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Sample records for radiolytic reactions involving

  1. Thermal and combined thermal and radiolytic reactions involving nitrous oxide, hydrogen, nitrogen, and ammonia in contact with tank 241-SY-101 simulated waste

    International Nuclear Information System (INIS)

    Bryan, S.A.; Pederson, L.R.

    1996-02-01

    Work described in this report was conducted at Pacific Northwest National Laboratory (PNNL) for the Flammable Gas Safety Project, the purpose of which is to develop information needed to support Westinghouse Hanford Company (WHC) in their efforts to ensure the safe interim storage of wastes at the Hanford Site. Described in this report are the results of tests to evaluate the rates of thermal and combined thermal and radiolytic reactions involving flammable gases in the presence of Tank 241-SY-101 simulated waste. Flammable gases generated by the radiolysis of water and by the thermal and radiolytic decomposition of organic waste constituents may themselves participate in further reactions. Examples include the decomposition of nitrous oxide to yield nitrogen and oxygen, the reaction of nitrous oxide and hydrogen to produce nitrogen and water, and the reaction of nitrogen and hydrogen to produce ammonia. The composition of the gases trapped in bubbles in the wastes might therefore change continuously as a function of the time that the gas bubbles are retained

  2. Radiolytic reactions in the coolant of helium cooled reactors

    International Nuclear Information System (INIS)

    Tingey, G.L.; Morgan, W.C.

    1975-01-01

    The success of helium cooled reactors is dependent upon the ability to prevent significant reaction between the coolant and the other components in the reactor primary circuit. Since the thermal reaction of graphite with oxidizing gases is rapid at temperatures of interest, the thermal reactions are limited primarily by the concentration of impurity gases in the helium coolant. On the other hand, the rates of radiolytic reactions in helium are shown to be independent of reactive gas concentration until that concentration reaches a very low level. Calculated steady-state concentrations of reactive species in the reactor coolant and core burnoff rates are presented for current U. S. designed, helium cooled reactors. Since precise base data are not currently available for radiolytic rates of some reactions and thermal reaction rate data are often variable, the accuracy of the predicted gas composition is being compared with the actual gas compositions measured during startup tests of the Fort Saint Vrain high temperature gas-cooled reactor. The current status of these confirmatory tests is discussed. 12 references

  3. Radiolytic and electron-transfer reactions in supercritical CO2

    International Nuclear Information System (INIS)

    Bartels, D. M.; Dimitrijevic, N. M.; Jonah, C. D.; Takahashi, K.

    2000-01-01

    Using supercritical fluids as solvents is useful for both practical and theoretical reasons. It has been proposed to use supercritical CO 2 as a solvent for synthesis because it eliminates the air pollution arising from other solvents. The properties of supercritical fluids can be easily varied with only modest changes in temperature and density, so they provide a way of testing theories of chemical reactions. It has also been proposed to use supercritical fluids for the treatment of hazardous mixed waste. For these reasons the authors have studied the production of radiolytic species in supercritical CO 2 and have measured their reactivity as a function of density. They have shown that the C 2 O 4 + is formed. They also have shown that the electron transfer reactions of dimethylaniline to C 2 O 4 + and CO 2 (e - ) to benzoquinone are diffusion controlled over a considerable density range

  4. A model for void-induced back reaction between radiolytic products in NaCl

    NARCIS (Netherlands)

    Turkin, A.A.; Dubinko, V.I.; Vainshtein, D.I.; Hartog, H.W. den

    A kinetic model is formulated for the chemical reaction between radiolytic sodium colloids and gas bubbles, which are brought into contact with each other during the exposure to ionising radiation by the growing voids. The reaction starts with the evaporation of Na atoms into the void due to the

  5. Radiolytic oxidation of propane: computer modeling of the reaction scheme

    International Nuclear Information System (INIS)

    Gupta, A.K.; Hanrahan, R.J.

    1991-01-01

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25 o C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases. (author)

  6. Radiolytic oxidation of propane: Computer modeling of the reaction scheme

    Science.gov (United States)

    Gupta, Avinash K.; Hanrahan, Robert J.

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25°C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. Minor products include i-butyl alcohol, t-amyl alcohol, n-butyl alcohol, n-amyl alcohol, and i-amyl alcohol. Small yields of i-hexyl alcohol and n-hexyl alcohol were also observed. There was no apparent difference in the G-values at pressures of 50, 100 and 150 torr. When the oxygen concentration was decreased below 5%, the yields of acetone, i-propyl alcohol, and n-propyl alcohol increased, the propionaldehyde yield decreased, and the yields of other products remained constant. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases.

  7. Chemical reaction networks as a model to describe UVC- and radiolytically-induced reactions of simple compounds.

    Science.gov (United States)

    Dondi, Daniele; Merli, Daniele; Albini, Angelo; Zeffiro, Alberto; Serpone, Nick

    2012-05-01

    When a chemical system is submitted to high energy sources (UV, ionizing radiation, plasma sparks, etc.), as is expected to be the case of prebiotic chemistry studies, a plethora of reactive intermediates could form. If oxygen is present in excess, carbon dioxide and water are the major products. More interesting is the case of reducing conditions where synthetic pathways are also possible. This article examines the theoretical modeling of such systems with random-generated chemical networks. Four types of random-generated chemical networks were considered that originated from a combination of two connection topologies (viz., Poisson and scale-free) with reversible and irreversible chemical reactions. The results were analyzed taking into account the number of the most abundant products required for reaching 50% of the total number of moles of compounds at equilibrium, as this may be related to an actual problem of complex mixture analysis. The model accounts for multi-component reaction systems with no a priori knowledge of reacting species and the intermediates involved if system components are sufficiently interconnected. The approach taken is relevant to an earlier study on reactions that may have occurred in prebiotic systems where only a few compounds were detected. A validation of the model was attained on the basis of results of UVC and radiolytic reactions of prebiotic mixtures of low molecular weight compounds likely present on the primeval Earth.

  8. Radiolytic reduction reaction of colloidal silver bromide solution

    International Nuclear Information System (INIS)

    Oya, Yasuhisa; Zushi, Takehiro; Hasegawa, Kunihiko; Matsuura, Tatsuo.

    1995-01-01

    The reduction reaction of colloidal silver bromide (AgBr 3 ) 2- in nitrous oxide gas saturated solution of some alcohols: methanol, ethanol, 2-propanol and 2-methyl-2-propanol by γ-irradiation was studied spectrophotometrically in order to elucidate the mechanism of the formation of colloidal silver bromide (AgBr 3 ) 3- at ambient temperature. The amount of colloidal silver bromide formed increases in the order: i-PrOH, EtOH, MeOH. In t-BuOH, colloidal silver bromide did not form. The relative reactivities of alcohols for colloidal silver bromide was also studied kinetically. (author)

  9. Concerted effects in the reaction of ·OH radicals with aromatics: radiolytic oxidation of salicylic acid

    International Nuclear Information System (INIS)

    Albarran, G.; Schuler, R.H.

    2003-01-01

    Liquid chromatographic and capillary electrophoretic studies have been used to resolve the products produced in the radiolytic oxidation of salicylic acid in aqueous solution. These studies have shown that, as in the case of phenol, · OH radicals preferentially add to the positions ortho and para to the OH substituent. However, in contrast to its reaction with phenol, addition at the ortho position is favored over addition at the para position. Because · OH radical is a strong electrophile this difference suggests that the electron population at the ortho position in the salicylate anion is enhanced as a result of the hydrogen bonding in salicylic acid

  10. The complex reaction sequence of the thermal and radiolytic degradation of polyvinyl chloride

    International Nuclear Information System (INIS)

    Reichert, W.

    1983-03-01

    The degradation of PVC-foils was been tested by thermal and radiolytic stress in N 2 - and O 2 -atmosphere. Additionally was determined the influence of plasticizers, Fe-, Zn- and Cu-stearates and other additives, which partially are known as stabilizators. Complex mechanisms of degradation are proposed, which were deduced from the HCl-elimination, consumption of oxygen and the shift of the molmass by the scission and crosslinking of main chains both for PVC as combination of PVC with additives. The mechanism corresponds to other known experimental results, too. It was shown, that the radiolytical degradation caused by radicals, which initiate a radical chain mechanism, if the temperature is higher than the glass temperature (Tg). The thermical degradation in a N 2 -atmosphere was explained by an ionic complex mechanism. At the presence of oxygen the ionic mechanism was superimposed by a radical chain mechanism following the oxidation of polyene structures. (author)

  11. Measurements of rates of some reactions related to radiolytic effect on aqueous iodide solution

    International Nuclear Information System (INIS)

    Shiraishi, H.; Okuda, H.; Ishigure, K.

    1986-01-01

    A number of reactions takes place concurrently when aqueous iodide solution is subjected to radiation field. In order to help analyze this complicated radiation effect measurements of rate constants were undertaken for several important reactions. One of these concerns reduction of hypoiodous acid by hydrogen peroxide. For this reaction catalytic effect was found to be significant, and old rate data was revised. Measurements on reactions involving radicals were carried out by use of pulse radiolysis technique, which also include reexamination of results by previous workers. The reactions studied are (1) oxidation of iodide ion by hydroxyl radical (2) recombination reactions of atomic iodine and diiodide ion and (3) reduction of atomic and molecular iodine either by superoxide ion or by hydroperoxyl radical

  12. The transient reaction characteristic of piperonal and anthraquinone derivative: a pulse radiolytic study

    International Nuclear Information System (INIS)

    Ma Jianhua; Lin Weizhen; Wang Wenfeng; Yao Side

    2006-01-01

    Piperonal belongs to naturally organic compound and anthraquinone-2-sulfate is a important anthraquinone derivative. In this work, the transient reaction characteristic of piperonal and anthraquinone derivative has been investigated. The transient absorption spectra of the product from electron transfer reaction between piperonal and anthraquinone-2-sulfate was obtained, the electron transfer between electron donor and acceptor was observed directly. (authors)

  13. Pulse radiolytic study of the reaction OH + O3 in aqueous medium

    International Nuclear Information System (INIS)

    Sehested, K.; Holcman, J.; Bjergbakke, E.; Hart, E.J.

    1984-01-01

    In slightly alkaline solution the ozonide radical ion, O 3 - , forms as a product of the hydroxyl radical reaction with ozone. For each O 3 - formed, two O 3 molecules are consumed. In acid solution the product of this reaction is the perhydroxyl radical, HO 2 , formed from one O 3 molecule. Our results are consistent with the gas-phase reaction where the products are HO 2 and O 2 . A rate constant of (1.1 +/- 0.2) x 10 8 dm 3 mol -1 s -1 is found for the reaction OH + O 3 → HO 2 + O 2 . This rate constant was obtained by three systems, by buildup of O 3 - in basic solutions, by competition of the OH radical with the carbonate ion, and directly by O 3 consumption in acid solution. The rate constant for the reaction of HO 2 with O 3 is very low, 4 dm 3 mol -1 s -1 . At pH greater than or equal to 1, HO 2 reacts with O 3 preferentially in its dissociated form, O 2 - . No spectroscopic evidence has been found for the HO 3 and HO 4 free-radical intermediates. 24 references, 4 figures, 2 tables

  14. Radiolytic oxidation

    International Nuclear Information System (INIS)

    Burns, W.G.; Ewart, F.T.; Hobley, J.; Smith, A.J.; Walters, W.S.; Williams, S.J.

    1991-01-01

    Work under the Radiolytic Oxidation Contract from 1986 until April 1989 is reported. The effects of alpha- and gamma-irradiation on the chemistries of plutonium, neptunium and technetium, under conditions representative of the near fields of intermediate and high level waste repositories, were investigated. Gamma-radiolysis of Np (IV) results in oxidation in solutions below pH 12. Solutions of Tc (VII) are reduced to Tc (IV) by gamma-irradiation in contact with blast furnace slag/ordinary Portland cement under an inert atmosphere but not when in contact with pulverized fuel ash/ordinary Portland cement. Tc (IV) is shown to be susceptible to oxidation by the products of the alpha-radiolysis of water. The results of 'overall effects' experiments, which combined representative components of typical ILW or HLW near fields, supported these observations and also showed enhanced plutonium concentrations in alpha-irradiated, HLW simulations. Mathematical models of the behaviour of plutonium and neptunium during gamma-radiolysis have been developed and indicate that oxidation to Pu (VI) is possible at dose rates typical of those expected for HLW. Simulations at ILW dose rates have indicated some effect upon the speciation of neptunium. Laboratory studies of the gamma-irradiation of Np (IV) in bentonite-equilibrated water have also been modelled. Computer code used: PHREEQE, 8 Figs.; 48 Tabs.; 38 refs

  15. Aldehydes, ketones, and carboxylic acids formed radiolytically in aqueous solutions of cyanides and simple nitriles

    International Nuclear Information System (INIS)

    Negron-Mendoza, A.; Draganic, Z.D.; Navarro-Gonzalez, R.; Graganic, I.G.

    1983-01-01

    A systematic search for aldehydes, ketones, and carboxylic acids was carried out in aqueous solutions of HCN, NH 4 CN, CH 3 CN, and C 2 H 4 CN, that had received multikilogray doses of 60 Co γ radiation. About 30 radiolytic products were identified, among them a large variety of dicarboxylic and tricarboxylic acids. Some of them might be of significant interest in molecular evolution studies of prebiotic processes. They originate in the free-radical-initiated chemical reactions where the additional oligomerization processes are particularly important. Most of the radiolytic products appear in both cyanides and nitriles and point to the importance of reactions involving the carbon-nitrogen triple bond

  16. Pulse radiolytic study of the oxidation reaction of uric acid in presence of bovine serum albumin: evidence of possible complex formation in the transient state

    International Nuclear Information System (INIS)

    Adhikari, S.; Gopinathan, C.

    1996-01-01

    The pulse radiolytic and spectrophotometric study of uric acid in presence of bovine serum albumin (BSA) has been carried out. In the spectrophotometric study there is no evidence for ground state interaction between BSA and uric acid. The reaction of CCl 3 OO . radical with uric acid produces a transient having absorption maximum at 330 nm and that with BSA produces transient having absorption maximum at 410 nm. In a composition of equal concentration of uric acid and BSA the CCl 3 OO . radical produces a transient absorption spectrum which shows two peaks at 330 nm and 350 nm and a shoulder at 410 nm. The peak at 350 nm is ascribed due to weak complex formation between BSA and uric acid radicals. The rate constant of CCl 3 OO . radical with uric acid increases with the increase in BSA concentration which is explained as protection of BSA by uric acid from radical attack. (author). 4 refs., 2 figs., 1 tab

  17. Calculus of radiolytic products generation in water due to alpha radiation. Determination of the spent nuclear fuels matrix alteration rate Determination of velocity of spent fuel matrix

    International Nuclear Information System (INIS)

    Quinones, J.; Serrano, J.; Diaz Arocas, P.; Rodriguez Almazan, J. L.; Bruno, J.; Cera, E.; Merino, J.; Esteban, J. A.; Martinez-Esparza, A.

    2000-01-01

    The generation of radiolytic products as a result of alpha radiation in the surface of the spent fuel is a key process in order to understand how the it becomes degraded in repository conditions. The present work has established a radiolytic model based on a set of reactions involving fuel oxidation-dissolution and radiolytic products recombination. It also includes the decrease of the dose rates as the main alpha emitters decay away. Four cases, with varying parameters of the system, have been assessed. The results show a decrease in both the concentration of the radiolytic products in the gap water and the degradation of the fuel matrix. It has been estimated that in the period of the evaluation (10''6 years) up to 52% of the pellet is altered in the conservative cases, whereas only 11% is altered in the realistic cases. No significant differences were observed when the carbonates reactions were included in the system. (Author)

  18. Radiolytic carbon gasification

    International Nuclear Information System (INIS)

    Shennan, J.V.

    1980-01-01

    A vast body of knowledge has been accumulated over the past thirty years related to the radiolytic oxidation of the graphite moderator in carbon dioxide cooled Reactors. In the last ten years the dominance of the internal pore structure of the graphite in controlling the rate of carbon gasification has been steadily revealed. The object of this paper is to sift the large body of evidence and show how internal gas composition and hence carbon gasification is controlled by the virgin pore structure and the changes in pore structure brought about by progressive radiolytic oxidation. (author)

  19. Radiolytic graphite oxidation revisited

    International Nuclear Information System (INIS)

    Minshall, P.C.; Sadler, I.A.; Wickham, A.J.

    1996-01-01

    The importance of radiolytic oxidation in graphite-moderated CO 2 -cooled reactors has long been recognised, especially in the Advanced Gas-Cooled Reactors where potential rates are higher because of the higher gas pressure and ratings than the earlier Magnox designs. In all such reactors, the rate of oxidation is partly inhibited by the CO produced in the reaction and, in the AGR, further reduced by the deliberate addition of CH 4 . Significant roles are also played by H 2 and H 2 O. This paper reviews briefly the mechanisms of these processes and the data on which they are based. However, operational experience has demonstrated that these basic principles are unsatisfactory in a number of respects. Gilsocarbon graphites produced by different manufacturers have demonstrated a significant difference in oxidation rate despite a similar specification and apparent equivalence in their pore size and distribution, considered to be the dominant influence on oxidation rate for a given coolant-gas composition. Separately, the inhibiting influence of CH 4 , which for many years had been considered to arise from the formation of a sacrificial deposit on the pore walls, cannot adequately be explained by the actual quantities of such deposits found in monitoring samples which frequently contain far less deposited carbon than do samples from Magnox reactors where the only source of such deposits is the CO. The paper also describes the current status of moderator weight-loss predictions for Magnox and AGR Moderators and the validation of the POGO and DIFFUSE6 codes respectively. 2 refs, 5 figs

  20. Radiolytic decomposition of 4-bromodiphenyl ether

    International Nuclear Information System (INIS)

    Tang Liang; Xu Gang; Wu Wenjing; Shi Wenyan; Liu Ning; Bai Yulei; Wu Minghong

    2010-01-01

    Polybrominated diphenyl ethers (PBDEs) spread widely in the environment are mainly removed by photochemical and anaerobic microbial degradation. In this paper, the decomposition of 4-bromodiphenyl ether (BDE -3), the PBDEs homologues, is investigated by electron beam irradiation of its ethanol/water solution (reduction system) and acetonitrile/water solution (oxidation system). The radiolytic products were determined by GC coupled with electron capture detector, and the reaction rate constant of e sol - in the reduction system was measured at 2.7 x 10 10 L · mol -1 · s -1 by pulsed radiolysis. The results show that the BDE-3 concentration affects strongly the decomposition ratio in the alkali solution, and the reduction system has a higher BDE-3 decomposition rate than the oxidation system. This indicates that the BDE-3 was reduced by effectively capturing e sol - in radiolytic process. (authors)

  1. Radiolytic decomposition of dioxins in liquid wastes

    International Nuclear Information System (INIS)

    Zhao Changli; Taguchi, M.; Hirota, K.; Takigami, M.; Kojima, T.

    2006-01-01

    The dioxins including polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are some of the most toxic persistent organic pollutants. These chemicals have widely contaminated the air, water, and soil. They would accumulate in the living body through the food chains, leading to a serious public health hazard. In the present study, radiolytic decomposition of dioxins has been investigated in liquid wastes, including organic waste and waste-water. Dioxin-containing organic wastes are commonly generated in nonane or toluene. However, it was found that high radiation doses are required to completely decompose dioxins in the two solvents. The decomposition was more efficient in ethanol than in nonane or toluene. The addition of ethanol to toluene or nonane could achieve >90% decomposition of dioxins at the dose of 100 kGy. Thus, dioxin-containing organic wastes can be treated as regular organic wastes after addition of ethanol and subsequent γ-ray irradiation. On the other hand, radiolytic decomposition of dioxins easily occurred in pure-water than in waste-water, because the reaction species is largely scavenged by the dominant organic materials in waste-water. Dechlorination was not a major reaction pathway for the radiolysis of dioxin in water. In addition, radiolytic mechanism and dechlorinated pathways in liquid wastes were also discussed. (authors)

  2. Calculus of radiolytic products generation in water due to alpha radiation. Determination of the spent nuclear fuels matrix alteration rate Determination of velocity of spent fuel matrix; Calculo de la generacion de productos radioliticos en agua por radiacion {alpha}. Determinacion de la velocidad de alteracion de la matriz del combustible nuclear gastado

    Energy Technology Data Exchange (ETDEWEB)

    Quinones, J.; Serrano, J.; Diaz Arocas, P.; Rodriguez Almazan, J. L. [Ciemat. Madrid (Spain); Bruno, J.; Cera, E.; Merino, J.; Esteban, J. A.; Martinez-Esparza, A. [Enresa. Madrid (Spain)

    2000-07-01

    The generation of radiolytic products as a result of alpha radiation in the surface of the spent fuel is a key process in order to understand how the it becomes degraded in repository conditions. The present work has established a radiolytic model based on a set of reactions involving fuel oxidation-dissolution and radiolytic products recombination. It also includes the decrease of the dose rates as the main alpha emitters decay away. Four cases, with varying parameters of the system, have been assessed. The results show a decrease in both the concentration of the radiolytic products in the gap water and the degradation of the fuel matrix. It has been estimated that in the period of the evaluation (10''6 years) up to 52% of the pellet is altered in the conservative cases, whereas only 11% is altered in the realistic cases. No significant differences were observed when the carbonates reactions were included in the system. (Author)

  3. Photo- and radiation chemical studies of intermediates involved in excited-state electron-transfer reactions

    International Nuclear Information System (INIS)

    Hoffman, M.Z.

    1985-01-01

    Excited-state inter- and intramolecular electron-transfer reactions lie at the heart of the most photochemical solar energy conversion schemes. The authors research, which has utilized the techniques of continuous and pulsed photolysis and radiolysis, has focused on three general aspects of these reactions involving transition metal coordination complexes and electron donor-acceptor complexes: i) the effect of solution medium on the properties and quenching of the excited states; ii) the control of the quantum yields of formation of redox products; iii) the mechanism by which reduced species interact with water to yield H 2 homogeneously and heterogeneously. EDTA is among the most popular sacrificial electron donors used in model systems. Its role is to scavenge the oxidized form of the photosensitizer in order to prevent its rapid reaction with the reduced form of the electron relay species that results from the electron-transfer quenching of the excited photosensitizer. In systems involving MV 2+ , the radicals resulting from the oxidation of EDTA can eventually lead to the generation of a second equivalent of MV + ; the reducing agent is believed to be a radical localized on the carbon atom alpha to the carboxylate group. The reaction of radiolytically-generated OH/H with EDTA produces this radical directly via H-abstraction or indirectly via deprotonation of the carbon atom adjacent to the nitrogen radical site in the oxidized amine moiety; it reduces MV 2+ with rate constants of 2.8 x 10 9 , 7.6 x 10 9 , and 8.5 x 10 6 M -1 s -1 at pH 12.5, 8.3, and 4.7, respectively. Degradative decarboxylation of EDTA-radicals and their back electron-transfer reactions are enhanced in acidic solution causing the yield of MV + to be severely diminished

  4. Structure elucidation and toxicity analyses of the radiolytic products of aflatoxin B{sub 1} in methanol-water solution

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Feng [Institute of Agro-food Science and Technology of Chinese Academy of Agricultural Sciences, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Key Opening Laboratory of Agricultural Products Processing and Quality Control, Ministry of Agriculture, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Graduate School of Chinese Academy of Agricultural Sciences, 12th Zhongguancun South Road, Hai Dian District, Beijing 100081 (China); Xie, Fang [Institute of Agro-food Science and Technology of Chinese Academy of Agricultural Sciences, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Key Opening Laboratory of Agricultural Products Processing and Quality Control, Ministry of Agriculture, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Xue, Xiaofeng [Bee Research Institute of Chinese Academy of Agricultural Sciences, 1st Xiangshan North Ditch, Hai Dian District, Beijing 100093 (China); Wang, Zhidong; Fan, Bei [Institute of Agro-food Science and Technology of Chinese Academy of Agricultural Sciences, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Key Opening Laboratory of Agricultural Products Processing and Quality Control, Ministry of Agriculture, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Ha, Yiming, E-mail: wxfay2011@hotmail.com [Institute of Agro-food Science and Technology of Chinese Academy of Agricultural Sciences, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Key Opening Laboratory of Agricultural Products Processing and Quality Control, Ministry of Agriculture, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China)

    2011-09-15

    Highlights: {yields} Radiolytic products of aflatoxin B{sub 1} were produced under gamma irradiation. {yields} Seven key radiolytic products were structure-elucidated. {yields} Free-radical species in radiolytic solution resulted in the formation of products. {yields} Based on the structure-activity relationship analysis, the toxicity of radiolytic products was significantly reduced compared with that of AFB{sub 1}. {yields} The addition reaction on furan ring double bond was the reason for the reduced toxicity. - Abstract: The identification of the radiolytic products of mycotoxins is a key issue in the feasibility study of gamma ray radiation detoxification. Methanol-water solution (60:40, v/v) spiked with aflatoxin B{sub 1} (AFB{sub 1}; 20 mg L{sup -1}) was irradiated with Co{sup 60} gamma ray to generate radiolytic products. Liquid chromatography-quadruple time-of-flight mass spectrometry was applied to identify the radiolytic products of AFB{sub 1}. Accurate mass and proposed molecular formulas with a high-matching property of more than 20 radiolytic products were obtained. Seven key radiolytic products were proposed based on the molecular formulas and tandem mass spectrometry spectra. The analyses of toxicity and formation pathways were proposed based on the structure of the radiolytic products. The addition reaction caused by the free-radical species in the methanol-water solution resulted in the formation of most radiolytic products. Based on the structure-activity relationship analysis, the toxicity of radiolytic products was significantly reduced compared with that of AFB{sub 1} because of the addition reaction that occurred on the double bond in the terminal furan ring. For this reason, gamma irradiation is deemed an effective tool for the detoxification of AFB{sub 1}.

  5. The radiolytic and radiolytically induced gas generation in Hanford waste tanks

    International Nuclear Information System (INIS)

    Jonah, C.D.; Meisel, D.; Sauer, M.C. Jr.

    1994-01-01

    A task force operating in ANL/CHM has been developing a mechanistic understanding of the radiolytic processes that lead to the generation and retention of gases within tanks of radioactive waste at the Hanford site. This chemistry is one of the important factors that must be considered in devising remediation procedures to eliminate the great potential hazard of these tanks. A quantitative description of much of the chemistry involved in the production of H 2 and, to a lesser extent, in the production of N 2 O has been achieved. Direct radiolytic generation was experimentally quantified and this new information was utilized in computer modeling to provide predictive capabilities so that changes of chemical composition of various waste tanks under different remediation procedures could be assessed. Oxygen in the waste solutions is effectively consumed upon irradiation and thus is of no concern. The mechanism of the radiolytic degradation of the chelators was established. The end products are simple organic molecules, in particularly, formaldehyde and glyoxylate, that are very efficient in the thermal generation of H 2

  6. Polycarbonate radiolytic degradation and stabilization

    International Nuclear Information System (INIS)

    Araujo, E.S. de

    1994-01-01

    Polycarbonate Durolon, useful for medical supplies fabrication, is submitted to gamma radiation for sterilization purposes. Scissions in main chain occur, in carbonyl groups, producing molecular degradations and yellowness. The radiolytic stabilization is obtained through additive to the polymer. In this work some degradation and stabilization aspects are presented. (L.C.J.A.). 7 refs, 7 figs, 2 tabs

  7. Radiolytic gas formation in high-level liquid waste solutions

    International Nuclear Information System (INIS)

    Brodda, B.-G.; Dix, Siegfried; Merz, E.R.

    1989-01-01

    High-level fission product waste solutions originating from the first-cycle raffinate stream of spent fast breeder reactor fuel reprocessing have been investigated gas chromatographically for their radiolytic and chemical gas production. The solutions showed considerable formation of hydrogen, carbon dioxide and dinitrogen oxide, whereas atmospheric oxygen was consumed completely within a short time. In particular, carbon dioxide resulted from the radiolytic degradation of entrained organic solvent. After nearly complete degradation of the organic solvent, the influence of hydrazine and nitrogen dioxide on hydrogen formation was investigated. Hydrazinium hydroxide led to the formation of dinitrogen oxide and nitrogen. After 60 d, the concentration of dinitrogen oxide had reduced to zero, whereas the amount of nitrogen formed had reached a maximum. This may be explained by simultaneous chemical and radiolytic reactions leading to the formation of dinitrogen oxide and nitrogen and photolytic fission of dinitrogen oxide. Addition of sodium nitrite resulted in the rapid formation of dinitrogen oxide. The rate of hydrogen production was not changed significantly after the addition of hydrazine or nitrite. The results indicate that under normal operating conditions no dangerous hydrogen radiolysis yields should develop in the course of reprocessing and high-level liquid waste tank storage. Organic entrainment may lead to enhanced radiolytic decomposition and thus to considerable hydrogen production rates and pressure build-up in closed systems. (author)

  8. On the thermalization achieved in the reactions involving superheavy nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Bansal, Rajni [Department of Physics, MCM DAV College for Women, Sector 36A, Chandigarh-160036, India rajnibansal.pu@gmail.com (India)

    2016-05-06

    In the present study, we aim to explore the role of Coulomb potential on the thermalization achieved in the reactions involving superheavy nuclei. Particularly, we shall study the degree of the equilibrium attained in a reaction by the 3D density plots, anisotropy ratio as well as by the rapidity distribution of the nucleons. Our study reveals that the degree of the equilibrium attained in the central reactions of the superheavy nuclei remains unaffected by the Coulomb potential.

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    African Journals Online (AJOL)

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    markets, fair trade products need LRs distribution channels and not the old system of using speciality ... analysis employed to identify customers' reaction to large retailers' involvement in selling ...... The Journal of Socio-Economics. Vol. 37: pp.

  10. Cortical involvement in anticipatory postural reactions in man

    DEFF Research Database (Denmark)

    Petersen, Tue Hvass; Rosenberg, Kasper; Petersen, Nicolas Caesar

    2009-01-01

    All movements are accompanied by postural reactions which ensure that the balance of the body is maintained. It has not been resolved that to what extent the primary motor cortex and corticospinal tract are involved in the control of these reactions. Here, we investigated the contribution...... of the corticospinal tract to the activation of the soleus (SOL) muscle in standing human subjects (n = 10) in relation to voluntary heel raise, anticipatory postural activation of the soleus muscle when the subject pulled a handle and to reflex activation of the soleus muscle when the subject was suddenly pulled...... was observed prior to EMG onset for the external perturbation. These data suggest that the primary motor cortex is involved in activating the SOL muscle as part of an anticipatory postural reaction....

  11. Catalytic and Gas-Solid Reactions Involving HCN over Limestone

    DEFF Research Database (Denmark)

    Jensen, Anker; Johnsson, Jan Erik; Dam-Johansen, Kim

    1997-01-01

    In coal-fired combustion systems solid calcium species may be present as ash components or limestone added to the combustion chamber. In this study heterogeneous reactions involving HCN over seven different limestones were investigated in a laboratory fixed-bed quartz reactor at 873-1,173 K...

  12. Investigation of Maillard reaction involvement in the steam ...

    African Journals Online (AJOL)

    Purpose: To explore the possible mechanism of Maillard reaction (MR) involvement in the steam processing of Panax notoginseng (PN) root. Methods: PN root was soaked in water for 24 h and then steamed at 100 °C using an autoclave for 1, 2, 3, 4, 5 and 6 h, respectively. Several indicators associated with MR during ...

  13. Radiolytic degradation and stability of polycarbonate

    International Nuclear Information System (INIS)

    Araujo, E.S. de.

    1993-01-01

    The radiolytic stability of polycarbonate was studied using national commercial additives, employed in the photo and thermo-oxidative stabilization of polymers. Among several additives tested only two showed the efficiency to radiolytic protection: one quencher and one radical scavenger. It was derived a linear relation that provides by slope of the straight line the degree of degradation (scissions), G, and the factors of radiolytic protection P (degree of protection) and CE (capture of energy) conferred by radioprotector additive easily. Therefore the method developed in this work (viscosity) to study the molecular degradation and stability of polymers is a simply and precise method. The synergic mixture of two additives (1% of weight total) confers at polycarbonate excellent radiolytic protection of 98% (20 - 40 kGy) reducing the G value of 16.7 to only 0.4. (author). 69 refs, 31 figs, 17 tabs

  14. Electron transfer reactions involving porphyrins and chlorophyll a

    International Nuclear Information System (INIS)

    Neta, P.; Scherz, A.; Levanon, H.

    1979-01-01

    Electron transfer reactions involving porphyrins (P) and quinones (Q) have been studied by pulse radiolysis. The porphyrins used were tetraphenylporphyrin (H 2 TPP), its tetracarboxy derivative (H 2 TCPP), the sodium and zinc compounds (Na 2 TPP and ZnTPP), and chlorophyll a (Chl a). These compounds were found to be rapidly reduced by electron transfer from (CH 3 ) 2 CO - . Reduction by (CH 3 ) 2 COH was rapid in aqueous solutions but relatively slow in i-PrOH solutions. Transient spectra of the anion radicals were determined and, in the case of H 2 TCPP - ., a pK = 9.7 was derived for its protonation. Electron-transfer reactions from the anion radical of H 2 TCPP to benzoquinone, duroquinone, 9,10-anthraquinone 2-sulfonate, and methylviologen occur in aqueous solutions with rate constants approx. 10 7 -10 9 M -1 s -1 which depend on the pH and the quinone reduction potential. Reactions of Na 2 TPP - ., ZnTPP - ., and Chl a - . with anthraquinone in basic i-PrOH solutions occur with rate constants approx. 10 9 M -1 s -1 . The spectral changes associated with these electron-transfer reactions as observed over a period of approx. 1 ms indicated, in some cases, the formation of an intermediate complex [P...Q - .]. 8 figures, 2 tables

  15. Unusual radiolytic behavior of neptunium ions in aqueous bicarbonate solutions

    International Nuclear Information System (INIS)

    Shilov, V.P.; Gogolev, A.V.; Pikaev, A.K.

    2000-01-01

    Behavior of neptunium ions in carbonate and bicarbonate aqueous solutions saturated with air, oxygen or argon during gamma radiation ( 60 Co) by doses up to 3 kGy at dose rates 10 and 25 Gy/min was studied by the method of spectrophotometry. It is shown that in neptunium (5) bicarbonate solution nearly complete (95%) neptunium ion oxidation occurs under the effect of radiation, whereas no oxidation is observed in carbonate solution. Radiation-chemical yield of neptunium (5) oxidation and stationary concentration of neptunium (6) ions depend on concentration of bicarbonate-ions. Explanation to the results obtained is made from the viewpoint of potential radiolytic reactions [ru

  16. Kynurenine pathway metabolites and enzymes involved in redox reactions.

    Science.gov (United States)

    González Esquivel, D; Ramírez-Ortega, D; Pineda, B; Castro, N; Ríos, C; Pérez de la Cruz, V

    2017-01-01

    Oxido-reduction reactions are a fundamental part of the life due to support many vital biological processes as cellular respiration and glucose oxidation. In the redox reactions, one substance transfers one or more electrons to another substance. An important electron carrier is the coenzyme NAD + , which is involved in many metabolic pathways. De novo biosynthesis of NAD + is through the kynurenine pathway, the major route of tryptophan catabolism, which is sensitive to redox environment and produces metabolites with redox capacity, able to alter biological functions that are controlled by redox-responsive signaling pathways. Kynurenine pathway metabolites have been implicated in the physiology process and in the physiopathology of many diseases; processes that also share others factors as dysregulation of calcium homeostasis, mitochondrial dysfunction, oxidative stress, inflammation and cell death, which impact the redox environment. This review examines in detail the available evidence in which kynurenine pathway metabolites participate in redox reactions and their effect on cellular redox homeostasis, since the knowledge of the main factors and mechanisms that lead to cell death in many neurodegenative disorders and other pathologies, such as mitochondrial dysfunction, oxidative stress and kynurenines imbalance, will allow to develop therapies using them as targets. This article is part of the Special Issue entitled 'The Kynurenine Pathway in Health and Disease'. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Radiolytic investigations of solutions of organophosphorus compounds in cyclohexane and benzene

    International Nuclear Information System (INIS)

    Otrebski, W.

    1981-01-01

    Organphosphorus compounds are used in various branches of the chemical industry, but in many cases the reaction mechanisms are not well elucidated and less is known about the intermediates of organophosphines. In order to learn more about these rather complicated processes several organophosphorus compounds were used as model substrates in cyclohexane or benzene solution. The systems have been investigated applying the pulse radiolysis technique and steady-state irradiation methods. As representative solutes were chosen diphenylphosphinous chloride, diphenylmethylphosphine, and triphenylphosphine. By means of the pulse radiolysis it was possible to obtain spectroscopic and kinetic data for characterization of the various transients. The final radiolytic products have been analyzed following steady-state and multipulse radiolysis. Since some of the rate constants were not directly accessible by the applied kinetic method, they have been determined by simulation computation. Thereby the experimental data obtained by pulse radiolysis were used. Based on the kinetic, spectroscopic and computed data as well as on the identification of final products, it was possible to elucidate the reaction mechanism of the diphenylphosphinous chloride/cyclohexane system. As a main primary specie was identified the diphenylphoshorus radical. Its spectral and kinetic data have been determined. The reactions of diphenylmethylphosphine involve the same radical, but only to a lesser extent. The reactions of the primary radiolysis products with triphenylphosphine yield mainly adducts. The results represent a contribution in the field of reaction kinetics of organophosphorus compounds. (author)

  18. Stress reactions involving the pars interarticularis in young athletes

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, D.W.; Wiltse, L.L.; Dingeman, R.D.; Hayes, M.

    A stress reaction involving the pars interarticularis of the lumbar spine was confirmed in seven young athletes with a positive technetium pyrophosphate bone scan. No pars defects were detectable on their lumbosacral roentgenograms, which included oblique views. The return to normal levels of radioactive uptake on repeat bone scans correlated closely with their clinical course. If the bony reaction is recognized early, it may heal at a subroentgenographic level and prevent the development of lumbar spondylolysis. These early lesions usually show unilateral increased uptake at one lumbar level on the bone scan and, initially, the athlete localizes the pain to the corresponding unilateral lumbar paraspinous area. The ''one-legged hyperextension test'' is positive on the ipsilateral side and aggravates the pain. Treatment consists of avoiding the aggravating activities and resting. The average time for return to pain-free competition was 7.3 months. These developing defects may be the source of considerable prolonged disability in the young athlete, particularly if undiagnosed and untreated.

  19. Stress reactions involving the pars interarticularis in young athletes

    International Nuclear Information System (INIS)

    Jackson, D.W.; Wiltse, L.L.; Dingeman, R.D.; Hayes, M.

    1981-01-01

    A stress reaction involving the pars interarticularis of the lumbar spine was confirmed in seven young athletes with a positive technetium pyrophosphate bone scan. No pars defects were detectable on their lumbosacral roentgenograms, which included oblique views. The return to normal levels of radioactive uptake on repeat bone scans correlated closely with their clinical course. If the bony reaction is recognized early, it may heal at a subroentgenographic level and prevent the development of lumbar spondylolysis. These early lesions usually show unilateral increased uptake at one lumbar level on the bone scan and, initially, the athlete localizes the pain to the corresponding unilateral lumbar paraspinous area. The ''one-legged hyperextension test'' is positive on the ipsilateral side and aggravates the pain. Treatment consists of avoiding the aggravating activities and resting. The average time for return to pain-free competition was 7.3 months. These developing defects may be the source of considerable prolonged disability in the young athlete, particularly if undiagnosed and untreated

  20. Iron release from ferritin and lipid peroxidation by radiolytically generated reducing radicals

    International Nuclear Information System (INIS)

    Reif, D.W.; Schubert, J.; Aust, S.D.

    1988-01-01

    Iron is involved in the formation of oxidants capable of damaging membranes, protein, and DNA. Using 137 Cs gamma radiation, we investigated the release of iron from ferritin and concomitant lipid peroxidation by radiolytically generated reducing radicals, superoxide and the carbon dioxide anion radical. Both radicals released iron from ferritin with similar efficiencies and iron mobilization from ferritin required an iron chelator. Radiolytically generated superoxide anion resulted in peroxidation of phospholipid liposomes as measured by malondialdehyde formation only when ferritin was included as an iron source and the released iron was found to be chelated by the phospholipid liposomes

  1. Radiolytic degradation of chlorinated hydrocarbons in water

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Xing-Zheng; Yamamoto, Takeshi [Fukui Univ., Faculty of Engineering, Dept. of Materials Science and Engineering, Fukui (Japan); Hatashita, Masanori [The Wakasa Wan Energy Research Center, Research Dept., Tsuruga, Fukui (Japan)

    2002-11-01

    Radiolytic degradation of chlorinated hydrocarbons (chloroform, trichloroethylene, and tetrachloroethylene) in water was carried out. Water solutions of the chlorinated hydrocarbons with different concentrations were irradiated with {gamma} rays. Concentrations of methane, ethane, CO, CO{sub 2}, H{sub 2}, and O{sub 2} after the irradiation were determined by gas chromatography. Concentration of chloride ion in the irradiated sample was determined by ion chromatography. Experimental results show that radiolytic degradation of the chlorinated hydrocarbon increased with the radiation dose. Methane, ethane, CO{sub 2}, H{sub 2}, and Cl{sup -} concentrations increased with the radiation dose and the sample concentration. On the other hand, O{sub 2} concentration decreased with the radiation dose and the sample concentration. When sample concentration was high, dissolved oxygen might be not enough for converting most of the C atoms in the sample into CO{sub 2}. This resulted in a low decomposition ratio. Addition of H{sub 2}O{sub 2} as an oxygen resource could increase the decomposition ratio greatly. Furthermore, gas chromatography-mass spectroscopy was applied to identify some intermediates of the radiolytic dehalogenation. Radiolytic degradation mechanisms are also discussed. (author)

  2. Modeling of Radiolytic Degradation of Cefaclor by Ionizing Energy

    International Nuclear Information System (INIS)

    Yu, Seungho; Choi, Dongkyu; Lee, Myunjoo

    2008-01-01

    Recently, many researches have been conducted on the treatments of antibiotics found in groundwater, surface water, and wastewater. Ingerslev et al. showed that antibiotics under aerobic and anaerobic conditions were not readily biodegradable. Advanced oxidation processes (AOPs) have been suggested in recent years as a suitable alternative for the removal of refractory organic compounds found in a variety of environment. AOPs by using free radicals such as the hydroxyl radical (·OH) include ozone, ozone/UV, TiO 2 photo catalysis, fenton's reaction, H 2 O 2 /UV, H 2 O 2 /O 3 and ionizing radiation. Herein are reported the results of the radiolytic degradation of cefaclor. This study focused on the use of gamma radiation as an AOP for the complete mineralization of antibiotics. Among the many kinds of antibiotics, the target antibiotic in this study was cefaclor, which a β lactam antibiotic widely used for the medical treatment of microbial infective diseases. The objectives of this study were: 1) to investigate the decomposition and mineralization of cefaclor using gamma irradiation; 2) to study the decomposition kinetics of cefaclor; and 3) to simulate radiolytic decomposition of cefaclor with experimentally measured kinetic parameters

  3. Rates for some reactions involving 42Ca and 44Ca

    International Nuclear Information System (INIS)

    Cheng, C.W.; King, J.D.

