of the total committed weighted dose equivalent is contributed by the lungs. Doses absorbed by these workers' lungs were high: 3.2 Gy to AI and 6.5 Gy to LNTH for Case 0202 (18 y post-intake) and 3.2 Gy to AI and 55.5 Gy to LNTH for Case 0407 (43 y post-intake). This evaluation

Comparative study of the catalytic activity of the complexes Cp*RuCl(PAr3)2 [Ar = -C6H5 and 4-CF3-C6H4] in the ATRP of styrene

International Nuclear Information System (INIS)

Villa-Hernandez, Alejandro M.; Rosales-Velazquez, Claudia P.; Torres-Lubian, Jose R.; Saldivar-Guerra, Enrique

2011-01-01

Styrene polymerization by ATRP was conducted independently using the complexes Cp * RuCl(PPh 3 ) 2 , and Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 as catalysts, in order to evaluate the influence of the electronic properties of the phosphine ligands on the rate and control of the polymerization. The kinetic data for polymerizations carried out with Cp * RuCl(PPh 3 ) 2 , show that molecular weights increase linearly with conversion with an average initiation efficiency of 0.77. The molecular weights obtained in the kinetic study with Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 also increase with conversion but show a marked deviation below the theoretical molecular weights. This behavior was explained by the gradual, irreversible, oxidation of catalyst Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 as confirmed by 31 P-NMR spectroscopy. Catalyst Cp * RuCl(PPh 3 ) 2 promotes the polymerization with a rate of polymerization higher than that obtained using Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 ; this is consistent with the better electron donating properties of PPh 3 versus P(4-CF 3 -C 6 H 4 ) 3 . Preliminary studies of styrene polymerization by ATRP in supercritical CO 2 , shows that only catalyst Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 , with fluorinated ligands, was active. (author)

Irradiation creep of the mixed oxide UPuO2

International Nuclear Information System (INIS)

Combette, Patrick; Milet, Claude

1976-01-01

The irradiation creep under compression of the mixed oxide UO 2 -PuO 2 was studied up to fission yields of 6x10 13 fcm -3 s -1 , under stresses -2 , in the temperature range 700-900 deg C. The creep rate is proportional to the applied stress and fission yield, athermal in the studied temperature range and non-dependent of burnup (up to 30000MWjt -1 ). In a sample under compression, swelling is observed due to the formation of fission products during the irradiation and the swelling rate is of the same order that in a cladded fuel element [fr

Translocation dynamics of Pu(NO3)4 and PuO2 from puncture wounds to lymph nodes and major organs of beagles

International Nuclear Information System (INIS)

Bistline, R.W.; Lebel, J.L.; Dagle, G.E.

1976-01-01

The translocation dynamics of plutonium and americium from simulated puncture wounds in the paws of beagle dogs following contamination with Pu(NO 3 ) 4 and high-fired PuO 2 was studied. Fractions of initial implant transported to the first major lymph node and to major body organs were measured with in vivo counting equipment and by radiochemical analysis of tissue material collected at necropsy. Samples were obtained from serial necropsies ranging from 2 weeks to 1 year after implant. The difference in lymph node and organ-accumulation dynamics between the two chemical forms and the effects of diethylenetriaminepentaacetate (DTPA) chelation treatment are presented. Active mechanisms to transport plutonium to and from the lymph system appear to exist. Equations for buildup in the lymph nodes and organs are included. The data suggest a buildup in the lymph node to a maximum, followed by a long negative slope, and a possible dose-rate effect from Pu(NO 3 ) 4 in lymph nodes

Modifying effects of preexisting pulmonary fibrosis on biological responses of rats to inhaled 239PuO2

International Nuclear Information System (INIS)

Lundgren, D.L.; Mauderly, J.L.; Rebar, A.H.; Gillett, N.A.; Hahn, F.F.

1991-01-01

We investigated the modifying effects of preexisting, bleomycin-induced pulmonary fibrosis on the deposition, retention, and biological effects of inhaled 239PuO2 in the rat. Among rats exposed to similar airborne concentrations of 239PuO2, initial lung burdens of 239Pu per kilogram body mass were similar whether or not pulmonary fibrosis was present. However, clearance of 239Pu from the lungs was significantly decreased in the rats with preexisting pulmonary fibrosis. The incidence of lung lesions (epithelial hyperplasia, diffuse macrophage increases and aggregation, and loose and dense connective tissue) was significantly greater among rats with preexisting pulmonary fibrosis than among the exposed controls. Rats with preexisting fibrosis had shorter life spans than 239PuO2-exposed control rats. When groups of rats with similar alpha doses to the lungs were compared, the incidences of neoplastic lesions in the lung, the times to death of rats with lung neoplasms, and the risk of lung tumors per unit of alpha dose to the lungs in rats with or without pulmonary fibrosis were similar. The results of this study suggest that humans with uncomplicated pulmonary fibrosis may not be more sensitive to the carcinogenic effects of inhaled 239PuO2 than are individuals with normal lungs, assuming that the total alpha doses to the lungs are similar

Tumor production in Syrian hamsters following inhalation of PuO2--ZrO2 aerosol

International Nuclear Information System (INIS)

Thomas, R.G.; Smith, D.M.

1978-01-01

Syrian golden hamsters of both sexes were exposed to aerosols of ZrO 2 containing PuO 2 . The starting material in the aerosol generator also had a small amount of 57 Co added as a tracer. The mixture of all three constituents was nebulized and the droplets passed through a heating column at 1000 0 C. Aerosol sampling was accomplished with a cascade impactor and electrostatic precipitator. The median aerodynamic diameters in all inhalation runs were approximately 2 μm with a geometric standard deviation of 2. One exposed group of 60 hamsters had 6-day lung burdens averaging 100 nCi. This group had a lung tumor incidence of 44% with an even distribution of adenomas and carcinomas. Two other groups had average 6-day lung burdens of 80 to 90 nCi plus 55 nCi of intravenously injected spheres localized in the lung. These animals had tumor incidences of approximately 30%

The synthesis and structural characterization of the technetium nitrosyl complexes [TcCl(NO)(SC5H4N)(PPh3)2] and [Tc(NO)(SC5H4N)2(PPh3)

Science.gov (United States)

Nicholson, Terrence L.; Mahmood, Ashfaq; Muller, Peter; Davison, Alan; Storm-Blanchard, Shannon; Jones, Alun G.

2011-01-01

The reaction of the Tc(I) complex [Tc(NO)Cl2(HOMe)(PPh3)2] with stoichiometric amounts of 2-mercatopyridine and a proton scavenger yields [Tc(NO)Cl(Spy)(PPh3)2] or [Tc(NO)(Spy)2(PPh3)], depending upon quantities of ligands employed. These two complexes have been structurally characterized. The small bite angles of the bidentate mercaptopyridine ligands cause significant deviation from octahedral coordination geometry. PMID:23750048

Enhancement of actinide incineration and transmutation rates in Ads EAP-80 reactor core with MOX PuO2 and UO2 fuel

International Nuclear Information System (INIS)

Kaltcheva-Kouzminava, S.; Kuzminov, V.; Vecchi, M.

2001-01-01

Neutronics calculations of the accelerator driven reactor core EAP-80 with UO 2 and PuO 2 MOX fuel elements and Pb-Bi coolant are presented in this paper. Monte Carlo optimisation computations of several schemes of the EAP-80 core with different types of fuel assemblies containing burnable absorber B4 C or H 2 Zr zirconium hydride moderator were performed with the purpose to enhance the plutonium and actinide incineration rate. In the first scheme the reactor core contains burnable absorber B4 C arranged in the cladding of fuel elements with high enrichment of plutonium (up to 45%). In the second scheme H2 Zr zirconium hydride moderated zones were located in fuel elements with low enrichment (∼20%). In both schemes the incineration rate of plutonium is about two times higher than in the reference EAP-80 core and at the same time the power density distribution remains significantly unchanged compared to the reference core. A hybrid core containing two fuel zones one of which is the inner fuel region with UO 2 and PuO 2 high enrichment plutonium fuel and the second one is the outer region with fuel elements containing zirconium hydride layer was also considered. Evolution of neutronics parameters and actinide transmutation rates during the fuel burn-up is presented. Calculations were performed using the MCNP-4B code and the SCALE 4.3 computational system. (author)

High risk of adrenal toxicity of N1-desoxy quinoxaline 1,4-dioxide derivatives and the protection of oligomeric proanthocyanidins (OPC) in the inhibition of the expression of aldosterone synthetase in H295R cells

International Nuclear Information System (INIS)

Wang, Xu; Yang, Chunhui; Ihsan, Awais; Luo, Xun; Guo, Pu; Cheng, Guyue; Dai, Menghong; Chen, Dongmei; Liu, Zhenli; Yuan, Zonghui

2016-01-01

Highlights: • N1-QCT, N1-MEQ and N1-CYA showed more adrenal toxicity than other metabolites. • N1-desoxy QdNOs reduced expression of CYP11B1, CYP11B2 and transcription factors. • OPC increased expression of transcription factors, including CYP11B1 and CYP11B2. • OPC reduced adrenal toxicity induced by N1-desoxy QdNOs. • The results provided a mechanism of adrenal damage caused by QdNO metabolites. - Abstract: Quinoxaline 1,4-dioxide derivatives (QdNOs) with a wide range of biological activities are used in animal husbandry worldwide. It was found that QdNOs significantly inhibited the gene expression of CYP11B1 and CYP11B2, the key aldosterone synthases, and thus reduced aldosterone levels. However, whether the metabolites of QdNOs have potential adrenal toxicity and the role of oxidative stress in the adrenal toxicity of QdNOs remains unclear. The relatively new QdNOs, cyadox (CYA), mequindox (MEQ), quinocetone (QCT) and their metabolites, were selected for elucidation of their toxic mechanisms in H295R cells. Interestingly, the results showed that the main toxic metabolites of QCT, MEQ, and CYA were their N1-desoxy metabolites, which were more harmful than other metabolites and evoked dose and time-dependent cell damage on adrenal cells and inhibited aldosterone production. Gene and protein expression of CYP11B1 and CYP11B2 and mRNA expression of transcription factors, such as NURR1, NGFIB, CREB, SF-1, and ATF-1, were down regulated by N1-desoxy QdNOs. The natural inhibitors of oxidant stress, oligomeric proanthocyanidins (OPC), could upregulate the expression of diverse transcription factors, including CYP11B1 and CYP11B2, and elevated aldosterone levels to reduce adrenal toxicity. This study demonstrated for the first time that N1-desoxy QdNOs have the potential to be the major toxic metabolites in adrenal toxicity, which may shed new light on the adrenal toxicity of these fascinating compounds and help to provide a basic foundation for the

No-carrier-added (NCA) synthesis of 6-[{sup 18}F]fluoro-L-DOPA using 3,5,6,7,8,8a-hexahydro-7,7,8a-trimethyl-[6S-(6{alpha}, 8{alpha}, 8{alpha}{beta})]-6,8-methano-2H-1,4-benzoxazin-2-one

Energy Technology Data Exchange (ETDEWEB)

Horti, A. [Yale Univ., New Haven, CT (United States). School of Medicine]|[Yale Univ., West Haven, CT (United States). PET Center; Redmond, D.E. Jr. [Yale Univ., New Haven, CT (United States). School of Medicine; Soufer, R. [Yale Univ., West Haven, CT (United States). PET Center

1995-12-31

3,5,6,7,8,8a-Hexahydro-7,7,8a-trimethyl-[6S-(6{alpha},8{alpha} , 8{alpha}{beta})]-6,8-methano-2H-1,4-benzoxazino-2-one (2) was investigated as chiral auxiliary for asymmetric NCA nucleophilic synthesis of 6-[{sup 18}F]Fluoro-L-DOPA. Direct condensation of 3,4-dimethoxy-2-[{sup 18}F]fluorobenzaldehyde (1a) or 6-[{sup 18}F]fluoro-piperonal (1b) in the presence of NaH with 2 gave the corresponding [{sup 18}F]-3-[(2-fluorophenyl)methylene]-3,5,6,7,8,8a-hexahydro-7,7,8 a-trimethyl-[6S-(3Z,3{alpha},6{alpha},8{alpha},8{alpha}{beta})]-6, 8-methano-2H-1,4-benzoxazin-2-one derivative 3a or 3b as a single stereoisomer. L-Selectride promoted hydrogenation of the olefinic double bond of these derivatives, in presence of tertbutyl alcohol, afforded the corresponding [{sup 18}F]-3-[(2-fluorophenyl) methyl]-3,5,6,7,8,8a-hexahydro-7,7,8a-trimethyl-[3S-(3{alpha}, 6{alpha}, 8{alpha}8{alpha}{beta})]-6,8-methano-2H-1,4-benzoxazin-2-one derivatives (4a,b) without affecting the orientation of diasterofacial discrimination. Deprotection of the derivatives 4a,b yielded 6-[{sup 18}F]fluoro-L-DOPA (e.e. >90%, 3% radiochemical yield (EOB), total synthesis time 125 min, specific activity >2000 mCi/{mu}mol). Direct deprotection/reduction of the compounds 3a,b provides the enantiomeric mixture of 6-[{sup 18}F]fluoro-D,L-DOPA (10-12% radiochemical yield) and, after chiral separation, 6-[{sup 18}F]fluoro-L-DOPA (e.e. 98%, 4-5% radiochemical yield). (author).