    1980-01-01

    Ground-state reaction rates have been deduced from recent cross section measurements for the 42 CA(α, n) 45 Ti, 42 Ca(p, γ) 43 Sc, and 44 Ca(p, n) 44 Sc reactions. Comparison of these rates with those calculated from a statistical model of nuclear reactions. (Woosley et al) shows good agreement for the first two, but the 44 Ca(p, n) rate is more than a factor of 2 less than the theoretical prediction. Stellar reaction rates have been derived from the ground-state rates by multiplying the ground-state rates by the ratio of stellar to ground-state rates given by the statistical model. Both ground-state and stellar rates have been represented by analytic functions of the temperature. The role of these reactions in the approach to quasi-equilibrium during explosive silicon burning is discussed

  4. Old Faithful Model for Radiolytic Gas-Driven Cryovolcanism at Enceladus

    Science.gov (United States)

    Cooper, John F.; Cooper, Paul D.; Sittler, Edward; Sturner, Steven J.; Rymer, Abigail M.

    2009-01-01

    A new model is presented on how chemically driven cryovolcanism might contribute to episodic outgassing at the icy moon Enceladus and potentially elsewhere including Europa and Kuiper Belt Objects. Exposed water ices can become oxidized from radiolytic chemical alteration of near-surface water ice by space environment irradiation. In contact with primordially abundant reductants such as NH3, CH4, and other hydrocarbons, the product oxidants can react exothermically to produce volatile gases driving cryovolcanism via gas-piston forces on any subsurface liquid reservoirs. Radiolytic oxidants such as H2O2 and O2 can continuously accumulate deep in icy regoliths and be conveyed by rheological flows to subsurface chemical reaction zones over million-year time scales indicated by cratering ages for active regions of Enceladus and Europa. Surface blanketing with cryovolcanic plume ejecta would further accelerate regolith burial of radiolytic oxidants. Episodic heating from transient gravitational tides, radioisotope decay, impacts, or other geologic events might occasionally accelerate chemical reaction rates and ignite the exothermic release of cumulative radiolytic oxidant energy. The time history for the suggested "Old Faithful" model of radiolytic gas-driven cryovolcanism at Enceladus and elsewhere therefore consists of long periods of chemical energy accumulation punctuated by much briefer episodes of cryovolcanic activity. The most probable sequence for detection of activity in the current epoch is a long evolutionary phase of slow but continuous oxidant accumulation over billions of years followed by continuous but variable high activity over the past 10(exp 7)-10(exp 8) years. Detectable cryovolcanic activity could then later decline due to near-total oxidation of the rheologically accessible ice crust and depletion the accessible reductant abundances, as may have already occurred for Europa in the more intense radiation environment of Jupiter's magnetosphere

  5. Flat Graphene-Enhanced Electron Transfer Involved in Redox Reactions.

    Science.gov (United States)

    Pan, Meilan; Zhang, Yanyang; Shan, Chao; Zhang, Xiaolin; Gao, Guandao; Pan, Bingcai

    2017-08-01

    Graphene is easily warped in the out-of-plane direction because of its high in-plane Young's modulus, and exploring the influence of wrinkled graphene on its properties is essential for the design of graphene-based materials for environmental applications. Herein, we prepared wrinkled graphene (WGN-1 and WGN-2) by thermal treatment and compared their electrochemical properties with those of flat graphene nanosheets (FGN). FGN exhibit activities that are much better than those of wrinkled graphene nanosheets (WGN), not only in the electrochemical oxidation of methylene blue (MB) but also in the electrochemical reduction of nitrobenzene (NB). Transformation ratios of MB and NB in FGN, WGN-1, and WGN-2 were 97.5, 80.1, and 57.9% and 94.6, 92.1, and 81.2%, respectively. Electrochemical impedance spectroscopy and the surface resistance of the graphene samples increased in the following order: FGN reaction charges transfer faster across the reaction interfaces and along the surface of FGN than that of WGN, and wrinkles restrict reaction charge transfer and reduce the reaction rates. This study reveals that the morphology of the graphene (flat or wrinkle) greatly affects redox reaction activities and may have important implications for the design of novel graphene-based nanostructures and for our understanding of graphene wrinkle-dependent redox reactions in environmental processes.

  6. Radiolytic generation of gases in reactors

    International Nuclear Information System (INIS)

    Ramshesh, V.; Venkateswarlu, K.S.

    1988-01-01

    Water or heavy water is used in different circuits in a reactor. Their most common use is as a moderator and/or as a coolant. Light water is used at other places such as in end shield, calandria vault etc., In the process they are exposed to intense ionizing radiation and undergo radiolytic degradation. The molecular produts of radiolysis are hydrogen, hydrogen peroxide and oxygen. As is commonly known if hydrogen is formed beyond a certain level, in the presence of oxygen it may lead to combustion or even explosion. Thus one should comprehend the basic principles of radiolysis and see whether the concentration of these gases under various conditions can be worked out. This report attempts to analyse in depth the radiolytic generation of gases in reactor systems. (author). 3 tabs

  7. Indirect Measurements for (p,α) Reactions Involving Boron Isotopes

    International Nuclear Information System (INIS)

    Lamia, L.; Spitaleri, C.; Romano, S.; Cherubini, S.; Crucilla, V.; Gulino, M.; La Cognata, M.; Pizzone, R. G.; Puglia, S. M. R.; Sergi, M. L.; Tudisco, S.; Tumino, A.; Carlin, N.; Szanto, M. G. del; Liguori Neto, R.; Moura, M. M. de; Munhoz, M. G.; Souza, F. A.; Suaide, A. A. P.; Szanto, E.

    2008-01-01

    Light elements lithium, beryllium and boron (LiBeB) were used in the last years as 'possible probe' for a deeper understanding of some extra-mixing phenomena occurring in young Main-Sequence stars. They are mainly destroyed by (p,α) reactions and cross section measurements for such channels are then needed. The Trojan Horse Method (THM) allows one to extract the astrophysical S(E)-factor without the experience of tunneling through the Coulomb barrier. In this work a resume of the recent results about the 11 B(p,α 0 ) 8 Be and 10 B(p,α) 7 Be reactions is shown

  8. The importance of variables and parameters in radiolytic chemical kinetics modeling

    International Nuclear Information System (INIS)

    Piepho, M.G.; Turner, P.J.; Reimus, P.W.

    1989-01-01

    Many of the pertinent radiochemical reactions are not completely understood, and most of the associated rate constants are poorly characterized. To help identify the important radiochemical reactions, rate constants, species, and environmental conditions, an importance theory code, SWATS (Sensitivitiy With Adjoint Theory-Sparse version)-LOOPCHEM, has been developed for the radiolytic chemical kinetics model in the radiolysis code LOOPCHEM. The LOOPCHEM code calculates the concentrations of various species in a radiolytic field over time. The SWATS-LOOPCHEM code efficiently calculates: the importance (relative to a defined response of interest) of each species concentration over time, the sensitivity of each parameter of interest, and the importance of each equation in the radiolysis model. The calculated results will be used to guide future experimental and modeling work for determining the importance of radiolysis on waste package performance. A demonstration (the importance of selected concentrations and the sensitivities of selected parameters) of the SWATS-LOOPCHEM code is provided for illustrative purposes

  9. Laboratory approaches of nuclear reactions involved in primordial and stellar nucleosynthesis

    International Nuclear Information System (INIS)

    Rolfs, C.; California Inst. of Tech., Pasadena

    1986-01-01

    Laboratory-based studies of primordial and stellar nucleosynthesis are reviewed, with emphasis on the nuclear reactions induced by charged particles. The analytical approach used to investigate nuclear reactions associated with stellar reactions is described, as well as the experimental details and procedures used to investigate nuclear reactions induced by charged particles. The present knowledge of some of the key reactions involved in primordial nucleosynthesis is discussed, along with the progress and problems of nuclear reactions involved in the hydrogen and helium burning phases of a star. Finally, a description is given of new experimental techniques which might be useful for future experiments in the field of nuclear astrophysics. (U.K.)

  10. Pulse and gamma radiolytic studies of Ag, Cd and mixed clusters in aqueous solutions of carboxymethyl cellulose and gelatin

    International Nuclear Information System (INIS)

    Kapoor, Sudhir; Gopinathan, C.

    1996-01-01

    Pulse and gamma radiolytic studies in aqueous solutions of Ag, Cd and mixed clusters were carried out in carboxymethylcellulose (CMC) or gelatin. The reaction rate of e aq - with Ag + is lower in the presence of CMC or gelatin and oligomeric clusters of silver, Cd and mixed clusters get stabilized in their presence. (author). 2 refs., 2 figs

  11. Kinetics and mechanisms of reactions involving small aromatic reactive intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Lin, M.C. [Emory Univ., Atlanta, GA (United States)

    1993-12-01

    Small aromatic radicals such as C{sub 6}H{sub 5}, C{sub 6}H{sub 5}O and C{sub 6}H{sub 4} are key prototype species of their homologs. C{sub 6}H{sub 5} and its oxidation product, C{sub 6}H{sub 5}O are believed to be important intermediates which play a pivotal role in hydrocarbon combustion, particularly with regard to soot formation. Despite their fundamental importance, experimental data on the reaction mechanisms and reactivities of these species are very limited. For C{sub 6}H{sub 5}, most kinetic data except its reactions with NO and NO{sub 2}, were obtained by relative rate measurements. For C{sub 6}H{sub 5}O, the authors have earlier measured its fragmentation reaction producing C{sub 5}H{sub 5} + CO in shock waves. For C{sub 6}H{sub 4}, the only rate constant measured in the gas phase is its recombination rate at room temperature. The authors have proposed to investigate systematically the kinetics and mechanisms of this important class of molecules using two parallel laser diagnostic techniques--laser resonance absorption (LRA) and resonance enhanced multiphoton ionization mass spectrometry (REMPI/MS). In the past two years, study has been focused on the development of a new multipass adsorption technique--the {open_quotes}cavity-ring-down{close_quotes} technique for kinetic applications. The preliminary results of this study appear to be quite good and the sensitivity of the technique is at least comparable to that of the laser-induced fluorescence method.

  12. Radiolytic decomposition of organic C-14 released from TRU waste

    International Nuclear Information System (INIS)

    Kani, Yuko; Noshita, Kenji; Kawasaki, Toru; Nishimura, Tsutomu; Sakuragi, Tomofumi; Asano, Hidekazu

    2007-01-01

    It has been found that metallic TRU waste releases considerable portions of C-14 in the form of organic molecules such as lower molecular weight organic acids, alcohols and aldehydes. Due to the low sorption ability of organic C-14, it is important to clarify the long-term behavior of organic forms under waste disposal conditions. From investigations on radiolytic decomposition of organic carbon molecules into inorganic carbonic acid, it is expected that radiation from TRU waste will decompose organic C-14 into inorganic carbonic acid that has higher adsorption ability into the engineering barriers. Hence we have studied the decomposition behavior of organic C-14 by gamma irradiation experiments under simulated disposal conditions. The results showed that organic C-14 reacted with OH radicals formed by radiolysis of water, to produce inorganic carbonic acid. We introduced the concept of 'decomposition efficiency' which expresses the percentage of OH radicals consumed for the decomposition reaction of organic molecules in order to analyze the experimental results. We estimated the effect of radiolytic decomposition on the concentration of organic C-14 in the simulated conditions of the TRU disposal system using the decomposition efficiency, and found that the concentration of organic C-14 in the waste package will be lowered when the decomposition of organic C-14 by radiolysis was taken into account, in comparison with the concentration of organic C-14 without radiolysis. Our prediction suggested that some amount of organic C-14 can be expected to be transformed into the inorganic form in the waste package in an actual system. (authors)

  13. Cross-section and reaction rates for some reactions involved in explosive nucleosynthesis

    International Nuclear Information System (INIS)

    Cheng, C.W.

    1979-03-01

    Total proton-induced and alpha-induced reaction cross sections have been determined for the 24 Mg(α,n), 25 Mg(p,n), 26 Mg(p,n), 27 Al(p,n), 28 Si(α,n), 42 Ca(p,γ), 42 Ca(α,n) and 44 Ca(p,n) reactions from energies near threshold (except the exothermic (p,γ) reaction) to about 3 to 4 MeV above threshold. The product nuclei are all positron emitters with half-lives ranging from about 3 sec to about 4 hours. From the measured cross sections reaction rates have been calculated in the temperature range 1 9 9 =1, at which the discrepancy is large. Included also are analytic forms for (p,n), (α,n), and (p,γ) reactions which can be used to describe the reaction rate within the temperature range 1 9 <=6 and which agree with the experimental rates at the discrete temperatures where the reaction rates have been calculated

  14. Influence of radiolytic products on the chemistry of uranium VI in brines

    International Nuclear Information System (INIS)

    Lucchini, J-F.; Reed, D.T.; Borkowski, M.; Rafalski, A.; Conca, J.

    2004-01-01

    In the near field of a salt repository of nuclear waste, ionizing radiations can strongly affect the chemistry of concentrated saline solutions. Radiolysis can locally modify the redox conditions, speciation, solubility and mobility of the actinide compounds. In the case of uranium VI, radiolytic products can not only reduce U(VI), but also react with uranium species. The net effect on the speciation of uranyl depends on the relative kinetics of the reactions and the buildup of molecular products in brine solutions. The most important molecular products in brines are expected to be hypochlorite ion, hypochlorous acid and hydrogen peroxide. Although U(VI) is expected not to be significantly affected by radiolysis, the combined effects of the major molecular radiolytic products on the chemistry of U(VI) in brines have not been experimentally established previously. (authors)

  15. An assessment of post-LOCA radiolytic generation of hydrogen in reactor containment of Indian PHWRs

    International Nuclear Information System (INIS)

    Bose, H.; Shah, G.C.; Dutta, S.

    2002-01-01

    Full text: An event-wise assessment has been carried out for the 220 MWe Indian PHWRs of standardized design, to estimate the post-LOCA release of radiolytic hydrogen inside reactor containment, in absence of steam-zirconium reaction. The assessment is based on (i) the dissolved hydrogen concentration build-up in water corresponding to the decaying gamma dose profile and (ii) the rate of concentration dependent mass-transfer of hydrogen from water to gas-space. It is observed that the total radiolytic hydrogen released is about three times less than that obtained by the conventional method of calculation which assumes the radiolytic yield of hydrogen to be equal to the primary yield G(H 2 ) = 0.44 molecules per 100 eV. It is also seen that a major part (∼90 %) of the total release is due to the spillage of fission product irradiated suppression pool water flowing through the core, followed by moderator and suppression pool surface releases respectively

  16. Structural and behavioral characteristics of radiolytically synthesized polyacrylic acid–polyacrylonitrile copolymeric hydrogels

    International Nuclear Information System (INIS)

    Bera, Anuradha; Misra, R.K.; Singh, Shailendra K.

    2013-01-01

    Copolymeric hydrogels of polyacrylic acid (PAA) – polyacrylonitrile (PAN) was radiolytically synthesized from their respective monomers with trimethyloltrimethacrylate (TMPTMA) as the crosslinker wherein both polymerization and crosslinking could be achieved in a single step reaction using 60 Co γ-radiation under varying doses and dose rates. The formation of the hydrogels was confirmed by their FT-IR analysis, while their thermal degradation patterns were investigated through thermogravimetric analysis in both the dry and swelled state. The water sorption studies showed rapid swelling behavior of these hydrogels, where swelling (%EWC) was found to be strongly dependent on the ratio of the two monomers in the hydrogels and the swelling kinetics dependent on the dose rates of hydrogel synthesis. These radiolytically synthesized hydrogels responded to electrical stimulus both in terms of the bending speed as well as bending angle under an applied voltage. The nature of the deformation was reversible and can be controlled through switching the voltage on and off. - Highlights: • Polyacrylic acid – polyacrilonitrile copolymeric hydrogel has been radiolytically synthesized. • Trimethyloltrimethacrylate (TMPTMA) used as crosslinker. • Hydrogel has been characterized and tested for electroresponsive character. • Bending angles and bending speed were found dependent upon applied voltage

  17. A theoretical study of the H-abstraction reactions from HOI by moist air radiolytic products (H, OH, and O (3P)) and iodine atoms (2P(3/2)).

    Science.gov (United States)

    Hammaecher, Catherine; Canneaux, Sébastien; Louis, Florent; Cantrel, Laurent

    2011-06-23

    The rate constants of the reactions of HOI molecules with H, OH, O ((3)P), and I ((2)P(3/2)) atoms have been estimated over the temperature range 300-2500 K using four different levels of theory. Geometry optimizations and vibrational frequency calculations are performed using MP2 methods combined with two basis sets (cc-pVTZ and 6-311G(d,p)). Single-point energy calculations are performed with the highly correlated ab initio coupled cluster method in the space of single, double, and triple (pertubatively) electron excitations CCSD(T) using the cc-pVTZ, cc-pVQZ, 6-311+G(3df,2p), and 6-311++G(3df,3pd) basis sets. Reaction enthalpies at 0 K were calculated at the CCSD(T)/cc-pVnZ//MP2/cc-pVTZ (n = T and Q), CCSD(T)/6-311+G(3df,2p)//MP2/6-311G(d,p), and CCSD(T)/6-311++G(3df,3pd)//MP2/6-311G(d,p) levels of theory and compared to the experimental values taken from the literature. Canonical transition-state theory with an Eckart tunneling correction is used to predict the rate constants as a function of temperature. The computational procedure has been used to predict rate constants for H-abstraction elementary reactions because there are actually no literature data to which the calculated rate constants can be directly compared. The final objective is to implement kinetics of gaseous reactions in the ASTEC (accident source term evaluation code) program to improve speciation of fission products, which can be transported along the reactor coolant system (RCS) of a pressurized water reactor (PWR) in the case of a severe accident.

  18. Modelling of Radiolytical Proceses in Polystyrenic Structures

    International Nuclear Information System (INIS)

    Postolache, C.

    2006-01-01

    The behavior of polystyrene, poly α-methylstyrene and poly β-methylstyrene structures in ionizing fields was analyzed using computational methods. In this study, the primary radiolytic effect was evaluated using a free radical mechanism. Molecular structures were built and geometrical optimized using quantum-chemical methods. Binding energies for different quantum states and peripheral orbitals distribution were determined. Based on obtained results it was proposed an evaluation model of radiolytical processes in polymers in solid phase. Suggested model suppose to distinguish the dominant processes by binding energies values analysis and LUMO peripheral orbital distribution. Computed binding energies analysis of energetically optimized molecular structures in ionized state (charge +1, multiplicity 2) reveals a high similitude of obtained binding energies for ionized states. The same similitude was observed also in case of total binding energies for neutral state (charge 0, multiplicity 1). Analyzed molecular structures can be associated with ionized molecule state right after one electron capture. This fact suggests that the determined stage of radiolitical fragmentation act is intermediate state of ionized molecule. This molecule captured one electron but it had no necessary time for atoms rearrangement in the molecule for new quantum state. This supposition is in accordance with literature, the time period between excitation act and fragmentation act being lower than 10 - 15 seconds. Based on realized model could be explained the behavior differences of polymeric structures in ionizing radiation field. Preferential fracture of main chains in fragmentation poly α-methylstirene can be explained in accordance with proposed model by C-C from main C bonding energies decreasing in the neighboring of quaternary C

  19. kinetics of the coupled gas-iron reactions involving silicon and carbon

    African Journals Online (AJOL)

    user

    1985-09-01

    Sep 1, 1985 ... out for the system involving liquid iron containing carbon and silicon and a gas ... in content with liquid iron at. 15600C, the ... of carbon monoxide bubbles at the. Slag - metal ..... equilibrium strongly make chemical reactions.

  20. Kinetics of the Coupled Gas-Iron Reactions Involving Silicon and ...

    African Journals Online (AJOL)

    The kinetic study of coupled gas-iron reactions at 15600 has been carried out for the system involving liquid iron containing carbon and silicon and a gas phase consisting carbon monoxide, silicon monoxide and carbon dioxide. The coupled reactions are: (1) 200(g) = CO2 + C. (2) SiO (g) + CO (g) = Si ¸ CO (g). (3) SiO (g) + ...

  1. Radiolytic studies of the cumyloxyl radical in aqueous solutions

    International Nuclear Information System (INIS)

    Neta, P.; Dizdaroglu, M.; Simic, M.G.

    1984-01-01

    Formation and reactions of the cumyloxyl radical in aqueous solutions were studied by steady-state and pulse radiolytic techniques. Cumene hydroperoxide reacts with esub(aq)sup(-) (k = 4.4x10 9 M -1 s -1 ) to yield the cumyloxyl radical. The spectrum recorded after the pulse indicates formation of a species absorbing at 250 nm. This product was identified as acetophenone, which is formed by the fragmentation of the cumyloxyl radical. By comparison of the pseudo-first-order rates of esub(aq)sup(-) decay at 600 nm with the rate of production of acetophenone at 245 nm at increasing concentrations of cumene hydroperoxide, it was possible to derive a rate constant of 1.0x10 7 s -1 for the cleavage of cumyloxyl to acetophenone and methyl radical. This value is higher than that measured previously in organic solvents (1x10 6 s -1 ), as expected. HPLC analysis of the radiation products acetophenone and cumyl alcohol permitted determination of rate constants for hydrogen abstraction by the cumyloxyl radical, in competition with the fragmentation. The rate constants for H abstraction from i-PrOH, EtOH, and MeOH by CmO were found to be 9.9x10 6 , 3.8x10 6 , and 8.5x10 5 M -1 s -1 , respectively

  2. Pulse-radiolytic investigations of catechols and catecholamines

    International Nuclear Information System (INIS)

    Bors, W.; Saran, M.; Michel, C.; Lengfelder, E.; Fuchs, C.; Spoettl, R.

    1975-01-01

    Adrenaline (epinephrine), adrenochrome and C 4 -substituted catechol model compounds were pulse-irradiated in aqueous neutral and alkaline solutions. Transient spectra are reported after oxidizing adrenaline and reducing adrenochrome. All species appearing during the 20 msec interval after the pulse have been identified: the OH adduct with an absorption maximum at 300 to 310 nm, the semiquinone (at 245 nm), and adrenaline quinone (at 340 nm). The reaction of superoxide anions (O 2 - ) with adrenaline was less efficient, compared with OH radicals. A novel oxidation product, derived from the semiquinone and O 2 - , has been identified as the 4-hydroxy-3,6-dioxo derivate. The pulse-radiolytic reduction of adrenochrome by hydrated electrons (esub(aq) - ) yielded the semiquinone of adrenochrome (absorbing at 470 nm), which subsequently decayed by a second-order process. The dismutation products leucoadrenochrome (absorbing at 300 nm, pH 9.8) and the adrenochrome tautomer (absorbing at 375 nm) were unstable, forming a 5,6-dihydro-N-methyl indole and regenerating adrenochrome. (author)

  3. Impact of different metal turbidities on radiolytic hydrogen generation in nuclear power plants

    International Nuclear Information System (INIS)

    Kumbhar, A.G.; Belapurkar, A.D.; Venkateswaran, G.; Kishore, K.

    2005-01-01

    Radiolytic hydrogen generation on γ irradiation of turbid solutions containing metal turbidities such as titanium, nickel, iron, chromium, copper, indium, and aluminium was studied. It is suggested that the chemical reactivity of the metal in the turbid solution with e aq -/H/OH produced by radiolysis of water interferes with the recombination reactions which destroy H 2 and H 2 O 2 , thus leading to higher yield of hydrogen. The rate of generation of hydrogen and the G(H 2 ) value is related to the reactivity of the metal ion/hydroxylated species with the free radicals. (orig.)

  4. Detailed determination of the fusion nuclear radius in reactions involving weakly bound projectiles

    International Nuclear Information System (INIS)

    Gomez Camacho, A.; Aguilera, E. F.; Quiroz, E. M.

    2007-01-01

    A detailed determination of the fusion radius parameter is performed within the Distorted Wave Born Approximation for reactions involving weakly bound projectiles. Specifically, a simultaneous X 2- analysis of elastic and fusion cross section data is done using a Woods-Saxon potential with volume and surface parts. The volume part is assumed to be responsible for fusion reactions while the surface part for all other direct reactions. It is proved that in order to fit fusion data, particularly for energies below the Coulomb barrier where fusion is enhanced, it is necessary to have a value of around 1.4 fm for the fusion radial parameter of the fusion potential (W F ). This value is much higher than that frequently used in Barrier Penetration models (1.0 fm). The calculations are performed for reactions involving the weakly bound projectile 9 Be with several medium mass targets. (Author)

  5. Interplay of break-up and transfer processes in reactions involving weakly-bound systems

    Science.gov (United States)

    Vitturi, Andrea; Moschini, Laura

    2018-02-01

    In this note we illustrate some applications of a simple model which has been devised to clarify the reaction mechanism and the interplay of different reaction channels (elastic, inelastic, transfer, break-up) in heavy-ion collisions. The model involves two potential wells moving in one dimension and few active particles; in spite of its simplicity, it is supposed to maintain the main features, the properties and the physics of the full three-dimensional case. Special attention is given to the role of continuum states in reactions involving weakly-bound systems, and different approximation schemes (as first-order or coupled-channels) as well as different continuum discretization procedures are tested. In the case of two active particles the reaction mechanism associated with two-particle transfer and the effect of pairing intearction are investigated. Work done in collaboration with Antonio Moro and Kouichi Hagino

  6. Radiolytic degradation of paracetamol in dilute aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Szabo, L [Hungarian Academy of Sciences, Budapest (Hungary). Inst. of Isotopes; Budapest University of Technology and Economics, Budapest (Hungary); Toth, T [Budapest University of Technology and Economics, Budapest (Hungary); Homlok, R; Takacs, E; Wojnarovits, L [Hungarian Academy of Sciences, Budapest (Hungary). Inst. of Isotopes

    2011-07-01

    Complete text of publication follows. Paracetamol or with name acetaminophen is widely used as analgesic and antipyretic drug. Due to its heavy use it is regularly detected in the surface waters. The degradation of the compound formerly was studied in several advanced oxidation processes (UV/H{sub 2}O{sub 2}, UV/TiO{sub 2}, electrochemical oxidation, ozonation). Here we report on the radiolytic degradation. In the experimental work we combined a wide variety of techniques. For the investigation of the intermediates pulse radiolysis, for end-product experiments (decolouration, mineralization) gamma irradiation were used together with UV-Vis spectroscopy, HPLC separation (with diode array and MS-MS detection), chemical oxygen demand, total organic carbon content and toxicity measurements. {sup {center_dot}O}H radicals are the main oxidative species during irradiation. They add to the aromatic ring producing hydroxycyclohexadienyl type radicals. These radicals either transform to hydroxy-paracetamol stable products in several reaction steps, or after water elimination transform to semi-iminoquinone radical. The reaction of hydroxycyclohexadienyl radicals with O{sub 2} yields peroxi radicals. The latter radicals may eliminate HO{sub 2}{sup {center_dot}} or undergo ring opening and transformation, first to different carboxylic acids, and finally (mineralization) to CO{sub 2}, H{sub 2}O and NH{sub 3} or NO{sub 2}. Paracetamol has a relatively low toxicity. In 10{sup -3} mol dm{sup -3} DCF solution after irradiation some products (e.g. hydroquinone, acetamide) are more toxic than paracetamol. By increasing the dose the toxicity suddenly decreases. It seems that the toxic products are highly sensitive to irradiation treatment.

  7. Radiolytic degradation of paracetamol in dilute aqueous solution

    International Nuclear Information System (INIS)

    Szabo, L.; Toth, T.; Homlok, R.; Takacs, E.; Wojnarovits, L.

    2011-01-01

    Complete text of publication follows. Paracetamol or with name acetaminophen is widely used as analgesic and antipyretic drug. Due to its heavy use it is regularly detected in the surface waters. The degradation of the compound formerly was studied in several advanced oxidation processes (UV/H 2 O 2 , UV/TiO 2 , electrochemical oxidation, ozonation). Here we report on the radiolytic degradation. In the experimental work we combined a wide variety of techniques. For the investigation of the intermediates pulse radiolysis, for end-product experiments (decolouration, mineralization) gamma irradiation were used together with UV-Vis spectroscopy, HPLC separation (with diode array and MS-MS detection), chemical oxygen demand, total organic carbon content and toxicity measurements. · OH radicals are the main oxidative species during irradiation. They add to the aromatic ring producing hydroxycyclohexadienyl type radicals. These radicals either transform to hydroxy-paracetamol stable products in several reaction steps, or after water elimination transform to semi-iminoquinone radical. The reaction of hydroxycyclohexadienyl radicals with O 2 yields peroxi radicals. The latter radicals may eliminate HO 2 · or undergo ring opening and transformation, first to different carboxylic acids, and finally (mineralization) to CO 2 , H 2 O and NH 3 or NO 2 . Paracetamol has a relatively low toxicity. In 10 -3 mol dm -3 DCF solution after irradiation some products (e.g. hydroquinone, acetamide) are more toxic than paracetamol. By increasing the dose the toxicity suddenly decreases. It seems that the toxic products are highly sensitive to irradiation treatment.

  8. Parametric studies of radiolytic oxidation of iodide solutions with and without paint: comparison with code calculations

    Energy Technology Data Exchange (ETDEWEB)

    Poletiko, C; Hueber, C [Inst. de Protection et de Surete Nucleaire, C.E. Cadarache, St. Paul-lez-Durance (France); Fabre, B [CISI, C.E. Cadarache, St. Paul-lez-Durance (France)

    1996-12-01

    In case of severe nuclear accident, radioactive material may be released into the environment. Among the fission products involved, are the very volatile iodine isotopes. However, the chemical forms are not well known due to the presence of different species in the containment with which iodine may rapidly react to form aerosols, molecular iodine, hydroiodic acid and iodo-organics. Tentative explanations of different mechanisms were performed through benchscale tests. A series of tests has been performed at AEA Harwell (GB) to study parameters such as pH, dose rate, concentration, gas flow rate, temperature in relation to molecular iodine production, under dynamic conditions. Another set of tests has been performed in AECL Whiteshell (CA) to study the behaviour of painted coupons, standing in gas phase or liquid phase or both, with iodine compounds under radiation. The purpose of our paper is to synthesize the data and compare the results to the IODE code calculation. Some parameters of the code were studied to fit the experimental result the best. A law, concerning the reverse reaction of iodide radiolytic oxidation, has been proposed versus: pH, concentrations and gas flow-rate. This law does not apply for dose rate variations. For the study of painted coupons, it has been pointed out that molecular iodine tends to be adsorbed or chemically absorbed on the surface in gas phase, but the mechanism should be more sophisticated in the aqueous phase. The iodo-organics present in liquid phase tend to be partly or totally destroyed by oxidation under radiation (depending upon the dose delivered). These points are discussed. (author) 18 figs., 3 tabs., 15 refs.

  9. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

    Science.gov (United States)

    Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

    2014-12-02

    Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

  10. REACT-Mod: a mathematical model for transient calculation of chemical reactions with U-Pu-Np-Tc in the aqueous nitric acid solution

    International Nuclear Information System (INIS)

    Tachimori, Shoichi; Kitamura, Tatsuaki.

    1996-10-01

    A computer code REACT-Mod which simulates various chemical reactions in an aqueous nitric acid solution involving uranium, plutonium, neptunium, technetium etc. e.g., redox, radiolytic and disproportionation reactions of 68, was developed based on the kinetics model. The numerical solution method adopted in the code are two, a kinetics model totally based on the rate law of which differential equations are solved by the modified Porsing method, and a two-step model based on both the rate law and equilibrium law. Only the former treats 27 radiolytic reactions. The latter is beneficially used to have a quick and approximate result by economical computation. The present report aims not only to explain the concept, chemical reactions treated and characteristics of the model but also to provide details of the program for users of the REACT-Mod code. (author)

  11. Clustering mechanism of oxocarboxylic acids involving hydration reaction: Implications for the atmospheric models

    Science.gov (United States)

    Liu, Ling; Kupiainen-Määttä, Oona; Zhang, Haijie; Li, Hao; Zhong, Jie; Kurtén, Theo; Vehkamäki, Hanna; Zhang, Shaowen; Zhang, Yunhong; Ge, Maofa; Zhang, Xiuhui; Li, Zesheng

    2018-06-01

    The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with different reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acid, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reactions using density functional theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. Under atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, and the product can further participate in the clustering process. The differences in cluster structures and properties induced by the hydration reaction lead to significant differences in cluster formation rates and pathways at relatively low temperatures.

  12. Radiation effects in moist-air systems and the influence of radiolytic product formation on nuclear waste glass corrosion

    International Nuclear Information System (INIS)

    Wronkiewicz, D.J.; Bates, J.K.; Buck, E.C.; Hoh, J.C.; Emery, J.W.; Wang, L.M.

    1997-07-01

    Ionizing radiation may affect the performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water to produce a variety of radiolytic products. Tests were conducted to examine the effects of radiolysis under high gas/liquid ratios. Results indicate that nitrate is the predominant radiolytic product produced following both gamma and alpha radiation exposure, with lesser amounts of nitrite and carboxylic acids. The formation of nitrogen acids during exposure to long-lived, alpha-particle-emitting transuranic elements indicates that these acids may play a role in influencing nuclear waste form reactions in a long-term unsaturated disposal scenario. Experiments were also conducted with samples that simulate the composition of Savannah River Plant nuclear waste glasses. Radiolytic product formation in batch tests (340 m -1 , 90 C) resulted in a small increase in the release rates of many glass components, such as alkali and alkaline earth elements, although silicon and uranium release rates were slightly reduced indicating an overall beneficial effect of radiation on waste form stability. The radiolytic acids increased the rate of ion exchange between the glass and the thin film of condensate, resulting in accelerated corrosion rates for the glass. The paragenetic sequence of alteration phases formed on both the irradiated and nonirradiated glass samples reacted in the vapor hydration tests matches closely with those developed during volcanic glass alteration in naturally occurring saline-alkaline lake systems. This correspondence suggests that the high temperatures used in these tests have not changed the underlying glass reaction mechanism relate to that which controls glass reactions under ambient surficial conditions

  13. Radiation effects in moist-air systems and the influence of radiolytic product formation on nuclear waste glass corrosion

    Energy Technology Data Exchange (ETDEWEB)

    Wronkiewicz, D.J.; Bates, J.K.; Buck, E.C.; Hoh, J.C.; Emery, J.W. [Argonne National Lab., IL (United States). Chemical Technology Div.; Wang, L.M. [Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Geology

    1997-07-01

    Ionizing radiation may affect the performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water to produce a variety of radiolytic products. Tests were conducted to examine the effects of radiolysis under high gas/liquid ratios. Results indicate that nitrate is the predominant radiolytic product produced following both gamma and alpha radiation exposure, with lesser amounts of nitrite and carboxylic acids. The formation of nitrogen acids during exposure to long-lived, alpha-particle-emitting transuranic elements indicates that these acids may play a role in influencing nuclear waste form reactions in a long-term unsaturated disposal scenario. Experiments were also conducted with samples that simulate the composition of Savannah River Plant nuclear waste glasses. Radiolytic product formation in batch tests (340 m{sup {minus}1}, 90 C) resulted in a small increase in the release rates of many glass components, such as alkali and alkaline earth elements, although silicon and uranium release rates were slightly reduced indicating an overall beneficial effect of radiation on waste form stability. The radiolytic acids increased the rate of ion exchange between the glass and the thin film of condensate, resulting in accelerated corrosion rates for the glass. The paragenetic sequence of alteration phases formed on both the irradiated and nonirradiated glass samples reacted in the vapor hydration tests matches closely with those developed during volcanic glass alteration in naturally occurring saline-alkaline lake systems. This correspondence suggests that the high temperatures used in these tests have not changed the underlying glass reaction mechanism relate to that which controls glass reactions under ambient surficial conditions.

  14. Radiolytic stabilization of poly(hydroxybutyrate)

    International Nuclear Information System (INIS)

    Santos, Renata F.S.; Araujo, Elmo S.

    2007-01-01

    Poly(hydroxybutyrate), PHB, is a thermoplastic polyester synthesized by many types of bacteria. PHB is of special interest in the manufacture of medical devices sterilizable by gamma radiation, because of remarkable characteristics like its great biocompatibility and biodegradability. However, ionizing radiation causes main chain scissions of PHB followed by the reduction in its molar mass. Then, the purpose of this study was to investigate the radiolytic stabilization of the structure and properties of Brazilian PHB by commercial additives used in photo and thermo-oxidative stabilization of polymers. Initially, casting solvent films were prepared adding 0.5 wt% of five different additives to the polymer system. These films were irradiated at 25 kGy and investigated viscosity-average molar mass (Mv) changes in order to select the best stabilizer. Among the tested additives only one, antioxidant type, provided a good radiostabilization. New polymeric films were prepared with the antioxidant, whose concentrations (wt%) were 0.3, 0.5, 0.7 and 1.0. In this case, the samples were submitted to doses that varied from 15 to 50 kGy. Viscometric analysis was performed in order to assess the radiation-induced main chain scissions. The G value (scissions/100eV of energy transferred to the system) was also obtained by the viscosity technique. The most effective additive, added to the polymer system at 0.5 wt%, promotes a decrease of 8.6 to 1.5 in G value at a dose range of 0 - 35 kGy. In addition, (FT-IR, NMR-1H) spectroscopic analyses on polymer system were also performed. (author)

  15. Preparation of molybdenum borides by combustion synthesis involving solid-phase displacement reactions

    International Nuclear Information System (INIS)

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

    2008-01-01

    Preparation of molybdenum borides of five different phases in the Mo-B binary system (including Mo 2 B, MoB, MoB 2 , Mo 2 B 5 , and MoB 4 ) was performed by self-propagating high-temperature synthesis (SHS) with two kinds of the reactant samples. When elemental powder compacts with an exact stoichiometry corresponding to the boride phase were employed, self-sustaining reaction was only achieved in the sample with Mo:B = 1:1 and nearly single-phase MoB was yielded. Therefore, the other four boride compounds were prepared from the reactant compacts composed of MoO 3 , Mo, and B powders, within which the displacement reaction of MoO 3 with boron was involved in combustion synthesis. Experimental evidence shows that the extent of displacement reaction in the overall reaction has a significant impact on sustainability of the synthesis reaction, combustion temperature, reaction front velocity, and composition of the end product. An increase in the solid-phase displacement reaction taking place during the SHS process contributes more heat flux to the synthesis reaction, thus resulting in the increase of combustion temperature and enhancement of the reaction front velocity. Based upon the XRD analysis, formation of Mo 2 B, MoB 2 , and Mo 2 B 5 as the dominant boride phase in the end product was successful through the SHS reaction with powder compacts under appropriate stoichiometries between MoO 3 , Mo, and B. However, a poor conversion was observed in the synthesis of MoB 4 . The powder compact prepared for the production of MoB 4 yielded mostly Mo 2 B 5

  16. GC of catalytic reactions products involved in the promising fuel synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Zheivot, V.; Sazonova, N. [Russian Academy of Sciences, Novosibirsk (Russian Federation). Boreskov Inst. of Catalysis

    2012-09-15

    Catalytic reactions involved in the synthesis of the promising kinds of novel fuel and products formed in these reactions were systematized according to the resulting fuel type. Generalization of the retention of the substances comprising these products is presented. Chromatograms exhibiting their separation on chromatographic materials with the surface of different chemical properties are summarized. We propose procedures for gas-chromatographic analysis of the catalytic reactions products formed in the synthesis of hydrogen, methanol, dimethyl ether and hydrocarbons as a new generation of fuel alternative to petroleum and coal. For partial oxidation of methane into synthesis gas, on-line determination of the components obtained in the reaction was carried out by gas chromatography and gas analyzer based on different physicochemical methods (IR spectroscopy and electrochemical methods). Similarity of the results obtained using these methods is demonstrated. (orig.)

  17. Radiolytic hydrogen production in the subseafloor basaltic aquifer

    Directory of Open Access Journals (Sweden)

    Mary E Dzaugis

    2016-02-01

    Full Text Available Hydrogen (H2 is produced in geological settings by dissociation of water due to radiation from radioactive decay of naturally occurring uranium (238U, 235U, thorium (232Th and potassium (40K. To quantify the potential significance of radiolytic H2 as an electron donor for microbes within the South Pacific subseafloor basaltic aquifer, we use radionuclide concentrations of 43 basalt samples from IODP Expedition 329 to calculate radiolytic H2 production rates in basement fractures. The samples are from three sites with very different basement ages and a wide range of alteration types. U, Th and K concentrations vary by up to an order of magnitude from sample to sample at each site. Comparison of our samples to each other and to the results of previous studies of unaltered East Pacific Rise basalt suggests that significant variations in radionuclide concentrations are due to differences in initial (unaltered basalt concentrations (which can vary between eruptive events and post-emplacement alteration. In our samples, there is no clear relationship between alteration type and calculated radiolytic yields. Local maxima in U, Th, and K produce hotspots of H2 production, causing calculated radiolytic rates to differ by up to a factor of 80 from sample to sample. Fracture width also greatly influences H2 production, where microfractures are hotspots for radiolytic H2 production. For example, H2 production rates normalized to water volume are 190 times higher in 1 μm wide fractures than in fractures that are 10 cm wide. To assess the importance of water radiolysis for microbial communities in subseafloor basaltic aquifers, we compare electron transfer rates from radiolysis to rates from iron oxidation in subseafloor basalt. Radiolysis appears likely to be a more important electron donor source than iron oxidation in old (>10 Ma basement basalt. Radiolytic H2 production in the volume of water adjacent to a square cm of the most radioactive SPG basalt may

  18. Radiolytic production of chemical fuels in fusion reactor systems

    Energy Technology Data Exchange (ETDEWEB)

    Fish, J D

    1977-06-01

    Miley's energy flow diagram for fusion reactor systems is extended to include radiolytic production of chemical fuel. Systematic study of the economics and the overall efficiencies of fusion reactor systems leads to a criterion for evaluating the potential of radiolytic production of chemical fuel as a means of enhancing the performance of a fusion reactor system. The ecumenicity of the schema is demonstrated by application to (1) tokamaks, (2) mirror machines, (3) theta-pinch reactors, (4) laser-heated solenoids, and (5) inertially confined, laser-pellet devices. Pure fusion reactors as well as fusion-fission hybrids are considered.

  19. Radiolytic production of chemical fuels in fusion reactor systems

    International Nuclear Information System (INIS)

    Fish, J.D.

    1977-06-01

    Miley's energy flow diagram for fusion reactor systems is extended to include radiolytic production of chemical fuel. Systematic study of the economics and the overall efficiencies of fusion reactor systems leads to a criterion for evaluating the potential of radiolytic production of chemical fuel as a means of enhancing the performance of a fusion reactor system. The ecumenicity of the schema is demonstrated by application to (1) tokamaks, (2) mirror machines, (3) theta-pinch reactors, (4) laser-heated solenoids, and (5) inertially confined, laser-pellet devices. Pure fusion reactors as well as fusion-fission hybrids are considered

  20. Photolytic and radiolytic destruction of natural polycyclic mycotoxins

    International Nuclear Information System (INIS)

    Mammadov, Kh. F

    2011-01-01

    Full text: The kinetics of degradation of natural polycyclic toxins in grains and dried fruits under the influence of UV-light and ionizing radiation 60 C and the probability of radiolytic detoxication of these products has been studied for the first time

  1. Pore-scale studies of multiphase flow and reaction involving CO2 sequestration in geologic formations

    Science.gov (United States)

    Kang, Q.; Wang, M.; Lichtner, P. C.

    2008-12-01

    In geologic CO2 sequestration, pore-scale interfacial phenomena ultimately govern the key processes of fluid mobility, chemical transport, adsorption, and reaction. However, spatial heterogeneity at the pore scale cannot be resolved at the continuum scale, where averaging occurs over length scales much larger than typical pore sizes. Natural porous media, such as sedimentary rocks and other geological media encountered in subsurface formations, are inherently heterogeneous. This pore-scale heterogeneity can produce variabilities in flow, transport, and reaction processes that take place within a porous medium, and can result in spatial variations in fluid velocity, aqueous concentrations, and reaction rates. Consequently, the unresolved spatial heterogeneity at the pore scale may be important for reactive transport modeling at the larger scale. In addition, current continuum models of surface complexation reactions ignore a fundamental property of physical systems, namely conservation of charge. Therefore, to better understand multiphase flow and reaction involving CO2 sequestration in geologic formations, it is necessary to quantitatively investigate the influence of the pore-scale heterogeneity on the emergent behavior at the field scale. We have applied the lattice Boltzmann method to simulating the injection of CO2 saturated brine or supercritical CO2 into geological formations at the pore scale. Multiple pore-scale processes, including advection, diffusion, homogeneous reactions among multiple aqueous species, heterogeneous reactions between the aqueous solution and minerals, ion exchange and surface complexation, as well as changes in solid and pore geometry are all taken into account. The rich pore scale information will provide a basis for upscaling to the continuum scale.

  2. Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

    International Nuclear Information System (INIS)

    Jaraula, Caroline M.B.; Schwark, Lorenz; Moreau, Xavier; Pickel, Walter; Bagas, Leon; Grice, Kliti

    2015-01-01

    Highlights: • Bulk kerogen compositions indicate land plant sources for organic matter in the uranium deposit. • Radiolysis led to cleavage of straight long chain forming medium chain length n-alkyl moieties. • Secondary and tertiary reactions with OH − radicals promoted the formation of alkanones. • “Radiolytic molecular markers” imply molecular markers resulting from radiolytic cracking. • A mechanism is proposed for the production of n-alkanes and n-alkanones. - Abstract: We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO 2 /g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C 27 –C 31 ) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are

  3. Radiolytic formation of organic iodides from organic compounds released from ripolin paint

    International Nuclear Information System (INIS)

    Attia, S.; Evans, G.J.

    2002-01-01

    The impact of a serious nuclear reactor accident is governed to a large extent by the possible release of airborne organic iodides to the environment. This research examines the identification and behavior of organic iodides formed in the containment due to the release of organic compounds from Ripolin paint, into the aqueous phase, following a nuclear reactor accident. A bench scale apparatus installed in the irradiation chamber of a Gammacell was used to analyze the formation of organic iodides. Iodo-organics, transferred to the gas phase above irradiated aqueous samples, were analyzed using a Thermal Desorption method coupled with gas chromatography and mass spectrometry. Detailed studies of the identity of the organic compounds released and the organic iodides formed were conducted. The effects of parameters such as irradiation dose were also examined. All the organic iodides formed, under radiolytic conditions, were identified as iodo-alkanes. The organic compounds that were released from the Ripolin paint, such as methyl isobutyl ketone, were found to decompose, by a series of reactions, to produce the organic iodides. The precursor organic compounds and the organic iodides formed were observed to consist of the same alkyl group. These results indicate that organic compounds released from surface paints directly influence the formation of radiolytic organic iodide. (author)

  4. Time extrapolation of radiolytic degradation product kinetics: the case of polyurethane

    International Nuclear Information System (INIS)

    Dannoux, A.

    2007-02-01

    The prediction of the environmental impact of organic materials in nuclear waste geological storage needs knowledge of radiolytic degradation mechanisms and kinetics in aerobic and anaerobic conditions. In this framework, the effect of high doses (> MGy) and the variation of dose rate have to be considered. The material studied is a polyurethane composed of polyether soft segment and aromatic hard segments. Mechanisms were built on the analysis of material submitted to irradiations of simulation (high energy electrons and gamma radiation) by FTIR spectroscopy and gaseous and liquid degradation products by gas mass spectrometry and size exclusion chromatography. The electron paramagnetic resonance study of radical process and the determination of oxygen consumption and gas formation radiolytic yields allowed us to acquire kinetic data and to estimate dose rate and high doses effects. The polyurethane radio-oxidation mainly concerns soft segments and induced cross-linkings and production by scissions of oxidised compounds (esters, alcohols, carboxylic acids). The kinetic of radical termination is rapid and the dose rate effect is limited. After 10 MGy, branching and scission reactions are in equilibrium and low molecular weight products accumulate. At last, the degradation products release in water is influenced by the oxidation rate and the temperature. After 10 MGy, the soluble fraction is stabilised at 25%. The water soluble products identified by electro-spray ionisation mass spectrometry (alcohols, aldehydes, carboxylic acids) potentially formed complexes with radionuclides. (author)

  5. Pulse radiolytic study of alpha-tocopherol radical mechanisms in ethanolic solution

    International Nuclear Information System (INIS)

    Jore, D.; Patterson, L.K.; Ferradini, C.

    1986-01-01

    Pulse radiolytic studies of alpha-tocopherol (alpha TH) oxidation-reduction processes were carried out with low doses (5 Gy) of high-energy electrons in O 2 -, N 2 -, and air-saturated ethanolic solutions. Depending on the concentration of oxygen in solution, two different radicals, A . and B ., were observed. The first, A ., was obtained under N 2 and results from alpha TH reaction with solvated electron (k alpha TH + e-solv = 3.4 X 10(8) mol-1 liter s-1) and with H 3 C-CH-OH, (R.) (k alpha TH + R. = 5 X 10(5) mol-1 liter s-1). B., observed under O 2 , is produced by alpha TH reaction with RO 2 . peroxyl radicals (k alpha TH + RO 2 . = 9.5 X 10(4) mol-1 liter s-1)

  6. Hot atom reactions involving multivalent and univalent species. Progress report, February 1979-January 1980

    International Nuclear Information System (INIS)

    Tang, Y.N.

    1980-01-01

    The major progress during this period was in the study of recoil 31 Si and recoil 11 C reactions and in the initiation of the studies on the interaction of molecular tritium on solid surfaces. For the recoil 31 Si systems, heterogeneous hydrogenation experiments have been designed to positively confirm that a major unknown product, derived from the interaction of 31 Si atoms with 1,3-butadiene, is 1-silacyclopenta-2,4-diene. This compound has been shown to be very sensitive to γ-ray irradiation and to be thermally unstable at a temperature higher than 100 0 C. Another recoil 31 Si experiment was designed to review the mechanism of the 31 Si abstraction reactions. From the fact that high yields of [ 31 Si]-1-fluorosilacyclopent-3-ene were obtained as a product from a mixture of PH 3 and PF 3 together with 1,3-butadiene, the stepwise abstraction mechanism is definitely much more predominant than the possible simultaneous abstraction. Other recoil 31 Si works involved a detailed systematic composition study of 31 SiF 2 reactions with 1,3-butadiene, some neon moderator studies, and the continuation of the studies on the reactions of 31 SiF 2 and 31 SiH 2 with conjugated hexadienes. By using 2- 14 C-propanone and 1,3- 14 C-propanone, the mechanism of solvent-free oxidative cleavage of propanone by KMnO 4 was elucidated. Information thus derived was used to degradate the 11 C-labelled propadiene derived from the reactions of recoil 11 C atoms with ethylene. Results indicate that 73% of the 11 C-labelled propadiene was center-labelled. This value was observed to change with additives. Various mechanistic studies on the heterogeneous interactions of molecular T 2 on solid surfaces such as Pd supported on active carbon have been initiated

  7. Evaluate the role of organic acids in the protection of ligands from radiolytic degradation

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Anneka [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mezyk, Stehpen [Idaho National Lab. (INL), Idaho Falls, ID (United States); Peterman, Dean [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2016-08-01

    In the Advanced TALSPEAK process, the bis(2-ethylhexyl)phosphoric acid (HDEHP) extractant used in the traditional TALSPEAK process is replaced by the extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). In addition, the aqueous phase complexant and buffer used in traditional TALSPEAK is replaced with the combination of N-(2-hydroxyethyl)ethylenediamine-N,N’,N’-triacetic acid (HEDTA) and citric acid. In order to evaluate the possible impacts of gamma radiolysis upon the efficacy of the Advanced TALSPEAK flowsheet, aqueous and organic phases corresponding to the extraction section of the proposed flowsheet were irradiated in the INL test loop under an ambient atmosphere. The results of these studies conducted at INL, led INL researchers to conclude that the scarcity of values of rate constants for the reaction of hydroxyl radical with the components of the Advanced TALSPEAK process chemistry was severely limiting the interpretation of the results of radiolysis studies performed at the INL. In this work, the rate of reaction of hydroxyl radical with citric acid at several pH values was measured using a competitive pulse radiolysis technique. This report describes those results and is written in completion of milestone M3FT-16IN030102028, the goal of which was to evaluate the role of organic acids in the protection of ligands from radiolytic degradation. The results reported here demonstrate the importance of obtaining hydroxyl radical reaction rate data for the conditions that closely resemble actual solution conditions expected to be used in an actual solvent extraction process. This report describes those results and is written in completion of milestone M3FT-16IN030102028, the goal of which was to evaluate the role of organic acids in the protection of ligands from radiolytic degradation.

  8. Investigation of large α production in reactions involving weakly bound 7Li

    Science.gov (United States)

    Pandit, S. K.; Shrivastava, A.; Mahata, K.; Parkar, V. V.; Palit, R.; Keeley, N.; Rout, P. C.; Kumar, A.; Ramachandran, K.; Bhattacharyya, S.; Nanal, V.; Palshetkar, C. S.; Nag, T. N.; Gupta, Shilpi; Biswas, S.; Saha, S.; Sethi, J.; Singh, P.; Chatterjee, A.; Kailas, S.

    2017-10-01

    The origin of the large α -particle production cross sections in systems involving weakly bound 7Li projectiles has been investigated by measuring the cross sections of all possible fragment-capture as well as complete fusion using the particle-γ coincidence, in-beam, and off-beam γ -ray counting techniques for the 7Li+93Nb system at near Coulomb barrier energies. Almost all of the inclusive α -particle yield has been accounted for. While the t -capture mechanism is found to be dominant (˜70 % ), compound nuclear evaporation and breakup processes contribute ˜15 % each to the inclusive α -particle production in the measured energy range. Systematic behavior of the t capture and inclusive α cross sections for reactions involving 7Li over a wide mass range is also reported.

  9. Thermal and combined thermal and radiolytic reactions involving nitrous oxide, hydrogen, and nitrogen in the gas phase; comparison of gas generation rates in supernate and solid fractions of Tank 241-SY-101 simulated waste

    International Nuclear Information System (INIS)

    Bryan, S.A.; Pederson, L.R.

    1995-03-01

    This report summarizes progress made in evaluating me by which flammable gases are generated in Hanford double-shell tank wastes, based on the results of laboratory tests using simulated waste mixtures. Work described in this report. was conducted at Pacific Northwest Laboratory (PNL) for the Flammable Gas Safety Project, the purpose of which is to develop information needed to support Westinghouse Hanford Company (WHC) in their efforts to ensure the safe interim storage of wastes at the Hanford Site. This work is related to gas generation studies being performed at Georgia Institute of Technology (GIT), under subcontract to PNL, using simulated wastes, and to studies being performed at VMC using actual wastes

  10. Chemical and radiolytical solvent degradation in the Purex process

    International Nuclear Information System (INIS)

    Stieglitz, L.; Becker, R.

    1985-01-01

    The state of the art of chemical and radiolytical solvent degradation is described. For the hydrolysis of tributylphosphate TBP->HDBP->H 2 MBP->H 3 PO 4 values are given for the individual constants in a temperature range from 23 to 90 0 C. Radiolytic yields were measured for HDBP as 80 mg/Wh, for H 2 MBP as 2 mg/Wh, and for H 3 PO 4 as 5 mg/Wh. Experimental results on the degradation products of the diluent are summarized and their influence on the process is discussed. Long chain acid phosphates and acid TBP oligomeres were identified as responsible for the retention of fission products. Techniques such as polarography, infrared spectrometry and electrolytic conductometry are applied to estimate concentrations of degradation products down to 10 -5 mol/l. (orig.) [de

  11. Chemical and radiolytical solvent degradation in the Purex process

    Energy Technology Data Exchange (ETDEWEB)

    Stieglitz, L; Becker, R

    1985-01-01

    The state of the art of chemical and radiolytical solvent degradation is described. For the hydrolysis of tributylphosphate TBP->HDBP->H/sub 2/MBP->H/sub 3/PO/sub 4/ values are given for the individual constants in a temperature range from 23 to 90/sup 0/C. Radiolytic yields were measured for HDBP as 80 mg/Wh, for H/sub 2/MBP as 2 mg/Wh, and for H/sub 3/PO/sub 4/ as 5 mg/Wh. Experimental results on the degradation products of the diluent are summarized and their influence on the process is discussed. Long chain acid phosphates and acid TBP oligomeres were identified as responsible for the retention of fission products. Techniques such as polarography, infrared spectrometry and electrolytic conductometry are applied to estimate concentrations of degradation products down to 10/sup -5/ mol/l.

  12. Radiolytic degradation of sorbic acid in isolated systems

    International Nuclear Information System (INIS)

    Thakur, B.R.; Trehan, I.R.; Arya, S.S.

    1990-01-01

    Effect of Co(60) gamma-irradiation on stability of sorbic acid (SA) in solutions, dough and chapaties has been investigated. SA was highly susceptible to radiolytic degradation in aqueous systems. Rate of degradation decreased with rise in pH. Sugars, hydrocolloids except pectin, citric acid, lactic acid, malic acid, arginine and threonine, catalyzed degradation while oxalic acid, maleic acid, Cu2+, nitrite, nitrate and phthalate had protective effects. SA was more stable in alcohols and vegetable oils than in aqueous solutions. In wheat flour radiolytic degradation of SA was less at lower moisture. Relatively SA was more stable in chapaties than in dough. Gelatinization and addition of oil in dough reduced degradation of SA

  13. Innocuous oil as an additive for reductive reactions involving zero valence iron

    International Nuclear Information System (INIS)

    Cary, J.W.; Cantrell, K.J.

    1994-11-01

    Reductive reactions involving zero valence iron appear to hold promise for in situ remediation of sites containing chlorinated hydrocarbon solvents and certain reducible metals and radionuclides. Treatment involves the injection of metallic iron and the creation of low levels of dissolved oxygen in the aqueous phase through oxidation of the metallic iron. The use of a biodegradable immiscible and innocuous organic liquid such as vegetable oil as an additive offers several intriguing possibilities. The oil phase creates a large oil-water interface that is immobile with respect to flow in the aqueous phase. This phase will act as a trap for chlorinated hydrocarbons and could potentially increase the reaction efficiency of reductive dehalogenation of chlorinated hydrocarbons by the metallic iron. When iron particles are suspended in the oil before injection they are preferentially held in the oil phase and tend to accumulate at the oil-water interface. Thus oil injection can serve as a mechanism for creating a stable porous curtain of metallic iron in the vadose to maintain a low oxygen environment which will minimize the consumption of the iron by molecular oxygen

  14. Gas chromatographic measurement of the radiolytic products of irradiated pork

    International Nuclear Information System (INIS)

    Zhou Yingcai; Wang Xiuying; Xu Peishu; Yuan Bihuai

    1988-01-01

    The radiolytic products of irradiated pork were isolated, analyzed and identified by the techniques of vacuum distillation, GC-MS. The higher boiling point compounds in fat were collected by cold-finger and its lower boiling point compounds were recovered on a short precolumn packed with alumina, and the volatiles of lean pork were collected on a short column packed with TCEP/Chromosovb. Some experimental conditions were studied. 49 compounds were identified. These compounds include hydrocarbons and sulphides etc. (author)

  15. A disposable electrochemical immunosensor for prolactin involving affinity reaction on streptavidin-functionalized magnetic particles

    International Nuclear Information System (INIS)

    Moreno-Guzman, Maria; Gonzalez-Cortes, Araceli; Yanez-Sedeno, Paloma; Pingarron, Jose M.

    2011-01-01

    A novel electrochemical immunosensor was developed for the determination of the hormone prolactin. The design involved the use of screen-printed carbon electrodes and streptavidin-functionalized magnetic particles. Biotinylated anti-prolactin antibodies were immobilized onto the functionalized magnetic particles and a sandwich-type immunoassay involving prolactin and anti-prolactin antibody labelled with alkaline phosphatase was employed. The resulting bio-conjugate was trapped on the surface of the screen-printed electrode with a small magnet and prolactin quantification was accomplished by differential pulse voltammetry of 1-naphtol formed in the enzyme reaction using 1-naphtyl phosphate as alkaline phosphatase substrate. All variables involved in the preparation of the immunosensor and in the electrochemical detection step were optimized. The calibration plot for prolactin exhibited a linear range between 10 and 2000 ng mL -1 with a slope value of 7.0 nA mL ng -1 . The limit of detection was 3.74 ng mL -1 . Furthermore, the modified magnetic beads-antiprolactin conjugates showed an excellent stability. The immunosensor exhibited also a high selectivity with respect to other hormones. The analytical usefulness of the immnunosensor was demonstrated by analyzing human sera spiked with prolactin at three different concentration levels.

  16. A disposable electrochemical immunosensor for prolactin involving affinity reaction on streptavidin-functionalized magnetic particles

    Energy Technology Data Exchange (ETDEWEB)

    Moreno-Guzman, Maria; Gonzalez-Cortes, Araceli [Department of Analytical Chemistry, Faculty of Chemistry, University Computense of Madrid, 28040 Madrid (Spain); Yanez-Sedeno, Paloma, E-mail: yseo@quim.ucm.es [Department of Analytical Chemistry, Faculty of Chemistry, University Computense of Madrid, 28040 Madrid (Spain); Pingarron, Jose M. [Department of Analytical Chemistry, Faculty of Chemistry, University Computense of Madrid, 28040 Madrid (Spain)

    2011-04-29

    A novel electrochemical immunosensor was developed for the determination of the hormone prolactin. The design involved the use of screen-printed carbon electrodes and streptavidin-functionalized magnetic particles. Biotinylated anti-prolactin antibodies were immobilized onto the functionalized magnetic particles and a sandwich-type immunoassay involving prolactin and anti-prolactin antibody labelled with alkaline phosphatase was employed. The resulting bio-conjugate was trapped on the surface of the screen-printed electrode with a small magnet and prolactin quantification was accomplished by differential pulse voltammetry of 1-naphtol formed in the enzyme reaction using 1-naphtyl phosphate as alkaline phosphatase substrate. All variables involved in the preparation of the immunosensor and in the electrochemical detection step were optimized. The calibration plot for prolactin exhibited a linear range between 10 and 2000 ng mL{sup -1} with a slope value of 7.0 nA mL ng{sup -1}. The limit of detection was 3.74 ng mL{sup -1}. Furthermore, the modified magnetic beads-antiprolactin conjugates showed an excellent stability. The immunosensor exhibited also a high selectivity with respect to other hormones. The analytical usefulness of the immnunosensor was demonstrated by analyzing human sera spiked with prolactin at three different concentration levels.

  17. Hot atom reactions involving multivalent and univalent species. Progress report, February 1979-January 1980

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Y.N.

    1980-01-01

    The major progress during this period was in the study of recoil /sup 31/Si and recoil /sup 11/C reactions and in the initiation of the studies on the interaction of molecular tritium on solid surfaces. For the recoil /sup 31/Si systems, heterogeneous hydrogenation experiments have been designed to positively confirm that a major unknown product, derived from the interaction of /sup 31/Si atoms with 1,3-butadiene, is 1-silacyclopenta-2,4-diene. This compound has been shown to be very sensitive to ..gamma..-ray irradiation and to be thermally unstable at a temperature higher than 100/sup 0/C. Another recoil /sup 31/Si experiment was designed to review the mechanism of the /sup 31/Si abstraction reactions. From the fact that high yields of (/sup 31/Si)-1-fluorosilacyclopent-3-ene were obtained as a product from a mixture of PH/sub 3/ and PF/sub 3/ together with 1,3-butadiene, the stepwise abstraction mechanism is definitely much more predominant than the possible simultaneous abstraction. Other recoil /sup 31/Si works involved a detailed systematic composition study of /sup 31/SiF/sub 2/ reactions with 1,3-butadiene, some neon moderator studies, and the continuation of the studies on the reactions of /sup 31/SiF/sub 2/ and /sup 31/SiH/sub 2/ with conjugated hexadienes. By using 2-/sup 14/C-propanone and 1,3-/sup 14/C-propanone, the mechanism of solvent-free oxidative cleavage of propanone by KMnO/sub 4/ was elucidated. Information thus derived was used to degradate the /sup 11/C-labelled propadiene derived from the reactions of recoil /sup 11/C atoms with ethylene. Results indicate that 73% of the /sup 11/C-labelled propadiene was center-labelled. This value was observed to change with additives. Various mechanistic studies on the heterogeneous interactions of molecular T/sub 2/ on solid surfaces such as Pd supported on active carbon have been initiated.

  18. Characterization of low-energy nuclear reactions involving emission of few non-relativistic particles

    International Nuclear Information System (INIS)

    Martinez Heimann, D.; Pacheco, A.J.; Capurro, O.A.

    2010-01-01

    We present a general procedure and the associated computational tool for the kinematical description and characterization of nuclear reactions with several fragments in the exit channel. For such processes the emphasis is placed on the purely experimental extraction of the most physically relevant magnitudes and their distributions, which can eventually be compared with the results of generic model calculations. The general capabilities of the approach are illustrated through the results of the application to selected examples, for which various aspects related to inclusive and exclusive measurements are discussed. For the particular case of sequential emission or non-capture breakup we analyze the general problem involved in the determination of intrinsic angular distributions in the rest frame of the decaying nucleus and the design of a specific experiment for a full and uniform coverage of the whole solid angle.

  19. Effects of hydroxylated benzaldehyde derivatives on radiation-induced reactions involving various organic radicals

    Science.gov (United States)

    Ksendzova, G. A.; Samovich, S. N.; Sorokin, V. L.; Shadyro, O. I.

    2018-05-01

    In the present paper, the effects of hydroxylated benzaldehyde derivatives and gossypol - the known natural occurring compound - on formation of decomposition products resulting from radiolysis of ethanol and hexane in deaerated and oxygenated solutions were studied. The obtained data enabled the authors to make conclusions about the effects produced by the structure of the compounds under study on their reactivity towards oxygen- and carbon-centered radicals. It has been found that 2,3-dihydroxybenzaldehyde, 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde and 4,6-di-tert-butyl-3-(1,3-dioxane-2-yl)-1,2-dihydroxybenzene are not inferior in efficiency to butylated hydroxytoluene - the industrial antioxidant - as regards suppression of the radiation-induced oxidation processes occurring in hexane. The derivatives of hydroxylated benzaldehydes were shown to have a significant influence on radiation-induced reactions involving α-hydroxyalkyl radicals.

  20. Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

    International Nuclear Information System (INIS)

    Bors, W.; Saran, M.; Michel, C.

    1982-01-01

    The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

  1. Studies on the radiation chemistry of biomolecules in aqueous solution with specific objective of minimizing their radiolytic degradation. Coordinated programme for Asia and the Pacific Region on radiation sterilization practices significant to local medical supplies and conditions

    International Nuclear Information System (INIS)

    Narayana Rao, K.

    1979-01-01

    As part of a study of radiolytic degradation of pharmaceuticals during radiosterilization, the basic radiation chemistry of the B-group vitamins, nicotinamide, pyridoxin, riboflavin and thiamine, and the reaction of hydrogen peroxide with these same materials has been investigated. The various aspects studied were - radiolysis under controlled conditions, effects of phase, temperature, pH and nature and concentration of additives. Some of the conclusions are: 1) with oxygen saturated aqueous solutions containing glucose, the radiolytic degradation of the vitamins is reduced: 2) results a similar for N 2 O saturated aqueous solutions; 3) in glucose-containing solutions, the protective effect is considerably modified at higher temperatures; and 4) irradiation of air-saturated aqueous solutions in the frozen state leads to reduced decomposition. It is concluded that in the presence of oxygen, in frozen matrices at low temperature, it appears possible to reduce the radiolytic breakdown of vitamins to low levels

  2. [Involvement of carbonate/bicarbonate ions in the superoxide-generating reaction of adrenaline autoxidation].

    Science.gov (United States)

    Sirota, T V

    2015-01-01

    An important role of carbonate/bicarbonate ions has been recognized in the superoxide generating reaction of adrenaline autooxidation in an alkaline buffer (a model of quinoid adrenaline oxidation in the body). It is suggested that these ions are directly involved not only in formation of superoxide anion radical (О(2)(-)) but also other radicals derived from the carbonate/bicarbonate buffer. Using various buffers it was shown that the rate of accumulation of adrenochrome, the end product of adrenaline oxidation, and the rate of О(2)(-)· formation depend on concentration of carbonate/bicarbonate ions in the buffer and that these ions significantly accelerate adrenaline autooxidation thus demonstrating prooxidant properties. The detectable amount of diformazan, the product of nitro blue tetrazolium (NBT) reduction, was significantly higher than the amount of adrenochrome formed; taking into consideration the literature data on О(2)(-)· detection by NBT it is suggested that adrenaline autooxidation is accompanied by one-electron reduction not only of oxygen dissolved in the buffer and responsible for superoxide formation but possible carbon dioxide also dissolved in the buffer as well as carbonate/bicarbonate buffer components leading to formation of corresponding radicals. The plots of the dependence of the inhibition of adrenochrome and diformazan formation on the superoxide dismutase concentration have shown that not only superoxide radicals are formed during adrenaline autooxidation. Since carbonate/bicarbonate ions are known to be universally present in the living nature, their involvement in free radical processes proceeding in the organism is discussed.

  3. Radiolytic synthesis and electrocatalytic activity of bimetallic nanoaggregates grafted upon various electrodes

    International Nuclear Information System (INIS)

    Amblard, J.; Belloni, J.; Platzer, O.

    1991-01-01

    We show how to utilize the radiolytic pathway for grafting metal nanoaggregates upon anodes or cathodes involved in the chlorine-soda process, thus enhancing their electrochemical behaviour. In both cases important overpotentials are usually measured on unmodified electrodes. The electrocatalytic efficiency of bimetallic nanoparticles (such as Pt-Ru and Ni-Ru), once grafted onto bulk metal electrodes (Ti or Ni), has been investigated by measuring the overpotential for chlorine or hydrogen evolution, respectively. Experimental conditions are similar to those of the industrial process. A synergistic effect is shown when Pt and Ru are alloyed in a 2: 1 atomic ratio. Then the chlorine overpotential is minimum. Conversely, there is no synergy between Ni and Ru, although a minimum amount of Ru in Ru-Ni (50% atomic) ensures a very low hydrogen overpotential [fr

  4. Cross sections and reaction rates of d+{sup 8}Li reactions involved in Big Bang nucleosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Balbes, M.J. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Farrell, M.M. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Boyd, R.N. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics]|[Department of Astronomy, Ohio State University, Columbus, OH 43210 (United States); Gu, X. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Hencheck, M. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Kalen, J.D. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Mitchell, C.A. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Kolata, J.J. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Lamkin, K. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Smith, R. [Division of Nuclear Medicine, Department of Radiology, Hospital of the University of Pennsylvania, Philadelphia, PA 19104 (United States); Tighe, R. [Lawrence Berkeley Laboratory, Berkeley, CA 94720 (United States); Ashktorab, K. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Becchetti, F.D. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Brown, J. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Roberts, D. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Wang, T.F. [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Humphrey, D. [Department of Physics, University of Western Kentucky, Bowling Green, KY 42101 (United States); Vourvopoulos, G. [Department of Physics, University of Western Kentucky, Bowling Green, KY 42101 (United States); Islam, M.S. [Department of Physics, Ball State University, Muncie, IN 47306 (United States)

    1995-02-20

    We have measured angular distributions of the {sup 2}H({sup 8}Li, {sup 7}Li){sup 3}H and {sup 2}H({sup 8}Li, {sup 9}Be)n reactions at E{sub c.m.}=1.5 to 2.8 MeV using an {sup 8}Li-radioactive-beam technique. Astrophysical S-factors and reaction rates were calculated from the measured cross sections. Although the {sup 2}H({sup 8}Li, {sup 9}Be)n cross section is small, it can contribute to {sup 9}Be synthesis. The {sup 2}H({sup 8}Li, {sup 7}Li){sup 3}H reaction has a sufficiently large cross section to destroy {sup 8}Li, which may decrease the synthesis of heavier elements. No products from the {sup 2}H({sup 8}Li, {sup 9}Li)p reaction were detected. We also present the results of calculations using the inhomogeneous model of primordial nucleosynthesis in several regions of parameter space. ((orig.))

  5. Reactivity Of Radiolytically-Produced Nitrogen Oxide Radicals Toward Aromatic Compounds

    International Nuclear Information System (INIS)

    Elias, Gracy

    2010-01-01

    radiolysis of the modifier (Cs-7SB), which solvates both metal complexes, is responsible for this change. These reactions presumably occur due to reactions with radiolytically-produced nitrogen-centered radicals like (sm b ullet)NO, (sm b ullet)NO 2 and (sm b ullet)NO 3 . Anisole (C 6 H 5 -OCH 3 ) was used in this study as a surrogate for Cs-7SB, since both are aryl ethers. Toluene was used as a surrogate for Cs-7SB because of the alkyl group on the benzene ring in both molecules. Anisole, highly reactive in acids, is a small molecule compared to Cs-7SB and the nitration products are easier to identify compared to those for the larger Cs-7SB molecule. Toluene is less reactive than anisole. Therefore, the highly reactive anisole and the less reactive toluene were considered in this study as model compounds to compare the reaction mechanisms and the nitrated products in acidic media under irradiation. Experiments were designed to elucidate the mechanism of the nitration of aromatic rings in γ-irradiated aqueous nitric acid. Since a suite of radical and ionic reactive species are produced in this condensed-phase system, solutions of nitric acid, neutral nitrate and neutral nitrite were irradiated in separate experiments to isolate selected reactive species. Product nitration species were assessed by high performance liquid chromatography (HPLC) with a reversed phase C-18 column and photodiode array detector. The nitrated anisole product distributions were the same with and without radiation in acidic solution, although more products were formed with radiation. In the irradiated acidic condensed phase, radiation-enhanced nitrous acid-catalyzed nitrosonium ion electrophilic aromatic substitution followed by oxidation reactions dominated over radical addition reactions. In contrast, the distribution of nitrated derivatives for toluene showed nitronium ion electrophilic substitution in the unirradiated acidic medium as a result of thermal nitration only at elevated temperatures

  6. Radiolytically-induced novel materials and their application to waste processing

    International Nuclear Information System (INIS)

    Massimo Bertino; Akira Tokuhiro; Tadashi Tokuhiro

    2007-01-01

    In the present NEER project we investigated two different types of gel materials with respect to potential applications in environmental remediation, including mixed waste generated from the nuclear fuel cycles. The materials under study were: (1) silica-polymer based aerogel composites into which specific metallic cations diffuse into and remain, and (2) polymer gels made of thermo-sensitive polymer networks, whose functional groups can be ''tailored'' to have a preferred affinity for specific cations, again diffusing into and remaining in the network under a volumetrically, contractive phase-transition. The molecular, diffusion of specific cations, including those of concern in low-level waste streams, into the gel materials studied here indicates that a scaled, engineered system can be designed so that it is passive; that is, minimal (human) intervention and risk would be involved in encapsulating LLW species. In addition, the gel materials hold potential significance in environmental remediation of and recovery of metallic cations identified in respective domains and physico-chemical processes. In brief, silica gels start as aqueous/liquid solutions of base catalyzed silica hydrogels and metal ions (targeted species), such as silver. The metal ions are reduced radiolytically and migrate through the solution to form clusters. Upon post-irradiation processing, aerogel monoliths, extremely lightweight but mechanically strong, that encapsulate the metals are produced. Interestingly the radiolytic or photonic source can be gamma-rays and/or other rays from ''artificial sources'', such as reactors, or ''inherent sources'' like those characterizing mixed waste. Polymer gels, in contrast exhibit thermally-induced volumetric contraction at 20-50 C by expelling water from the gels physical state. Further, some functional groups that capture di- or tri-valent cations from aqueous solutions can be incorporated into the polymer networks on synthesis, including by radiolytic

  7. Radiolytically-induced novel materials and their application to waste processing

    Energy Technology Data Exchange (ETDEWEB)

    Massimo Bertino, Akira Tokuhiro, Tadashi Tokuhiro

    2007-12-05

    In the present NEER project we investigated two different types of gel materials with respect to potential applications in environmental remediation, including mixed waste generated from the nuclear fuel cycles. The materials under study were: (1) silica-polymer based aerogel composites into which specific metallic cations diffuse into and remain, and (2) polymer gels made of thermo-sensitive polymer networks, whose functional groups can be ''tailored'' to have a preferred affinity for specific cations, again diffusing into and remaining in the network under a volumetrically, contractive phase-transition. The molecular, diffusion of specific cations, including those of concern in low-level waste streams, into the gel materials studied here indicates that a scaled, engineered system can be designed so that it is passive; that is, minimal (human) intervention and risk would be involved in encapsulating LLW species. In addition, the gel materials hold potential significance in environmental remediation of and recovery of metallic cations identified in respective domains and physico-chemical processes. In brief, silica gels start as aqueous/liquid solutions of base catalyzed silica hydrogels and metal ions (targeted species), such as silver. The metal ions are reduced radiolytically and migrate through the solution to form clusters. Upon post-irradiation processing, aerogel monoliths, extremely lightweight but mechanically strong, that encapsulate the metals are produced. Interestingly the radiolytic or photonic source can be gamma-rays and/or other rays from ''artificial sources'', such as reactors, or ''inherent sources'' like those characterizing mixed waste. Polymer gels, in contrast exhibit thermally-induced volumetric contraction at 20-50 C by expelling water from the gels physical state. Further, some functional groups that capture di- or tri-valent cations from aqueous solutions can be incorporated

  8. Influence of radiolytic degradation products from organic phase

    International Nuclear Information System (INIS)

    Azevedo, H.L.P. de.

    1980-01-01

    The influence of primary and secondary degradation products from TBP - dodecane on zirconium extraction is studied. The presence of radiolytical degradation at organic phase, in systems of initial concentration of HNO 3 1 and 4M, and absorbed γ radiation doses from 0,5 to 4,5 Wh/l, lead to an increase of zirconium extraction, being the HDBP the main product of degradation responsable by this effect. The influence of secondary degradation products is significative in systems of HNO 3 1M initial concentration. The formation of precipitator in extractions of Zr in HNO 3 1M with irradiated TBP-dodecane was observed. (M.C.K.) [pt

  9. Radiolytic gas production in the alpha particle degradation of plastics

    International Nuclear Information System (INIS)

    Reed, D.T.; Hoh, J.; Emery, J.; Hobbs, D.

    1992-01-01

    Net gas generation due to alpha particle irradiation of polyethylene and polyvinyl chloride was investigated. Experiments were performed in an air environment at 30, 60, and 100 degree C. The predominant radiolytic degradation products of polyethylene were hydrogen and carbon dioxide with a wide variety of trace organic species noted. Irradiation of polyvinyl chloride resulted in the formation of HCl in addition to the products observed for polyethylene. For both plastic materials, a strong enhancement of net yields was noted at 100 degree C

  10. A mathematical model for chemical reactions with actinide elements in the aqueous nitric acid solution: REACT

    International Nuclear Information System (INIS)

    Tachimori, Shoichi

    1990-02-01

    A mathematical model of chemical reactions with actinide elements: REACT code, was developed to simulate change of valency states of U, Pu and Np in the aqueous nitric acid solution. Twenty seven rate equations for the redox reactions involving some reductants, disproportionation reactions, and radiolytic growth and decay reaction of nitrous acid were programmed in the code . Eight numerical solution methods such as Porsing method to solve the rate equations were incorporated parallel as options depending on the characteristics of the reaction systems. The present report gives a description of the REACT code, e.g., chemical reactions and their rate equations, numerical solution methods, and some examples of the calculation results. A manual and a source file of the program was attached to the appendix. (author)

  11. Radiolytic reduction of nifurtimose by CO2-· free radicals

    International Nuclear Information System (INIS)

    Filali-Mouhim, A.; Champion, B.; Jore, D.; Ferradini, C.; Hickel, B.

    1991-01-01

    Nifurtimox is an antiparasitic drug often used in the treatment of the Chagas disease. Its therapeutic action seems to involve its monoelectronic reduction leading to a reduced radical capable of providing superoxide anion by reaction with oxygen. The oxidation reduction mechanisms involved in this action have been studied by steady state and pulse radiolysis methods. This study is devoted to the monoelectronic exchanges observed in the absence of air, the reducing radicals being the CO 2 - · anions [fr

  12. Radiolytic gas generation in salt cake technical task plan

    International Nuclear Information System (INIS)

    Walker, D.D.; Crawford, C.L.; Bibler, N.E.

    1993-01-01

    High-level radioactive wastes are stored in large, steel tanks in the Savannah River Site Tank Farms. The liquid levels in these tanks are monitored to detect leakage of waste out of tanks or leakage of liquids into the tanks. Recent unexplained level fluctuations in high-level waste (HLW) tanks have caused High Level Waste Engineering (HLWE) to develop a program to better understand tank level behavior. Interim Waste Technology (IWT) has been requested by HLWE to obtain data which will lead to a better understanding of the radiolytic generations of gases in salt cake. The task described below will provide data from laboratory experiments with simulated wastes which can be used in tank level fluctuation modeling. The following experimental programs have been formulated to meet the task requirements of the customer: (A) determine whether radiolytically generated gas bubbles can be trapped in salt cake; (B) determine the composition of gases produced by radiolysis; (C) determine the yield of radiolysis gases as a function of radiation dose; (D) determine bubble distribution

  13. Radiolytic Syntheses of Nanoparticles and Inorganic-Polymer Hybrid Microgels

    International Nuclear Information System (INIS)

    Chen, Q.; Shi, J.; Zhao, R.; Shen, X.