Comparison of Lethal Concentrations (LC50-96 H of Cdcl2, Crcl3, and Pb (NO32 in Common Carp (Cyprinus carpio and Sutchi Catfish (Pangasius Hypophthalmus

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Zeynab Abedi

2012-11-01

Full Text Available Background: The present study compared lethal concentrations (LC50-96 h of CdCl2, CrCl3, and Pb (NO32 between two scaled and scaleless freshwater fish species: Cyprinus carpio (Cyprinidae and Pangasius hypophthalmus (Pangasiidae. Methods: The experimental fishes were obtained from fish markets/ponds with average lengths and weights of approximately 11.68 ±1.92 and 9.8±1.9 cm, and 25.92±6.3 and 18.61±3.22 g for C. carpio and P. hypophthalmus, respectively. The fishes were exposed to different concentrations of cadmium (Cd (0, 10, 20, 40, 80, 100, 120, 200 mg L−1 lead (Pb (0, 20, 40, 50, 60, 90, 150 mg L−1, and chromium (Cr (0, 5, 10, 20, 30, 40 mg L−1 for 96 h. Physicochemical parameters, such as dissolved oxygen, pH, and temperature of aquaria as well as mortality rate of the fishes, were monitored daily. Results: The 50% lethal concentrations (LC50-96 h of CdCl2, CrCl3, and Pb (NO32 for P. hypophthalmus were found at 64.89, 7.46, and 48.06 mg L−1, and those of CdCl 2, CrCl 3, Pb (NO32 for C. carpio were detected at 84.8, 17.05, and 77.33 mg L−1. The ratios of heavy metal toxicity factors (TF were greater for common carp compared to those for the catfish. Conclusion: Our preliminary findings suggest that common carp C. carpio with higher LC50 (and LC100 values appears to be more tolerant to heavy metals exposure than the catfish (P. hypophthalmus. This may be due to the resistance to the heavy metals through protection from the carp's scaled body versus scaleless body of the catfish.

Ground and excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters: Insight into the electronic structure of the [Fe(H2O)6]2+ – [Fe(H2O)6]3+ complex

Energy Technology Data Exchange (ETDEWEB)

Miliordos, Evangelos; Xantheas, Sotiris S.

2015-04-14

We report the ground and low lying electronically excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters using multi-configuration electronic structure theory. In particular, we have constructed the Potential Energy Curves (PECs) with respect to the iron-oxygen distance when removing all water ligands at the same time from the cluster minima and established their correlation to the long range dissociation channels. Due to the fact that both the second and third ionization potentials of iron are larger than the one for water, the ground state products asymptotically correlate with dissociation channels that are repulsive in nature at large separations as they contain at least one H2O+ fragment and a positive metal center. The most stable equilibrium structures emanate – via intersections and/or avoided crossings – from the channels consisting of the lowest electronic states of Fe2+(5D; 3d6) or Fe3+(6S; 3d5) and six neutral water molecules. Upon hydration, the ground state of Fe2+(H2O)6 is a triply (5Tg) degenerate one with the doubly (5Eg) degenerate state lying slightly higher in energy. Similarly, Fe3+(H2O)6 has a ground state of 6Ag symmetry under Th symmetry. We furthermore examine a multitude of electronically excited states of many possible spin multiplicities, and report the optimized geometries for several selected states. The PECs for those cases are characterized by a high density of states. Focusing on the ground and the first few excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters, we studied their mutual interaction in the gas phase. We obtained the optimal geometries of the Fe2+(H2O)6 – Fe3+(H2O)6 gas phase complex for different Fe–Fe distances. For distances shorter than 6.0 Å, the water molecules in the respective first solvation shells located between the two metal centers were found to interact via weak hydrogen bonds. We examined a total of ten electronic states for this complex, including those corresponding to the

The moisture content monitoring device for PuO2 using self neutron radiation

International Nuclear Information System (INIS)

Bulanenko, Valeriy I.; Sviridov, Victor; Frolov, Vladimir V.; Ryazanov, Boris G.; Talanov, Vladimir V.

2003-01-01

Solutions technology of plutonium dioxide powders production inevitably leads to free or chemically bound hydrogen to be present in these powders. This work is devoted to the nondestructive method of PuO 2 powder moisture measurement based on application of the effect of neutron moderation caused by water. Plutonium dioxide is fast neutron source, while 3 He counters located in the nickel and polyethylene annular reflectors surrounding PuO 2 serve as detectors. In the work wide range of issues are considered related to practical implementation of the moisture measurement method by detecting inherent neutron radiation of plutonium dioxide powder. The most practical design of the detector has been chosen, which include two 3 He detectors having different reflectors mounted to the device. The absolute error of measurement does not exceed 0.2wt% with confidence coefficient of 0.95. Duration of analysis ∼5 minutes. (author)

Interoperability between OPC UA and AutomationML

OpenAIRE

Henßen, Robert; Schleipen, Miriam

2014-01-01

OPC UA (OPC Unified Architecture) is a platform-independent standard series (IEC 62541) [1], [2] for communication of industrial automation devices and systems. The OPC Unified Architecture is an advanced communication technology for process control. Certainly the launching costs for the initial information model are quite high. AutomationML (Automation Markup Language) is an upcoming open standard series (IEC 62714) [3], [4] for describing production plants or plant components. The goal of t...