    2010-01-01

    In the second year of the project, we have gotten progress mainly in two directions. Firstly, for the first time, Prussian blue (PB) nanoparticles (NPs) were successfully synthesized by the partly radiolytic reduction of Fe3+ and Fe(CN)63 in the presence of poly(N-vinyl pyrrolidine) (PVP) under N2 atmospheres at room temperature. With the increase of the concentration of PVP, the size and the size distribution of the synthesized quasi-spherical PB NPs decreased obviously, leading to a hypsochromic shift on their peak position of the characteristic absorption. In the experiment, we further found that the smaller ones have a larger capacity to Cs+, suggesting that the application of PB NPs in curing thallotoxicosis may decrease the usage of PB for the patient to great extent. Secondly, through a series of preliminary experiments, we got a clear picture about the one-step radiolytic preparation of inorganic-poly(methacrylic acid-co-methyl methacrylate) hybrid microgels by surfactant-free emulsion polymerization. Besides, unpurified N-carbamothioylmethacrylamide was synthesized via the methacrylation of thiourea. These created favorable conditions for the one-step synthesis of metal sulfide-poly(methacrylic acid-co-methyl methacrylate) hybrid microgels by -irradiation and surfactant-free emulsion polymerization. (author)

  14. Radiolytic Syntheses of Nanoparticles and Inorganic-Polymer Hybrid Microgels

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Q.; Shi, J.; Zhao, R.; Shen, X., E-mail: qdchen@pku.edu.cn [Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, No. 5, Yiheyuan Load, Haidian District Beijing 100871 (China)

    2010-07-01

    In the second year of the project, we have gotten progress mainly in two directions. Firstly, for the first time, Prussian blue (PB) nanoparticles (NPs) were successfully synthesized by the partly radiolytic reduction of Fe3+ and Fe(CN)63 in the presence of poly(N-vinyl pyrrolidine) (PVP) under N2 atmospheres at room temperature. With the increase of the concentration of PVP, the size and the size distribution of the synthesized quasi-spherical PB NPs decreased obviously, leading to a hypsochromic shift on their peak position of the characteristic absorption. In the experiment, we further found that the smaller ones have a larger capacity to Cs+, suggesting that the application of PB NPs in curing thallotoxicosis may decrease the usage of PB for the patient to great extent. Secondly, through a series of preliminary experiments, we got a clear picture about the one-step radiolytic preparation of inorganic-poly(methacrylic acid-co-methyl methacrylate) hybrid microgels by surfactant-free emulsion polymerization. Besides, unpurified N-carbamothioylmethacrylamide was synthesized via the methacrylation of thiourea. These created favorable conditions for the one-step synthesis of metal sulfide-poly(methacrylic acid-co-methyl methacrylate) hybrid microgels by -irradiation and surfactant-free emulsion polymerization. (author)

  15. Radiolytic stabilization of industrial poly(methyl methacrylate)

    International Nuclear Information System (INIS)

    Aquino, Katia Aparecida da Silva

    2005-03-01

    Poly(methyl methacrylate), PMMA, Acrigel, a Brazilian polymer, is used in the manufacture of medical supplies sterilisable by ionizing radiation. However, when PMMA is gamma-irradiated it undergoes main chain scissions, which promote molecular degradation causing reduction in its physical properties. Therefore, radiolytic stabilization of PMMA is important for to become it commercially radio sterilisable. In this work we investigated the radiolytic stabilization of PMMA by using HALS (Hindered Amine Light Stabilizer) additive, commercially used for photo and thermo oxidative stabilization of polymers. The investigation of the radiation-induced main chain scissions was carried out by viscometric method. The additive added to the polymer system at 0.3 % w/w promotes a molecular radioprotection of 61%. That means a reduction of G value (scissions/100 eV) from 2.6 to 1.0. In addition, the glassy transition temperature (Tg) of PMMA (no additive), significantly changed by radiation, does not change when PMMA (with additive) is irradiated. TGA analysis showed that the additive promotes thermal stability to the system, increasing decomposition temperature of PMMA. Spectroscopy analysis, FT-IR and RMN ( 1 H), showed that the radioprotector additive added to the system does not change the PMMA structure. Analysis on mechanical (tensile strength and elongation at break) and optical (yellowness index and refractive index) properties showed a good influence of the additive on polymer system. (author)

  16. Advances in heterocycle synthesis via [3+m]-cycloaddition reactions involving an azaoxyallyl cation as the key intermediate.

    Science.gov (United States)

    Xuan, Jun; Cao, Xia; Cheng, Xiao

    2018-05-17

    Heterocyclic compounds are widely found in many natural isolates and medicinally relevant compounds, as well as some fine chemicals. The development of general and efficient methods for the construction of heterocyclic compounds is one of the most important tasks in synthetic organic chemistry. Along these lines, [3+m]-cycloaddition reactions involving in situ generated azaoxyallyl cations as the 3-atom units have emerged as a powerful method for the synthesis of nitrogen-containing heterocycles. In this feature article, we highlight recent advances in this rapidly growing area, mainly focusing on the reaction design as well as the reaction mechanism.

  17. A pulse radiolytic study of some radiosensitizing and radioprotective substances

    International Nuclear Information System (INIS)

    Sjoeberg, L.

    1981-01-01

    The one-electron reduction potentials for substituted nitroimidazoles and nitrobenzenes in aqueous solution have been correlated to their electron affinities calculated by the semiempirical quantum mechanical method HAM/3. This procedure implies the validity of a Hammet like equation for the substances studied. Glutathione has been shown to compete with oxygen for radiation induced radicals. Hence the reaction of the hydroxyl radical with glutathione in neutral and alkaline aqueous solution was investigated in some detail. A reaction scheme involving a pH dependent formation of thiyl, and carbon centered radicals is given. (Auth.)

  18. Radiolytic degradation of gallic acid and its derivatives in aqueous solution

    International Nuclear Information System (INIS)

    Melo, R.; Leal, J.P.; Takacs, E.; Wojnarovits, L.

    2009-01-01

    Polyphenols, like gallic acid (GA) released in the environment in larger amount, by inducing some unwanted oxidations, may constitute environmental hazard: their concentration in wastewater should be controlled. Radiolytic degradation of GA was investigated by pulse radiolysis and final product techniques in dilute aqueous solution. Subsidiary measurements were made with 3,4,5-trimethoxybenzoic acid (TMBA) and 3,4,5-trihydroxy methylbenzoate (MGA). The hydroxyl radical and hydrogen atom intermediates of water radiolysis react with the solute molecules yielding cyclohexadienyl radicals. The radicals formed in GA and MGA solutions in acid/base catalyzed water elimination decay to phenoxyl radicals. This reaction is not observed in TMBA solution. The hydrated electron intermediate of water decomposition adds to the carbonyl oxygen, the anion thus formed protonates on the ring forming cyclohexadienyl radical or on the carbonyl group forming carbonyl centred radical. The GA intermediates formed during reaction with primary water radicals in presence of oxygen transform to non-aromatic molecules, e.g., to aliphatic carboxylic acids.

  19. Radiolytic degradation of gallic acid and its derivatives in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Melo, R. [Instituto Tecnologico e Nuclear, UCQR, Estrada Nacional No. 10, Apartado 21, 2686-953, Sacavem (Portugal); Leal, J.P. [Instituto Tecnologico e Nuclear, UCQR, Estrada Nacional No. 10, Apartado 21, 2686-953, Sacavem (Portugal); Centro Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, 1749-016 Lisboa (Portugal); Takacs, E., E-mail: takacs@iki.kfki.hu [Institute of Isotopes, Hungarian Academy of Sciences, P.O. Box 77, H-1525 Budapest (Hungary); Wojnarovits, L. [Institute of Isotopes, Hungarian Academy of Sciences, P.O. Box 77, H-1525 Budapest (Hungary)

    2009-12-30

    Polyphenols, like gallic acid (GA) released in the environment in larger amount, by inducing some unwanted oxidations, may constitute environmental hazard: their concentration in wastewater should be controlled. Radiolytic degradation of GA was investigated by pulse radiolysis and final product techniques in dilute aqueous solution. Subsidiary measurements were made with 3,4,5-trimethoxybenzoic acid (TMBA) and 3,4,5-trihydroxy methylbenzoate (MGA). The hydroxyl radical and hydrogen atom intermediates of water radiolysis react with the solute molecules yielding cyclohexadienyl radicals. The radicals formed in GA and MGA solutions in acid/base catalyzed water elimination decay to phenoxyl radicals. This reaction is not observed in TMBA solution. The hydrated electron intermediate of water decomposition adds to the carbonyl oxygen, the anion thus formed protonates on the ring forming cyclohexadienyl radical or on the carbonyl group forming carbonyl centred radical. The GA intermediates formed during reaction with primary water radicals in presence of oxygen transform to non-aromatic molecules, e.g., to aliphatic carboxylic acids.

  20. Study of the main parameters involved in carbothermal reduction reaction of silica aiming to obtain silicon nitride powder

    International Nuclear Information System (INIS)

    Rocha, J.C. da; Greca, M.C.

    1989-01-01

    The influence of main parameters involved in the method of silicon nitride attainment by carbothermal reduction of silica followed by nitridation were studied in isothermal experiments of fine powder mixtures of silica and graphite in a nitrogen gas flow. The time, temperature, rate C/SiO 2 and flow of nitrogen were varied since they are the main parameters involved in this kind of reaction. The products of reaction were analysed by X-ray diffraction to identify the crystalline phases and as a result was obtained the nucleation of silicon nitride phase. Meanwhile, corroborating prior results, we verified to be difficult the progress of the reaction and the inhibition of formation of silicon carbide phase, the last one being associated to the formation of silicon nitride phase due to thermodynamic matters [pt

  1. Staff's reactions towards partnered sexual expressions involving people with dementia living in long-term care facilities.

    Science.gov (United States)

    Villar, Feliciano; Celdrán, Montserrat; Serrat, Rodrigo; Fabà, Josep; Martínez, Teresa

    2018-05-01

    To explore staff responses, in terms of common practices, towards partnered sexual relationships in long-term care facilities where one or both people involved have dementia. It also tries to determine personal and institutional factors influencing these responses. Although some studies, mostly qualitative, have focused on reactions to residents' sexual expressions so far the issue has not been assessed in a study using large and diverse samples. Cross-sectional quantitative study using vignette technique. Participants were 2,295 staff members at 152 Spanish long-term care facilities. Data were collected during 2016. A vignette describing sexual situations involving people with dementia was presented to participants. After the vignette, participants had to answer the question: "What do you think most of your colleagues would do in this situation?" with nine possible responses. Results showed that relationships involving persons with dementia were perceived as potentially problematic by staff. In both conditions, discussing the case with a colleague or supervisor was the most frequently chosen reaction. More restrictive reactions were mentioned when only one person with dementia was involved in the relationship. Factors such as participants" age and years of experience, professional post and commitment to person-centred care practices were related with the frequency of common restriction practices. Results highlight the importance of providing staff with clear guidelines regarding the management of specific sexual situations to avoid stereotyped restrictive reactions. © 2017 John Wiley & Sons Ltd.

  2. Kinetics of isotope exchange reactions involving intra- and intermolecular reactions: 1. Rate law for a system with two chemical compounds and three exchangeable atoms

    International Nuclear Information System (INIS)

    Xuelei Chu; Ohmoto, Hiroshi

    1991-01-01

    For an isotopic exchange reaction between two compounds (X and AB) in a homogeneous system, such as a gaseous or aqueous system, where one (AB) of them possesses two exchangeable atoms in non-equivalent positions and where one intramolecular isotope exchange (A ↔ B) and two intermolecular isotope exchange reactions (X ↔ A and X ↔ B) may occur, its rate law no longer obeys a pseudo-first order rate equation described for simple two-component systems by many previous investigators. The change with time of the δ value of each of the three components (X, A, and B) in a closed and homogeneous system is a complicated function of the initial δ values of the three components, the chemical concentrations of the two compounds, and the overall rate constants of the forward and reverse reactions involving the two intermolecular and one intramolecular reactions of isotope exchanges. Also, for some one of the three components, the change of its δ value with time may not be monotonic, and the relationship of 1n (1 - F) with time may be non-linear in a plot of 1n (1 - F) vs. t. In addition, the rate law of the isotope exchange reaction in this system also provides a quantitative method to estimate the overall rate constants for the one-intra-and two intermolecular isotope exchanges and the equilibrium isotopic fractionation factors among the three components

  3. The Atmospherically Important Reaction of Hydroxyl Radicals with Methyl Nitrate: A Theoretical Study Involving the Calculation of Reaction Mechanisms, Enthalpies, Activation Energies, and Rate Coefficients.

    Science.gov (United States)

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2017-09-07

    A theoretical study, involving the calculation of reaction enthalpies, activation energies, mechanisms, and rate coefficients, was made of the reaction of hydroxyl radicals with methyl nitrate, an important process for methyl nitrate removal in the earth's atmosphere. Four reaction channels were considered: formation of H 2 O + CH 2 ONO 2 , CH 3 OOH + NO 2 , CH 3 OH + NO 3 , and CH 3 O + HNO 3 . For all channels, geometry optimization and frequency calculations were performed at the M06-2X/6-31+G** level, while relative energies were improved at the UCCSD(T*)-F12/CBS level. The major channel is found to be the H abstraction channel, to give the products H 2 O + CH 2 ONO 2 . The reaction enthalpy (ΔH 298 K RX ) of this channel is computed as -17.90 kcal mol -1 . Although the other reaction channels are also exothermic, their reaction barriers are high (>24 kcal mol -1 ), and therefore these reactions do not contribute to the overall rate coefficient in the temperature range considered (200-400 K). Pathways via three transition states were identified for the H abstraction channel. Rate coefficients were calculated for these pathways at various levels of variational transition state theory including tunneling. The results obtained are used to distinguish between two sets of experimental rate coefficients, measured in the temperature range of 200-400 K, one of which is approximately an order of magnitude greater than the other. This comparison, as well as the temperature dependence of the computed rate coefficients, shows that the lower experimental values are favored. The implications of the results to atmospheric chemistry are discussed.

  4. Radiolytic products of irradiated authentic fatty acids and triacylglycerides

    International Nuclear Information System (INIS)

    Kim, K.-S.; Lee, Jeong-Min; Seo, Hye-Young; Kim, Jun-Hyoung; Song, Hyun-Pa; Byun, Myung-Woo; Kwon, Joong-Ho

    2004-01-01

    Radiolytic products of authentic fatty acids (palmitic, stearic, oleic, linoleic and linolenic acids) and triacylglycerides (tripalmitin, tristearin, triolein, trilinolein and trilinolenin) were determined. Concentrations of hydrocarbons from the saturated fatty acids were higher than the unsaturated fatty acids. Authentic fatty acids were mainly decomposed in the α-carbon position and C n-1 hydrocarbons occurred in higher than C n-2 hydrocarbons. Concentrations of 2-alkylcyclobutanones from the saturated fatty acids were lower than the unsaturated fatty acids. Concentrations of hydrocarbons from tripalmitin and tristearin were not a significant change compared with triolein, trilinolein and trilinolenin. For all triacylglycerides except triolein, C n-1 hydrocarbons were higher than C n-2 hydrocarbons. Radioproduction rates of 2-alkylcyclobutanones from tripalmitin and tristearin were higher than triolein, trilinolein and trilinolenin

  5. Radiolytic gas generation in Salt Cake Quality Assurance Plan

    International Nuclear Information System (INIS)

    Walker, D.D.

    1993-01-01

    High-level radioactive wastes are stored in large, steel tanks in the Savannah River Site's Tank Farms. The liquid levels in these tanks are monitored to detect leakage of waste out of tanks or leakage of liquids into the tanks. Recent unexplained level fluctuations in high-level waste (HLW) tanks have caused High Level Waste Engineering (HLWE) to develop a program to better understand tank level behavioral Interim Waste Technology (IWT) has been requested by HLWE to obtain data which will lead to a better understanding of the radiolytic generation of gases in salt cake. A task plan has been written in response to this request. This document details the controls necessary to ensure the quality of the results of the activities described in the task plan

  6. Effect of radiolytic products on bacteria in a food system

    International Nuclear Information System (INIS)

    Dickson, J.S.; Maxcy, R.B.

    1984-01-01

    Inhibitory effects of radiolytic products were studied using Escherichia coli, Pediococcus cerevisiae, and two radiation-resistant microorganisms, an isolate of Moraxella-Acinetobacter and a Micrococcus sp. End Products of an irradiation dose of 300 Krads completely inhibited resistant organisms on an experimental medium with a very low concentration of nutrients. Plate count agar, with higher nutrient concentration, required 600 Krads to produce the same inhibition. On the same medium, radiation-sensitive organisms could tolerate products generated by a 1000 Krad dose. However, no inhibition could be detected when either Escherichia coli or Moraxella-Acinetobacter was incubated at 5 0 C on the surface of fresh meat irradiated to 1500 Krad. The effects of inhibitory products in culture media could be mitigated by the addition of catalase or sodium pyruvate. 19 references, 2 figures, 4 tables

  7. Local radiolytic effectiveness of Auger electrons of iodine-125 in benzene-iodine solutions

    International Nuclear Information System (INIS)

    Uenak, P.; Uenak, T.

    1987-01-01

    High radiotoxicity of iodine-125 has been mainly attributed to the local radiolytic effects of Auger electrons on biological systems. In the present study, experimental and theoretical results are compared. The agreement between the experimental and theoretical results explains that the energy absorption of iodine aggregates has an important role in the radiolytic effectiveness of Auger electrons and iodine-125 in benzene-iodine solutions. (author) 18 refs.; 3 figs

  8. Microwave-Enhanced Cross-Coupling Reactions Involving Alkynyltrifluoroborates with Aryl Bromides

    Directory of Open Access Journals (Sweden)

    George W. Kabalka

    2013-01-01

    Full Text Available Palladium-catalyzed alkynylation has emerged as one of the most reliable methods for the synthesis of alkynes which are often used in natural product syntheses and material science. An efficient method for coupling alkynyltrifluoroborates with various aryl bromides in the presence of a palladium catalyst has been developed using microwave irradiation. The microwave reactions are rapid and efficient.

  9. Hot atom reactions involving multivalent and univalent species. Progress report, February 1976--January 1977

    International Nuclear Information System (INIS)

    Tang, Y.N.

    1977-01-01

    Multivalent hot atoms formed by the nuclear recoil method were studied: 31 Si, 32 P, and 11 C. For the recoil 31 Si reactions, we have completed the study on the reactivities of conjugated dienes towards monomeric 31 SiF 2 . The relative reactivities of 1,3-butadiene, trans-pentadiene, cis-pentadiene and 2-methyl-1,3-butadiene towards 31 SiF 2 have been measured as: 1.0:0.89:0.91:1.06 for singlet 31 SiF 2 ; and as 1.0:0.80:0.52:0.89 for the triplet. The large steric effect detected here between cis- and trans-pentadienes for their reactivities towards triplet 31 SiF 2 -donor indicates that a direct 1,4-addition process is possible for such 31 SiF 2 donating complexes. 2-methyl-1,1-diflorosilacyclopent-3-ene and its 3-methyl isomer were successfully synthesized by the co-pyrolysis technique. Experiments to evaluate the relative addition efficiencies of 31 SiH 2 towards various conjugated dienes; and to study to H- and F-abstraction mechanism by 31 Si atoms were begun. For recoil 32 P reactions, some progress has been made towards evaluating the mechanism of abstraction reactions by recoil 32 P atoms in PF 3 -PCl 3 system, and the moderator effect for recoil 32 P reactions with PF 3 -CH 4 mixtures. The possible formation of 32 PH, and the formation of 32 P atoms via the 32 S(n,p) 32 P process have also been explored. For recoil 11 C reactions, major progress has been obtained in the moderator studies of its reactions with 1,3-butadiene. With the successive addition of Ne as a moderator, the yield of acetylene- 11 C decreased, the yield of cyclopentene- 11 C increased while those of both 1,2,4-pentatriene- 11 C and cyclopentadiene- 11 C went through a minimum. Some progress for the identification of the last unknown 11 C-labeled product from this system has also been made

  10. Isospin aspects in nuclear reactions involving Ca beams at 25 MeV/nucleon

    Energy Technology Data Exchange (ETDEWEB)

    Lombardo, I., E-mail: ilombardo@lns.infn.it; Agodi, C.; Alba, R.; Amorini, F.; Anzalone, A. [INFN Laboratori Nazionali del Sud (Italy); Auditore, L. [Universita di Messina, and INFN-Gr. Coll. Messina, Dipartimento di Fisica (Italy); Berceanu, I. [Institute for Physics and Nuclear Engineering (Romania); Cardella, G. [INFN, Sezione di Catania (Italy); Cavallaro, S. [INFN Laboratori Nazionali del Sud (Italy); Chatterjee, M. B. [Saha Institute of Nuclear Physics (India); Filippo, E. De [INFN, Sezione di Catania (Italy); Di Pietro, A.; Figuera, P. [INFN Laboratori Nazionali del Sud (Italy); Giuliani, G.; Geraci, E.; Grassi, L. [Dipartimento di Fisica e Astronomia Universita di Catania (Italy); Grzeszczuk, A. [University of Silesia, Institute of Physics (Poland); Han, J. [INFN Laboratori Nazionali del Sud (Italy); La Guidara, E. [INFN, Sezione di Catania (Italy); Lanzalone, G. [INFN Laboratori Nazionali del Sud (Italy); and others

    2011-11-15

    Isospin dependence of dynamical and thermodynamical properties observed in reactions {sup 40}Ca+ {sup 40,48}Ca and {sup 40}Ca + {sup 46}Ti at 25 MeV/nucleon has been studied. We used the CHIMERA multi-detector array. Strong isospin effects are seen in the isotopic distributions of light nuclei and in the competition between different reaction mechanisms in semi-central collisions. We will show also preliminary results obtained in nuclear collision {sup 48}Ca + {sup 48}Ca at 25MeV/nucleon, having very high N/Z value in the entrance channel (N/Z = 1.4). The enhancement of evaporation residue production confirms the strong role played by the N/Z degree of freedom in nuclear dynamics.

  11. Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

    Science.gov (United States)

    Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

    2016-03-14

    Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.

  12. A method for carrying out radiolysis and chemical reactions by means of the radiations resulting from a thermonuclear reaction

    International Nuclear Information System (INIS)

    Gomberg, H.J.

    1974-01-01

    The invention relates to the use of the radiations resulting from thermonuclear reactions. It deals with a method comprising a combination of thermo-chemical and radiolytic reactions for treating a molecule having a high absorption rate, by the radiations of a thermonuclear reaction. This is applicable to the dissociation of water into oxygen and hydrogen [fr

  13. Degradation of phenylethylamine and tyramine by gamma radiation process and docking studies of its radiolytes

    Energy Technology Data Exchange (ETDEWEB)

    Cardozo, Monique; Souza, Stefânia Priscila de; Lima, Keila dos Santos Cople; França, Tanos Celmar Costa; Lima, Antonio Luis dos Santos, E-mail: santoslima@ime.eb.br [Instituto Militar de Engenharia (IME), Rio de Janeiro, RJ (Brazil). Departamanto de Engenharia Quimica; Oliveira, Aline Alves [Universidade de Sao Paulo (USP), São Carlos, SP (Brazil). Instituto de Quimica; Rezende, Cláudia Moraes [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica

    2014-07-01

    Biogenic amines (BA) are toxic low molecular weight organic bases with aliphatic or heterocyclic structures that can be found in several foods. The consumption of food containing large amounts of BA can result in allergic reactions, rash, vomiting, and hypertension. Besides, BA are also known as possible precursors of carcinogens. In the present study we evaluated the effect of different gamma irradiation doses on methanol and water solutions of the BA phenylethylamine and tyramine. Our best results showed that, at a dose of 5 kGy (SI unit used for measurement of absorbed dose of ionizing radiation), it was possible to reduce the content of these two BA up to 85 and 60%, respectively, suggesting that the use of the irradiation process can be an efficient tool for its degradation. Further docking studies also suggested that the radiolytes produced in the irradiation process have more affinity for the human detoxifying enzymes monoaminoxidases type A and B (MAO-A and MAO-B) being, therefore, less toxic than its precursors. (author)

  14. On the nature of the olefination reaction involving ditungsten hexaalkoxides and aldehydes or ketones

    Energy Technology Data Exchange (ETDEWEB)

    Chisholm, M.H.; Huffman, J.C.; Lucas, E.A.; Sousa, A.; Streib, W.E. [Indiana Univ., Bloomington, IN (United States)

    1992-03-25

    Reductive coupling of aldehydes and ketones to olefins under the action of ditungsten hexaalkoxides was investigated. In these reactions, reductive cleavage of the aldehyde or ketone carbonyl is followed by formation of the olefinic C-C bond and breaking of the carbonyl C-O bond of the second aldehyde or ketone. Observations concerning the initial C-O bond cleavage and subsequent C-C bond formation are presented. 10 refs., 4 figs.

  15. Intermediate products of radiolytic conversions of 6-aminophenalenone in ethanol

    International Nuclear Information System (INIS)

    Semenova, G.V.; Ponomarev, A.V.; Kartasheva, L.I.; Pikaev, A.K.

    1992-01-01

    Intermediate products of the conversions of 6-aminophenalenone in ethanol were investigated by pulse radiolysis. In alkaline medium the main product is the 6-aminophenalenone radical cation, the optical absorption spectrum of which contains two bands with maxima at 355 and 400 nm. The precursors of this particle are e s , CH 3 CHOH and CH 3 CHO - radicals. In neutral and acid medium, radical cations are protonated in reactions with alcohol and hydrogen ions. The H-adduct of 6-aminophenalenone that arises has optical absorption maxima at 350 and 390 nm. The presence of two maxima is due to two different structures of the product. The molar extinction coefficients of the radical anions and H-adducts of 6-aminophenalenone and the rate constants of the reactions involving them were estimated. 6 refs., 4 figs., 2 tabs

  16. Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide

    International Nuclear Information System (INIS)

    Jin, Jun-Cheng; Tong, Wen-Quan; Fu, Ai-Yun; Xie, Cheng-Gen; Chang, Wen-Gui; Wu, Ju; Xu, Guang-Nian; Zhang, Ya-Nan; Li, Jun; Li, Yong; Yang, Peng-Qi

    2015-01-01

    Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1–3 contain four types of 2 1 helical chains. While the Nd(III) ions are bridged through μ 2 -HIDC 2− and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of solvent DMF to formate acid or oxalic acid under solvothermal conditions. The isostructural complexes 1–3 contain four types of different 2 1 helical chains in the 2D layer and 1 exhibits bright red solid-state phosphorescence upon UV radiation. - Highlights: • Four unexpected 2D lanthanide coordination compounds have been synthesized through in situ reactions under solvothermal conditions. • The complexes 1–3 contain four types of 2 1 helical chains in the layer. • Complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature

  17. Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope

    Energy Technology Data Exchange (ETDEWEB)

    Abellan Baeza, Patricia; Parent, Lucas R.; Al Hasan, Naila M.; Park, Chiwoo; Arslan, Ilke; Karim, Ayman M.; Evans, James E.; Browning, Nigel D.

    2016-01-07

    Synthesizing nanomaterials of uniform shape and size is of critical importance to access and manipulate the novel structure-property relationships arising at the nanoscale. In this work we synthesize Pd nanoparticles with well-controlled size using in situ liquid-stage scanning transmission electron microscopy (STEM) and demonstrate a match between the reaction kinetics and products of the radiolytic and chemical syntheses of size-stabilized Pd nanoparticles. We quantify the effect of electron dose on the nucleation kinetics, and compare these results with in situ small angle X-ray scattering (SAXS) experiments investigating the effect of temperature during chemical synthesis. This work introduces methods for precise control of nanoparticle synthesis in the STEM and provides a means to uncover the fundamental processes behind the size and shape stabilization of nanoparticles.

  18. A computational study of the Diels Alder reactions involving acenes: reactivity and aromaticity

    Science.gov (United States)

    Cheng, Mei-Fun; Li, Wai-Kee

    2003-01-01

    Ab initio and DFT methods have been used to study the Diels-Alder reactivity and the aromaticity of four linear acenes, namely, naphthalene, anthracene, tetracene and pentacene. In total, eight additional pathways between ethylene and four acenes have been studied and all of them are concerted and exothermic reactions. It is found that the most reactive sites on the acenes are the center ring's meso-carbons. Also, reactivity decreases along the series pentacene > tetracene > anthracene > naphthalene. In addition, the NICS results indicate that the most reactive rings in the acenes are those with the highest aromaticity. These results are consistent with those of other theoretical studies and experiments.

  19. Exclusive and restricted inclusive reactions involving the 11Be one-neutron halo

    International Nuclear Information System (INIS)

    Anne, R.; Emling, H.; Hansen, P.G.; Hornshoj, P.; Bimbot, R.; Dogny, S.

    1993-01-01

    Reactions of a 41 MeV/u beam of the radioactive halo nucleus 11 Be have been studied with a counter telescope coupled to an array of neutron detectors. The technique allows to determine single-neutron inclusive and exclusive angular distributions. The targets (Be, Ti and Au) were chosen to illustrate the relative roles played by nuclear and Coulomb mechanisms. It is shown that for the dissociation process it is possible to account almost quantitatively for the integral, single- and double-differential cross-sections from models without free parameters including the Coulomb, Serber and Glauber (diffraction dissociation) mechanisms. (K.A.). 56 refs., 11 figs., 1 tab

  20. Numerical study for melting heat transfer and homogeneous-heterogeneous reactions in flow involving carbon nanotubes

    Science.gov (United States)

    Hayat, Tasawar; Muhammad, Khursheed; Alsaedi, Ahmed; Asghar, Saleem

    2018-03-01

    Present work concentrates on melting heat transfer in three-dimensional flow of nanofluid over an impermeable stretchable surface. Analysis is made in presence of porous medium and homogeneous-heterogeneous reactions. Single and multi-wall CNTs (carbon nanotubes) are considered. Water is chosen as basefluid. Adequate transformations yield the non-linear ordinary differential systems. Solution of emerging problems is obtained using shooting method. Impacts of influential variables on velocity and temperature are discussed graphically. Skin friction coefficient and Nusselt number are numerically discussed. The results for MWCNTs and SWCNTs are compared and examined.

  1. Tritium conversion in tritiated water: study of the involved reactions: a literature survey

    International Nuclear Information System (INIS)

    Ballereau, P.

    1987-10-01

    According to ICRP publication 30, hazards due to molecular tritium are not significant in comparison to hazards due to the oxidated form: tritiated water. It is thus important to know the kinetics of tritium/tritiated water conversion to obtain a realistic evaluation of the risks for the environment at level of present facilities and of future nuclear fusion facilities. Laboratory experiments in static contained conditions have shown that tritiated water is produced by two mechanisms: gas phase oxidation, hydrogen isotopic exchange with water. The periods found are relatively long and difficult to specify. In terrestrial atmosphere, the two mechanisms intervening in tritiated water formation are photochemical oxidation and biochemical reactions occurring in soil and in vegetation aerial parts. The corresponding periods are of some years for the first one, of some hours for the second one [fr

  2. [Lichen planus, a T-lymphocyte mediated reaction involving the skin and mucous membranes].

    Science.gov (United States)

    van den Akker, T W

    2001-10-06

    Lichen planus concerns a benign skin disorder without involvement of other organ systems. Its course is generally limited to less than a year. Classic lichen planus is characterized by pruritic, violaceous, plane papules which occur most commonly on the inside of the wrists, the lower back, the lower legs and the perimalleolar region of adults aged between 30-60 years. Frequently, oral and genital mucous membrane lesions are involved. Erosive mucosal lesions are particularly painful and long-lasting. Many clinical variants have been described ranging from lichenoid drug eruptions to associations with graft-versus-host disease. The cause of lichen planus is unknown. An immunopathological pathogenesis with T-lymphocytes directed against basal keratinocytes or the basal membrane zone is assumed. Multiple therapeutic options exist: local and systemic corticosteroids, psoralens with ultraviolet A light (PUVA), retinoids, cyclosporin.

  3. Radiolytic stabilization of poly(methyl methacrylate) using commercial additives

    International Nuclear Information System (INIS)

    Aquino, Katia Aparecida da Silva

    2000-04-01

    Poly(methyl methacrylate), PMMA, Acrigel, a Brazilian polymer, is used in the manufacture of medical supplies sterelizable by ionizing radiation. However, when PMMA is gamma-irradiated it undergoes main chain scissions, which promote molecular degradation causing reduction in its mechanical properties. Therefore, radiolytic of PMMA is important for it to become commercially radiosterizable. In this work some commercial additives, originally used in photo-and thermo-oxidate stabilization of polymers, were tested. Only two additives, type HALS (Hindered Amine Light Stabilizer), denoted Scavenger, showed a good protective quality. The investigation of radiation-induced main scissions was carried out by viscosimetric method. The most effective additive, added to the polymer system at 0.3 w/w%, promotes a great molecular radioprotection of 93%. That means a reduction of G-value (scissions/100 eV) from 0.611 to 0.053. In addition, the glassy transition temperature (T g ) of PMMA (no additive) significantly changed by radiation does not change when PMMA (with additive) is irradiated. The spectroscopy analysis, FT-IR and NMR ( 1 H), showed that the radioprotector added to the system does not change the PMMA structure. (author)

  4. Investigations of the Fundamental Surface Reactions Involved in the Sorption and Desorption of Radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Czerwinski, Ken; Heske, Clemens; Moser, Duane; Misra, Mnoranjan; McMillion, Glen

    2011-04-20

    Models for describing solution- and surface-phase reactions have been used for 30 years, but only recently applicable to complex surfaces. Duff et al., using micro-XANES, found that Pu was concentrated on Mn-oxide and smectite phases of zeolitic tuff, providing an evaluation of contaminant speciation on surfaces for modeling. Experiments at Los Alamos demonstrated that actinides display varying surface residence time distributions, probably reflective of mineral surface heterogeneity. We propose to investigate the sorption/desorption behavior of radionuclides from mineral surfaces, as effected by microorganisms, employing isolates from Nevada Test Site deep alluvium as a model system. Characterizations will include surface area, particle size distribution, x-ray diffraction (XRD), microprobe analysis, extractions, and microbiology. Surface interactions will be assessed by electron spectroscopy (XPS), x-ray absorption fine structure spectroscopy (XAFS), X-ray emission spectroscopy, transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Desert Research Institute (DRI), University of Nevada, Reno (UNR), and University of Nevada, Las Vegas (UNLV) researchers will collaborate to enhance scientific infrastructure and the understanding of contaminant behavior on surfaces, with broader implications for the management of DOE sites.

  5. Chemical reactions involved in the initiation of hot corrosion of IN-738

    Science.gov (United States)

    Fryburg, G. C.; Kohl, F. J.; Stearns, C. A.

    1984-01-01

    Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions; Cr203 + 2 Na2S04(1) + 3/2 02 yields 2 Na2Cr04(1) + 2 S03(g)n TiO2 + Na2S04(1) yields Na20(T102)n + 503(g)n T102 + Na2Cro4(1) yields Na2(T102)n + Cr03(g).

  6. Investigations of the Fundamental Surface Reactions Involved in the Sorption and Desorption of Radionuclides

    International Nuclear Information System (INIS)

    Czerwinski, Ken; Heske, Clemens; Moser, Duane; Misra, Mnoranjan; McMillion, Glen

    2011-01-01

    Models for describing solution- and surface-phase reactions have been used for 30 years, but only recently applicable to complex surfaces. Duff et al., using micro-XANES, found that Pu was concentrated on Mn-oxide and smectite phases of zeolitic tuff, providing an evaluation of contaminant speciation on surfaces for modeling. Experiments at Los Alamos demonstrated that actinides display varying surface residence time distributions, probably reflective of mineral surface heterogeneity. We propose to investigate the sorption/desorption behavior of radionuclides from mineral surfaces, as effected by microorganisms, employing isolates from Nevada Test Site deep alluvium as a model system. Characterizations will include surface area, particle size distribution, x-ray diffraction (XRD), microprobe analysis, extractions, and microbiology. Surface interactions will be assessed by electron spectroscopy (XPS), x-ray absorption fine structure spectroscopy (XAFS), X-ray emission spectroscopy, transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Desert Research Institute (DRI), University of Nevada, Reno (UNR), and University of Nevada, Las Vegas (UNLV) researchers will collaborate to enhance scientific infrastructure and the understanding of contaminant behavior on surfaces, with broader implications for the management of DOE sites.

  7. Involvement of active oxygen in lipid peroxide radical reaction of epidermal homogenate following ultraviolet light exposure

    International Nuclear Information System (INIS)

    Nishi, J.; Ogura, R.; Sugiyama, M.; Hidaka, T.; Kohno, M.

    1991-01-01

    To elucidate the radical mechanism of lipid peroxidation induced by ultraviolet light (UV) irradiation, an electron spin resonance (ESR) study was made on epidermal homogenate prepared from albino rat skin. The exposure of the homogenate to UV light resulted in an increase in lipid peroxide content, which was proportional to the time of UV exposure. Using ESR spin trapping (dimethyl-1-pyrroline-N-oxide, DMPO), the DMPO spin adduct spectrum of lipid radicals (L.) was measured following UV exposure (DMPO-L.:aN = 15.5 G, aH = 22.7 G), as was the spectrum of DMPO-hydroxyl radical (DMPO-OH, aN = aH = 15.5 G). In the presence of superoxide dismutase, the DMPO spin adduct spectrum of lipid radicals was found to be reduced remarkably. Therefore, it was shown that the generation of the lipid radicals partially involves superoxide anion radicals, in addition to hydroxyl radicals. In the ESR free-radical experiment, an ESR signal appeared at g = 2.0064 when the ESR tube filled with homogenate was exposed to UV light at -150 degrees C. The temperature-dependent change in the ESR free radical signal of homogenate exposed to UV light was observed at temperatures varying from -150 degrees C to room temperature. By using degassed samples, it was confirmed that oxygen is involved in the formation of the lipid peroxide radicals (LOO.) from the lipid radicals (L.)

  8. Global distribution of radiolytic H2 production in marine sediment and implications for subsurface life

    Science.gov (United States)

    Sauvage, J.; Flinders, A. F.; Spivack, A. J.; D'Hondt, S.

    2017-12-01

    We present the first global estimate of radiolytic H2production in marine sediment. Knowledge of microbial electron donor production rates is critical to understand the bioenergetics of Earth's subsurface ecosystems In marine sediment, radiolysis of water by radiation from naturally occurring radionuclides leads to production of reduced (H2) and oxidized (H2O2, O2) species. Water radiolysis is catalyzed by marine sediment. The magnitude of catalysis depends on sediment composition and radiation type. Deep-sea clay is especially effective at enhancing H2 yields, increasing yield by more than an order of magnitude relative to pure water. This previously unrecognized catalytic effect of geological materials on radiolytic H2 production is important for fueling microbial life in the subseafloor, especially in sediment with high catalytic power. Our estimate of radiolytic H2 production is based on spatially integrating a previously published model and uses (i) experimentally constrained radiolytic H2 yields for the principal marine sediment types, (ii) bulk sediment radioactive element content of sediment cores in three ocean basins (N. Atlantic, N. and S. Pacific), and global distributions of (iii) seafloor lithology, (iv) sediment porosity, and (v) sediment thickness. We calculate that global radiolytic H2 production in marine sediment is 1.6E+12 mol H2 yr-1. This production rate is small relative to the annual rate of photosynthetic organic-matter production in the surface ocean. The globally integrated ratio of radiolytic H2 production relative to photosynthetic primary production is 4.1E-4, based on electron equivalences. Although small relative to global photosynthetic biomass production, sediment-catalyzed production of radiolytic products is significant in the subseafloor. Our analysis of 9 sites in the N. Atlantic, N. and S. Pacific suggests that H2 is the primary microbial fuel in organic-poor sediment older than a few million years; at these sites, calculated

  9. Identifying genes involved in the interaction of Aggregatibacter actinomycetemcomitans with Maillard reaction products (MRP)

    Science.gov (United States)

    Jaha, Raniah Abdulmohsen

    Aggregatibacter (Actinobacillus) actinomycelemcomitcrns is a gram-negative bacterium that is a facultative anaerobe which can grow in either aerobic or anaerobic conditions. The bacteria cause localized aggressive periodontitis that can result in the loss of teeth and endocarditis, which is an infection of the heart valves. A rich medium is an essential requirement for its growth. There arc some difficulties associated with growing the bacteria as they easily switch from the rough to smooth phenotype under no specific conditions. The bacteria start to lose viability after about 19 hours of growth in broth or about three days on plates. Colonies in the dense part of the streak on plates die earlier. It was shown that acid secreted by the colonies is responsible for the loss of viability as the bacteria are extremely sensitive to low pH. Autoclaving the growth medium for A. actinomycetemcomitans causes the bacteria to grow slowly because of the formation of Maillard reaction products (MRPs). A method has been developed to make the A. actinomycetemcomitans growth medium using the microwave instead of the autoclave. This method produces much less of the inhibitory product since the heating time is only six minutes, compared to more than an hour when using the autoclave. Two approaches were sought in this research. The first approach was the identification of genes responsible for the interaction between the MRP and A. actinomycetemcomitans. The gene responsible for this interaction was found to be a Lys M protein which is found in many genes responsible for the cell wall integrity. The second approach was to develop a new drug made of glucose and lysine with a minimum inhibitory concentration as 75mM.

  10. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  11. Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species with Application to DSMC Simulations

    Science.gov (United States)

    Liechty, Derek S.

    2014-01-01

    The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for near-equilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion.

  12. Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species With Application to DSMC Simulations

    Science.gov (United States)

    Liechty, Derek S.

    2013-01-01

    The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for nearequilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion of the heating and is then compared to the total heating measured in flight.

  13. Radiolytic and thermal generation of gases from Hanford grout samples

    Energy Technology Data Exchange (ETDEWEB)

    Meisel, D.; Jonah, C.D.; Kapoor, S.; Matheson, M.S.; Mulac, W.A.

    1993-10-01

    Gamma irradiation of WHC-supplied samples of grouted Tank 102-AP simulated nonradioactive waste has been carried out at three dose rates, 0.25, 0.63, and 130 krad/hr. The low dose rate corresponds to that in the actual grout vaults; with the high dose rate, doses equivalent to more than 40 years in the grout vault were achieved. An average G(H{sub 2}) = 0.047 molecules/100 eV was found, independent of dose rate. The rate of H2 production decreases above 80 Mrad. For other gases, G(N{sub 2}) = 0.12, G(O{sub 2}) = 0.026, G(N{sub 2}O) = 0.011 and G(CO) = 0.0042 at 130 krad/hr were determined. At lower dose rates, N{sub 2} and O{sub 2} could not be measured because of interference by trapped air. The value of G(H{sub 2}) is higher than expected, suggesting segregation of water from nitrate and nitrite salts in the grout. The total pressure generated by the radiolysis at 130 krad/h has been independently measured, and total amounts of gases generated were calculated from this measurement. Good agreement between this measurement and the sum of all the gases that were independently determined was obtained. Therefore, the individual gas measurements account for most of the major components that are generated by the radiolysis. At 90 {degree}C, H{sub 2}, N{sub 2}, and N{sub 2}O were generated at a rate that could be described by exponential formation of each of the gases. Gases measured at the lower temperatures were probably residual trapped gases. An as yet unknown product interfered with oxygen determinations at temperatures above ambient. The thermal results do not affect the radiolytic findings.

  14. Contribution to the study of solvated electrons in water and alcohols and of radiolytic processes in organic carbonates by picosecond pulse radiolysis

    International Nuclear Information System (INIS)

    Torche, Faycal

    2012-01-01

    This work is part of the study area of the interaction of radiation with polar liquids. Using the picosecond electron accelerator ELYSE, studies were conducted using the techniques of pulse radiolysis combined with absorption spectrophotometry Time-resolved in the field of a picosecond. This work is divided into two separate chapters. The first study addresses the temporal variation of the radiolytic yield of solvated electron in water and simple alcohols. Due to original detection system mounted on the accelerator ELYSE, composed of a flash lamp specifically designed for the detection and a streak-camera used for the first time in absorption spectroscopy, it was possible to record the time-dependent radiolytic yields of the solvated electron from ten picoseconds to a few hundred nanoseconds. The scavenging of the electron solvated by methyl viologen, was utilized to reevaluate the molar extinction coefficient of the absorption spectrum of solvated electron in water and ethanol from isobestic points which corresponds to the intersection of the absorption spectra of solvated electron which disappears and methyl viologen which is formed during the reaction. The second chapter is devoted to the study of liquid organic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and propylene carbonate (PC). This family of carbonate which compose the electrolytes lithium batteries, has never been investigated by pulse radiolysis. The studies were focused on the PC in the light of these physicochemical characteristics, including its very high dielectric constant and its strong dipole moment of 4.9 D. The first results were obtained on aqueous solutions containing propylene carbonate to observe the reactions of reduction and oxidation of PC by radiolytic species of water (solvated electron and OH radicals). Then, after the identification (spectral and kinetic) of the species formed by interaction with the OH radical as the PC* radical resulting from the

  15. CdSe nanoparticles grown via radiolytic methods in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Shalini [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Rath, M.C., E-mail: madhab@barc.gov.i [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Singh, A.K. [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Mukherjee, T. [Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Jayakumar, O.D.; Tyagi, A.K. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Sarkar, S.K. [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

    2011-06-15

    Cadmium selenide, CdSe, nanoparticles have been synthesized in aqueous solution containing equimolar ammoniated CdSO{sub 4} and Na{sub 2}SeSO{sub 3} as the starting materials without any capping agents, using gamma and electron beam irradiation under a reducing condition. The radiolytic processes occurring in water result in the formation of CdSe nanoparticles through the reactions mediated by hydrated electrons, e{sub aq}{sup -}. TEM measurements revealed that the CdSe nanoparticles were found to exist in agglomerates of dimension of about 100 nm, consisting of primary nanoparticles of dimensions within 5 nm. The as-grown nanoparticles were of cubic crystalline phase as supported by the XRD measurements. These bare CdSe nanoparticles exhibit room temperature ferromagnetic (RTFM) behavior. However, the RTFM behavior was found to be 30% higher in the case of CdSe nanoparticles prepared on electron beam irradiation as compared to those obtained by gamma irradiation, which was attributed to their relatively smaller size (2-3 nm) and disordered structures as compared to those obtained in the later case (3-5 nm). -- Research highlights: {yields} CdSe nanoparticles could be synthesized in aqueous solutions containing equimolar ammoniated CdSO{sub 4} and Na{sub 2}SeSO{sub 3} as the starting materials using gamma and electron beam irradiation under a reducing condition. {yields} CdSe nanoparticles were found to exist in agglomerates of dimension of about 100 nm, consisting of primary nanoparticles of dimensions within 5 nm. {yields} CdSe nanoparticles exhibit room temperature ferromagnetic (RTFM) behavior. {yields} The RTFM behavior was found to be 30% higher in the case of CdSe nanoparticles prepared on electron beam irradiation as compared to those obtained by gamma irradiation.

  16. CdSe nanoparticles grown via radiolytic methods in aqueous solutions

    International Nuclear Information System (INIS)

    Singh, Shalini; Rath, M.C.; Singh, A.K.; Mukherjee, T.; Jayakumar, O.D.; Tyagi, A.K.; Sarkar, S.K.

    2011-01-01

    Cadmium selenide, CdSe, nanoparticles have been synthesized in aqueous solution containing equimolar ammoniated CdSO 4 and Na 2 SeSO 3 as the starting materials without any capping agents, using gamma and electron beam irradiation under a reducing condition. The radiolytic processes occurring in water result in the formation of CdSe nanoparticles through the reactions mediated by hydrated electrons, e aq - . TEM measurements revealed that the CdSe nanoparticles were found to exist in agglomerates of dimension of about 100 nm, consisting of primary nanoparticles of dimensions within 5 nm. The as-grown nanoparticles were of cubic crystalline phase as supported by the XRD measurements. These bare CdSe nanoparticles exhibit room temperature ferromagnetic (RTFM) behavior. However, the RTFM behavior was found to be 30% higher in the case of CdSe nanoparticles prepared on electron beam irradiation as compared to those obtained by gamma irradiation, which was attributed to their relatively smaller size (2-3 nm) and disordered structures as compared to those obtained in the later case (3-5 nm). -- Research highlights: → CdSe nanoparticles could be synthesized in aqueous solutions containing equimolar ammoniated CdSO 4 and Na 2 SeSO 3 as the starting materials using gamma and electron beam irradiation under a reducing condition. → CdSe nanoparticles were found to exist in agglomerates of dimension of about 100 nm, consisting of primary nanoparticles of dimensions within 5 nm. → CdSe nanoparticles exhibit room temperature ferromagnetic (RTFM) behavior. → The RTFM behavior was found to be 30% higher in the case of CdSe nanoparticles prepared on electron beam irradiation as compared to those obtained by gamma irradiation.

  17. Reaction Time of Motor Responses in Two-Stimulus Paradigms Involving Deception and Congruity with Varying Levels of Difficulty

    Directory of Open Access Journals (Sweden)

    Jennifer M. C. Vendemia

    2005-01-01

    Full Text Available Deception research has focused on identifying peripheral nervous system markers while ignoring cognitive mechanisms underlying those markers. Cognitive theorists argue that the process of deception may involve such constructs as attentional capture, working memory load, or perceived incongruity with memory, while psychophysiologists argue for stimulus salience, arousal, and emotion. Three studies were conducted to assess reaction time (RT in relation to deception, response congruity, and preparedness to deceive. Similar to a semantic verification task, participants evaluated sentences that were either true or false, and then made truthful or deceptive evaluations of the sentence’s base truth-value. Findings indicate that deceptive responses have a longer RT than truthful responses, and that this relationship remains constant across response type and preparedness to deceive. The authors use these findings in preliminary support of a comprehensive cognitive model of deception.

  18. Pair natural orbital and canonical coupled cluster reaction enthalpies involving light to heavy alkali and alkaline earth metals: the importance of sub-valence correlation

    KAUST Repository

    Minenkov, Yury; Bistoni, Giovanni; Riplinger, Christoph; Auer, Alexander A.; Neese, Frank; Cavallo, Luigi

    2017-01-01

    In this work, we tested canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) for a set of 32 ligand exchange and association/dissociation reaction enthalpies involving ionic complexes

  19. Measurements of the radiolytic oxidation of aqueous CsI using a sparging apparatus

    International Nuclear Information System (INIS)

    Ashmore, C.B.; Brown, D.; Sims, H.E.; Gwyther, J.R.

    1996-01-01

    Radiolytic oxidation is considered to be the main mechanism for the formation of I 2 from aqueous CsI in containment of a water cooled reactor after a LOCA. Despite the amount of study over the last 60 years on the radiation chemistry of iodine there has been no consistent set of experiments spanning a wide enough range of conditions to verify models with confidence. This paper describes results from a set of experiments carried out in order to remedy this deficiency. In this work the rate of evolution of I 2 from sparged irradiated CsI solution labeled with 131 I was measured on-line over a range of conditions. This work involved the measurement of the effects of pH, temperature, O 2 concentration, I - concentration, phosphate concentration, dose-rate and impurities on the rate of evolution of I 2 . The range of conditions was chosen in order to span as closely as possible conditions expected in a LOCA but also to help to elucidate some of the mechanisms especially at high pH. pH was found to be a very important factor influencing iodine volatility, over the temperature range studied the extent of oxidation reduced with temperature but this was compensated for by the decrease in partition coefficient. Oxygen concentration was more important in solutions not containing phosphate. The fractional oxidation was not particularly dependent on iodide concentration but G I2 was very dependent on [I - ]. There was no effect of added impurities, Fe, Mn, Mo or organics although in separate work silver was found to have a very important effect. During attempts to interpret the data it was found that it was necessary to include the iodine atom as a volatile species with a partition coefficient of 1.9 taken from thermodynamic data. The modelling work is described in a separate paper. (author) 15 figs., 1 tab., 19 refs

  20. Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules.

    Science.gov (United States)

    Ateshian, Gerard A; Nims, Robert J; Maas, Steve; Weiss, Jeffrey A

    2014-10-01

    Mechanobiological processes are rooted in mechanics and chemistry, and such processes may be modeled in a framework that couples their governing equations starting from fundamental principles. In many biological applications, the reactants and products of chemical reactions may be electrically charged, and these charge effects may produce driving forces and constraints that significantly influence outcomes. In this study, a novel formulation and computational implementation are presented for modeling chemical reactions in biological tissues that involve charged solutes and solid-bound molecules within a deformable porous hydrated solid matrix, coupling mechanics with chemistry while accounting for electric charges. The deposition or removal of solid-bound molecules contributes to the growth and remodeling of the solid matrix; in particular, volumetric growth may be driven by Donnan osmotic swelling, resulting from charged molecular species fixed to the solid matrix. This formulation incorporates the state of strain as a state variable in the production rate of chemical reactions, explicitly tying chemistry with mechanics for the purpose of modeling mechanobiology. To achieve these objectives, this treatment identifies the specific theoretical and computational challenges faced in modeling complex systems of interacting neutral and charged constituents while accommodating any number of simultaneous reactions where reactants and products may be modeled explicitly or implicitly. Several finite element verification problems are shown to agree with closed-form analytical solutions. An illustrative tissue engineering analysis demonstrates tissue growth and swelling resulting from the deposition of chondroitin sulfate, a charged solid-bound molecular species. This implementation is released in the open-source program FEBio ( www.febio.org ). The availability of this framework may be particularly beneficial to optimizing tissue engineering culture systems by examining the

  1. Different frontal involvement in ALS and PLS revealed by Stroop event-related potentials and reaction times

    Directory of Open Access Journals (Sweden)

    Ninfa eAmato

    2013-12-01

    Full Text Available BACKGROUND: A growing body of evidence suggests a link between cognitive and pathological changes in amyotrophic lateral sclerosis (ALS and in frontotemporal lobar dementia (FTLD. Cognitive deficits have been investigated much less extensively in primary lateral sclerosis (PLS than in ALS. OBJECTIVE: to investigate bioelectrical activity to Stroop test, assessing frontal function, in ALS, PLS and control groups. METHODS: 32 non-demented ALS patients, 10 non-demented PLS patients and 27 healthy subjects were included. Twenty-nine electroencephalography (EEG channels with binaural reference were recorded during covert Stroop task performance, involving mental discrimination of the stimuli and not vocal or motor response. Group effects on event related potentials (ERPs latency were analyzed using statistical multivariate analysis. Topographic analysis was performed using low resolution brain electromagnetic tomography (LORETA. RESULTS: ALS patients committed more errors in the execution of the task but they were not slower, whereas PLS patients did not show reduced accuracy, despite a slowing of reaction times (RTs. The main ERP components were delayed in ALS, but not in PLS, compared with controls. Moreover, RTs speed but not ERP latency correlated with clinical scores. ALS had decreased frontotemporal activity in the P2, P3 and N4 time windows compared to controls. CONCLUSION: These findings suggest a different pattern of psychophysiological involvement in ALS compared with PLS. The former is increasingly recognized to be a multisystems disorder, with a spectrum of executive and behavioural impairments reflecting frontotemporal dysfunction. The latter seems to mainly involve the motor system, with largely spared cognitive functions. Moreover, our results suggest that the covert version of the Stroop task used in the present study, may be useful to assess cognitive state in the very advanced stage of the disease, when other cognitive tasks are not

  2. Time extrapolation of radiolytic degradation product kinetics: the case of polyurethane; Extrapolation dans le temps des cinetiques de production des produits de degradation radiolytique: application a un polyurethane

    Energy Technology Data Exchange (ETDEWEB)

    Dannoux, A

    2007-02-15

    The prediction of the environmental impact of organic materials in nuclear waste geological storage needs knowledge of radiolytic degradation mechanisms and kinetics in aerobic and anaerobic conditions. In this framework, the effect of high doses (> MGy) and the variation of dose rate have to be considered. The material studied is a polyurethane composed of polyether soft segment and aromatic hard segments. Mechanisms were built on the analysis of material submitted to irradiations of simulation (high energy electrons and gamma radiation) by FTIR spectroscopy and gaseous and liquid degradation products by gas mass spectrometry and size exclusion chromatography. The electron paramagnetic resonance study of radical process and the determination of oxygen consumption and gas formation radiolytic yields allowed us to acquire kinetic data and to estimate dose rate and high doses effects. The polyurethane radio-oxidation mainly concerns soft segments and induced cross-linkings and production by scissions of oxidised compounds (esters, alcohols, carboxylic acids). The kinetic of radical termination is rapid and the dose rate effect is limited. After 10 MGy, branching and scission reactions are in equilibrium and low molecular weight products accumulate. At last, the degradation products release in water is influenced by the oxidation rate and the temperature. After 10 MGy, the soluble fraction is stabilised at 25%. The water soluble products identified by electro-spray ionisation mass spectrometry (alcohols, aldehydes, carboxylic acids) potentially formed complexes with radionuclides. (author)

  3. Identification of radiolytic products from N-nitrosodimethylamine and N-nitrosopyrrolidine by gas chromatography and mass spectrometry

    International Nuclear Information System (INIS)

    Ahn, H.-J.; Lee, C.-H.; Kim, J.-H.; Han, S.-B.; Jo, Cheorun; Kim, Sung; Byun, M.-W.

    2004-01-01

    The radiolytic products of N-nitrosodimethylamine (NDMA) and N-nitrosopyrrolidine (NPYR) dissolved in dichloromethane (DCM) were identified after gamma irradiation. The UV spectra of NDMA and NPYR indicated that irradiation reduced the typical peak of NDMA at 258 nm and NPYR at 260 nm.The major radiolytic components identified in irradiated NDMA were ethyl acetate and 2-dimethyl propanol. The irradiated NPYR dissolved in DCM and produced 2-butanone and 2-methyl-6-propyl piperidine as the major radiolytic components. 2-Methyl-6-propyl piperidine was the component detected in the greatest concentration in irradiated NPYR

  4. A model to estimate volume change due to radiolytic gas bubbles and thermal expansion in solution reactors

    International Nuclear Information System (INIS)

    Souto, F.J.; Heger, A.S.

    2001-01-01

    To investigate the effects of radiolytic gas bubbles and thermal expansion on the steady-state operation of solution reactors at the power level required for the production of medical isotopes, a calculational model has been developed. To validate this model, including its principal hypotheses, specific experiments at the Los Alamos National Laboratory SHEBA uranyl fluoride solution reactor were conducted. The following sections describe radiolytic gas generation in solution reactors, the equations to estimate the fuel solution volume change due to radiolytic gas bubbles and thermal expansion, the experiments conducted at SHEBA, and the comparison of experimental results and model calculations. (author)

  5. Considerations for the independent reaction times and step-by-step methods for radiation chemistry simulations

    Science.gov (United States)

    Plante, Ianik; Devroye, Luc

    2017-10-01

    Ionizing radiation interacts with the water molecules of the tissues mostly by ionizations and excitations, which result in the formation of the radiation track structure and the creation of radiolytic species such as H.,.OH, H2, H2O2, and e-aq. After their creation, these species diffuse and may chemically react with the neighboring species and with the molecules of the medium. Therefore radiation chemistry is of great importance in radiation biology. As the chemical species are not distributed homogeneously, the use of conventional models of homogeneous reactions cannot completely describe the reaction kinetics of the particles. Actually, many simulations of radiation chemistry are done using the Independent Reaction Time (IRT) method, which is a very fast technique to calculate radiochemical yields but which do not calculate the positions of the radiolytic species as a function of time. Step-by-step (SBS) methods, which are able to provide such information, have been used only sparsely because these are time-consuming in terms of calculation. Recent improvements in computer performance now allow the regular use of the SBS method in radiation chemistry. The SBS and IRT methods are both based on the Green's functions of the diffusion equation (GFDE). In this paper, several sampling algorithms of the GFDE and for the IRT method are presented. We show that the IRT and SBS methods are exactly equivalent for 2-particles systems for diffusion and partially diffusion-controlled reactions between non-interacting particles. We also show that the results obtained with the SBS simulation method with periodic boundary conditions are in agreement with the predictions by classical reaction kinetics theory, which is an important step towards using this method for modelling of biochemical networks and metabolic pathways involved in oxidative stress. Finally, the first simulation results obtained with the code RITRACKS (Relativistic Ion Tracks) are presented.

  6. Basic aspects of photocatalytic detoxification of organic halogens by TiO2 nanocrystallites. Photolytic and radiolytic investigations

    International Nuclear Information System (INIS)

    Rabani, J.

    1998-01-01

    Various forms of TiO 2 (nanocrystallites in colloid solutions, powders and layers) are considered as promising photocatalysts for detoxification of persistent organic chemicals which are present as pollutants in waste water effluents from industrial manufacturers and even from regular households. Such pollutants penetrate and reach water sources and must be removed or destroyed in order to prevent damage to people or to the environment. Some of the toxins, such as organic halogenated compounds is difficult to remove by moderate chemical redox reactions, but can be mineralized by a free radical mechanism. Pilot plants for detoxification of industrial wastes on TiO 2 surface are currently being tested in several countries. In view of this recent development it is of particular interest to investigate yields of the reactive intermediates and reaction mechanisms of reactions of representative organic substrates. Such work is presently going on in many laboratories. In the present contribution we focus on the nature of the primary oxidizing species and the possible ways to increase photolytic yields, with particular attention to chain reactions in organic halogen compounds. Although the work concerns photocatalysis, radiation chemistry may provide useful results regarding kinetic parameters and comparative tests. Thus, comparison between photocatalytic (TiO 2 ), radiolytic and chemical hydroxylations of phenol provides evidence that the reactive hydroxylation agent is an OH· radical adsorbed to the TiO 2 surface. The initial photochemical products are conduction band electrons and valence band holes in the TiO 2 nanocrystallites, which become 'trapped' within less than 30 ps. (author)

  7. A STUDY ON ADVERSE DRUG REACTIONS INVOLVING CENTRAL NERVOUS SYSTEM, ITS SEVERITY AND CAUSALITY ASSESSMENT IN PEDIATRIC PATIENTS ADMITTED TO A TERTIARY CARE HOSPITAL

    Directory of Open Access Journals (Sweden)

    Arati

    2015-09-01

    Full Text Available A retrospective study was conducted in Department of pediatrics SCB Medical College and SVPPGIP for a period of 2 years i.e. September 2012 to August 2014 . All the patients from birth to 14 years admitted to the pediatric ward in this study were under ADR surveillance. Patients admitted to our hospital with adverse drug reaction o r patients developing adverse drug reaction in our hospital were studied; only those cases where the central nervous system was involved were taken in our study. The cases were compiled and the causality of offending drugs was found using WHO - UMC causality assessment score. The severity of drug reaction in every case was determined by using HARTWIG’s severity scoring scale. Total 350 Adverse reactions were reported in this period with prevalence rate of 2.04% i.e. 20 out of 1000 children faced ADR due to dr ugs, with annual incidence rate of 0.9% and 1.14% over two years. Out of total 350 cases dermatological system was most commonly involved i.e. 207 cases (59.14%. This is followed by involvement of central nervous system 46 number of cases (13.14%. The GI system was involved in 34 cases i.e. (9.71%. Life threatening reactions like anaphylaxis, angioedema and shock like immediate life threatening ADRs were reported in 16 cases. Our study group was the patient in whom the ADR involved the CNS. Out of 46 suc h cases, there were 25 female and 21 male. Various reaction due to drug were encephalopathy , eps, febrile seizure, tremor, head reeling, ototoxicity, persistant cry, pseudotumor cerebri, psychosis, seizure, status epilepticus, toxic amblyopia, tremor, atax ia etc. The most common CNS manifestation was Extra pyramidal side effects (EPS involving 21% of cases. The most common Drug causing CNS manifestation was ATT (HRZE causing blindness, Eps, psychosis , toxic amblyopia blindness etc.

  8. Radiolytic decomposition of pesticide carbendazim in waters and wastes for environmental protection

    International Nuclear Information System (INIS)

    Bojanowska-Czajka, A.; Drzewicz, P.; Meczynska, S.; Kruszewski, M.; Zimek, Z.; Nichipor, H.; Galezowska, A.; Nalecz-Jawecki, G.; Trojanowicz, M.; Warsaw University, Warsaw

    2011-01-01

    The radiolytic degradation of widely used fungicide, carbendazim, in synthetic aqueous solutions and industrial wastewater was investigated employing γ-irradiation. The effect of the absorbed dose, initial concentration and pH of irradiated solution on the effectiveness of carbendazim decomposition were investigated. Decomposition of carbendazim in 100 μM concentration in synthetic aqueous solutions required irradiation with 600 Gy dose. The aqueous solutions of carbendazim have been irradiated in different conditions, where particular active radical species from water radiolysis predominate. The obtained data have been compared with the kinetic modeling. The reversed-phase high-performance liquid chromatography was used for the determination of carbendazim and its radiolytic decomposition products in irradiated solutions. The changes of toxicity of irradiated solutions were examined with different test organisms and human leukemia cells. (author)

  9. Radiolytic modelling of spent fuel oxidative dissolution mechanism. Calibration against UO2 dynamic leaching experiments

    International Nuclear Information System (INIS)

    Merino, J.; Cera, E.; Bruno, J.; Quinones, J.; Casas, I.; Clarens, F.; Gimenez, J.; Pablo, J. de; Rovira, M.; Martinez-Esparza, A.

    2005-01-01

    Calibration and testing are inherent aspects of any modelling exercise and consequently they are key issues in developing a model for the oxidative dissolution of spent fuel. In the present work we present the outcome of the calibration process for the kinetic constants of a UO 2 oxidative dissolution mechanism developed for using in a radiolytic model. Experimental data obtained in dynamic leaching experiments of unirradiated UO 2 has been used for this purpose. The iterative calibration process has provided some insight into the detailed mechanism taking place in the alteration of UO 2 , particularly the role of · OH radicals and their interaction with the carbonate system. The results show that, although more simulations are needed for testing in different experimental systems, the calibrated oxidative dissolution mechanism could be included in radiolytic models to gain confidence in the prediction of the long-term alteration rate of the spent fuel under repository conditions

  10. Determination of non-volatile radiolytic compounds in ethylene co-vinyl alcohol

    International Nuclear Information System (INIS)

    Kothapalli, A.; Sadler, G.

    2003-01-01

    The use of ionizing radiation on food contact polymers is increasing due to the critical role of the package in holding or containing the irradiated foods [Food Add. Contam. 18(6) (2001) 475]. Irradiation benefits the food if properly applied and the food is pre-packaged prior to irradiation to protect it from subsequent recontamination. The United States Food and Drug Administration (USFDA) has approved the use of ionizing radiation within the dosage range of 0-60 kGy on limited films since the 1960s [USFDA 21CFR 179.45]. The obstacle in the way of approval of additional polymers is that FDA fears that these materials may undergo changes during irradiation producing toxic radiolytic fragments. Ethylene co-vinyl alcohol (EVOH), which is often used in food applications, is not approved by the FDA for pre-packaged irradiated foods. The present work examines the non-volatile radiolytic compounds, which may be formed due to exposure to gamma irradiation at the dosage levels of 3 and 10 kGy versus a non-radiated control. Irradiated EVOH is subjected to extraction with 95:5 ethanol and water (by volume) as the food simulating solvent (FSS) for a period of 10 days at 40 deg. C, which models the amount of radiolytic compound a food would extract in 1 year [USFDA Chemistry Requirement for Food Contact Notification]. The FSS is then analyzed for the presence of non-volatile compounds using advanced liquid chromatographic techniques. The chromatograms obtained from different dosages show that non-volatile radiolytic compounds are not formed in EVOH and it would, therefore be in compliance with safety demands of USFDA [Available at: http://www.cfsan.fda.gov/~dms/opa-guid.htmlref and http://www.access.gpo.gov/nara/cfr/cfr-table-search.htmlpage1

  11. Determination of non-volatile radiolytic compounds in ethylene co-vinyl alcohol

    Science.gov (United States)

    Kothapalli, A.; Sadler, G.

    2003-08-01

    The use of ionizing radiation on food contact polymers is increasing due to the critical role of the package in holding or containing the irradiated foods [Food Add. Contam. 18(6) (2001) 475]. Irradiation benefits the food if properly applied and the food is pre-packaged prior to irradiation to protect it from subsequent recontamination. The United States Food and Drug Administration (USFDA) has approved the use of ionizing radiation within the dosage range of 0-60 kGy on limited films since the 1960s [USFDA 21CFR 179.45]. The obstacle in the way of approval of additional polymers is that FDA fears that these materials may undergo changes during irradiation producing toxic radiolytic fragments. Ethylene co-vinyl alcohol (EVOH), which is often used in food applications, is not approved by the FDA for pre-packaged irradiated foods. The present work examines the non-volatile radiolytic compounds, which may be formed due to exposure to gamma irradiation at the dosage levels of 3 and 10 kGy versus a non-radiated control. Irradiated EVOH is subjected to extraction with 95:5 ethanol and water (by volume) as the food simulating solvent (FSS) for a period of 10 days at 40 °C, which models the amount of radiolytic compound a food would extract in 1 year [USFDA Chemistry Requirement for Food Contact Notification]. The FSS is then analyzed for the presence of non-volatile compounds using advanced liquid chromatographic techniques. The chromatograms obtained from different dosages show that non-volatile radiolytic compounds are not formed in EVOH and it would, therefore be in compliance with safety demands of USFDA [Available at: http://www.cfsan.fda.gov/~dms/opa-guid.html#ref and http://www.access.gpo.gov/nara/cfr/cfr-table-search.html#page1].

  12. Capture and photonuclear reaction rates involving charged-particles: Impacts of nuclear ingredients and future measurement on ELI-NP

    Directory of Open Access Journals (Sweden)

    Xu Y.

    2018-01-01

    Full Text Available The astrophysical p-process is an important way of nucleosynthesis to produce the stable and proton-rich nuclei beyond Fe which can not be reached by the s- and r-processes. In the present study, the impact of nuclear ingredients, especially the nuclear potential, level density and strength function, to the astrophysical re-action rates of (p,γ, (α,γ, (γ,p, and (γ,α reactions are systematically studied. The calculations are performed basad on the modern reaction code TALYS for about 3000 stable and proton-rich nuclei with 12≤Z≤110. In particular, both of the Wood-Saxon potential and the microscopic folding potential are taken into account. It is found that both the capture and photonuclear reaction rates are very sensitive to the nuclear potential, thus the better determination of nuclear potential would be important to reduce the uncertainties of reaction rates. Meanwhile, the Extreme Light Infrastructure-Nuclear Physics (ELI-NP facility is being developed, which will provide the great opportunity to experimentally study the photonuclear reactions in p-process. Simulations of the experimental setup for the measurements of the photonuclear reactions 96Ru(γ,p and 96Ru(γ,α are performed. It is shown that the experiments of photonuclear reactions in p-process based on ELI-NP are quite promising.

  13. Capture and photonuclear reaction rates involving charged-particles: Impacts of nuclear ingredients and future measurement on ELI-NP

    Science.gov (United States)

    Xu, Y.; Goriely, S.; Balabanski, D. L.; Chesnevskaya, S.; Guardo, G. L.; La Cognata, M.; Lan, H. Y.; Lattuada, D.; Luo, W.; Matei, C.

    2018-05-01

    The astrophysical p-process is an important way of nucleosynthesis to produce the stable and proton-rich nuclei beyond Fe which can not be reached by the s- and r-processes. In the present study, the impact of nuclear ingredients, especially the nuclear potential, level density and strength function, to the astrophysical re-action rates of (p,γ), (α,γ), (γ,p), and (γ,α) reactions are systematically studied. The calculations are performed basad on the modern reaction code TALYS for about 3000 stable and proton-rich nuclei with 12≤Z≤110. In particular, both of the Wood-Saxon potential and the microscopic folding potential are taken into account. It is found that both the capture and photonuclear reaction rates are very sensitive to the nuclear potential, thus the better determination of nuclear potential would be important to reduce the uncertainties of reaction rates. Meanwhile, the Extreme Light Infrastructure-Nuclear Physics (ELI-NP) facility is being developed, which will provide the great opportunity to experimentally study the photonuclear reactions in p-process. Simulations of the experimental setup for the measurements of the photonuclear reactions 96Ru(γ,p) and 96Ru(γ,α) are performed. It is shown that the experiments of photonuclear reactions in p-process based on ELI-NP are quite promising.

  14. Gamma radiolytic degradation of 4-chlorophenol determination of degraded products with HPLC and GC-MS

    International Nuclear Information System (INIS)

    Butt, S.B.; Masood, M.N.

    2007-01-01

    Contamination by chlorophenols of surface water and groundwater is an emerging issue in environmental science and engineering. After their usage as pesticide, herbicide and disinfectant, these organic compounds subsequently enter the aquatic environment through a number of routes. Some of the chlorophenols are slightly biodegradable, while others are more persistent and mobile in the aquatic environment especially chlorophenols. Gamma radiolytic degradation is one of advance oxidation process that has been thought to be one of the promising treatments to deal with this problem. This radiolytic study was carried out in methanolic 4-CP (4-chlorophenol) samples. Among several factors effecting radiolytic degradation of 4-CP, dose and concentration are important that were evaluated under atmospheric conditions. A degradation yield (G -value) for 4- CP of 0.38 and 1.35 was achieved in 20 and 100 mg/dm/sup 3/ solution. It was observed that degradation yield decreases with increasing 4-CP concentration. Gamma radiolysis produce free radicals in solvent which further react with 4-CP molecules to generate different products. The identification of degradation products was proposed using HPLC and GC-MS. (author)

  15. The impact of radiolytic yield on the calculated ECP in PWR primary coolant circuits

    International Nuclear Information System (INIS)

    Urquidi-Macdonald, Mirna; Pitt, Jonathan; Macdonald, Digby D.

    2007-01-01

    A code, PWR-ECP, comprising chemistry, radiolysis, and mixed potential models has been developed to calculate radiolytic species concentrations and the corrosion potential of structural components at closely spaced points around the primary coolant circuits of pressurized water reactors (PWRs). The pH(T) of the coolant is calculated at each point of the primary-loop using a chemistry model for the B(OH) 3 + LiOH system. Although the chemistry/radiolysis/mixed potential code has the ability to calculate the transient reactor response, only the reactor steady state condition (normal operation) is discussed in this paper. The radiolysis model is a modified version of the code previously developed by Macdonald and coworkers to model the radiochemistry and corrosion properties of boiling water reactor primary coolant circuits. In the present work, the PWR-ECP code is used to explore the sensitivity of the calculated electrochemical corrosion potential (ECP) to the set of radiolytic yield data adopted; in this case, one set had been developed from ambient temperature experiments and another set reported elevated temperatures data. The calculations show that the calculated ECP is sensitive to the adopted values for the radiolytic yields

  16. A study on radiolytic nitrogen compounds in bwr primary systems

    International Nuclear Information System (INIS)

    Ibe, Eishi; Karasawa, Hidetoshi; Endo, Masao; Suzuki, Kazumichi; Etho, Yoshinori

    1988-01-01

    Behavior of nitrogen compounds in a γ radiation field was evaluated. Twenty-four species and 73 reactions were proposed for analysis of the system. It was pointed out that reactions dominating analysis reliability were primary reactions which lead to evolution of atomic nitrogen and reactions related to ammonium ion decomposition. Theoretical calculations for the BWR primary system revealed that: (i) in-leaked nitrogen from a condenser did not deteriorate the oxygen reduction efficiency due to hydrogen addition in reactor water; (ii) most 16 N atmos released in the main steam line were in the form of nitrogen mono-oxide under both hydrogen and normal water chemistry; (iii) 16 N atoms in nitric and nitrous acids under normal water chemistry were reduced by hydrogen atom to 16 NO and then released to the main steam line under hydrogen water chemistry; and (iv) 16 N in the main steam under normal water chemistry could be suppressed one order of magnitude by addition of non-radioactive nitrous acid into the reactor water. (author)

  17. LC-MS analysis in the e-beam and gamma radiolysis of metoprolol tartrate in aqueous solution: Structure elucidation and formation mechanism of radiolytic products

    Energy Technology Data Exchange (ETDEWEB)

    Slegers, Catherine [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium)]. E-mail: catherine.slegers@skynet.be; Maquille, Aubert [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium); Deridder, Veronique [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium); Sonveaux, Etienne [Unite de Chimie Pharmaceutique et de Radiopharmacie, Universite Catholique de Louvain, Brussels (Belgium); Habib Jiwan, Jean-Louis [Laboratoire de Spectrometrie de Masse, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium); Tilquin, Bernard [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium)

    2006-09-15

    E-beam and gamma products from the radiolysis of aqueous solutions of ({+-})-metoprolol tartrate, saturated in nitrogen, are analyzed by HPLC with on-line mass and UV detectors. The structures of 10 radiolytic products common to e-beam and gamma irradiations are elucidated by comparing their fragmentation pattern to that of ({+-})-metoprolol. Two of the radiolytic products are also metabolites. Different routes for the formation of the radiolytic products are proposed.

  18. LC-MS analysis in the e-beam and gamma radiolysis of metoprolol tartrate in aqueous solution: Structure elucidation and formation mechanism of radiolytic products

    International Nuclear Information System (INIS)

    Slegers, Catherine; Maquille, Aubert; Deridder, Veronique; Sonveaux, Etienne; Habib Jiwan, Jean-Louis; Tilquin, Bernard

    2006-01-01

    E-beam and gamma products from the radiolysis of aqueous solutions of (±)-metoprolol tartrate, saturated in nitrogen, are analyzed by HPLC with on-line mass and UV detectors. The structures of 10 radiolytic products common to e-beam and gamma irradiations are elucidated by comparing their fragmentation pattern to that of (±)-metoprolol. Two of the radiolytic products are also metabolites. Different routes for the formation of the radiolytic products are proposed

  19. Effect of electron affinic hypoxic cell sensitizers on the radiolytic depletion of oxygen in mammalian cells irradiated at ultrahigh dose rates

    International Nuclear Information System (INIS)

    Michaels, H.B.

    1982-01-01

    When CHO cells are equilibrated with a low level of oxygen (e.g. 0.4% O 2 ) and irradiated with single 3 ns pulses of electrons, a breaking survival curve is observed. This effect is believed to be the result of radiolytic oxygen depletion and can be prevented by the presence of a relatively low concentraton of hypoxic cell radiosensitizer. This prevention of the breaking survival curve has been observed for 2- and 5-nitroimidazoles, nitrofurans, and diamide. It is hypothesized that the sensitizer acts by competing wth oxygen for the radiation-induced intracellular oxygen-binding species, perhaps a hydrated electron adduct, leaving oxygen free to participate in radiosensitization reactions during the lifetime of the oxygen-sensitive radiation-induced target sites for lethal damage, probably DNA radicals produced by hydroxyl radical attack. The proposed role of the sensitizer in the interference with oxygen depletion is a transient phenomenon, occuring on the microsecond to millisecond time scale

  20. Measurements of the radiolytic oxidation of aqueous CsI using a sparging apparatus

    Energy Technology Data Exchange (ETDEWEB)

    Ashmore, C B; Brown, D; Sims, H E [AEA Technology, Harwell (United Kingdom); Gwyther, J R [NE plc Berkeley Technology Centre, Berkeley (United Kingdom)

    1996-12-01

    Radiolytic oxidation is considered to be the main mechanism for the formation of I{sub 2} from aqueous CsI in containment of a water cooled reactor after a LOCA. Despite the amount of study over the last 60 years on the radiation chemistry of iodine there has been no consistent set of experiments spanning a wide enough range of conditions to verify models with confidence. This paper describes results from a set of experiments carried out in order to remedy this deficiency. In this work the rate of evolution of I{sub 2} from sparged irradiated CsI solution labeled with {sup 131}I was measured on-line over a range of conditions. This work involved the measurement of the effects of pH, temperature, O{sub 2} concentration, I{sup -} concentration, phosphate concentration, dose-rate and impurities on the rate of evolution of I{sub 2}. The range of conditions was chosen in order to span as closely as possible conditions expected in a LOCA but also to help to elucidate some of the mechanisms especially at high pH. pH was found to be a very important factor influencing iodine volatility, over the temperature range studied the extent of oxidation reduced with temperature but this was compensated for by the decrease in partition coefficient. Oxygen concentration was more important in solutions not containing phosphate. The fractional oxidation was not particularly dependent on iodide concentration but G{sub I2} was very dependent on [I{sup -}]. There was no effect of added impurities, Fe, Mn, Mo or organics although in separate work silver was found to have a very important effect. During attempts to interpret the data it was found that it was necessary to include the iodine atom as a volatile species with a partition coefficient of 1.9 taken from thermodynamic data. The modelling work is described in a separate paper. (author) 15 figs., 1 tab., 19 refs.

  1. The roles of polycarboxylates in Cr(VI)/sulfite reaction system: Involvement of reactive oxygen species and intramolecular electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Bo, E-mail: bjiang86upc@163.com [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266033 (China); Wang, Xianli; Liu, Yukun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); Wang, Zhaohui [College of Environmental Science and Engineering, Donghua University, Shanghai 201620 (China); Southern Cross GeoScience, Southern Cross University, Lismore, NSW 2480 (Australia); Zheng, Jingtang, E-mail: jtzheng03@163.com [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); Wu, Mingbo, E-mail: wumb@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China)

    2016-03-05

    Highlights: • The formations of SO{sub 4}·{sup −} and OH·, involve in Cr(VI) reduction induced by S(IV). • Affinity of polycarboxylate to Cr(VI) accelerates Cr(VI) reduction rate. • Polycarboxylates can act as electron donors for Cr(VI) reduction retrenching S(IV). • Only oxalate can enhance the formations of SO{sub 4}·{sup −} and OH· in Cr(VI)/S(IV) system. - Abstract: In this study, the effects of polycarboxylates on both Cr(VI) reduction and S(IV) consumption in Cr(VI)/S(IV) system was investigated in acidic solution. Under aerobic condition, the productions of reactive oxygen species (ROS), i.e., SO{sub 4}·{sup −} and OH·, have been confirmed in S(IV) reducing Cr(VI) process by using electron spin resonance and fluorescence spectrum techniques, leading to the excess consumption of S(IV). However, when polycarboxylates (oxalic, citric, malic and tartaric acid) were present in Cr(VI)/S(IV) system, the affinity of polycarboxylates to CrSO{sub 6}{sup 2−} can greatly promote the reduction of Cr(VI) via expanding the coordination of Cr(VI) species from tetrahedron to hexahedron. Besides, as alternatives to S(IV), these polycarboxylates can also act as electron donors for Cr(VI) reduction via intramolecular electron transfer reaction, which is dependent on the energies of the highest occupied molecular orbital of these polycarboxylates. Notably, the variant electron donating capacity of these polycarboxylates resulted in different yield of ROS and therefore the oxidation efficiencies of other pollutants, e.g., rhodamine B and As(III). Generally, this study does not only shed light on the mechanism of S(IV) reducing Cr(VI) process mediated by polycarboxylates, but also provides an escalated, cost-effective and green strategy for the remediation of Cr(VI) using sulfite as a reductant.