Depth profiling of oxide-trapped charges in 6H-SiC MOS structures by slant etching method

Energy Technology Data Exchange (ETDEWEB)

Saitoh, Kazunari; Takahashi, Yoshihiro; Ohnishi, Kazunori [Nihon Univ., Tokyo (Japan). Coll. of Science and Technology; Yoshikawa, Masahito; Ohshima, Takeshi; Itoh, Hisayoshi; Nashiyama, Isamu

1997-03-01

In this paper, we propose a method to evaluate the depth profile of trapped charges in an oxide layer on SiC. Using this method, 6H-SiC MOS structures with different oxide thickness were fabricated on the same substrate under the same oxidation condition, and the depth profile of oxide-trapped charges before and after {sup 60}Co-gamma ray irradiation were obtained. It is found, from the depth profiling, that the trapping mechanism of electrons and holes in the oxide strongly depends on the bias polarity during irradiation, and these charges are trapped near 6H-SiC/SiO{sub 2} interface. We believe that this method is very useful for estimation of the oxide-trapped charges in 6H-SiC MOS structures. (author)

Design and synthesis of a redox-active tc-99m radiopharmaceutical with ferrocenedithiocarboxylate [FcCS=Fe(C{sub 5}H{sub 4}CS{sub 2})(C{sub 5}H{sub 5}){sup -}

Energy Technology Data Exchange (ETDEWEB)

Uccelli, Licia; Bolzati, Cristina; Boschi, Alessandra; Duatti, Adriano E-mail: dta@ifeuniv.unife.it; Morin, Christophe; Pasqualini, Roberto; Giganti, Melchiore; Piffanelli, Adriano

1999-01-01

The synthesis, at tracer level, of two Tc-99m complexes having the same chemical composition and structure, but differing by one electron in the total electron counting, is reported. These compounds have been prepared by reacting [{sup 99m}TcO{sub 4}]{sup -} with the piperidinium salt of the ligand ferrocenedithiocarboxylate {l_brace}[Fe(II)(C{sub 5}H{sub 4}CS{sub 2})(C{sub 5}H{sub 5})]{sup -}=FcCS{r_brace}, in the presence of N-methyl S-methyldithiocarbazate as donor of N{sup 3-} groups, and triphenylphosphine or SnCl{sub 2} as reducing agents. The formation of the neutral complex [{sup 99m}Tc(N)(FcCS){sub 2}] (compound A) and of the monocationic, mixed-valence complex [{sup 99m}Tc(N)(FcCS) (FcCS*)]{sup +} (compound B) {l_brace}FcCS* [Fe(III)(C{sub 5}H{sub 4}CS{sub 2})(C{sub 5}H{sub 5})]{r_brace} was obtained in high yield. Both complexes comprise a terminal Tc{identical_to}N multiple bond and two FcCS ligands coordinated to the metal center through the two sulfur atoms of the -CS{sub 2} group, but they differ in the oxidation state of one of the two iron atoms of the coordinated FcCS ligands. In complex A, the two Fe atoms are both in the +2 oxidation state, while in B, one Fe atom is in the +2 and the other is in the +3 oxidation state. Thus, B is a mixed-valence Fe(II)-Fe(III) complex. B is easily converted into A by one-electron exchange with various reductants such as triphenylphosphine and excess SnCl{sub 2}. Biodistribution studies in rats showed that complexes A and B are mostly retained in lungs and liver without any significant uptake in organs such as heart and brain.

4-(2,4-Dichlorophenyl-6-(1H-indol-3-yl-2,2′-bipyridine-5-carbonitrile

Directory of Open Access Journals (Sweden)

M. N. Ponnuswamy

2009-05-01

Full Text Available The title compound, C25H14Cl2N4, crystallizes with two independent molecules in the asymmetric unit. The two pyridine rings are almost coplanar, making dihedral angles of 3.2 (1 and 8.6 (1° in the two independent molecules. The dichlorophenyl and indole rings are twisted away from the bipyridine ring by 64.32 (5 and 18.46 (4°, respectively in the first molecule and by 51.0 (1 and 27.99 (5°, respectively in the second molecule. The crystal packing is stabilized by C—H...N, C—H...Cl, N—H...N and C—H...π interactions.

Tris(dibenzoylmethanido-κ2O,O′[(6S,8S-(+-7,7-dimethyl-3-(2-pyridyl-5,6,7,8-tetrahydro-6,8-methanoisoquinoline-κ2N,N′]gadolinium(III

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Xi-Li Li

2009-09-01

Full Text Available In the title compound, [Gd(C15H11O23(C17H18N2], the GdIII atom is coordinated by six O atoms from three β-diketonate ligands and two N atoms from a chiral ligand LS,S-(+-7,7-dimethyl-3-(2-pyridyl-5,6,7,8-tetrahydro-6,8-methanoisoquinoline, in a coordination geometry best described as distorted square-antiprismatic.

Exposure of F344 rats to aerosols of 239PuO2 and chronically inhaled cigarette smoke

International Nuclear Information System (INIS)

Finch, G.L.; Nikula, K.J.; Barr, E.B.; Bechtold, W.E.; Chen, B.T.; Griffith, W.C.; Hobbs, C.H.; Hoover, M.D.; Mauderly, J.L.

1994-01-01

Nuclear workers may be accidently exposed to radioactive materials such as 239 PuO 2 by inhalation, and thus have increased risk for lung cancer compared to the general population. Of additional concern is the possibility that interactions between radionuclides and other carcinogens may increase the risk of cancer induction. An important and common lung carcinogen is cigarette smoke. This study is being conducted to better determine the combined effects of inhaled 239 PuO 2 and cigarette smoke on the induction of lung cancer in rats

Toxicity of inhaled 238PuO2 in beagle dogs. A. Monodisperse 1.5 μm 238PuO2. B. Monodisperse 3.0 μm 238PuO2 particles. III

International Nuclear Information System (INIS)

Lustgarten, C.S.; Mewhinney, J.A.; Hobbs, C.H.; Halliwell, W.H.; Jones, R.K.; Mauderly, J.L.; McClellan, R.O.; Mo, T.; Pickrell, J.A.

1976-01-01

To obtain essential information on the importance of the homogeneity or non-homogeneity of the radiation dose to lung (the hot particle question), Beagle dogs have been exposed to monodisperse aerosols (sigma/sub g/ 238 PuO 2 of either 1.5 μm or 3.0 μm aerodynamic diameter (AD). By using monodisperse particles of these two sizes, the average dose to lung is held constant for a given initial lung burden, but the local alpha dose around the two sizes of particles varies by a factor of about ten. All exposures have been completed with 72 days exposed to each of the two particle sizes of 238 PuO 2 (total of 144 dogs) resulting in graded initial lung burdens which range from .005 to 2.2 μCi/kg of body weight. Twenty-four dogs exposed to the diluent aerosol are serving as controls. The animals will be studied over their total life span. Two exposed dogs have died from pulmonary injury: Dog 710C (with an initial lung burden of 2.0 μCi/kg) died at 631 days after inhalation of 3.0 μm AD aerosol. The cause of death was radiation pneumonitis and pulmonary fibrosis, Dog 746B (with an initial lung burden of 1.3 μCi/kg) died at 791 days after inhalation of 1.5 μm AD aerosol. Death was attributed to intrapulmonic hemorrhage resulting from a degenerative vasculitis. One control dog (721A) was euthanized at 820 days after exposure due to a meningitis and encephalomalacia that caused a severe central nervous system disorder that made the dog difficult to handle.A leukopenia in exposed dogs to date has occurred earlier and to a greater degree in dogs exposed to 3.0 μm AD particles than in dogs that recevied 1.5 μm AD particles. One hundred forty-two exposed and 23 control dogs are surviving at 175 to 1024 days after exposure