  2. Intermediates of radiolytic transformations of 6-aminophenalenone in ethanol

    International Nuclear Information System (INIS)

    Semenova, G.V.; Ponomarev, A.V.; Kartasheva, L.I.; Pikaev, A.K.

    1992-01-01

    Pulsed radiolysis method is used to study transformations intermediates of 6-aminophenalenone in ethanol. In alkaline medium the main product is radical-anion of 6-aminophenalenone, which optical absorption spectrum contains two bands with maxima at 355 and 400 nm. The particle precursors are e s , CH 3 CHOH and CH 3 CHO - radicals. In neutral and acid medium radical-anions are protonated in reactions with alcohol and hydrogen ions. The resulting H-adduct of 6-aminophenalenone has optical absorption maxima at 350 and 390 nm. Availability of two maxima is related to two various product structures. Molar extinction coefficients of radical-anions and H-adducts of 6-aminophenalenone and rate constants of reactions with their participation are estimated

  3. Oxidoreduction reactions involving the electrostatic and the covalent complex of cytochrome c and plastocyanin: Importance of the protein rearrangement for the intracomplex electron-transfer reaction

    International Nuclear Information System (INIS)

    Peerey, L.M.; Kostic, N.M.

    1989-01-01

    Horse heart cytochrome c and French bean plastocyanin are cross-linked one-to-one by a carbodiimide in the same general orientation in which they associate electrostatically. The reduction potentials of the Fe and Cu atoms in the covalent diprotein complex are respectively 245 and 385 mV vs NHE; the EPR spectra of the two metals are not perturbed by cross-linking. For isomers of the covalent diprotein complex, which probably differ slightly from one another in the manner of cross-linking, are separated efficiently by cation-exchange chromatography. Stopped-flow spectrophotometric experiments with the covalent diprotein complex show that the presence of plastocyanin somewhat inhibits oxidation of ferrocytochrome c by [Fe(CN) 6 ] 3- and somewhat promotes oxidation of this protein by [Fe(C 5 H 5 ) 2 ] + . These changes in reactivity are explained in terms of electrostatic and steric effects. Pulse-radiolysis experiments with the electrostatic diprotein complex yield association constants of ≥5 x 10 6 and 1 x 10 5 M -1 at ionic strengths of 1 and 40 mM, respectively, and the rate constant of 1.05 x 10 3 s -1 , regardless of the ionic strength, for the intracomplex electron-transfer reaction. Analogous pulse-radiolysis experiments with each of the four isomers of the covalent diprotein complex, at ionic strengths of both 2 and 200 mM, show an absence of the intracomplex electron-transfer reaction. A rearrangement of the proteins for this reaction seems to be possible (or unnecessary) in the electrostatic complex but impossible in the covalent complex

  4. Chemical processes induced radiolytically in well defined aqueous systems

    International Nuclear Information System (INIS)

    Thomas, J.K.

    1979-01-01

    The radiation chemistry of dilute aqueous systems is discussed in terms of the simple primary radicals and ions produced, and also in terms of reactions of secondary radicals produced via attack of the primary species on organic solutes. These simple systems are extended to 3 more complex systems: (a) solutions of polymers, (b) micelles and vesicles, and (c) inverted micelles containing water bubbles. These latter systems all contain new and interesting features not exhibited by dilute solutions of simple molecules, and are of particular importance with respect to bio-systems

  5. How computational methods and relativistic effects influence the study of chemical reactions involving Ru-NO complexes?

    Science.gov (United States)

    Orenha, Renato Pereira; Santiago, Régis Tadeu; Haiduke, Roberto Luiz Andrade; Galembeck, Sérgio Emanuel

    2017-05-05

    Two treatments of relativistic effects, namely effective core potentials (ECP) and all-electron scalar relativistic effects (DKH2), are used to obtain geometries and chemical reaction energies for a series of ruthenium complexes in B3LYP/def2-TZVP calculations. Specifically, the reaction energies of reduction (A-F), isomerization (G-I), and Cl - negative trans influence in relation to NH 3 (J-L) are considered. The ECP and DKH2 approaches provided geometric parameters close to experimental data and the same ordering for energy changes of reactions A-L. From geometries optimized with ECP, the electronic energies are also determined by means of the same ECP and basis set combined with the computational methods: MP2, M06, BP86, and its derivatives, so as B2PLYP, LC-wPBE, and CCSD(T) (reference method). For reactions A-I, B2PLYP provides the best agreement with CCSD(T) results. Additionally, B3LYP gave the smallest error for the energies of reactions J-L. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  6. A new pathway for transmembrane electron transfer in photosynthetic reaction centers of Rhodobacter sphaeroides not involving the excited special pair.

    NARCIS (Netherlands)

    van Brederode, M.E.; Jones, M.R.; van Mourik, F.; van Stokkum, I.H.M.; van Grondelle, R.

    1997-01-01

    It is generally accepted that electron transfer in bacterial photosynthesis is driven by the first singlet excited state of a special pair of bacteriochlorophylls (P*). We have examined the first steps of electron transfer in a mutant of the Rhodobacter sphaeroides reaction center in which charge

  7. A new pathway for transmembrane electron transfer in photosyntetic reaction centers of Rhodobacter sphaeroides not involving the excited special pair.

    NARCIS (Netherlands)

    van Brederode, M.E.; Jones, M.R.; van Mourik, F.; van Stokkum, I.H.M.; van Grondelle, R.

    1997-01-01

    It is generally accepted that electron transfer in bacterial photosynthesis is driven by the first singlet excited state of a special pair of bacteriochlorophylls (P*). We have examined the first steps of electron transfer in a mutant of the Rhodobacter sphaeroides reaction center in which charge

  8. An Experimental Test of the Roles of Audience Involvement and Message Frame in Shaping Public Reactions to Celebrity Illness Disclosures.

    Science.gov (United States)

    Myrick, Jessica Gall

    2018-04-13

    Much research has investigated what happens when celebrities disclose an illness (via media) to the public. While audience involvement (i.e., identification and parasocial relationships) is often the proposed mechanism linking illness disclosures with audience behavior change, survey designs have prevented researchers from understanding if audience involvement prior to the illness disclosure actually predicts post-disclosure emotions, cognitions, and behaviors. Rooted in previous work on audience involvement as well as the Extended Parallel Process Model, the present study uses a national online experiment (N = 1,068) to test how pre-disclosure audience involvement may initiate post-disclosure effects for the message context of skin cancer. The data demonstrate that pre-disclosure audience involvement as well as the celebrity's framing of the disclosure can shape emotional responses (i.e., fear and hope), and that cognitive perceptions of the illness itself also influence behavioral intentions.

  9. Gibbs free energy of reactions involving SiC, Si3N4, H2, and H2O as a function of temperature and pressure

    Science.gov (United States)

    Isham, M. A.

    1992-01-01

    Silicon carbide and silicon nitride are considered for application as structural materials and coating in advanced propulsion systems including nuclear thermal. Three-dimensional Gibbs free energy were constructed for reactions involving these materials in H2 and H2/H2O. Free energy plots are functions of temperature and pressure. Calculations used the definition of Gibbs free energy where the spontaneity of reactions is calculated as a function of temperature and pressure. Silicon carbide decomposes to Si and CH4 in pure H2 and forms a SiO2 scale in a wet atmosphere. Silicon nitride remains stable under all conditions. There was no apparent difference in reaction thermodynamics between ideal and Van der Waals treatment of gaseous species.

  10. Studies of transfer reactions of photosensitized electrons involving complexes of transition metals in view of solar energy storage

    International Nuclear Information System (INIS)

    Takakubo, Masaaki

    1984-01-01

    This research thesis addresses electron transfer reactions occurring during photosynthesis, for example, photosensitized reaction in which chlorophyll is the sensitizer. More specifically, the author studied experimentally electron photo-transfers with type D sensitizers (riboflavin, phenoxazine and porphyrin), and various complexes of transition metals. After a presentation of these experiments, the author describes the photosensitisation process (photo-physics of riboflavin, oxygen deactivation, sensitized photo-oxidation and photo-reduction). The theoretical aspect of electron transfer is then addressed: generalities, deactivation of the riboflavin triplet, initial efficiency of electron transfer. Experimental results on three basic processes (non-radiative deactivation, energy transfer, electron transfer) are interpreted in a unified way by using the non-radiative transfer theory. Some applications are described: photo-electrochemical batteries, photo-oxidation and photo-reduction of the cobalt ion

  11. The radiolytic reduction of mercuric chloride in aqueous sugar solutions

    International Nuclear Information System (INIS)

    Johnston, F.J.

    1991-01-01

    The reduction of HgCl 2 has been measured in Co-60 γ-irradiated aqueous glucose, fructose and sucrose solutions. G-values for reduction, G(R), are substantially greater than 6 molecules per 100 eV in all systems from 1% by weight sugar to greater than 50%. Chain reduction occurs in glucose and fructose solutions with maximum G(R) values of 18-20 molecules per 100 eV occurring at 24% (1.0 M) sugar. The results are consistent with a mechanism in which HgCl radicals react with the organic solute to produce chain propagating free radicals. A dose rate independence of the chain length, after a brief ''induction'' period, is explained in terms of a chain termination by the incorporation of HgCl in growing Hg 2 Cl 2 particles. Reduction of Ag(I) and Cu(II) in aqueous sucrose and fructose systems took place with G(R) < 6 indicating the absence of reaction chains in these cases. (author)

  12. Oxidation of benzene by radiolytically produced OH radicals. [x rays

    Energy Technology Data Exchange (ETDEWEB)

    Klein, G W; Schuler, R H [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA)

    1978-01-01

    The radiolysis of N/sub 2/O saturated-aqueous solutions of benzene-/sup 14/C has been examined using radio-liquid chromatographic methods to follow the quantitative aspects of the reactions of hydroxycyclohexadienyl radicals. In the absence of a radical oxidant, at least five important products are produced. The total yield of 5.8 observed for the incorporation of benzene into products accounts for essentially all of the radicals initially produced from the water. Dimeric products predominate with a total yield of 4.1. Phenol is produced with a yield of only 0.8 indicating a disproportionation/combination ratio for hydroxycyclohexadienyl radicals of < = 0.4. In the presence of 2mM ferricyanide the hydroxycyclohexadienyl radicals are quantitatively oxidized to phenol with no trace (< 1%) remaining of dimeric or other high molecular weight products. The initial yield for phenol formation (6.0 molecules/100 eV) provides a measure for OH production in N/sub 2/O saturated aqueous solutions.

  13. Changes in porosity of graphite caused by radiolytic gasification by carbon dioxide

    International Nuclear Information System (INIS)

    Murdie, Neil; Edwards, I.A.S.; Marsh, Harry

    1986-01-01

    Methods have been developed to study porosity in nuclear grade graphite. The changes induced during the radiolytic gasification of graphite in carbon dioxide have been investigated. Porosity in radiolytically gasified graphite (0-22.8% wt. loss) was examined by optical microscopy and scanning electron microscopy (SEM). Each sample was vacuum impregnated with a slow-setting resin containing a fluorescent dye. Optical microscopy was used to study pores >2 μm 2 c.s.a. A semi-automatic image analysis system linked to the optical microscope enabled pore parameter data including cross-sectional areas, perimeters, Feret's diameters and shape factors, to be collected. The results showed that radiolytic gasification produced a large increase in the number of pores 2 c.s.a. New open pores 2 c.s.a. were developed by gasification of existing open porosity into the closed porosity ( 2 c.s.a.) within the binder-coke. Open pores, 2-100 μm 2 c.s.a., which were gasified within the coarse-grained mosaics of the binder-coke. In the gasification process to 22.8% wt. loss, the apparent open pore volume increased from 6.6 to 33.8% and the apparent closed pore volumes decreased from approx. 3% to 0.1%. The increase in apparent open porosity from 6.6% (virgin) to 33.8% resulted from gasification within original open porosity and by the opening and development of closed porosity. There was no evidence for creation of porosity from within the 'bulk' graphite, it being developed from existing fine porosity. The structure of pores > 100 μm 2 c.s.a. showed no change because of the inhibition of oxidation by deposition of carbonaceous species from the CH 4 inhibitor. Such species diffuse to the pore wall and are sacrificially oxidised. (author)

  14. Observation of Radiolytic Field Alteration of the Uranyl Cation in Bicarbonate Solution

    Energy Technology Data Exchange (ETDEWEB)

    Snow, Lanee A.; McNamara, Bruce K.; Sinkov, Sergey I.; Cho, Herman M.; Friese, Judah I.

    2006-12-01

    In previous work we demonstrated that radiolysis of uranyl tris carbonate in near neutral pH to alkaline carbonate solutions, could be followed by 13C NMR. Radiolysis of the complex produced novel uranyl peroxo carbonate solution state species, whose structures depended on the pH and radiolytic dose rate. In this work, we investigate speciation of the uranyl carbonate trimer which is predominant in bicarbonate solution near pH 5.9. We observe radiolytically derived speciation to different mixed peroxy carbonate species than seen in the higher pH solutions. Auto radiolysis of uranium (VI) carbonate solutions between pH 5.9 and 7.2 is shown to alter the uranium speciation over relatively short periods of time and was followed by 13C NMR and visible spectrophotometry, using dissolved 233(UO2)3(CO3)6 6- both as the radiolysis source (D= 14.9 Gy/hr) and as a trap for the newly formed hydrogen peroxide. Direct addition of hydrogen peroxide to solutions of the uranyl-carbonate trimer is shown to reproduce the 13 C NMR signatures of the complexe(s) formed by radiolysis, but additionally a variety of new complexes are revealed. Ratios of H2O2/trimer < 1.5 produced a uranyl peroxo carbonate adduct, that is shown to be common to the radiolytically produced species. Ratios of H2O2/ trimer >1 resulted in formation of stable higher order peroxo carbonate complexes. The 13C NMR signatures and visible spectra of these complexes are described here. Rigorous characterization of the species is an ongoing effort.

  15. Radiolytic oxidation of iodine in the containment at high temperature and dose rate

    International Nuclear Information System (INIS)

    Guilbert, S.; Bosland, L.; Jacquemain, D.; Clement, B.; Andreo, F.; Ducros, G.; Dickinson, S.; Herranz, L.; Ball, J.

    2007-01-01

    Iodine Chemistry is one of the areas of top interest in the field of nuclear power plants (NPP) severe accidents studies. The strong radiological impact of iodine on man health and environment, mostly through its isotope I-131, has made it a key point to get an accurate prediction of the potential iodine release from the NPP containment to the environment in the low probable event of an accident leading to core melt. Released from the fuel as a gaseous form, iodine enters the containment in gaseous or particulate form and undergoes deposition processes that eventually take it to the containment surfaces and sump. Once in the sump, iodine, when present as soluble compounds, gets dissolved as non volatile iodide (I-). Nonetheless, in the presence of radiation and particularly in acidic sumps, iodine can be oxidized to volatile forms such as molecular iodine (I 2 ) and can escape from the sump to the containment atmosphere (sump radiolysis process), thus increasing its potential contribution to the iodine source term. Iodine sump radiolysis has been extensively studied experimentally in the past decades. Experiments have revealed that parameters such as pH, temperature and total iodine concentration have a large impact on iodine volatility. However, experimental data at elevated temperatures (> 80 O C) and elevated dose rates (> 1 kGy.h -1 ) anticipated in containment during a postulated severe accident are too scarce to provide for these relevant conditions an accurate determination of the volatile iodine fractions. Furthermore, some data were obtained from post-irradiation analysis and iodine concentration may be underestimated at the time of measurements compared with that during irradiation, due to post-irradiation reactions. To complete the existing database, the EPICUR program was launched by IRSN (Institut de Radioprotection et de Surete Nucleaire) and experiments have been performed in the frame of the International Source Term Program (ISTP) to provide on

  16. Complexing properties of the main organic acids used in decontamination solutions and reactions involved in their degradation or elimination

    International Nuclear Information System (INIS)

    Noel, D.; Kerrec, O.; Lantes, B.; Rosset, R.; Bayri, B.; Desbarres, J.; Jardy, A.

    1994-09-01

    This paper presents a study that, parallel with the industrial development of the decontamination chemical process, has been performed more fundamentally on the chemical properties of used products: degradation reaction during process or after decontamination and during wastes treatment. In particular, results show that the organic compounds used have no interaction with resins during radioactive wastes storage and therefore they do not present leaching risk. (authors). 8 refs., 3 figs., 4 tabs

  17. Account of the intratrack radiolytic processes for interpretation of the AMOC spectrum of liquid water

    International Nuclear Information System (INIS)

    Zvezhinskiy, D S; Stepanov, S V; Butterling, M; Wagner, A; Krause-Rehberg, R

    2013-01-01

    Recent development of the Gamma-induced Positron Spectroscopy (GiPS) setup significantly extends applicability of the Age-Momentum Correlation technique (AMOC) for studies of the bulk samples. It also provides many advantages comparing with conventional positron annihilation experiments in liquids, such as extremely low annihilation fraction in vessel walls, absence of a positron source and positron annihilations in it. We have developed a new approach for processing and interpretation of the AMOC-GiPS data based on the diffusion recombination model of the intratrack radiolytic processes. This approach is verified in case of liquid water, which is considered as a reference medium in the positron and positronium chemistry.

  18. Account of the intratrack radiolytic processes for interpretation of the AMOC spectrum of liquid water

    Science.gov (United States)

    Zvezhinskiy, D. S.; Butterling, M.; Wagner, A.; Krause-Rehberg, R.; Stepanov, S. V.

    2013-06-01

    Recent development of the Gamma-induced Positron Spectroscopy (GiPS) setup significantly extends applicability of the Age-Momentum Correlation technique (AMOC) for studies of the bulk samples. It also provides many advantages comparing with conventional positron annihilation experiments in liquids, such as extremely low annihilation fraction in vessel walls, absence of a positron source and positron annihilations in it. We have developed a new approach for processing and interpretation of the AMOC-GiPS data based on the diffusion recombination model of the intratrack radiolytic processes. This approach is verified in case of liquid water, which is considered as a reference medium in the positron and positronium chemistry.

  19. The radiolytic cracking decomposion of the plant cellulose materials and their chemcial properties

    International Nuclear Information System (INIS)

    Shou Hongxia

    1987-01-01

    Under the treatment with high energy radiation, plant cellulose materials undergo a series of changes in chemical and physical properties. This paper describes the chemical changes of water-soluble carbohydrate, easy-to-hydrolyse carbohydrate, hard-to-hydrolyse carbohydrate, amino acid and protein in rice straw after irradiation with 60 Co γ-ray. The content of water-soluble carbohydrate in rice straw can be increased significantly by such treatment. The combination treatment of irradiation and acid or alkali soaker can reduce the dose for the radiolytic cracking decomposition and produce a good effect

  20. Hydrogen output from radiolytic split of water in the presence of some zeolites

    International Nuclear Information System (INIS)

    Cecal, A.; Colisnic, D.; Popa, K.; Paraschivescu, A.; Bilba, N.

    2002-01-01

    Radiolytic decomposition of water under the action of gamma rays in the presence of some zeolites such as ZSM-5, SAPO-5 and MOR was studied. The irradiation was performed using a gamma 60 Co source at an activity of 3 . 10 4 Ci and dose rate 8.3 KGy/h. The stable products of radiolysis as well as the other chemical species were identified by mass spectrometry. The calculated radiochemical yield decreased in order: H-ZSM-5 > Na-ZSM-5 > H-SAPO-5 > MOR and was higher in the presence of these catalysts than in their absence

  1. Iron hexacyanide/cytochrome-C - intramolecular electron transfer and binding constants - (pulse radiolytic study). Progress report

    International Nuclear Information System (INIS)

    Ilan, Y.; Shafferman, A.

    Internal oxidation and reduction rates of horse cytochrome-c in the complexes, CII.Fe/sup III/(CN) -3 6 and CIII.Fe/sup II/(CN) -4 6 , are 4.6.10 4 s -1 and 3.3.10 2 s -1 , respectively. The binding sites of the iron hexacyanide ions on either CII or CIII are kinetically almost indistinguishable; binding constants range from 0.87.10 3 to 2.10 3 M -1 . The present pulse radiolytic kinetic data are compared with that from N.M.R, T-jump and equilibrium dialysis studies

  2. Radiolytic gas generation from cement-based waste hosts for DOE low-level radioactive wastes

    International Nuclear Information System (INIS)

    Dole, L.R.; Friedman, H.A.

    1986-01-01

    Using cement-based immobilization binders with simulated radioactive waste containing sulfate, nitrate, nitrite, phosphate, and fluoride anions, the gamma- and alpha-radiolytic gas generation factors (G/sub t/, molecules/100 eV) and gas compositions were measured on specimens of cured grouts. These tests studied the effects of; (1) waste composition; (2) the sample surface-to-volume ratio; (3) the waste slurry particle size; and (4) the water content of the waste host formula. The radiolysis test vessels were designed to minimize the ''dead'' volume and to simulate the configuration of waste packages

  3. Step-by-Step Simulation of Radiation Chemistry Using Green Functions for Diffusion-Influenced Reactions

    Science.gov (United States)

    Plante, Ianik; Cucinotta, Francis A.

    2011-01-01

    Radiolytic species are formed approximately 1 ps after the passage of ionizing radiation through matter. After their formation, they diffuse and chemically react with other radiolytic species and neighboring biological molecules, leading to various oxidative damage. Therefore, the simulation of radiation chemistry is of considerable importance to understand how radiolytic species damage biological molecules [1]. The step-by-step simulation of chemical reactions is difficult, because the radiolytic species are distributed non-homogeneously in the medium. Consequently, computational approaches based on Green functions for diffusion-influenced reactions should be used [2]. Recently, Green functions for more complex type of reactions have been published [3-4]. We have developed exact random variate generators of these Green functions [5], which will allow us to use them in radiation chemistry codes. Moreover, simulating chemistry using the Green functions is which is computationally very demanding, because the probabilities of reactions between each pair of particles should be evaluated at each timestep [2]. This kind of problem is well adapted for General Purpose Graphic Processing Units (GPGPU), which can handle a large number of similar calculations simultaneously. These new developments will allow us to include more complex reactions in chemistry codes, and to improve the calculation time. This code should be of importance to link radiation track structure simulations and DNA damage models.

  4. Reactions Involving Calcium and Magnesium Sulfates as Potential Sources of Sulfur Dioxide During MSL SAM Evolved Gas Analyses

    Science.gov (United States)

    McAdam, A. C.; Knudson, C. A.; Sutter, B.; Franz, H. B.; Archer, P. D., Jr.; Eigenbrode, J. L.; Ming, D. W.; Morris, R. V.; Hurowitz, J. A.; Mahaffy, P. R.; hide

    2016-01-01

    The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) have analyzed several subsamples of 860 C). Sulfides or Fe sulfates were detected by CheMin (e.g., CB, MJ, BK) and could contribute to the high temperature SO2 evolution, but in most cases they are not present in enough abundance to account for all of the SO2. This additional SO2 could be largely associated with x-ray amorphous material, which comprises a significant portion of all samples. It can also be attributed to trace S phases present below the CheMin detection limit, or to reactions which lower the temperatures of SO2 evolution from sulfates that are typically expected to thermally decompose at temperatures outside the SAM temperature range (e.g., Ca and Mg sulfates). Here we discuss the results of SAM-like laboratory analyses targeted at understanding this last possibility, focused on understanding if reactions of HCl or an HCl evolving phase (oxychlorine phases, chlorides, etc.) and Ca and Mg sulfates can result in SO2 evolution in the SAM temperature range.

  5. The hnRNP 2H9 gene, which is involved in the splicing reaction, is a multiply spliced gene

    DEFF Research Database (Denmark)

    Honoré, B

    2000-01-01

    The hnRNP 2H9 gene products are involved in the splicing process and participate in early heat shock-induced splicing arrest. By combining low/high stringency hybridisation, database search, Northern and Western blotting it is shown that the gene is alternatively spliced into at least six...

  6. Physicochemical properties and radiolytic degradation studies on tri-iso-amyl phosphate (TiAP)

    Energy Technology Data Exchange (ETDEWEB)

    Sreenivasulu, B.; Sivaraman, Nagarajan [Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu (India). Homi Bhabha National Inst.; Suresh, A.; Rajeswari, S.; Ramanathan, N.; Antony, M.P.; Joseph, M. [Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu (India). Chemistry Group

    2017-06-01

    The solvent composed of tri-iso-amyl phosphate (TiAP) in n-dodecane (n-DD) is regarded as a promising candidate for reprocessing of spent fuel. In this context, the radiolytic degradation of a solution of TiAP in n-dodecane was investigated by irradiating the solvent to various absorbed dose levels of γ-radiation. The neat extractant or a solution of extractant in n-dodecane was irradiated in the presence of nitric acid. Physicochemical properties such as density, viscosity and interfacial tension (IFT) were measured for unirradiated and irradiated solutions. The extent of degradation was determined by measuring the variation in extraction behavior of U(VI) and Pu(IV) with irradiated solvent systems. Uranium and plutonium retention with irradiated solvents was also measured. The distribution ratio of uranium and plutonium increased with increase in absorbed dose. Effect of alpha degradation was studied by plutonium retention as a function of time using 1.1 M TiAP/n-DD. Laser desorption/ionization mass spectrometric technique was employed to identify the possible radiolytic degradation products. Similar studies were also carried out with tri-n-butyl phosphate (TBP) based solvent system under identical experimental conditions and the results are compared.

  7. γ-radiolytical degradation of levofloxacin lactate and the activity of the byproducts

    International Nuclear Information System (INIS)

    Cao Dongmei; Zhang Xiaohong; Guan Yu; Zhu Wei; Zhang HaiQian

    2010-01-01

    Recently antibiotics wastewater in environment has induced the increment of bacterial resistance. This paper is to investigate the gamma radiolysis of wastewater containing 10 μg/mL levofloxacin lactate (LVF). It has been found that the antibiotic was removed more than 99% with 1 kGy under air while the G-value decreased with the dose increment.Five main degraded products (m/z 346, 330, 318, 302, 274) and the most probable radiolysis pathway were identified by liquid chromatography-mass spectrometry (LC-MS). Compared with the degradation under N 2 , the radiolytical mechanism was suggested.In the active assay, 2 μg/mL was the inhibitory concentration.Compared with the concentration of 4 μg/mL, the minimal inhibitory concentration (MIC), degraded products analysis can be suggested that the byproduct m/z 346 might have the anti-E. coli activity. It has been shown that 3 kGy is the appropriate dose for the radiolytical treatment of LVF. To sum up, the gamma radiation technique is an effective method for decomposing antibiotics, and it is necessary to take the activity of degraded products into consideration. (authors)

  8. Structural, optical and thermal properties of PVA/CdS nanocomposites synthesized by radiolytic method

    International Nuclear Information System (INIS)

    Kharazmi, Alireza; Saion, Elias; Faraji, Nastaran; Hussin, Roslina Mat; Yunus, W. Mahmood Mat

    2014-01-01

    Monodispersed spherical CdS nanoparticles stabilized in PVA solution were synthesized by the gamma radiolytic method and found the average particle size increased from 12 to 13 nm with the increment of dose from 10 to 40 kGy. The XRD results show that it has crystalline planes of cubic structure with crystal lattice parameter of 5.832 Å. The optical reflectance revealed a band-edge of CdS nanoparticles at about 475 nm and the reflectance wavelength red shifted with increasing dose due to increasing particle size. The thermal conductivity of CdS/PVA nanocomposites measured by the transient hot wire method that revealed a decrement of the thermal conductivity with an increase of dose caused by effect of radiation on crystallinity of the polymer structure. - Highlights: • CdS/PVA nanocomposite was synthesized by radiolytic method from 10 to 40 kGy doses. • The structure of nanocomposite and the effect of dose on structure were investigated by X-ray powder diffraction. • The morphology of nanoparticles and the effect of dose on nanoparticles were observed by transmission electron microscope. • The optical properties of nanocomposite and the effect of radiation were studied by UV–visible spectroscopy and fluorescence spectroscopy. • The thermal properties of nanocomposite and the effect of dose were investigated by the transient hot wire method

  9. Facile radiolytic synthesis of ruthenium nanoparticles on graphene oxide and carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Rojas, J.V., E-mail: jvrojas@vcu.edu [Mechanical and Nuclear Engineering Department, Virginia Commonwealth University, 401 West Main Street, Richmond, Virginia, 23284 (United States); Toro-Gonzalez, M.; Molina-Higgins, M.C. [Mechanical and Nuclear Engineering Department, Virginia Commonwealth University, 401 West Main Street, Richmond, Virginia, 23284 (United States); Castano, C.E., E-mail: cecastanolond@vcu.edu [Nanomaterials Core Characterization Facility, Chemical and Life Science Engineering Department, Virginia Commonwealth University, 601 West Main Street, Richmond, Virginia, 23284 (United States)

    2016-03-15

    Graphical abstract: - Highlights: • Facile radiolytic synthesis of Ru nanoparticles on graphene oxide and carbon nanotubes. • Homogeneously distributed Rh nanoparticles on supports are ∼2.5 nm in size. • Simultaneous reduction of graphene oxide and Ru ions occurs during the synthesis. • Ru-O bonds evidenced the interaction of the nanoparticles with the support. - Abstract: Ruthenium nanoparticles on pristine (MWCNT) and functionalized carbon nanotubes (f-MWCNT), and graphene oxide have been prepared through a facile, single step radiolytic method at room temperature, and ambient pressure. This synthesis process relies on the interaction of high energy gamma rays from a {sup 60}Co source with the water in the aqueous solutions containing the Ru precursor, leading to the generation of highly reducing species that further reduce the Ru metal ions to zero valence state. Transmission electron microscopy and X-Ray diffraction revealed that the nanoparticles were homogeneously distributed on the surface of the supports with an average size of ∼2.5 nm. X-ray Photoelectron spectroscopy analysis showed that the interaction of the Ru nanoparticles with the supports occurred through oxygenated functionalities, creating metal-oxygen bonds. This method demonstrates to be a simple and clean approach to produce well dispersed nanoparticles on the aforementioned supports without the need of any hazardous chemical.

  10. Radiolytic generation of chloro-organic compounds in transuranic and low-level radioactive waste

    International Nuclear Information System (INIS)

    Reed, D.T.; Armstrong, S.C.; Krause, T.R.

    1993-01-01

    The radiolytic degradation of chloro-plastics is being investigated to evaluate the formation of chlorinated volatile organic compounds in radioactive waste. These chlorinated VOCs, when their subsequent migration in the geosphere is considered, are potential sources of ground-water contamination. This contamination is an important consideration for transuranic waste repositories being proposed for the Waste Isolation Pilot Plant project and the several additional low-level radioactive waste sites being considered throughout the United States. The production of chlorinated volatile organic compounds due to the interaction of ionizing radiation with chloro-plastic materials has been well-established in both this work and past studies. This occurs as a result of gamma, beta, and alpha particle interactions with the plastic material. The assemblage of organic compounds generated depends on the type of plastic material, the type of ionizing radiation, the gaseous environment present and the irradiation temperature. In the authors' experiments, gas generation data were obtained by mounting representative plastics near (3 mm) an alpha particle source (Am-241 foil). This assembly was placed in an irradiation vessel which contained air, nitrogen, or a hydrogen/carbon dioxide mixture, at near-atmospheric pressures, to simulate the range of atmospheres likely to be encountered in the subsurface. The gas phase in the vessels are periodically sampled for net gas production. The gas phase concentrations are monitored over time to determine trends and calculate the radiolytic yield for the various gaseous products

  11. Facile radiolytic synthesis of ruthenium nanoparticles on graphene oxide and carbon nanotubes

    International Nuclear Information System (INIS)

    Rojas, J.V.; Toro-Gonzalez, M.; Molina-Higgins, M.C.; Castano, C.E.

    2016-01-01

    Graphical abstract: - Highlights: • Facile radiolytic synthesis of Ru nanoparticles on graphene oxide and carbon nanotubes. • Homogeneously distributed Rh nanoparticles on supports are ∼2.5 nm in size. • Simultaneous reduction of graphene oxide and Ru ions occurs during the synthesis. • Ru-O bonds evidenced the interaction of the nanoparticles with the support. - Abstract: Ruthenium nanoparticles on pristine (MWCNT) and functionalized carbon nanotubes (f-MWCNT), and graphene oxide have been prepared through a facile, single step radiolytic method at room temperature, and ambient pressure. This synthesis process relies on the interaction of high energy gamma rays from a "6"0Co source with the water in the aqueous solutions containing the Ru precursor, leading to the generation of highly reducing species that further reduce the Ru metal ions to zero valence state. Transmission electron microscopy and X-Ray diffraction revealed that the nanoparticles were homogeneously distributed on the surface of the supports with an average size of ∼2.5 nm. X-ray Photoelectron spectroscopy analysis showed that the interaction of the Ru nanoparticles with the supports occurred through oxygenated functionalities, creating metal-oxygen bonds. This method demonstrates to be a simple and clean approach to produce well dispersed nanoparticles on the aforementioned supports without the need of any hazardous chemical.

  12. Investigation of the hydrolytic and radiolytic degradation of HEH[EHP

    International Nuclear Information System (INIS)

    Peterman, Dean Richard; McDowell, Rocklan George; Zarzana, Christopher Andrew; Johnson, Kristyn Marie; Rowe, Salene Marie; Groenewold, Gary Steven

    2016-01-01

    The extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) is a component used in both the Advanced TALSPEAK and ALSEP solvent extraction processes. The most likely compound formed via hydrolytic or radiolytic degradation of HEH[EHP] would be the phosphonic acid 2-ethylhexylphosphonic acid (H2EHP) that is formed by cleavage of the P-O-R bond. Thus far, attempts to detect H2EHP by gas chromatography or mass spectrometry have not been successful. The inability to detect this proposed degradation product in analytical samples is likely due to inadequate analysis techniques, lack of H2EHP production, further decomposition of H2EHP forming products not detectable by the employed analytical techniques, or a combination of all of the above scenarios. In order to address this problem, commercially available alkylphosphonic acids were acquired and used as surrogates for H2EHP in the gas chromatography and mass spectrometry analysis of samples. Once the ability to detect alkylphosphonic acid compounds was confirmed, these analytical techniques were used to confirm the production of H2EHP in samples of HEH[EHP] exposed to nitric acid and nitric acid plus gamma radiation. This report provides a brief summary of results and serves as documentation of the completion the level four milestone M4FT-16IN030102025 “Investigate the hydrolytic and radiolytic degradation of HEH[EHP]”.

  13. The release of stored energy in heavily irradiated NaCl explosive reactions

    NARCIS (Netherlands)

    Vainshtein, D.; Bemt, M. van den; Seinen, J.; Datema, H.C.; Hartog, H.W. den

    1995-01-01

    During irradiation of NaCl with ionizing radiation at moderate temperatures (50-150 degrees C) irregular structures of very fine Na and Cl nano-precipitates are formed. The increase of the temperature to a value between 50 and 250 degrees C might induce explosive reactions between radiolytic Na and

  14. Value of the polymerase chain reaction method for detecting tuberculosis in the bronchial tissue involved by anthracosis.

    Science.gov (United States)

    Mirsadraee, Majid; Shafahie, Ahmad; Reza Khakzad, Mohammad; Sankian, Mojtaba

    2014-04-01

    Anthracofibrosis is the black discoloration of the bronchial mucosa with deformity and obstruction. Association of this disease with tuberculosis (TB) was approved. The objective of this study was to find the additional benefit of assessment of TB by the polymerase chain reaction (PCR) method. Bronchoscopy was performed on 103 subjects (54 anthracofibrosis and 49 control subjects) who required bronchoscopy for their pulmonary problems. According to bronchoscopic findings, participants were classified to anthracofibrosis and nonanthracotic groups. They were examined for TB with traditional methods such as direct smear (Ziehl-Neelsen staining), Löwenstein-Jensen culture, and histopathology and the new method "PCR" for Mycobacterium tuberculosis genome (IS6110). Age, sex, smoking, and clinical findings were not significantly different in the TB and the non-TB groups. Acid-fast bacilli could be detected by a direct smear in 12 (25%) of the anthracofibrosis subjects, and adding the results of culture and histopathology traditional tests indicated TB in 27 (31%) of the cases. Mycobacterium tuberculosis was diagnosed by PCR in 18 (33%) patients, but the difference was not significant. Detection of acid-fast bacilli in control nonanthracosis subjects was significantly lower (3, 6%), but PCR (20, 40%) and accumulation of results from all traditional methods (22, 44%) showed a nonsignificant difference. The PCR method showed a result equal to traditional methods including accumulation of smear, culture, and histopathology.

  15. Hydrogen radiolytic production in light and heavy water mixtures under conditions similar to LOCA (loss of coolant accidents)

    International Nuclear Information System (INIS)

    Garcia Rodenas, L.; Ali, S.P.; Liberman, S.J.

    1987-01-01

    H 2 , HD and D 2 radiolytic yield in heavy and light water mixtures has been determined to supply the necessary data which will allow to make a realistic estimation of the solution of such gas under LOCA conditions as a function of time. (Author)

  16. Pair natural orbital and canonical coupled cluster reaction enthalpies involving light to heavy alkali and alkaline earth metals: the importance of sub-valence correlation

    KAUST Repository

    Minenkov, Yury

    2017-03-07

    In this work, we tested canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) for a set of 32 ligand exchange and association/dissociation reaction enthalpies involving ionic complexes of Li, Be, Na, Mg, Ca, Sr, Ba and Pb(ii). Two strategies were investigated: in the former, only valence electrons were included in the correlation treatment, giving rise to the computationally very efficient FC (frozen core) approach; in the latter, all non-ECP electrons were included in the correlation treatment, giving rise to the AE (all electron) approach. Apart from reactions involving Li and Be, the FC approach resulted in non-homogeneous performance. The FC approach leads to very small errors (<2 kcal mol-1) for some reactions of Na, Mg, Ca, Sr, Ba and Pb, while for a few reactions of Ca and Ba deviations up to 40 kcal mol-1 have been obtained. Large errors are both due to artificial mixing of the core (sub-valence) orbitals of metals and the valence orbitals of oxygen and halogens in the molecular orbitals treated as core, and due to neglecting core-core and core-valence correlation effects. These large errors are reduced to a few kcal mol-1 if the AE approach is used or the sub-valence orbitals of metals are included in the correlation treatment. On the technical side, the CCSD(T) and DLPNO-CCSD(T) results differ by a fraction of kcal mol-1, indicating the latter method as the perfect choice when the CPU efficiency is essential. For completely black-box applications, as requested in catalysis or thermochemical calculations, we recommend the DLPNO-CCSD(T) method with all electrons that are not covered by effective core potentials included in the correlation treatment and correlation-consistent polarized core valence basis sets of cc-pwCVQZ(-PP) quality.

  17. EncM, a versatile enterocin biosynthetic enzyme involved in Favorskii oxidative rearrangement, aldol condensation, and heterocycle-forming reactions

    Science.gov (United States)

    Xiang, Longkuan; Kalaitzis, John A.; Moore, Bradley S.

    2004-01-01

    The bacteriostatic natural product enterocin from the marine microbe “Streptomyces maritimus” has an unprecedented carbon skeleton that is derived from an aromatic polyketide biosynthetic pathway. Its caged tricyclic, nonaromatic core is derived from a linear poly-β-ketide precursor that formally undergoes a Favorskii-like oxidative rearrangement. In vivo characterization of the gene encM through mutagenesis and heterologous biosynthesis demonstrated that its protein product not only is solely responsible for the oxidative C—C rearrangement, but also facilitates two aldol condensations plus two heterocycle forming reactions. In total, at least five chiral centers and four rings are generated by this multifaceted flavoprotein. Heterologous expression of the enterocin biosynthesis genes encABCDLMN in Streptomyces lividans resulted in the formation of the rearranged metabolite desmethyl-5-deoxyenterocin and the shunt products wailupemycins D-G. Addition of the methyltransferase gene encK, which was previously proposed through mutagenesis to additionally assist EncM in the Favorskii rearrangement, shifted the production to the O-methyl derivative 5-deoxyenterocin. The O-methyltransferase EncK seems to be specific for the pyrone ring of enterocin, because bicyclic polyketides bearing pyrone rings are not methylated in vivo. Expression of encM with different combinations of homologous actinorhodin biosynthesis genes did not result in the production of oxidatively rearranged enterocin-actinorhodin hybrid compounds as anticipated, suggesting that wild-type EncM may be specific for its endogenous type II polyketide synthase or for benzoyl-primed polyketide precursors. PMID:15505225

  18. Attack modes and defence reactions in pathosystems involving Sclerotinia sclerotiorum, Brassica carinata, B. juncea and B. napus.