Characterization and Catalytic Activity of Mn-Co/TiO2 Catalysts for NO Oxidation to NO2 at Low Temperature

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Lu Qiu

2016-01-01

Full Text Available A series of Mn-Co/TiO2 catalysts were prepared by wet impregnation method and evaluated for the oxidation of NO to NO2. The effects of Co amounts and calcination temperature on NO oxidation were investigated in detail. The catalytic oxidation ability in the temperature range of 403–473 K was obviously improved by doping cobalt into Mn/TiO2. These samples were characterized by nitrogen adsorption-desorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscope (TEM and hydrogen temperature programmed reduction (H2-TPR. The results indicated that the formation of dispersed Co3O4·CoMnO3 mixed oxides through synergistic interaction between Mn-O and Co-O was directly responsible for the enhanced activities towards NO oxidation at low temperatures. Doping of Co enhanced Mn4+ formation and increased chemical adsorbed oxygen amounts, which also accelerated NO oxidation.

The CD control improvement by using CDSEM 2D measurement of complex OPC patterns

Science.gov (United States)

Chou, William; Cheng, Jeffrey; Lee, Adder; Cheng, James; Tzeng, Alex C.; Lu, Colbert; Yang, Ray; Lee, Hong Jen; Bandoh, Hideaki; Santo, Izumi; Zhang, Hao; Chen, Chien Kang

2016-10-01

As the process node becomes more advanced, the accuracy and precision in OPC pattern CD are required in mask manufacturing. CD SEM is an essential tool to confirm the mask quality such as CD control, CD uniformity and CD mean to target (MTT). Unfortunately, in some cases of arbitrary enclosed patterns or aggressive OPC patterns, for instance, line with tiny jogs and curvilinear SRAF, CD variation depending on region of interest (ROI) is a very serious problem in mask CD control, even it decreases the wafer yield. For overcoming this situation, the 2-dimensional (2D) method by Holon is adopted. In this paper, we summarize the comparisons of error budget between conventional (1D) and 2D data using CD SEM and the CD performance between mask and wafer by complex OPC patterns including ILT features.

N-(2-Methylphenyl-1,2-benzoselenazol-3(2H-one

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Xu Zhu

2013-10-01

Full Text Available In the title Ebselen [systematic name: (2-phenyl-1,2-benzoisoselenazol-3-(2H-one] analogue, C14H11NOSe, the benzisoselenazolyl moiety (r.m.s. deviation = 0.0209 Å is nearly perpendicular to the N-arenyl ring, making a dihedral angle of 78.15 (11°. In the crystal, molecules are linked by C—H...O and Se...O interactions into chains along the c-axis direction. The Se...O distance [2.733 (3 Å] is longer than that in Ebselen (2.571 (3 Å].

5-Fluoro-6′H,7′H,8′H-spiro[indoline-3,7′-pyrano[3,2-c:5,6-c′]di-1-benzopyran]-2,6′,8′-trione

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J. Suresh

2012-03-01

Full Text Available In the title compound, C26H12FNO6, the central pyran ring and both benzopyran systems are nonplanar, having total puckering amplitudes of 0.139 (2, 0.050 (1 and 0.112 (2 Å, respectively. The central pyran ring adopts a boat conformation. The crystal structure is stabilized by C—H...O, N—H...O, N—H...F and C—H...π interactions.

Oxidation mode of pyranose 2-oxidase is controlled by pH.

Science.gov (United States)

Prongjit, Methinee; Sucharitakul, Jeerus; Palfey, Bruce A; Chaiyen, Pimchai

2013-02-26

Pyranose 2-oxidase (P2O) from Trametes multicolor is a flavoenzyme that catalyzes the oxidation of d-glucose and other aldopyranose sugars at the C2 position by using O₂ as an electron acceptor to form the corresponding 2-keto-sugars and H₂O₂. In this study, the effects of pH on the oxidative half-reaction of P2O were investigated using stopped-flow spectrophotometry. The results showed that flavin oxidation occurred via different pathways depending on the pH of the environment. At pH values lower than 8.0, reduced P2O reacts with O₂ to form a C4a-hydroperoxyflavin intermediate, leading to elimination of H₂O₂. At pH 8.0 and higher, the majority of the reduced P2O reacts with O₂ via a pathway that does not allow detection of the C4a-hydroperoxyflavin, and flavin oxidation occurs with decreased rate constants upon the rise in pH. The switching between the two modes of P2O oxidation is controlled by protonation of a group which has a pK(a) of 7.6 ± 0.1. Oxidation reactions of reduced P2O under rapid pH change as performed by stopped-flow mixing were different from the same reactions performed with enzyme pre-equilibrated at the same specified pH values, implying that the protonation of the group which controls the mode of flavin oxidation cannot be rapidly equilibrated with outside solvent. Using a double-mixing stopped-flow experiment, a rate constant for proton dissociation from the reaction site was determined to be 21.0 ± 0.4 s⁻¹.

N-Substituted 5-Chloro-6-phenylpyridazin-3(2H-ones: Synthesis, Insecticidal Activity Against Plutella xylostella (L. and SAR Study

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Song Yang

2012-08-01

Full Text Available A series of N-substituted 5-chloro-6-phenylpyridazin-3(2H-one derivatives were synthesized based on our previous work; all compounds were characterized by spectral data and tested for in vitro insecticidal activity against Plutella xylostella. The results showed that the synthesized pyridazin-3(2H-one compounds possessed good insecticidal activities, especially the compounds 4b, 4d, and 4h which showed > 90% activity at 100 mg/L. The structure-activity relationships (SAR for these compounds were also discussed.

Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

Science.gov (United States)

Lange, R. A.; Waters, L.

2014-12-01

The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels

2,6-Diaminopyridinium bis(4-hydroxypyridine-2,6-dicarboxylato-κ3O2,N,O6ferrate(III dihydrate

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Andya Nemati

2008-10-01

Full Text Available The reaction of iron(II sulfate heptahydrate with the proton-transfer compound (pydaH(hypydcH (pyda = pyridine-2,6-diamine; hypydcH2 = 4-hydroxypyridine-2,6-dicarboxylic acid in an aqueous solution led to the formation of the title compound, (C5H8N3[Fe(C7H3NO52]·2H2O. The anion is a six-coordinated complex with a distorted octahedral geometry around the FeIII atom. Extensive intermolecular O—H...O, N—H...O and C—H...O hydrogen bonds, involving the complex anion, (pydaH+ counter-ion and two uncoordinated water molecules, and π–π [centroid-to-centroid distance 3.323 (11 Å] and C—O...π [O–centroid distance 3.150 (15 Å] interactions connect the various components into a supramolecular structure.