    Science.gov (United States)

    Uloth, Margaret B; Clode, Peta L; You, Ming Pei; Barbetti, Martin J

    2016-01-01

    Sclerotinia stem rot (SSR, Sclerotinia sclerotiorum) is a damaging disease of oilseed brassicas world-wide. Host resistance is urgently needed to achieve control, yet the factors that contribute to stem resistance are not well understood. This study investigated the mechanisms of resistance to SSR. Stems of 5-week-old Brassica carinata, B. juncea and B. napus of known resistance were infected via filter paper discs impregnated with S. sclerotiorum mycelium under controlled conditions. Transverse sections of the stem and portions of the stem surface were examined using optical and scanning electron microscopy. The association of anatomical features with the severity of disease (measured by mean lesion length) was determined. Several distinct resistance mechanisms were recorded for the first time in these Brassica-pathogen interactions, including hypersensitive reactions and lignification within the stem cortex, endodermis and in tissues surrounding the lesions. Genotypes showing a strong lignification response 72 h post-infection (hpi) tended to have smaller lesions. Extensive vascular invasion by S. sclerotiorum was observed only in susceptible genotypes, especially in the vascular fibres and xylem. Mean lesion length was negatively correlated with the number of cell layers in the cortex, suggesting progress of S. sclerotiorum is impeded by more cell layers. Hyphae in the centre of lesions became highly vacuolate 72 hpi, reflecting an ageing process in S. sclerotiorum hyphal networks that was independent of host resistance. The infection process of S. sclerotiorum was analogous in B. carinata and B. napus. Infection cushions of the highly virulent isolate of S. sclerotiorum MBRS-1 were grouped together in dense parallel bundles, while hyphae in the infection cushions of a less aggressive isolate WW-3 were more diffuse, and this was unaffected by host genotype. A variety of mechanisms contribute to host resistance against S. sclerotiorum across the three

  19. Identification of radiolytic products from N-nitrosodimethylamine and N-nitrosopyrrolidine by gas chromatography and mass spectrometry[Gamma irradiation; N-Nitrosodimethylamine; N-Nitrosopyrrolidine; Radiolysis

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, H -J; Lee, C -H; Kim, J -H; Han, S -B; Jo, Cheorun; Kim, Sung; Byun, M -W

    2004-01-01

    The radiolytic products of N-nitrosodimethylamine (NDMA) and N-nitrosopyrrolidine (NPYR) dissolved in dichloromethane (DCM) were identified after gamma irradiation. The UV spectra of NDMA and NPYR indicated that irradiation reduced the typical peak of NDMA at 258 nm and NPYR at 260 nm.The major radiolytic components identified in irradiated NDMA were ethyl acetate and 2-dimethyl propanol. The irradiated NPYR dissolved in DCM and produced 2-butanone and 2-methyl-6-propyl piperidine as the major radiolytic components. 2-Methyl-6-propyl piperidine was the component detected in the greatest concentration in irradiated NPYR.

  20. How bimetallic electrocatalysts does work for reactions involved in fuel cells? Example of ethanol oxidation and comparison to methanol

    Energy Technology Data Exchange (ETDEWEB)

    Leger, J.-M.; Rousseau, S.; Coutanceau, C.; Hahn, F.; Lamy, C. [UMR 6503, Electrocatalysis Group, CNRS - University of Poitiers, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex (France)

    2005-09-05

    Carbon-supported Pt-based nanosized electrocatalysts can be synthesized for methanol and ethanol electrooxidation. The electrocatalytic activity of Pt can be greatly enhanced by using Pt-Ru/C for methanol oxidation or Pt-Sn/C for ethanol oxidation. In situ IR reflectance spectroscopy is a convenient tool to better understand the importance of the different adsorption steps involved in the mechanisms of electrooxidation. With Pt/C, it appears clearly that linearly adsorbed CO is the poisoning species formed during methanol and ethanol oxidation. In the case of methanol, even with Pt-Ru/C (the most active catalyst), adsorbed CO is also a reactive intermediate. The enhancement of activity observed in such a case is due to the possibility to activate water at lower potentials in the presence of Ru. With Pt-Sn/C, the mechanism of the electrooxidation of ethanol is strongly modified. If at low potentials, poisoning with adsorbed CO still exists (as with Pt/C), the oxidation of ethanol at potentials greater than 0.4 V versus RHE occurs through an adsorbed acetyl species which can lead to the formation of acetaldehyde and acetic acid as final products in addition to carbon dioxide. (author)

  1. Early events following radiolytic and photogeneration of radical cations in hydrocarbons

    International Nuclear Information System (INIS)

    Werst, D.W.; Trifunac, A.D.

    1992-01-01

    Real-time studies in hydrocarbons have revealed a richness of chemistry involving the initial ionic species produced in radiolysis and photoionization. A modified radical cation mechanism patterned after the core mechanism for alkane radiolysis-formation of radical cations and their disappearance via ion-molecule reactions - is capable of explaining a wide range of observations in high-energy photochemistry, and thus unifies two high-energy regimes. Fundamental studies of radical cations suggest strategies for mitigating radiation effects in materials

  2. Radiolytic preparation of ETFE and PFA based anion exchange membranes for alkaline fuel cell

    International Nuclear Information System (INIS)

    Ko, Beom-Seok; Sohn, Joon-Yong; Nho, Young-Chang; Shin, Junhwa

    2011-01-01

    In this study, a versatile monomer, vinylbenzyl chloride (VBC) was radiolytically grafted onto a partially fluorinated ETFE and perfluorinated polymer PFA films. The VBC grafted films were treated with trimethylamine to prepare the alkaline anion exchange membranes (AAEMs). No significant differences in the ion exchange capacities and water uptakes were observed between the ETFE and PFA based AAEMs with similar degree of grafting (DOG). However, the distribution patterns of the graft chains over the cross-section of the ETFE and PFA based AAEMs were found to be quite different; the even distribution was observed from the ETFE based AAEMs while the uneven distribution was observed from the PFA based AAEMs. It was also found that the PFA based AAEMs have the higher ionic conductivity and chemical stability, compared to the ETFE based AAEMs.

  3. Safety operation of chromatography column system with discharging hydrogen radiolytically generated

    International Nuclear Information System (INIS)

    Watanabe, S; Sano, Y.; Nomura, K.; Koma, Y.; Okamoto, Y.

    2015-01-01

    The extraction chromatography technology is one of the promising methods for the partitioning of minor actinides (Am and Cm) from spent nuclear fuels. In the extraction chromatography system, the accumulation of hydrogen gas in the chromatography column is suspected to lead to fire or explosion. In order to prevent hazardous accidents, it is necessary to evaluate behaviors of gas radiolytically generated inside the column. In this study, behaviors of gas inside the extraction chromatography column were investigated through experiments and Computation Fluid Dynamics (CFD) simulation. N_2 gas once accumulated as bubbles in the packed bed was hardly discharged by the flow of mobile phase. However, the CFD simulation and X-ray imaging on γ-ray irradiated column revealed that during operation the hydrogen gas generated in the column was dissolved into the mobile phase without accumulation and then discharged. (authors)

  4. Radiolytic effect on the chemical state of iodine in aqueous solution

    International Nuclear Information System (INIS)

    Shiraishi, H.; Kimiya, T.; Ohmae, M.; Ishigure, K.

    1988-01-01

    The oxidation state of iodine dissolved in an aqueous solution is easily changed in the presence of radiation field. Hence, it is essential to take the radiolytic effect into account when one is to estimate chemical forms of iodine after being released into the containment under an LOCA condition. This paper summarizes results of γ-radiolysis experiments on aqueous solutions containing iodine species, which have been carried out to extend the previously reported study on the same system. Variation in iodine product distribution with time has been examined as before, utilizing a flow system under irradiation. Attention has been paid to the effect of oxygen, to that of an initial oxidation state of iodine, and to the influence of temperature. Some kinetic analysis on the system was also undertaken

  5. Gamma Radiolytic Degradation of Heptachlor in Methanol and Monitoring of Degradation by HPLC

    International Nuclear Information System (INIS)

    Riaz, M.; Butt, S.B.

    2014-01-01

    Removal of known insecticide Heptachlor (HPTC) in methanol solution by gamma-rays under varied experimental conditions has been optimized. Air saturated solution of HPTC was irradiated at x-rays dose from 1 to 10 kGys. The extent of radiolytic degradation was monitored by reversed phase high performance liquid chromatography (HPLC) coupled with UV detector. At dose of 10 kGys gamma 98 % of HPTC was degraded. The degradation of HPTC occurs by CH/sub 3/O and CH/sub 2/OH radicals generated by methanol radiolysis. It is concluded that gamma-rays can remove Persistent Organic Pollutants (POPs) form environmental matrices. It can decrease the harmful properties of these POPs by their transformation into less resistant fragments to biological / natural elimination in the aquatic atmosphere. (author)

  6. Fast repair of oxidizing OH adducts of DNA by hydroxycinnamic acid derivatives. A pulse radiolytic study

    International Nuclear Information System (INIS)

    Yue Jiang; Lin Weizhen; Yao Side; Lin Nianyun; Zhu Dayuan

    1999-01-01

    Using pulse radiolytic techniques, it has been demonstrated that the interactions of oxidizing OH adducts of DNA (ssDNA and dsDNA), polyA and polyG with hydroxycinnamic acid derivatives proceed via an electron transfer process (k=5-30x10 8 dm 3 mol -1 s -1 ). In addition, the rates for fast repair of OH adducts of dAMP, polyA and DNA (ssDNA and dsDNA) are slower than the corresponding rates for the rest OH adducts of DNA constituents. The slower rates for repair of oxidizing OH adducts of dAMP may be the rate determining step during the interaction of hydroxycinnamic acid derivatives with OH adducts of DNA containing the varieties of OH adducts of DNA constituents

  7. Pair natural orbital and canonical coupled cluster reaction enthalpies involving light to heavy alkali and alkaline earth metals: the importance of sub-valence correlation.

    Science.gov (United States)

    Minenkov, Yury; Bistoni, Giovanni; Riplinger, Christoph; Auer, Alexander A; Neese, Frank; Cavallo, Luigi

    2017-04-05

    In this work, we tested canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) for a set of 32 ligand exchange and association/dissociation reaction enthalpies involving ionic complexes of Li, Be, Na, Mg, Ca, Sr, Ba and Pb(ii). Two strategies were investigated: in the former, only valence electrons were included in the correlation treatment, giving rise to the computationally very efficient FC (frozen core) approach; in the latter, all non-ECP electrons were included in the correlation treatment, giving rise to the AE (all electron) approach. Apart from reactions involving Li and Be, the FC approach resulted in non-homogeneous performance. The FC approach leads to very small errors (correlation effects. These large errors are reduced to a few kcal mol -1 if the AE approach is used or the sub-valence orbitals of metals are included in the correlation treatment. On the technical side, the CCSD(T) and DLPNO-CCSD(T) results differ by a fraction of kcal mol -1 , indicating the latter method as the perfect choice when the CPU efficiency is essential. For completely black-box applications, as requested in catalysis or thermochemical calculations, we recommend the DLPNO-CCSD(T) method with all electrons that are not covered by effective core potentials included in the correlation treatment and correlation-consistent polarized core valence basis sets of cc-pwCVQZ(-PP) quality.

  8. Complexation of Cu2+, Ni2+ and UO22+ by radiolytic degradation products of bitumen

    International Nuclear Information System (INIS)

    Loon, L.R. Van; Kopajtic, Z.

    1990-05-01

    The radiolytic degradation of bitumen was studied under conditions which reflect those which will exist in the near field of a cementitious radioactive waste repository. The potential complexation capacity of the degradation products was studied and complexation experiments with Cu 2+ , Ni 2+ and UO 2 2+ were performed. In general 1:1 complexes with Cu 2+ , Ni 2+ and UO 2 2+ , with log K values of between 5.7 and 6.0 for Cu 2+ , 4.2 for Ni 2+ and 6.1 for UO 2 2+ , were produced at an ionic strength of 0.1 M. The composition of the bitumen water was analysed by GC-MS and IC. The major proportion of the bitumen degradation products in solution were monocarboxylic acids (acetic acid, formic acid, myric acid, stearic acid ...), dicarboxylic acids (oxalic acid, phthalic acid) and carbonates. The experimentally derived log K data are in good agreement with the literature and suggest that oxalate determines the speciation of Cu 2+ , Ni 2+ and UO 2 2+ in the bitumen water below pH=7. However, under the high pH conditions typical of the near field of a cementitious repository, competition with OH-ligands will be large and oxalate, therefore, will not play a significant role in the speciation of radionuclides. The main conclusion of the study is that the radiolytic degradation products of bitumen will have no influence on radionuclide speciation in a cementitious near field and, as such, need not to be considered in the appropriate safety assessment models. (author) 12 figs., 11 tabs., 31 refs

  9. Toxicological potential of 2-alkylcyclobutanones--specific radiolytic products in irradiated fat-containing food--in bacteria and human cell lines

    NARCIS (Netherlands)

    Hartwig, A; Pelzer, A; Burnouf, D; Titéca, H; Delincée, H; Briviba, K; Soika, C; Hodapp, C; Raul, F; Miesch, M; Werner, D; Horvatovich, P; Marchioni, E

    2007-01-01

    Food irradiation has been considered as a safe processing technology to improve food safety and preservation, eliminating efficiently bacterial pathogens, parasites and insects. This study aims to characterize the toxicological potential of 2-alkylcyclobutanones (2-ACBs), radiolytic derivatives of

  10. Role of radiolytically generated species in radiation induced polymerization of sodium p-styrene sulphonate (SSS) in aqueous solution: Steady state and pulse radiolysis study

    International Nuclear Information System (INIS)

    Bhardwaj, Y.K.; Mohan, H.; Sabharwal, S.; Majali, A.B.

    2000-01-01

    Radiation induced polymerization of sodium p-styrene sulphonate (SSS) in aqueous solution has been investigated by steady state and pulse radiolysis techniques. Effect of dose, dose rate, monomer concentration, pH and ambient conditions on polymerization was investigated. The reactions of primary radicals of water radiolysis such as OH radical, e - aq , H atom, O· - and some oxidizing radicals like N· 3 , Cl· - 2 ,Br· - 2 , and reducing specie like CO· - 2 with SSS have also been investigated. SSS reacts with OH radical with a rate constant of 5.9x10 9 dm 3 mol -1 s -1 at pH 6.3. The results indicate that ∼83% of OH radicals undergo electron transfer reaction resulting in a cation radical species while remaining ∼17% react via addition reaction. The hydrated electron reacts with SSS with a rate constant 1.3x10 10 dm 3 mol -1 s -1 to form an anion that undergoes fast protonation to form H-adduct at pH 6.3. At high pH (>10) the anion is able to transfer electron to methyl vilogen and p-nitro aceto phenone (p-NAP) where as H-adduct is unable to transfer electron. At pH ∼1 H atom reaction with SSS is diffusion controlled with a rate constant of 5x10 9 dm 3 mol -1 s -1 and results in formation of H adduct. It was seen that anion reacts with solute an order faster than cation generated radiolytically indicating anionic initiation of polymerization of SSS. Molecular weight of the polymer formed by radiation polymerization, determined by viscosity measurement, are of the order of 10 7 and higher molecular weight polymers are obtained at lower dose rates. In presence of a crosslinking agent gelation of polymer is much faster than the monomer and a polymer concentration ∼20% is most efficiently crosslinked. (author)

  11. Understanding the sorption behavior of Pu{sup 4+} on poly(amidoamine) dendrimer functionalized carbon nanotube. Sorption equilibrium, mechanism, kinetics, radiolytic stability, and back-extraction studies

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Parveen [Indian Institute of Technology, Himachal Pradesh (India); Sengupta, Arijit [Bahbha Atomic Research Centre, Mumbai (India). Radiochemistry Div.; Deb, Ashish Kumar Singha; Ali, S. Musharaf [Bahbha Atomic Research Centre, Mumbai (India). Chemical Engineering Div.; Homi Bhabha National Institute, Mumbai (India); Dasgupta, Kinshuk [Bhabha National Institute, Mumbai (India). Mechanical Metallurgy Div.

    2017-07-01

    Poly(amidoamine) dendrimer functionalized carbon nanotube was demonstrated as highly efficient sorbent of the Pu{sup 4+} from radioactive waste solution. The second generation dendrimer was found to have more efficiency as compared to the 1{sup st} generation might be due to the availability of more functionality for coordinating to the Pu{sup 4+} ion. Analysis of different isotherm models revealed that, Langmuir isotherm was predominantly operating through chemi-sorption (with the sorption energy 10.07 and 16.95 kJ mol{sup -1} for 1{sup st} and 2{sup nd} generation dendrimer) with the sorption capacity 89.22 mg g{sup -1} and 92.48 mg g{sup -1} for 1{sup st} and 2{sup nd} generation dendrimer, respectively. Analysis of different sorption kinetics model revealed that the sorption proceeded via pseudo 2{sup nd} order reaction. The 2{sup nd} generation dendrimer was found to be radiolytically more stable while oxalic acid was found to be suitable for quantitative back extraction of Pu{sup 4+}.

  12. Proton-transfer reactions in ionized gases

    International Nuclear Information System (INIS)

    Stiller, W.; Schmidt, R.; Schuster, R.

    1985-01-01

    Ion-molecule reactions play an important role in various radiolytic processes, e.g. gas-pulse radiolysis, environmental research. For a discussion of mechanisms rate coefficients have to be assessed. Here gas-phase rate coefficients of ion-(polar) molecule reactions are calculated using the ideas of interaction potentials, reactive cross-sections and distribution functions of the translational energies of both the reactants (ions I, molecules M). The starting point of our approach, directed especially to gas-phase proton-transfer reactions, is the idea that the rate coefficient k can be calculated as an ion-molecule capture-rate coefficient multiplied by a 'steric factor' representing the probability for proton transfer. Mutual capture of the reaction partners within a possible reaction zone is caused by the physical interaction between an ion and a polar molecule. A model is discussed. Results are presented. (author)

  13. Reactions of melatonin with radicals in deoxygenated aqueous solution

    International Nuclear Information System (INIS)

    Stasica, P.; Ulanski, P.; Rosiak, J.M.

    1998-01-01

    Reactions of melatonin (N-acetyl-5-methoxytryptamine) with radiolytically generated radicals were studied. Reaction of melatonin with OH radicals is diffusion-controlled (k=1.2 x 10 10 dm 3 mol -1 x s -1 ), the main (but not the only one) intermediate being the indolyl-type radical, while the rate constant for the reaction with hydrated electrons is k=4.3 x 10 8 dm 3 x mol -1 x s -1 . Melatonin is capable of scavenging tert-butanol radicals, while its reactivity towards polymer radicals of poly(acrylic acid) and poly(vinyl pyrrolidone) is very low. (author)

  14. Degradation Mechanism of Poly(Ether-Urethane) Estane Induced by High Energy Radiation (III) : Radiolytic Gases and Water Soluble Products

    International Nuclear Information System (INIS)

    Dannoux, A.

    2006-01-01

    Within the framework of nuclear waste management, there is interest in the prediction of long-term behaviour of organic materials subjected to high energy radiation. Once organic waste has been stored, gases and low molecular products might be generated from materials irradiated by radionuclides. Long-term behaviour of organic material in nuclear waste has several common concerns with radiation ageing of polymers. But a more detailed description of the chemical evolution is needed for nuclear waste management. In a first approach, an extensive work on radiation ageing is used to identify the different processes encountered during the degradation of a polyurethane, including oxidation dose rate-effects and influence of dose on the oxidation mechanism. In a second approach, a study is performed to identify and quantify gases and possible production of water soluble chemical complexing agents which might enhance radionuclides migration away from the repository. In this work, we present results concerning the production of radiolytic gases and the formation of water soluble oligomers reached with leaching tests Films were made from a poly(ether-urethane) synthesized from methylene bis(p-phenyl isocyanate) (MDI) and poly(tetramethylene glycol) (PTMG) with 1,4 butanediol (BD) and were irradiated by high-energy electron beam to cover a wide doses range and by γ rays to determine the formation/consumption yields of gases. They were measured by mass spectrometry and gas-chromatography/mass spectrometry (GC/MS). The migration of water soluble oligomers in water was reached by measuring the weight loss versus leaching time. The identification of oligomers was performed by using a mass spectrometry with an electrospray ionisation interface (ESI-MS-MS). The analysis of radiolytic gases indicates the formation of H 2 , CO 2 and CO with respective radiolytic yields of 1, 0.5 and 0.3 molecule/100 eV. The consumption of O 2 is evaluated to 6 molecules/100 eV. For absorbed doses

  15. Atypical profiles and modulations of heme-enzymes catalyzed outcomes by low amounts of diverse additives suggest diffusible radicals' obligatory involvement in such redox reactions.

    Science.gov (United States)

    Manoj, Kelath Murali; Parashar, Abhinav; Venkatachalam, Avanthika; Goyal, Sahil; Satyalipsu; Singh, Preeti Gunjan; Gade, Sudeep K; Periyasami, Kalaiselvi; Jacob, Reeba Susan; Sardar, Debosmita; Singh, Shanikant; Kumar, Rajan; Gideon, Daniel A

    2016-06-01

    Peroxidations mediated by heme-enzymes have been traditionally studied under a single-site (heme distal pocket), non-sequential (ping-pong), two-substrates binding scheme of Michaelis-Menten paradigm. We had reported unusual modulations of peroxidase and P450 reaction outcomes and explained it invoking diffusible reactive species [Manoj, 2006; Manoj et al., 2010; Andrew et al., 2011, Parashar et al., 2014 & Venkatachalam et al., 2016]. A systematic investigation of specific product formation rates was undertaken to probe the hypothesis that involvement of diffusible reactive species could explain undefined substrate specificities and maverick modulations (sponsored by additives) of heme-enzymes. When the rate of specific product formation was studied as a function of reactants' concentration or environmental conditions, we noted marked deviations from normal profiles. We report that heme-enzyme mediated peroxidations of various substrates are inhibited (or activated) by sub-equivalent concentrations of diverse redox-active additives and this is owing to multiple redox equilibriums in the milieu. At low enzyme and peroxide concentrations, the enzyme is seen to recycle via a one-electron (oxidase) cycle, which does not require the substrate to access the heme centre. Schemes are provided that explain the complex mechanistic cycle, kinetics & stoichiometry. It is not obligatory for an inhibitor or substrate to interact with the heme centre for influencing overall catalysis. Roles of diffusible reactive species explain catalytic outcomes at low enzyme and reactant concentrations. The current work highlights the scope/importance of redox enzyme reactions that could occur "out of the active site" in biological or in situ systems. Copyright © 2016 Elsevier B.V. and Société française de biochimie et biologie Moléculaire (SFBBM). All rights reserved.

  16. Hydrogen radiolytic release from zeolite 4A/water systems under γ irradiations

    International Nuclear Information System (INIS)

    Frances, Laëtitia; Grivet, Manuel; Renault, Jean-Philippe; Groetz, Jean-Emmanuel; Ducret, Didier

    2015-01-01

    Although the radiolysis of bulk water is well known, some questions remain in the case of adsorbed or confined water, especially in the case of zeolites 4A, which are used to store tritiated water. An enhancement of the production of hydrogen is described in the literature for higher porous structures, but the phenomenon stays unexplained. We have studied the radiolysis of zeolites 4A containing different quantities of water under 137 Cs gamma radiation. We focused on the influence of the water loading ratio. The enhancement of hydrogen production compared with bulk water radiolysis has been attributed to the energy transfer from the zeolite to the water, and to the influence of the water structure organization in the zeolite. Both were observed separately, with a maximum efficiency for energy transfer at a loading ratio of about 13%, and a maximum impact of structuration of water at a loading ratio of about 4%. - Highlights: • We irradiated samples of zeolites 4A which contained different quantities of water. • We measured the quantity of hydrogen released. • Hydrogen radiolytic yields, present two maxima, for two water loading ratios. • Hydrogen release is enhanced by the strength of the zeolite/water interaction. • Hydrogen release is enhanced by the quantity of water interacting with the zeolite

  17. Structural, Optical and Electrical Properties of PVA/PANI/Nickel Nanocomposites Synthesized by Gamma Radiolytic Method

    Directory of Open Access Journals (Sweden)

    Abdo Mohd Meftah

    2014-09-01

    Full Text Available This article reports a simultaneous synthesis of polyaniline (PANI and nickel (Ni nanoparticles embedded in polyvinyl alcohol (PVA film matrix by gamma radiolytic method. The mechanism of formation of PANI and Ni nanoparticles were proposed via oxidation of aniline and reduction of Ni ions, respectively. The effects of dose and Ni ions concentration on structural, optical, and electrical properties of the final PVA/PANI/Ni nanocomposites film were carefully examined. The structural and morphological studies show the presence of PANI with irregular granular microstructure and Ni nanoparticles with spherical shape and diameter less than 60 nm. The average particle size of Ni nanoparticles decreased with increasing dose and decreasing of precursor concentration due to increase of nucleation process over aggregation process during gamma irradiation. The optical absorption spectra showed that the absorption peak of Ni nanoparticles at about 390 nm shifted to lower wavelength and the absorbance increased with increasing dose. The formation of PANI was also revealed at 730 nm absorption peak with the absorbance increasing by the increase of dose. The electrical conductivity increased with increasing of dose and chlorine concentration due to number of polarons formation increases in the PVA/PANI/Ni nanocomposites.

  18. Time-dependent radiolytic product concentrations in the water flow of a spinning wheel target

    International Nuclear Information System (INIS)

    Burns, W.G.; Goodall, J.A.B.

    1989-01-01

    Using the Harwell Facsimile computer simulation package, values of water radiolytic product concentrations, for both transient radicals and stable molecules were calculated for a single revolution of the cooling water at 75 0 C in a spallation neutron source target wheel irradiated with 1000 MeV protons and consequential secondary radiation. The radiation was pulsed except for part of the γ radiation, which was continuous. The stable product concentrations at first rose and eventually came to steady values before the end of the revolution. Comparison with results for steady radiation suggested that with the mixed radiation molecular products from the more densely ionizing radiation were largely destroyed by the radicals from the more lightly ionizing radiation. The distribution of the dose rate in time and space also tended to give a lower extent of radiolysis than calculated for uniform irradiation at the arithmetic mean dose rate. The effect of a second revolution on the diluted products showed a smaller increase in product concentrations than for the first revolution. The Authors consider that the extent of radiolysis should be manageable. (author)

  19. Influence of concentration on the radiolytic decomposition of thiamine, riboflavin, and pyridoxine in aqueous solution

    Directory of Open Access Journals (Sweden)

    Guadalupe Albarrán

    2014-10-01

    Full Text Available Vitamin loss during irradiation has been claimed as a critical area in food irradiation technology, especially that of thiamine (B1, which has been considered as the most sensitive to radiation. Although it has been suggested that no vitamin deficiency could result from consuming irradiated food, a long debate on the loss of vitamins and other nutrients during food irradiation has been maintained by the lack of experimental studies monitoring decomposition rates at different concentrations and doses. Since thiamine, riboflavin, and pyridoxine are labile vitamins, this study has focused on their radiolytic decomposition in dilute aqueous solutions in the presence of air. The decomposition process was followed by HPLC and UV-spectroscopy. The results obtained in aqueous solutions showed a dependence of the decomposition as a nonlinear function of the dose. Of these three compounds, the decomposition was higher for thiamine than for riboflavin and even less in pyridoxine.

  20. Novel Radiolytic Rotenone Derivative, Rotenoisin B with Potent Anti-Carcinogenic Activity in Hepatic Cancer Cells

    Directory of Open Access Journals (Sweden)

    Srilatha Badaboina

    2015-07-01

    Full Text Available Rotenone, isolated from roots of derris plant, has been shown to possess various biological activities, which lead to attempting to develop a potent drug against several diseases. However, recent studies have demonstrated that rotenone has the potential to induce several adverse effects such as a neurodegenerative disease. Radiolytic transformation of the rotenone with gamma-irradiation created a new product, named rotenoisin B. The present work was designed to investigate the anticancer activity of rotenoisin B with low toxicity and its molecular mechanism in hepatic cancer cells compared to a parent compound, rotenone. Our results showed rotenoisin B inhibited hepatic cancer cells’ proliferation in a dose dependent manner and increased in apoptotic cells. Interestingly, rotenoisin B showed low toxic effects on normal cells compared to rotenone. Mitochondrial transmembrane potential has been decreased, which leads to cytochrome c release. Down regulation of anti-apoptotic Bcl-2 levels as well as the up regulation of proapoptotic Bax levels were observed. The cleaved PARP (poly ADP-ribose polymerase level increased as well. Moreover, phosphorylation of extracellular signal regulated kinase (ERK and p38 slightly up regulated and intracellular reactive oxygen species (ROS increased as well as cell cycle arrest predominantly at the G2/M phase observed. These results suggest that rotenoisin B might be a potent anticancer candidate similar to rotenone in hepatic cancer cells with low toxicity to normal cells even at high concentrations compared to rotenone.

  1. Surface capped fluorescent semiconductor nanoparticles: radiolytic synthesis and some of its biological applications

    International Nuclear Information System (INIS)

    Saha, A.

    2006-01-01

    Semiconductor nanocrystals or colloidal quantum dots (QD's) have generated great research interest because of their unusual properties arising out of quantum confinement effects. Many researchers in the field of nanotechnology focus on the 'high quality' semiconductor quantum dots. A good synthetic route should yield nanoparticles with narrow size distribution, good crystallinity, high photostability, desired surface properties and high photoluminescence quantum efficiency. In the domain of colloidal chemistry, reverse micellar synthesis, high temperature thermolysis using organometallic precursors and synthesis in aqueous media using polyphosphates or thiols as stabilizers are the most prominent ones. In contrast, γ-radiation assisted synthesis can offer a simplified approach to prepare size-controlled nanoparticles at room temperature. Syntheses of thiol-capped II-VI nanoparticles by radiolytic method, its characterization and some of its luminescence-based applications of biological relevance will be presented. The versatility of thiols (RSH) can be emphasized here as changing the R-group imparts different functionality to the particles and thus chemical behavior of the particles can be manipulated according to the application intended for. (authors)

  2. Effects of urban air pollution on the inflammatory reaction: involvement of the chemokine pathways; Impact de la pollution atmospherique urbaine sur la reponse inflammatoire: implication des chimiokines

    Energy Technology Data Exchange (ETDEWEB)

    Fahy, O.

    2000-12-01

    Urban air pollution is both gaseous and particulate, and diesel exhausts are now the main source of particles. Diesel particles consist of a carbon core with multiple adsorbed organic compounds, among witch poly-aromatic hydrocarbons. These diesel particles and associated poly-aromatic hydrocarbons are likely to play a role in the recent increase in allergic diseases. In this study, we evaluated the effects of diesel organic extracts on the initiation and the orientation of the allergen-dependent inflammatory reaction by analyzing the dis-regulation of a family of mediators involved in cellular recruitment: the chemokines. We demonstrated that mononuclear cells and alveolar macrophages from normal subjects displayed a dis-regulation in pro-inflammatory chemokine expression and production (IL-8, MCP-1, RANTES) when exposed to diesel organic extracts. In addition we observed a synergy between the effects of diesel and allergen when cells from allergic patients were exposed to both simultaneously, leading to a strong over-production of chemokines, and to the increased capacity of recruiting effector cells such as neutrophils and eosinophils. The MAP kinase pathways seemed largely involved in the transduction of diesel and allergen stimulus, since a specific inhibition almost abolished the dis-regulation of chemokine production. Diesel and allergen also appeared to favour the establishment of a type 2 immune response (pro-allergenic), by preferentially recruiting Th2 lymphocytes via the dis-regulation of chemokine expression (MDC and IP-10). Finally, the humanized SCID mouse model grafted with autologous human skin allowed the in vivo evaluation of a local over-production of chemokine, by analyzing the cellular recruitment in the skin after intra-dermal injection of recombinant chemokines. This model appears useful for the study of the mechanisms of cellular recruitment by chemokines and the potential therapeutic approaches. In conclusion, our study underlines the

  3. The regio- and stereospecific synthesis of diarylpropenyllithium compounds from dimethylamino- and dimethylaminomethyl-substituted diarylacetylenes viatransmetallation reactions involving diarylpropenylmagnesium and tin compounds

    NARCIS (Netherlands)

    Koten, G. van; Hoedt, R.W.M. ten; Noltes, J.G.

    1979-01-01

    Dimethylamino- and dimethylaminomethyl-substituted diarylacetylenes were prepared by the Pd(PPh{3}){4}-catalyzed coupling reaction of dimethylamino- and dimethylaminomethyl-substituted aryl halides with arylacetylenes.Reaction of the asymmetric diarylacetylenes with methylmagnesium bromide in the

  4. cycloaddition reactions

    Indian Academy of Sciences (India)

    Unknown

    Molecular Modeling Group, Organic Chemical Sciences, Indian Institute of Chemical Technology,. Hyderabad ... thus obtained are helpful to model the regioselectivity ... compromise to model Diels–Alder reactions involving ...... acceptance.

  5. The diagnosis of microorganism involved in infective endocarditis (IE by polymerase chain reaction (PCR and real-time PCR: A systematic review

    Directory of Open Access Journals (Sweden)

    Reza Faraji

    2018-02-01

    Full Text Available Broad-range bacterial rDNA polymerase chain reaction (PCR followed by sequencing may be identified as the etiology of infective endocarditis (IE from surgically removed valve tissue; therefore, we reviewed the value of molecular testing in identifying organisms' DNA in the studies conducted until 2016. We searched Google Scholar, Scopus, ScienceDirect, Cochrane, PubMed, and Medline electronic databases without any time limitations up to December 2016 for English studies reporting microorganisms involved in infective endocarditis microbiology using PCR and real-time PCR. Most studies were prospective. Eleven out of 12 studies used valve tissue samples and blood cultures while only 1 study used whole blood. Also, 10 studies used the molecular method of PCR while 2 studies used real-time PCR. Most studies used 16S rDNA gene as the target gene. The bacteria were identified as the most common microorganisms involved in infective endocarditis. Streptococcus spp. and Staphylococcus spp. were, by far, the most predominant bacteria detected. In all studies, PCR and real-time PCR identified more pathogens than blood and tissue cultures; moreover, the sensitivity and specificity of PCR and real-time PCR were more than cultures in most of the studies. The highest sensitivity and specificity were 96% and 100%, respectively. The gram positive bacteria were the most frequent cause of infective endocarditis. The molecular methods enjoy a greater sensitivity compared to the conventional blood culture methods; yet, they are applicable only to the valve tissue of the patients undergoing cardiac valve surgery.

  6. The diagnosis of microorganism involved in infective endocarditis (IE) by polymerase chain reaction (PCR) and real-time PCR: A systematic review.

    Science.gov (United States)

    Faraji, Reza; Behjati-Ardakani, Mostafa; Moshtaghioun, Seyed Mohammad; Kalantar, Seyed Mehdi; Namayandeh, Seyedeh Mahdieh; Soltani, Mohammadhossien; Emami, Mahmood; Zandi, Hengameh; Firoozabadi, Ali Dehghani; Kazeminasab, Mahmood; Ahmadi, Nastaran; Sarebanhassanabadi, Mohammadtaghi

    2018-02-01

    Broad-range bacterial rDNA polymerase chain reaction (PCR) followed by sequencing may be identified as the etiology of infective endocarditis (IE) from surgically removed valve tissue; therefore, we reviewed the value of molecular testing in identifying organisms' DNA in the studies conducted until 2016. We searched Google Scholar, Scopus, ScienceDirect, Cochrane, PubMed, and Medline electronic databases without any time limitations up to December 2016 for English studies reporting microorganisms involved in infective endocarditis microbiology using PCR and real-time PCR. Most studies were prospective. Eleven out of 12 studies used valve tissue samples and blood cultures while only 1 study used whole blood. Also, 10 studies used the molecular method of PCR while 2 studies used real-time PCR. Most studies used 16S rDNA gene as the target gene. The bacteria were identified as the most common microorganisms involved in infective endocarditis. Streptococcus spp. and Staphylococcus spp. were, by far, the most predominant bacteria detected. In all studies, PCR and real-time PCR identified more pathogens than blood and tissue cultures; moreover, the sensitivity and specificity of PCR and real-time PCR were more than cultures in most of the studies. The highest sensitivity and specificity were 96% and 100%, respectively. The gram positive bacteria were the most frequent cause of infective endocarditis. The molecular methods enjoy a greater sensitivity compared to the conventional blood culture methods; yet, they are applicable only to the valve tissue of the patients undergoing cardiac valve surgery. Copyright © 2017. Published by Elsevier Taiwan.

  7. CrWSKP1, an SKP1-like Gene, Is Involved in the Self-Incompatibility Reaction of "Wuzishatangju" (Citrus reticulata Blanco).

    Science.gov (United States)

    Li, Peng; Miao, Hongxia; Ma, Yuewen; Wang, Lu; Hu, Guibing; Ye, Zixing; Zhao, Jietang; Qin, Yonghua

    2015-09-09

    Plant S-phase kinase-associated protein 1 (SKP1) genes play crucial roles in plant development and differentiation. However, the role of SKP1 in citrus is unclear. Herein, we described a novel SKP1-like gene, designated as CrWSKP1, from "Wuzishatangju" (Citrus reticulata Blanco). The cDNA sequence of CrWSKP1 is 779 base pairs (bp) and contains an open reading frame (ORF) of 477 bp. The genomic sequence of the CrWSKP1 gene is 1296 bp with two exons and one intron. CrWSKP1 has high identity with SKP1-like genes from other plant species within two conserved regions. Approximately 85% of pollen tubes of self-pollinated CrWSKP1 transgenic tobaccos became twisted at four days after self-pollination. Pollen tube numbers of self-pollinated CrWSKP1 transformants entering into ovules were significantly fewer than that of the control. Seed number of self-pollinated CrWSKP1 transformants was significantly reduced. These results suggested that the CrWSKP1 is involved in the self-incompatibility (SI) reaction of "Wuzishatangju".

  8. Study of nuclear reactions involving heavy nuclei and intermediate- and high-energy protons and an application in nuclear reactor physics (ADS)

    International Nuclear Information System (INIS)

    Matuoka, Paula Fernanda Toledo

    2016-01-01

    In the present work, intermediate- and high-energy nuclear reactions involving heavy nuclei and protons were studied with the Monte Carlo CRISP (Rio - Ilheus - Sao Paulo Collaboration) model. The most relevant nuclear processes studied were intranuclear cascade and fission-evaporation competition. Preliminary studies showed fair agreement between CRISP model calculation and experimental data of multiplicity of evaporated neutrons (E 20 MeV) were emitted mostly in the intranuclear cascade stage, while evaporation presented larger neutron multiplicity. Fission cross section of 209 mb and spallation cross section of 1788 mb were calculated { both in agreement with experimental data. The fission process resulted in a symmetric mass distribution. Another Monte Carlo code, MCNP, was used for radiation transport in order to understand the role of a spallation neutron source in a ADS (Accelerator Driven System) nuclear reactor. Initially, a PWR reactor was simulated to study the isotopic compositions in spent nuclear fuel. As a rst attempt, a spallation neutron source was adapted to an industrial size nuclear reactor. The results showed no evidence of incineration of transuranic elements and modifications were suggested. (author)

  9. Determination of H-atom reaction rate constants by the competition kinetic technique using riboflavin as a standard solute [Paper No. RD-7

    International Nuclear Information System (INIS)

    Kishore, Kamal; Moorthy, P.N.; Rao, K.N.

    1982-01-01

    Riboflavin has been used as a standard solute to evaluate H-atom rate constants of other solutes by steady state radiolytic competition kinetic method. The bleaching of absorbance of riboflavin at 445 nm as a result of its reaction with H-atoms is made use of in estimating its decomposition. The merits and demerits of this method are discussed. (author)

  10. Mixing of radiolytic hydrogen generated within a containment compartment following a LOCA

    International Nuclear Information System (INIS)

    Willcutt, G.J.E. Jr.; Gido, R.G.