Concentration dependences of the density, viscosity, and refraction index of Cu(NO3)2 · 3H2O solutions in DMSO at 298 K

Science.gov (United States)

Mamyrbekova, A. K.

2013-03-01

Physicochemical properties (density, dynamic viscosity, refraction index) of the DMSO-Cu(NO3)2 · 3H2O system are studied in the concentration range of 0.01-2 M at 298 K. The refraction index of a solution of copper(II) nitrate in dimethylsulfoxide (DMSO) is measured at 288-318 K. The excess and partial molar volumes of the solvent and dissolved substance are calculated analytically.

The application of a monolithic triphenylphosphine reagent for conducting Appel reactions in flow microreactors.

Science.gov (United States)

Roper, Kimberley A; Lange, Heiko; Polyzos, Anastasios; Berry, Malcolm B; Baxendale, Ian R; Ley, Steven V

2011-01-01

Herein we describe the application of a monolithic triphenylphosphine reagent to the Appel reaction in flow-chemistry processing, to generate various brominated products with high purity and in excellent yields, and with no requirement for further off-line purification.

Synthesis, solvatochromism and crystal structure of trans-[Cu(Et2NCH2CH2NH2)2.H2O](NO3)2 complex: Experimental with DFT combination

Science.gov (United States)

Warad, Ismail; Musameh, Sharif; Badran, Ismail; Nassar, Nashaat N.; Brandao, Paula; Tavares, Carlos Jose; Barakat, Assem

2017-11-01

In this study, two dicationic asymmetrical diamine/copper(II) nitrate salt complexes of the general formula trans-[CuII(NN‧)2.H2O](NO3)2 were successfully synthesized using N,N-dimethylethylenediamine and N,N-diethylethylenediamine as asymmetrical diamine ligands. The structure of complex 2 was identified by X-ray single crystal diffraction analysis confirming that the bidentate ligand N,N-dimethylethylenediamine forms a penta-coordinated complex with an H2O molecule located around the copper(II) ion in a trans configuration. It was found that the metal centre is coordinated in a distorted square pyramidal fashion with a τ value of 0.274. The desired complexes were fully characterized using, MS, UV-Vis, CV, FTIR, TG/DTA, and Hirshfeld surface computational analysis. High level theoretical calculations were also performed in order to investigate the complexes structure, conformers, vibrational frequencies, and their excited states.

Chemical behaviour of plutonium in aqueous chloride solutions

International Nuclear Information System (INIS)

Bueppelmann, K.; Kim, J.I.

1988-06-01

The chemical behaviour of Plutonium has been investigated in concentrated NaCl solutions in the neutral pH range. The α-radiation induced radiolysis reactions oxidize the Cl - -ion to Cl 2 , HClO, ClO - and other species, which produce a strongly oxidizing medium. Under these conditions the Pu ions of lower oxidation states are readily oxidized to Pu(VI), which then undergo depending on the pH of the solution, various chemical reactions to produce PuO 2 Cl n , PuO 2 (ClO) m or PuO 2 (OH) x species. In addition to primary radiolysis reactions taking place in NaCl solutions, the reactions leading to the PuO 2 (Cl) n and PuO 2 (ClO) m species have been characterized and quantified systematically by spectroscopic and thermodynamic evaluation. The redox and complexation reactions of Pu ions under varying NaCl concentration, specific α-activity and pH are discussed. (orig.) [de

Kinetics of oxidation of H2 and reduction of H2O in Ni-YSZ based solid oxide cells

DEFF Research Database (Denmark)

Ebbesen, Sune Dalgaard; Mogensen, Mogens Bjerg

2012-01-01

Reduction of H2O and oxidation of H2 was studied in a Ni-YSZ electrode supported Solid Oxide Cells produced at DTU Energy conversion (former Risø DTU). Polarisation (i-V) and electrochemical impedance spectroscopic characterisation show that the kinetics for reduction of H 2O is slower compared...... to oxidation of H2. The kinetic differences cannot be explained by the reaction mechanisms which are similar in the two cases but are rather an effect of the thermodynamics. The preliminary analysis performed in this study show that the slow kinetic for reduction is partly related to the endothermic nature...... of the reaction, cooling the active electrode, thereby leading to slower kinetics at low current densities. Likewise, the increased kinetic for oxidation was found to be related to the exothermic nature of the reaction, heating the active electrode, and thereby leading to faster kinetics. At higher current...

[Pr2(pdc3(Hpdc(H2O4]n·n(H3hp·8n(H2O, a One-Dimensional Coordination Polymer Containing PrO6N3 Tri-Capped Trigonal Prisms and PrO8N Mono-Capped Square Anti-Prisms (H2pdc = Pyridine 2,6-Dicarboxylic Acid, C7H5NO4; 3hp = 3-Hydroxy Pyridine, C5H5NO

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Shahzad Sharif

2012-08-01

Full Text Available The synthesis, structure and some properties of the one-dimensional coordination polymer, [Pr2(pdc3(Hpdc]n·n(H3hp·8n(H2O, (H2pdc = pyridine 2,6-dicarboxylic acid, C7H5NO4; 3hp = 3-hydroxypyridine, C5H5NO are described. One of the Pr3+ ions is coordinated by two O,N,O-tridentate pdc2− ligands and one tridentate Hpdc− anion to generate a fairly regular PrO6N3 tri-capped trigonal prism, with the N atoms acting as the caps. The second Pr3+ ion is coordinated by one tridentate pdc2− dianion, four water molecules and two monodentate bridging pdc2− ligands to result in a PrO8N coordination polyhedron that approximates to a mono-capped square-anti-prism. The ligands bridge the metal-atom nodes into a chain, which extends in the [100] direction. The H3hp+ cation and uncoordinated water molecules occupy the inter-chain regions and an N–HLO and numerous O–HLO hydrogen bonds consolidate the structure. The H3hp+ species appears to intercalate between pendant pdc rings to consolidate the polymeric structure. Crystal data: 1 (C33H43N5O29Pr2, Mr = 1255.54, triclinic,  (No. 2, Z = 2, a = 13.2567(1 Å, b = 13.6304(2 Å, c = 13.6409(2 Å, α = 89.695(1°, β = 63.049(1°, γ = 86.105(1°, V = 2191.16(5 Å3, R(F = 0.033, wR(F2 = 0.084.

Superstructure Ta2O5 mesocrystals derived from (NH4)2Ta2O3F6 mesocrystals with efficient photocatalytic activity.

Science.gov (United States)

Yu, Xin; Li, Wei; Huang, Jian; Li, Zhonghua; Liu, Jiawen; Hu, PingAn

2018-02-06

Superstructured mesocrystalline Ta 2 O 5 nanosheets were successfully prepared from mesocrystalline (NH 4 ) 2 Ta 2 O 3 F 6 nanorods by the annealing method for the first time. The as-prepared mesocrystalline Ta 2 O 5 nanosheets in this work showed remarkable visible light absorption, mainly due to the formation of oxygen vacancy defects in the mesocrystalline Ta 2 O 5 nanosheets, which was also confirmed by XPS spectra, Raman spectra and EPR spectra. Besides, the mesocrystalline Ta 2 O 5 nanosheets showed a highly enhanced photocatalytic activity of 11 268.24 μmol g -1 h -1 , about 3.95 times that of commercial Ta 2 O 5 . Moreover, the specific surface area of the mesocrystalline Ta 2 O 5 -800 nanosheets was 16.34 m 2 g -1 , about 5.32 times that of the commercial Ta 2 O 5 (3.072 m 2 g -1 ). The valence band XPS spectra indicated a strong oxidizing ability of the mesocrystalline Ta 2 O 5 nanosheets in comparison to that of commercial Ta 2 O 5 . The formation of superstructured Ta 2 O 5 mesocrystals generated long lifetime carriers and effective conduction pathways, which greatly enhanced the photocatalytic activity for hydrogen production.

Effects of moisture and extrusion temperatures on the oxidative stability of milling oat products with granularity below 532 µm

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Luiz Carlos Gutkoski

1998-08-01

Full Text Available The present research had as objective to study the effects of moisture and extrusion temperatures on the oxidative stability of oat fine (Estudos foram realizados com o objetivo avaliar os efeitos de umidade inicial da matéria-prima e da temperatura de extrusão na estabilidade oxidativa de produtos de aveia (Avena sativa L. Cariopses de aveia foram moídas em moinho de rolos Brabender e obtidas frações de granulometrias superior e inferior a 532 µm. A fração de granulometria inferior a 532 µm, de alto teor de a,mido e baixos teores de proteínas, lipídios e fibra alimentar, foi condicionada na umidade desejada (15,5-25,5% e extrusada em extrusor de laboratório Brabender monorosca. As condições usadas na extrusão foram taxa de compressão de 3:1, rotação de 100 rpm, matriz de 6 mm de diâmetro e temperaturas entre 77,6 e 162,4ºC nas 2ª e 3ª zonas e de 80ºC na 1ª zona. O material extrusado foi seco em estufa, moído, acondicionado em sacos plásticos e utilizado periodicamente nas determinações de peróxidos e de n-hexanal. O conteúdo de ácidos graxos insaturados no óleo da fração de aveia estudada foi elevado (79,20%. Independentemente do teor de umidade inicial da matéria-prima, todos os produtos extrusados em temperaturas inferiores a 120 ºC apresentaram baixa rancidez oxidativa.

Oxygen-to-metal ratio control during fabrication of mixed oxide fast breeder reactor fuel pellets

International Nuclear Information System (INIS)

Rasmussen, D.E.; Benecke, M.W.; Jentzen, W.R.; McCord, R.B.

1979-05-01

Oxygen-to-metal ratio (O/M) of mixed oxide fuel pellets can be controlled during fabrication by proper selection of binder (type and content) and sintering conditions. Sintering condition adjustments involved the passing of Ar--8% H 2 sintering gas across a cryostat ice bath controlled to temperatures ranging from -5 to -60 0 C to control as-sintered pellet O/M ratio. As-sintered fuel pellet O/M decreased with increasing Sterotex binder and PuO 2 concentrations, increasing sintering temperature, and decreasing sintering gas dew point. Approximate relationships between Sterotex binder level and O/M were established for PuO 2 --UO 2 and PuO 2 --ThO 2 fuels. O/M was relatively insensitive to Carbowax binder concentration. Several methods of increasing O/M using post-sintering pellet heat treatments were demonstrated, with the most reliable being a two-step process of first raising the O/M to 2.00 (stoichiometric) at 650 0 C in Ar--8% H 2 bubbled through H 2 O, followed by hydrogen reduction to specification O/M in oxygen-gettered Ar-8% H 2 at temperatures ranging from 1200 to 1690 0 C

Is Oxidative Stress in Mice Brain Regions Diminished by 2-[(2,6-Dichlorobenzylideneamino]-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile?

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A. C. Fortes

2013-01-01

Full Text Available 2-[(2,6-Dichlorobenzylideneamino]-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile, 5TIO1, is a new 2-aminothiophene derivative with promising pharmacological activities. The aim of this study was to evaluate its antioxidant activity in different areas of mice central nervous system. Male Swiss adult mice were intraperitoneally treated with Tween 80 dissolved in 0.9% saline (control group and 5TIO1 (0.1, 1, and 10 mg kg−1. Brain homogenates—hippocampus, striatum, frontal cortex, and cerebellum—were obtained after 24 h of observation. Superoxide dismutase and catalase activities, lipid peroxidation and nitrite content were measured using spectrophotometrical methods. To clarify the 5TIO1’s mechanism on oxidative stress, western blot analysis of superoxide dismutase and catalase was also performed. 5TIO1 decreased lipid peroxidation and nitrite content in all brain areas and increased the antioxidant enzymatic activities, specially, in cerebellum. The data of Western blot analysis did not demonstrate evidence of the upregulation of these enzymes after the administration of this compound. Our findings strongly support that 5TIO1 can protect the brain against neuronal damages regularly observed during neuropathologies.

A Convenient and Direct Route to 1,2-Dichlorovinylphosphine ...

African Journals Online (AJOL)

NICO

additions of P(O)H compounds to alkynes, but relatively few papers on the synthesis of 1,2-dichloro vinylphosphine oxide derivatives have been reported. There is only Ismailov's report on the synthesis of 1,2-dichlorovinylphosphonates from. 1,1-dichloro-2-oxoethylphosphonate and triphenylphosphine.14. This sparked our ...

Absorption of SO2 and NO through an integrative process with a cost-effective aqueous oxidant

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Chelluboyana Vaishnava Raghunath

2016-09-01

Full Text Available Due to the substantial influence on the environment and health, there has been an intensifying environmental concern on sulfur dioxide (SO2 and nitrogen oxide (NO discharge to the atmosphere all over the world. Flue gas of coal-fired power stations is major leading source for the emission of SO2 and NO. Cost-effective and balanced technologies for the reduction of these pollutants from flue gas have become increasingly essential at the present time. The preliminary experimental attributes were retrieved in a batch scale agitating bubbling reactor for instantaneous absorption of SO2 and NO using aqueous oxidant. The prime conditions for instantaneous absorption examined were including absorbent concentration, reaction temperature, and pH in the fabricated flue gas system. Removal efficiencies of 99% for SO2 and 85% for NO were acquired, respectively under absorbent concentration 5 g/100 ml, reaction temperature 313 K, and pH 5.6.

Contribution of the pre-ionized H2 and the ionized H2+ subsystems to the HHG Spectra of H2 in intense laser fields

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Iravani, Hossein; Sabzyan, Hassan; Vafaee, Mohsen; Buzari, Behnaz

2018-04-01

Contributions of the pre-ionized H2 (PI-H2) and ionized {{{H}}}2+ subsystems of the two-electron H2 system to its high-order harmonic generation in eight-cycle sin2-like ultrafast intense laser pulses are calculated and analyzed based on the solution of the time-dependent Schrödinger equation for the one-dimensional two-electronic H2 system with fixed nuclei. The laser pulses have λ = 390 and 532 nm wavelengths and I = 1 × 1014, 5 × 1014, 1 × 1015 and 5 × 1015 W cm‑2 intensities. It is found that at the two lower intensities, the PI-H2 subsystem dominantly produces the HHG spectra. However, at the two higher intensities, both PI-H2 and ionized {{{H}}}2+ subsystems contribute comparably to the HHG spectra. In the {{{H}}}2+ subsystem, the symmetry of the populations of {{{H}}}2+(I) and {{{H}}}2+(II) regions (left and right regions of {{{H}}}2+ subsystem) is broken by increasing the laser intensity. Complex patterns and even harmonics also appear at these two higher intensities. For instance, at 1 × 1015 W cm‑2 intensity and λ = 532 nm wavelength, the even harmonics are appeared near cutoff region. Interestingly, at 5 × 1015 W cm‑2 intensity and λ = 390 nm wavelength, the even harmonics replaced by the odd harmonics with red shift. At λ = 390 and 532 nm wavelengths and I = 1 × 1015 intensity, the two-electron cutoffs corresponding to nonsequential double-recombination with maximum return kinetic energy of 4.70Up are detected. The HHG spectra of the whole H2 system obtained with and without nuclear dynamics treated classically are approximately similar. However, at 1 × 1015 W cm‑2 intensity and λ = 532 nm wavelength, if we take into account nuclear dynamics, the even harmonics which are appeared near cutoff region, replaced by the odd harmonics with blue shift.

H2S Attenuates LPS-Induced Acute Lung Injury by Reducing Oxidative/Nitrative Stress and Inflammation

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Hong-Xia Zhang

2016-12-01

Full Text Available Background: Hydrogen sulfide (H2S, known as the third endogenous gaseous transmitter, has received increasing attention because of its diverse effects, including angiogenesis, vascular relaxation and myocardial protection.We aimed to investigate the role of H2S in oxidative/nitrative stress and inflammation in acute lung injury (ALI induced by endotoxemia. Methods: Male ICR mice were divided in six groups: (1 Control group; (2 GYY4137treatment group; (3 L-NAME treatment group; (4 lipopolysaccharide (LPS treatment group; (5 LPS with GYY4137 treatment group; and (6 LPS with L-NAME treatment group. The lungs were analysed by histology, NO production in the mouse lungs determined by modified Griess (Sigma-Aldrich reaction, cytokine levels utilizing commercialkits, and protein abundance by Western blotting. Results: GYY4137, a slowly-releasing H2S donor, improved the histopathological changes in the lungs of endotoxemic mice. Treatment with NG-nitro-L-arginine methyl ester (L-NAME, a nitric oxide synthase (NOS inhibitor, increased anti-oxidant biomarkers such as thetotal antioxidant capacity (T-AOC and theactivities of catalase (CAT and superoxide dismutase (SOD but decreased a marker of peroxynitrite (ONOO- action and 3-nitrotyrosine (3-NT in endotoxemic lung. L-NAME administration also suppressed inflammation in endotoxemic lung, as evidenced by the decreased pulmonary levels of interleukin (IL-6, IL-8, and myeloperoxidase (MPO and the increased level of anti-inflammatory cytokine IL-10. GYY4137 treatment reversed endotoxin-induced oxidative/nitrative stress, as evidenced by a decrease in malondialdehyde (MDA, hydrogenperoxide (H2O2 and 3-NT and an increase in the antioxidant biomarker ratio of reduced/oxidized glutathione(GSH/GSSG ratio and T-AOC, CAT and SOD activity. GYY4137 also attenuated endotoxin-induced lung inflammation. Moreover, treatment with GYY4137 inhibited inducible NOS (iNOS expression and nitric oxide (NO production in the

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

The oxidation mode of pyranose 2-oxidase is controlled by pH

Science.gov (United States)

Prongjit, Methinee; Sucharitakul, Jeerus; Palfey, Bruce A.; Chaiyen, Pimchai

2013-01-01

Pyranose 2-oxidase (P2O) from Trametes multicolor is a flavoenzyme that catalyzes the oxidation of D-glucose and other aldopyranose sugars at the C2 position by using O2 as an electron acceptor to form the corresponding 2-keto-sugars and H2O2. In this study, the effects of pH on the oxidative half-reaction of P2O were investigated using stopped-flow spectrophotometry. The results showed that flavin oxidation occurred via different pathways depending on the pH of the environment. At pH values lower than 8.0, reduced P2O reacts with O2 to form a C4a-hydroperoxy-flavin intermediate, leading to elimination of H2O2. At pH 8.0 and higher, the majority of the reduced P2O reacts with O2 via a pathway which does not allow detection of the C4a-hydroperoxy-flavin, and flavin oxidation occurs with decreased rate constants upon the rise in pH. The switching between the two modes of P2O oxidation is controlled by protonation of a group which has a pKa of 7.6 ± 0.1. Oxidation reactions of reduced P2O under rapid pH change as performed by stopped-flow mixing were different from the same reactions performed with enzyme pre-equilibrated at the same specified pH values, implying that the protonation of the group which controls the mode of flavin oxidation cannot be rapidly equilibrated with outside solvent. Using a double-mixing stopped-flow experiment, a rate constant for proton dissociation from the reaction site was determined to be 21.0 ± 0.4 s-1. PMID:23356577