    1978-07-01

    The objective of this work was to determine hydrogen concentration variations with position and time in a closed containment compartment with radiolytic hydrogen generation in the water on the compartment floor following a Loss-of-Coolant-Accident (LOCA). One application is to determine the potential difference between the compartment maximum hydrogen concentration and a hydrogen detector reading, due to the detector location. Three possible mechanisms for hydrogen transport in the compartment were investigated: (1) molecular diffusion, (2) possible bubble formation and motion, and (3) natural convection flows. A base case cubic compartment with 6.55-m (21.5-ft) height was analyzed. Parameter studies were used to determine the sensitivity of results to compartment size, hydrogen generation rates, diffusion coefficients, and the temperature difference between the floor and the ceiling and walls of the compartment. Diffusion modeling indicates that if no other mixing mechanism is present for the base case, the maximum hydrogen volume percent (vol percent) concentration difference between the compartment floor and ceiling will be 4.8 percent. It will be 24.5 days before the maximum concentration difference is less than 0.5 percent. Bubbles do not appear to be a potential source of hydrogen pocketing in a containment compartment. Compartment natural convection circulation rates for a 2.8 K (5 0 F) temperature difference between the floor and the ceiling and walls are estimated to be at least the equivalent of 1 compartment volume per hour and probably in the range of 4 to 9 compartment volumes per hour. Related natural convection studies indicate there will be turbulent mixing in the compartment for a 2.8 K (5 0 F) temperature difference between the floor and the ceiling and walls

  11. Radiolytic stabilization of poly(methyl methacrylate) in blends with polystyrene

    International Nuclear Information System (INIS)

    Lima, Ivania Soares de

    2002-04-01

    In this work the radiolytic stabilization of poly(methyl methacrylate) was analyzed by three radioprotective agents: polystyrene (PS) and hindered amine light stabilizers (HEALS), respectively, PMMA/PS systems, so a called polymeric blends were prepared with different compositions, where the miscibility of these blends were studied using viscometric, microscopy (SEM) and spectroscopy (FT-IR) techniques. The results show that PMMA/PS blends in the compositions below 10 wt% of PS are miscible, on films casting from solution of toluene and methyl-ethyl-ketone (1;1) mixture. On the other hand, in the composition above 10 wt% of PS, PMMA/PS blends show imminiscibility behavior. These polymer solutions were irradiated with gamma rays ( 60 Co) and viscometric, microscopic and spectroscopic experiments show gamma radiation-induced compatibilization on PMMA/PS blends on proportion 50/50 and 30/70 take place. Viscometric interaction parameters of miscible and compatibilized PMMA/PS bends were calculated in the range of - 50 kGy, with the goal to find out the polymeric interactions after irradiation of the films. G values of PMMA, PMMA/PS and PMMA+St systems were calculated in order to analyze the radioprotection of PS and St into PMMA matrix. The results show that (90/10) PMMA/PS and PMMA+1,5%St systems promote protection against the gamma the radiation-induced scissions, effect that leads to polymer degradation. Moreover, a small amount of crosslinking observed in irradiated blends has contributed to stabilize mechanical properties of PMMA films. PMMA+0,3% HALS system irradiated in doses above 60 kGy showed little stabilization of the mechanical properties of PMMA, since it was observed mechanical degradation this system. Based on these results, PS and St showed to be the best radioprotective agents to PMMA. (author)

  12. Using positive-ion electrospray ionization mass spectrometry and H/D exchange study phosphoryl group transfer reactions involved in amino acid ester isopropyl phosphoramidates of Brefeldin A

    International Nuclear Information System (INIS)

    Fang, Mei-Juan; Zhang, He; Liao, Chao; Qiu, Ying-Kun; Fang, Hua; Zheng, Zhen-Yu; Gao, Xiang; Zhao, Yu-Fen; Wu, Zhen

    2015-01-01

    Highlights: • ESI-MS n , HRMS and H/D exchange were used. • The fragmentation pathways of NPAAE-BFA in ESI-MS n were described. • Fragment ions involved in phosphorus group’s rearrangement reactions were observed. • Two rearrangement mechanisms about phosphorylation–dephosphorylation were proposed. - Abstract: As mini-chemical models, amino acid ester isopropyl phosphoramidates of Brefeldin A (compounds 2a–2d) were synthesized and investigated by electrospray ionization tandem mass spectrometry in combination with H/D exchange. To further confirm the fragments’s structures, off-line Fourier transform resonance tandem mass spectrometry (FT-ICR-MS/MS) was also performed. The fragmentation rules of compounds 2a–2d have been summarized and the plausible schemes for the fragmentation pathways were proposed. In this study, one dephosphorylated ion and two phosphorylated ions were observed in ESI-MS 2 spectra of [M + Na] + ions for compounds 2a–2d. The possible mechanisms about phosphorylation and dephosphorylation were proposed and confirmed by H/D exchange. For the “dephosphorylation” rearrangement, a nitrogen atom was migrated from the phosphoryl group to the carbon atom of Brefeldin A’s backbone with losing a molecule of C 3 H 7 PO 3 (122 Da). For the “phosphorylation” rearrangement, an oxygen atom of one phosphoryl group attacked the sideward phosphorus atom to form a nine-member ring intermediate, then two steps of C-H covalent bond cleavage with consecutive migration of hydrogen atom to lose a molecule of C 16 H 20 O 2 (244 Da). The two proposed rearrangement mechanisms about phosphoryl group transfer might be valuable for the structure analysis of other analogs and provide insights into elucidating the dynamic process of the phosphorylation–dephosphorylation of proteins

  13. Using positive-ion electrospray ionization mass spectrometry and H/D exchange study phosphoryl group transfer reactions involved in amino acid ester isopropyl phosphoramidates of Brefeldin A

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Mei-Juan; Zhang, He; Liao, Chao; Qiu, Ying-Kun [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); Fang, Hua [The Third Institute of Oceanography of the State Oceanic Administration, Xiamen 361005 (China); Zheng, Zhen-Yu [College of Chemistry and Chemical Engineering, Department of Chemistry, Xiamen University, Xiamen 361005 (China); Gao, Xiang [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); Zhao, Yu-Fen [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); College of Chemistry and Chemical Engineering, Department of Chemistry, Xiamen University, Xiamen 361005 (China); Wu, Zhen, E-mail: wuzhen@xmu.edu.cn [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China)

    2015-01-01

    Highlights: • ESI-MS{sup n}, HRMS and H/D exchange were used. • The fragmentation pathways of NPAAE-BFA in ESI-MS{sup n} were described. • Fragment ions involved in phosphorus group’s rearrangement reactions were observed. • Two rearrangement mechanisms about phosphorylation–dephosphorylation were proposed. - Abstract: As mini-chemical models, amino acid ester isopropyl phosphoramidates of Brefeldin A (compounds 2a–2d) were synthesized and investigated by electrospray ionization tandem mass spectrometry in combination with H/D exchange. To further confirm the fragments’s structures, off-line Fourier transform resonance tandem mass spectrometry (FT-ICR-MS/MS) was also performed. The fragmentation rules of compounds 2a–2d have been summarized and the plausible schemes for the fragmentation pathways were proposed. In this study, one dephosphorylated ion and two phosphorylated ions were observed in ESI-MS{sup 2} spectra of [M + Na]{sup +} ions for compounds 2a–2d. The possible mechanisms about phosphorylation and dephosphorylation were proposed and confirmed by H/D exchange. For the “dephosphorylation” rearrangement, a nitrogen atom was migrated from the phosphoryl group to the carbon atom of Brefeldin A’s backbone with losing a molecule of C{sub 3}H{sub 7}PO{sub 3} (122 Da). For the “phosphorylation” rearrangement, an oxygen atom of one phosphoryl group attacked the sideward phosphorus atom to form a nine-member ring intermediate, then two steps of C-H covalent bond cleavage with consecutive migration of hydrogen atom to lose a molecule of C{sub 16}H{sub 20}O{sub 2} (244 Da). The two proposed rearrangement mechanisms about phosphoryl group transfer might be valuable for the structure analysis of other analogs and provide insights into elucidating the dynamic process of the phosphorylation–dephosphorylation of proteins.

  14. Retention of radiolytic CO gas in irradiated pepper grains and irradiation detection of spices and dry grains with the level of stocked CO gas

    International Nuclear Information System (INIS)

    Furuta, M.; Dohmaru, T.; Katayama, T.; Toratani, H.; Takeda, A.

    1995-01-01

    The release of radiolytic CO gas from 60Co gamma-irradiated pepper seeds was unexpectedly slower than that of radiolytic H2 gas during a storage period after irradiation. These gases were retained in the grains and could be recovered by pulverization under gaslight condition. Using this procedure, 10-kGy-irradiated pepper grains could be distinguished from nonirradiated samples for more than 2 months by the level of CO and H2 gases. The patterns of CO change at 10, 20, and 30 kGy were similar, and the CO amounts were proportional to irradiation doses at any point of the storage period after irradiation. 60Co gamma-irradiated grains of allspice, cinnamon, cumin, polished rice, and wheat could be distinguished from nonirradiated ones by the level of retained CO gas even after 2 months of storage at room temperature. Thus, radiolytic CO gas could be an effective probe for rapid screening of irradiated pepper and dry grains

  15. Water Ice Radiolytic O2, H2, and H2O2 Yields for Any Projectile Species, Energy, or Temperature: A Model for Icy Astrophysical Bodies

    Science.gov (United States)

    Teolis, B. D.; Plainaki, C.; Cassidy, T. A.; Raut, U.

    2017-10-01

    O2, H2, and H2O2 radiolysis from water ice is pervasive on icy astrophysical bodies, but the lack of a self-consistent, quantitative model of the yields of these water products versus irradiation projectile species and energy has been an obstacle to estimating the radiolytic oxidant sources to the surfaces and exospheres of these objects. A major challenge is the wide variation of O2 radiolysis yields between laboratory experiments, ranging over 4 orders of magnitude from 5 × 10-7 to 5 × 10-3 molecules/eV for different particles and energies. We revisit decades of laboratory data to solve this long-standing puzzle, finding an inverse projectile range dependence in the O2 yields, due to preferential O2 formation from an 30 Å thick oxygenated surface layer. Highly penetrating projectile ions and electrons with ranges ≳30 Å are therefore less efficient at producing O2 than slow/heavy ions and low-energy electrons (≲ 400 eV) which deposit most energy near the surface. Unlike O2, the H2O2 yields from penetrating projectiles fall within a comparatively narrow range of (0.1-6) × 10-3 molecules/eV and do not depend on range, suggesting that H2O2 forms deep in the ice uniformly along the projectile track, e.g., by reactions of OH radicals. We develop an analytical model for O2, H2, and H2O2 yields from pure water ice for electrons and singly charged ions of any mass and energy and apply the model to estimate possible O2 source rates on several icy satellites. The yields are upper limits for icy bodies on which surface impurities may be present.

  16. Time-dependent radiolytic yields at room temperature and temperature-dependent absorption spectra of the solvated electrons in polyols

    International Nuclear Information System (INIS)

    Lin Mingzhang; Mostafavi, M.; Lampre, I.; Muroya, Y.; Katsumura, Y.

    2007-01-01

    The molar extinction coefficients at the absorption maximum of the solvated electron spectrum have been evaluated to be 900, 970, and 1000 mol -1 ·m 2 for 1,2-ethanediol (12ED), 1,2-propanediol (12PD), and 1,3-propanediol (13PD), respectively. These values are two-third or three-fourth of the value usually reported in the published report. Picosecond pulse radiolysis studies have aided in depicting the radiolytic yield of the solvated electron in these solvents as a function of time from picosecond to microsecond. The radiolytic yield in these viscous solvents is found to be strongly different from that of the water solution. The temperature dependent absorption spectra of the solvated electron in 12ED, 12PD, and 13PD have been also investigated. In all the three solvents, the optical spectra shift to the red with increasing temperature. While the shape of the spectra does not change in 13PD, a widening on the blue side of the absorption band is observed in 12ED and 12PD at elevated temperatures. (authors)

  17. Radiolytic stabilization of industrial poly(methyl methacrylate); Estabilizacao radiolitica do poli(metacrilato de metila) industrial

    Energy Technology Data Exchange (ETDEWEB)

    Aquino, Katia Aparecida da Silva

    2005-03-15

    Poly(methyl methacrylate), PMMA, Acrigel, a Brazilian polymer, is used in the manufacture of medical supplies sterilisable by ionizing radiation. However, when PMMA is gamma-irradiated it undergoes main chain scissions, which promote molecular degradation causing reduction in its physical properties. Therefore, radiolytic stabilization of PMMA is important for to become it commercially radio sterilisable. In this work we investigated the radiolytic stabilization of PMMA by using HALS (Hindered Amine Light Stabilizer) additive, commercially used for photo and thermo oxidative stabilization of polymers. The investigation of the radiation-induced main chain scissions was carried out by viscometric method. The additive added to the polymer system at 0.3 % w/w promotes a molecular radioprotection of 61%. That means a reduction of G value (scissions/100 eV) from 2.6 to 1.0. In addition, the glassy transition temperature (Tg) of PMMA (no additive), significantly changed by radiation, does not change when PMMA (with additive) is irradiated. TGA analysis showed that the additive promotes thermal stability to the system, increasing decomposition temperature of PMMA. Spectroscopy analysis, FT-IR and RMN ({sup 1}H), showed that the radioprotector additive added to the system does not change the PMMA structure. Analysis on mechanical (tensile strength and elongation at break) and optical (yellowness index and refractive index) properties showed a good influence of the additive on polymer system. (author)

  18. Radiolytic oxidation of UO{sub 2} pellets doped with alpha-emitters ({sup 238/239}Pu)

    Energy Technology Data Exchange (ETDEWEB)

    Muzeau, B. [Commissariat a l' Energie Atomique, Rhone Valley Research Center DTCD/SECM/LMPA, BP 17 171, 30207 Bagnols-sur-Ceze Cedex (France); Jegou, C. [Commissariat a l' Energie Atomique, Rhone Valley Research Center DTCD/SECM/LMPA, BP 17 171, 30207 Bagnols-sur-Ceze Cedex (France)], E-mail: christophe.jegou@cea.fr; Delaunay, F. [Commissariat a l' Energie Atomique, Valduc Research Center, 21120 Is-sur-Tille (France); Broudic, V. [Commissariat a l' Energie Atomique, Rhone Valley Research Center DTCD/SECM/LMPA, BP 17 171, 30207 Bagnols-sur-Ceze Cedex (France); Brevet, A. [Commissariat a l' Energie Atomique, Valduc Research Center, 21120 Is-sur-Tille (France); Catalette, H. [Electricite de France, Les Renardieres Research Center, Route de Sens Ecuelles, 77250 Moret-sur-Loing (France); Simoni, E. [Institut de Physique Nucleaire, Bat. 100, 91406 Orsay Cedex (France); Corbel, C. [Laboratoire des Solides Irradies, UMR 7642-CNRS-CEA-Ecole Polytechnique, Ecole Polytechnique, 91128 Palaiseau Cedex (France)

    2009-01-07

    To assess the impact of alpha radiolysis of water on the oxidative dissolution of UO{sub 2} under anoxic conditions, two series of plutonium-doped samples (specific alpha activity 385 and 18 MBqg{sub UO{sub 2}}{sup -1}) were fabricated, characterized and leached in water of varying complexity (pure water, carbonated water, dissolved hydrogen). Given the very high reactivity of these samples in the presence of air and in order to minimize any prior surface oxidation, a strict experimental protocol was developed based on high-temperature annealing in Ar + 4% H{sub 2} with preleaching cycles. Failure to follow this protocol prevents absolute quantification of oxidation of the UO{sub 2} surface by water radiolysis in solutions. Preoxidation of the pellet surface can lead to uranium release in solution that is dependent on the alpha particle flux, revealing initial oxidation by radiolysis in air including potential traces of water. This makes difficult the accurate quantification of the radiolytic oxidation in water solutions. Controlling the initial surface condition of the samples finally allowed us to demonstrate that radiolytic oxidation in water-saturated media is governed by several threshold effects for which the main parameters are the sample alpha activity and the hydrogen concentration.

  19. Characterization of the Unusual Product from the Reaction between Cobalt(II) Chloride, Ethane-1,2-diamine, and Hydrochloric Acid: An Undergraduate Project Involving an Unknown Metal Complex.

    Science.gov (United States)

    Curtis, Neil F.; And Others

    1986-01-01

    Discusses the need for student research-type chemistry projects based upon "unknown" metal complexes. Describes an experiment involving the product from the reaction between cobalt(II) chloride, ethane-1,2-diamine (en) and concentrated hydrochloric acid. Outlines the preparation of the cobalt complex, along with procedure, results and…

  20. Radiolytic and thermal stability of selected plutonium salts containing nitrate groups

    International Nuclear Information System (INIS)

    Bryan, G.H.

    1976-04-01

    (Pu(NO 3 ) 4 . XH 2 O, K 2 Pu(NO 3 ) 6 , and (NH 4 ) 2 Pu(NO 3 ) 6 ) were studied to evaluate their ability to serve as shipping forms that meet criteria. The radiolytic gas evolution study eliminated (NH 4 ) 2 Pu(NO 3 ) 6 from further consideration. None of the compounds produced H 2 or O 2 in sufficient quantity to produce a flammable mixture, except Pu(NO 3 ) 4 . XH 2 O which produced O 2 and H 2 in a ratio that is above explosive limits after long storage time. The ammonium salt decomposition appears to be about the same as that observed upon heating of NH 4 NO 3 to produce N 2 , H 2 O, and nitrous oxides. Plutonium nitrate contains hydration water. This water is of some concern due to the production of hydrogen by alpha-radiolysis. Two waters of hydration appear to be the lower limit to which Pu(NO 3 ) 4 . XH 2 O may be taken before decomposition of the solid begins. TGA results indicate the simple nitrate (Pu(NO 3 ) 4 . XH 2 O) is somewhat less thermally stable than either the ammonium or potassium hexanitrato plutonate which detracts somewhat from its suitability as a shipping form. Maintaining large quantities of this compound with a high 238 Pu content (less than 1 percent 238 Pu) may require specially designed and larger containers to prevent thermal degradation and gas pressure buildup problems. The informaion was presented to plutonium processors; the final consensus of this group was that in spite of some thermal instability of Pu(NO 3 ) 4 . XH 2 O at fairly low temperatures, it was preferable to K 2 Pu(NO 3 ) 6 due to the additional waste disposal problems the potassium would present. (Pu(NO 3 ) 4 . XH 2 O also has several other advantages. A possible problem that could arise due to the variable weight of plutonium nitrate could be in plutonium accountability, but this would be prevented if the plutonium content of the solution prior to evaporation to the solid is known

  1. Hydrolytic and radiolytic degradation of TBP in TBP.30% V/V-dodecane/UO2(NO3)2.HNO3.H2O systems

    International Nuclear Information System (INIS)

    Barreta, L.G.

    1980-01-01

    The hydrolytic and radiolytic degradation of TBP is investigated in systems of TBP 30% V/V-dodecane/H 2 O . HNO 3 . UO 2 (NO 3 ) 2 by gas chromatographic determination of HDBP. No direct relation between the concentration of HDBP formed and the quantity of HNO 3 extracted by the organic phase is observed in the studies of hydrolysis of TBP. The HDBP concentration is seen to increase non-linearly with the concentration of HNO 3 extracted by the organic phase. Radiolytic studies show that for doses greater than 1 Wh/l, the concentration of HDBP formed increases with the dose absorbed by the system. Whith doses smaller than 1 Wh/l and acid concentration greater than 2 M, two distinct patterns of behavior are observed. The concentration of HDBP as a function of the radiation dose absorbed by the system presents a minimum for uranyl nitrate concentrations smaller than 0.9 M; for uranyl nitrate concentrations greater than 1.3 M the concentration of radiolytic HDBP cannot be calculated because the concentration of the hydrolytic HDBP determined is greater than the sum of the experimental concentrations of hydrolytic and radiolytic HDBP. It is known that the dose absorbed by the process solutions during the reprocessing of light water reactor fuel elements is smaller than one Wh/l. Thus, dose rates between zero and one Wh/l should be studied for this system. (Author) [pt

  2. PARIS project: Radiolytic oxidation of molecular iodine in containment during a nuclear reactor severe accident

    Energy Technology Data Exchange (ETDEWEB)

    Bosland, L. [Institut de Radioprotection et de Surete Nucleaire, DPAM, SEMIC, LETR - CEN Cadarache, BP 3, 13115 Saint Paul Lez Durance (France)], E-mail: loic.bosland@irsn.fr; Funke, F. [AREVA NP GmbH, Technical Center, P.O. Box 1109, D-91001 Erlangen (Germany); Girault, N. [Institut de Radioprotection et de Surete Nucleaire, DPAM, SEMIC, LETR - CEN Cadarache, BP 3, 13115 Saint Paul Lez Durance (France); Langrock, G. [AREVA NP GmbH, Technical Center, P.O. Box 1109, D-91001 Erlangen (Germany)

    2008-12-15

    In case of a hypothetical severe accident in a nuclear LWR (light water reactor), the high radiation fields reached in the reactor containment building due to the release of fission products from the reactor core could induce air radiolysis. The air radiolysis products could, in turn, oxidise gaseous molecular iodine into aerosol-borne iodine-oxygen-nitrogen compounds. Thereby, this reaction involves a change of iodine speciation and a decrease of iodine volatility in the reactor containment atmosphere. Kinetic data were produced within the PARIS project on the air radiolysis products formation and destruction, and on their reaction with molecular iodine, with the objective of developing and validating existing kinetic models. The current paper includes the non-iodine tests of the PARIS project whose objective was to determine the rates of formation and destruction of air radiolysis products in the presence of both structural containment surfaces (decontamination coating ('paint') and stainless steel), aerosol particles such as silver rich particles (issued from the control rods) in boundary conditions representative for LWR or PHEBUS facility containments. It is found that the air radiolysis products concentration increases with dose and tend to approach saturation levels at doses higher than about 1 kGy. This behaviour is more evident in oxygen/steam atmospheres, producing ozone, than in air/30% (v/v) steam atmospheres, the latter favouring the model-predicted on-going production of nitrogen dioxide even at very high doses. No significant effect of temperature, dose rate and hydrogen addition (4%, v/v) was observed. Furthermore, the inserted surfaces do not exhibit significant effects on the air radiolysis concentrations. However, these 'non-noticeable influence' could be due to a masking of small effects by the appreciable scattering of the experimental air radiolysis product concentrations. The PARIS results are then analysed using two

  3. PARIS project: Radiolytic oxidation of molecular iodine in containment during a nuclear reactor severe accident

    International Nuclear Information System (INIS)

    Bosland, L.; Funke, F.; Girault, N.; Langrock, G.

    2008-01-01

    In case of a hypothetical severe accident in a nuclear LWR (light water reactor), the high radiation fields reached in the reactor containment building due to the release of fission products from the reactor core could induce air radiolysis. The air radiolysis products could, in turn, oxidise gaseous molecular iodine into aerosol-borne iodine-oxygen-nitrogen compounds. Thereby, this reaction involves a change of iodine speciation and a decrease of iodine volatility in the reactor containment atmosphere. Kinetic data were produced within the PARIS project on the air radiolysis products formation and destruction, and on their reaction with molecular iodine, with the objective of developing and validating existing kinetic models. The current paper includes the non-iodine tests of the PARIS project whose objective was to determine the rates of formation and destruction of air radiolysis products in the presence of both structural containment surfaces (decontamination coating ('paint') and stainless steel), aerosol particles such as silver rich particles (issued from the control rods) in boundary conditions representative for LWR or PHEBUS facility containments. It is found that the air radiolysis products concentration increases with dose and tend to approach saturation levels at doses higher than about 1 kGy. This behaviour is more evident in oxygen/steam atmospheres, producing ozone, than in air/30% (v/v) steam atmospheres, the latter favouring the model-predicted on-going production of nitrogen dioxide even at very high doses. No significant effect of temperature, dose rate and hydrogen addition (4%, v/v) was observed. Furthermore, the inserted surfaces do not exhibit significant effects on the air radiolysis concentrations. However, these 'non-noticeable influence' could be due to a masking of small effects by the appreciable scattering of the experimental air radiolysis product concentrations. The PARIS results are then analysed using two different kinetic models

  4. Inhibition of the radiolytic hydrogen production in the nuclear waste of 'bitumen coated' type: study of the interaction between hydrogen and cobalt hydroxo-sulphide

    International Nuclear Information System (INIS)

    Pichon, C.

    2006-11-01

    In the nuclear field in France, the bitumen is mainly used for the conditioning of the radioactive muds generated by the fuel reprocessing. However, the self-irradiation of the bitumen induces a production of hydrogen which generates safety problems. The comparison of various storage sites showed that the presence of cobalt hydroxo sulphide limited such a production. Consequently, this compound was regarded as an 'inhibitor of radiolytic hydrogen production'. However, the origin of this phenomenon was not clearly identified. In order to propose an explanation to this inhibition phenomenon, model organic molecules were used to represent the components of the bitumen. Irradiations were carried out by protons to simulate the alpha radiolysis. The organic molecules irradiations by a proton beam showed that cobalt hydroxo sulphide CoSOH, does not act as a hydrogenation catalyst of unsaturated hydrocarbons, nor as a radicals scavenger, but consists of a trap of hydrogen. Experiments of hydrogen trapping at ambient temperature were carried out according to two techniques: gravimetry and manometry. The solid was characterized before and after interaction with hydrogen (infrared and Raman spectroscopies, X-ray diffraction). The initial solid was composed of amorphous cobalt hydroxo sulphide and a minor phase of cobalt hydroxide. The gravimetry and manometry experiments showed that the maximum of hydrogen trapping capacity is equal to 0.59 ± 0.18 mole of hydrogen per mole of cobalt. After interaction with hydrogen, the Co(OH) 2 phase disappeared and a new solid phase appeared corresponding to Co 9 S 8 . These observations, as well as the analysis of the gas phase, made it possible to conclude with the following reaction (1): 9 CoSOH + 11/2 H 2 = Co 9 S 8 + 9 H 2 O + H 2 S (1). Gravimetry experiments at temperatures between 50 and 210 C revealed the desorption of water but not of hydrogen sulphide. The absence of hydrogen sulphide in gaseous phase and the Co(OH) 2 phase

  5. Direct Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Austern, N. [University of Pittsburgh, Pittsburgh, PA (United States)

    1963-01-15

    In order to give a unified presentation of one point of view, these lectures are devoted only to a detailed development of the standard theories of direct reactions, starting from basic principles. Discussion is given of the present status of the theories, of the techniques used for practical calculation, and of possible future developments. The direct interaction (DI) aspects of a reaction are those which involve only a few of the many degrees of freedom of a nucleus. In fact the minimum number of degrees of freedom which must be involved in a reaction are those required to describe the initial and final channels, and DI studies typically consider these degrees of freedom and no others. Because of this simplicity DI theories may be worked out in painstaking detail. DI processes concern only part of the wave function for a problem. The other part involves complicated excitations of many degrees of freedom, and gives the compound nucleus (CN) effects. While it is extremely interesting to learn how to separate DI and CN effects in an orderly manner, if they are both present in a reaction, no suitable method has yet been found. Instead, current work stresses the kinds of reactions and the kinds of final states in which DI effects dominate and in which CN effects may almost be forgotten. The DI cross-sections which are studied are often extremely large, comparable to elastic scattering cross-sections. (author)

  6. Possible influence of the Kuramoto length in a photo-catalytic water splitting reaction revealed by Poisson-Nernst-Planck equations involving ionization in a weak electrolyte

    Science.gov (United States)

    Suzuki, Yohichi; Seki, Kazuhiko

    2018-03-01

    We studied ion concentration profiles and the charge density gradient caused by electrode reactions in weak electrolytes by using the Poisson-Nernst-Planck equations without assuming charge neutrality. In weak electrolytes, only a small fraction of molecules is ionized in bulk. Ion concentration profiles depend on not only ion transport but also the ionization of molecules. We considered the ionization of molecules and ion association in weak electrolytes and obtained analytical expressions for ion densities, electrostatic potential profiles, and ion currents. We found the case that the total ion density gradient was given by the Kuramoto length which characterized the distance over which an ion diffuses before association. The charge density gradient is characterized by the Debye length for 1:1 weak electrolytes. We discuss the role of these length scales for efficient water splitting reactions using photo-electrocatalytic electrodes.

  7. Radcalc: A computer program to calculate the radiolytic production of hydrogen gas from radioactive wastes in packages

    International Nuclear Information System (INIS)

    Green, J.R.; Schwarz, R.A.; Hillesland, K.E.; Roetman, V.E.; Field, J.G.

    1995-11-01

    Radcalc for Windows' is a menu-driven Microsoft2 Windows-compatible computer code that calculates the radiolytic production of hydrogen gas in high- and low-level radioactive waste. In addition, the code also determines US Department of Transportation (DOT) transportation classifications, calculates the activities of parent and daughter isotopes for a specified period of time, calculates decay heat, and calculates pressure buildup from the production of hydrogen gas in a given package geometry. Radcalc for Windows was developed by Packaging Engineering, Transportation and Packaging, Westinghouse Hanford Company, Richland, Washington, for the US Department of Energy (DOE). It is available from Packaging Engineering and is issued with a user's manual and a technical manual. The code has been verified and validated

  8. Pulse-radiolytic investigation of the reduction of titanium(III) ions in aqueous solutions

    International Nuclear Information System (INIS)

    Micic, O.I.; Nenadovic, M.T.

    1979-01-01

    The absorption spectrum and decay kinetics of intermediates formed by the reaction of titanium(III) ions with H atoms, hydrated electrons, and carboxyl radicals have been studied in aqueous solution using the pulse-radiolysis technique. The product of the reaction with H atoms in acid solution is a Ti 3+ -H hydride intermediate which decomposes by a first-order process with a half-life of ca. 3 s. Titanium(II) is formed by reaction with hydrated electrons and CO 2 H radicals. The absorption spectrum of titanium(II) and the kinetics of its reactions are reported and discussed. The formation of molecular hydrogen by reaction of Ti 2+ with water is suppressed by the other solutes in the solutions. Titanium(III) reacts with CO 2 H, CH 2 CO 2 H, and CH(CO 2 H) 2 radicals to give titanium-radical complexes. (author)

  9. RADIOLYTIC HYDROGEN GENERATION INSAVANNAH RIVER SITE (SRS) HIGH LEVEL WASTETANKS COMPARISON OF SRS AND HANFORDMODELING PREDICTIONS

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, C; Ned Bibler, N

    2009-04-15

    In the high level waste tanks at the Savannah River Site (SRS), hydrogen is produced continuously by interaction of the radiation in the tank with water in the waste. Consequently, the vapor spaces of the tanks are purged to prevent the accumulation of H{sub 2} and possible formation of a flammable mixture in a tank. Personnel at SRS have developed an empirical model to predict the rate of H{sub 2} formation in a tank. The basis of this model is the prediction of the G value for H{sub 2} production. This G value is the number of H{sub 2} molecules produced per 100 eV of radiolytic energy absorbed by the waste. Based on experimental studies it was found that the G value for H{sub 2} production from beta radiation and from gamma radiation were essentially equal. The G value for H{sub 2} production from alpha radiation was somewhat higher. Thus, the model has two equations, one for beta/gamma radiation and one for alpha radiation. Experimental studies have also indicated that both G values are decreased by the presence of nitrate and nitrite ions in the waste. These are the main scavengers for the precursors of H{sub 2} in the waste; thus the equations that were developed predict G values for hydrogen production as a function of the concentrations of these two ions in waste. Knowing the beta/gamma and alpha heat loads in the waste allows one to predict the total generation rate for hydrogen in a tank. With this prediction a ventilation rate can be established for each tank to ensure that a flammable mixture is not formed in the vapor space in a tank. Recently personnel at Hanford have developed a slightly different model for predicting hydrogen G values. Their model includes the same precursor for H{sub 2} as the SRS model but also includes an additional precursor not in the SRS model. Including the second precursor for H{sub 2} leads to different empirical equations for predicting the G values for H{sub 2} as a function of the nitrate and nitrite concentrations in

  10. On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

    Science.gov (United States)

    Marcus, R. A.

    1962-01-01

    Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

  11. Transcript Quantification of Genes Involved in Steviol Glycoside Biosynthesis in Stevia rebaudiana Bertoni by Real-Time Polymerase Chain Reaction (RT-PCR).

    Science.gov (United States)

    Modi, Arpan; Kumar, Nitish; Narayanan, Subhash

    2016-01-01

    Stevia (Stevia rebaudiana Bertoni) is a medicinal plant having sweet, diterpenoid glycosides known as steviol glycosides which are 200-300 times sweeter than sucrose (0.4 % solution). They are synthesized mainly in the leaves via plastid localized 2-C-methyl-D-erythrose-4-phosphate pathway (MEP pathway). Fifteen genes are involved in the formation of these glycosides. In the present protocol, a method for the quantification of transcripts of these genes is shown. The work involves RNA extraction and cDNA preparation, and therefore, procedures for the confirmation of DNA-free cDNA preparation have also been illustrated. Moreover, details of plant treatments are not mentioned as this protocol may apply to relative gene expression profile in any medicinal plant with any treatment. The treatments are numbered as T0 (Control), T1, T2, T3, and T4.

  12. The chemiluminescence of luminol in aqueous solutions, a pulse radiolytic study

    International Nuclear Information System (INIS)

    Lind, J.

    1980-01-01

    The mechanism of chemiluminescence was studied when the luminol radical and superoxide were generated simultaneously. Hydroperoxide was formed at the first reaction step with a pKa value between 11 and 12. The dissociated form was found to undergo a monomolecular reaction leading to light generation and having a rate constant > 2 x 10 5 s -1 . The protonated form had the rate constant of approx. 2000 s -1 and formed a product which absorbed around 390 nm without light emission. The reaction of the two-electron oxidation product of luminol, 5-aminophthalazine-1, 4 dione (azaquinone), with hydrogenperoxide was stoichiometrically equivalent to the recombination of superoxide with the luminol radical. The pulseradiolytic generation of the chlorinedioxide radical ClO 2 in aqueous solution of sodium chlorite is described, and the oxidation of luminol by ClO 2 in two steps is reported: 1. Radical adducts are formed. 2. The reaction of ClO 2 x radical with the adduct to form azaquinone. The chemiluminescent reaction between the azaquinone and hydrogenperoxide consists of a second order reaction between HO 2 and the azaquinone to form a hydroperoxide followed by a monomolecular rearrangement of the dissociated form of the latter. Its acidbase equilibrium has a pKa of 10.6. A nitrogencentered structure is ascribed to the hydroperoxide formed by cross-recombination of the luminolradical and superoxide while the reaction between HO 2 and azaquinone yields a carboncentered hydroperoxide. The existence of two different emitters is evidenced by the following observations. 1. A slight difference in chemiluminescence spectra. 2. The formation of an endproduct with pKa approx. 10.2 in the luminolradical superoxide system. 3. The formation of an endproduct which acts as an efficient radial scavenger in the luminol radical superoxide system. (G.B.)

  13. Thalamic inputs to dorsomedial striatum are involved in inhibitory control: evidence from the five-choice serial reaction time task in rats.

    Science.gov (United States)

    Saund, Jasjot; Dautan, Daniel; Rostron, Claire; Urcelay, Gonzalo P; Gerdjikov, Todor V

    2017-08-01

    Corticostriatal circuits are widely implicated in the top-down control of attention including inhibitory control and behavioural flexibility. However, recent neurophysiological evidence also suggests a role for thalamic inputs to striatum in behaviours related to salient, reward-paired cues. Here, we used designer receptors exclusively activated by designer drugs (DREADDs) to investigate the role of parafascicular (Pf) thalamic inputs to the dorsomedial striatum (DMS) using the five-choice serial reaction time task (5CSRTT) in rats. The 5CSRTT requires sustained attention in order to detect spatially and temporally distributed visual cues and provides measures of inhibitory control related to impulsivity (premature responses) and compulsivity (perseverative responses). Rats underwent bilateral Pf injections of the DREADD vector, AAV2-CaMKIIa-HA-hM4D(Gi)-IRES-mCitrine. The DREADD agonist, clozapine N-oxide (CNO; 1 μl bilateral; 3 μM) or vehicle, was injected into DMS 1 h before behavioural testing. Task parameters were manipulated to increase attention load or reduce stimulus predictability respectively. We found that inhibition of the Pf-DMS projection significantly increased perseverative responses when stimulus predictability was reduced but had no effect on premature responses or response accuracy, even under increased attentional load. Control experiments showed no effects on locomotor activity in an open field. These results complement previous lesion work in which the DMS and orbitofrontal cortex were similarly implicated in perseverative responses and suggest a specific role for thalamostriatal inputs in inhibitory control.

  14. Ethamsylate (Dicynone) interference in determination of serum creatinine, uric acid, triglycerides, and cholesterol in assays involving the Trinder reaction; in vivo and in vitro.

    Science.gov (United States)

    Dastych, Milan; Wiewiorka, Ondrej; Benovská, Miroslava

    2014-01-01

    The aim of our research was the quantification of interfering properties of the haemostatic drug Dicynone (ethamsylate) in serum creatinine, uric acid, cholesterol, and triglyceride assays using the Trinder reaction. Blood from patients was collected before and 15 minutes after administration of 500 mg Dicynone dose i.v. and the above mentioned analytes were quantified using Roche assays (Cobas 8000). In our in vitro experiment, we measured concentrations of the analytes in pooled serum aliquots with final concentrations of Dicynone additions 0, 30, 60, 150, and 300 mg/L. Aliquots with 60 mg/L Dicynone were also measured at 2, 6, and 8 hours after initial measurement when stored in 22 degrees C and 4 degrees C for comparison. Concentrations of the measured analytes in samples from patients administered with a 500 mg dose of Dicynone were lower in all cases (n = 10) when compared to values in samples taken immediately before treatment. The in vitro samples showed that considerable negative interference occurred even with the low concentrations of Dicynone additions (30 and 60 mg/L), showing the strongest negative interference in creatinine values, followed by uric acid, triglycerides, and cholesterol. Using in vitro samples, we showed strong time and temperature dependence on Dicynone interference. We found and proved significant negative interference of the drug Dicynone (ethamsylate) in the clinical analysis of blood using in vivo and in vitro experiments. Furthermore, we observed a change of this effect in serum matrix over time and at different storage temperatures.

  15. Review of the microbiological, chemical and radiolytic degradation of organic material likely to be present in intermediate level and low level radioactive wastes

    International Nuclear Information System (INIS)

    Greenfield, B.F.; Rosevear, A.; Williams, S.J.

    1990-11-01

    A review has been made of the microbiological, chemical and radiolytic degradation of the solid organic materials likely to be present in intermediate-level and low-level radioactive wastes. Possible interactions between the three routes for degradation are also discussed. Attention is focussed on the generation of water-soluble degradation products which may form complexes with radioelements. The effects of complexation on radioelement solubility and sorption are considered. Recommendations are made for areas of further research. (author)

  16. Reaction of hydroxyl radicals with ammonia in liquid water at elevated temperatures

    DEFF Research Database (Denmark)

    Hickel, B.; Sehested, K.

    1992-01-01

    The reaction of hydroxyl radical with ammonia in aqueous solutions has been studied by pulse radiolysis in the temperature range 20-200-degrees-C. The rate constant of the reaction was determined by monitoring the decay of the OH radical absorption at 260 nm for different concentrations of ammonia....... At room temperature the rate constant is (9.7 +/- 1) x 10(7) dm3 mol-1 s-1. In the whole range of temperatures the Tate constant follows Arrhenius law with an activation energy of (5.7 +/- 1) kJ mol-1. The protective effect of dissolved hydrogen on the radiolytic decomposition of ammon a is discussed....

  17. Evolution of heavy ions (He{sup 2+}, H{sup +}) radiolytic yield of molecular hydrogen vs. ''Track-Segment'' LET values

    Energy Technology Data Exchange (ETDEWEB)

    Crumiere, Francis; Vandenborre, Johan; Blain, Guillaume; Fattahi, Massoud [Nantes Univ., CNRS/IN2P3 (France). SUBATECH Unite Mixte de Recherche 6457; Haddad, Ferid [Nantes Univ., CNRS/IN2P3 (France). SUBATECH Unite Mixte de Recherche 6457; Cyclotron Arronax, Saint Herblain (France)

    2017-08-01

    Ionizing radiation's effects onto water molecules lead to the ionization and/or the excitation of them. Then, these phenomena are followed by the formation of radicals and molecular products. The linear energy transfer (LET), which defines the energy deposition density along the radiation length, is different according to the nature of ionizing particles. Thus, the values of radiolytic yields, defined as the number of radical and molecular products formed or consumed by unit of deposited energy, evolve according to this parameter. This work consists in following the evolution of radiolytic yield of molecular hydrogen and ferric ions according to the ''Track-Segment'' LET of ionizing particles (protons, helions). Concerning G(Fe{sup 3+}) values, it seems that the energy deposited into the Bragg peak does not play the main role for the Fe{sup 3+} radiolytic formation, whereas for the G(H{sub 2}) it is the case with a component around 40% of the Bragg peak in the dihydrogen production. Therefore, as main results of this work, for high energetic Helion and Proton beams, the G(Fe{sup 3+}) values, which can be used for further dosimetry studies for example during the α radiolysis experiments, and the primary g(H{sub 2}) values for the Track-Segment LET, which can be used to determine the dihydrogen production by α-emitters, are published.

  18. Electrochemical corrosion studies on a selected carbon steel for application in nuclear waste disposal containers: Influence of radiolytic products on corrosion in brines

    International Nuclear Information System (INIS)

    Farvaque-Bera, A.M.; Smailos, E.

    1994-07-01

    In previous corrosion studies, carbon steels were identified as promising materials for the manufacturing of long-lived high-level waste containers that could act as a radionuclide barrier in a rock-salt repository. In the present work, the influence of some important oxidizing radiolytic products generated in gamma irradiated brines on the electrochemical corrosion behaviour of the preselected fine-grained steel TStE 355 was studied. The steel was examined by potentiodynamic and potentiostatic polarization methods at 90 C in a disposal relevant NaCl-rich brine containing radiolytic products such as H 2 O 2 , ClO - , ClO 3 - and ClO 4 - at concentrations between 10 -4 and 10 -2 M/l. The significance of the radiolytic products to steel corrosion depends on their concentration at the metal-brine interface, which in turn, depends on many factors such as the dose rate, the amount of water present in the disposal area, the escape of gases (e.g. H 2 )

  19. Thermal and Radiolytic Gas Generation Tests on Material from Tanks 241-U-103, 241-AW-101, 241-S-106, and 241-S-102: Status Report

    International Nuclear Information System (INIS)

    King, C.M.; Bryan, S.A.

    1999-01-01

    This report summarizes progress in evaluating thermal and radiolytic flammable gas generation in actual Hanford single-shell tank wastes. The work described was conducted at Pacific Northwest National Laboratory (PNNL) for the Flammable Gas Safety Project, whose purpose is to develop information to support DE and S Hanford (DESH) and Project Management Hanford Contract (PHMC) subcontractors in their efforts to ensure the safe interim storage of wastes at the Hanford Site. This work is related to gas generation studies performed by Numatec Hanford Corporation (formerly Westinghouse Hanford Company). This report describes the results of laboratory tests of gas generation from actual convective layer wastes from Tank 241-U-103 under thermal and radiolytic conditions. Accurate measurements of gas generation rates from highly radioactive tank wastes are needed to assess the potential for producing and storing flammable gases within the tanks. The gas generation capacity of the waste in Tank 241-U-103 is a high priority for the Flammable Gas Safety Program due to its potential for accumulating gases above the flammability limit (Johnson et al, 1997). The objective of this work was to establish the composition of gaseous degradation products formed in actual tank wastes by thermal and radiolytic processes as a function of temperature. The gas generation tests on Tank 241-U-103 samples focused first on the effect of temperature on the composition and rate of gas generation Generation rates of nitrogen, nitrous oxide, methane, and hydrogen increased with temperature, and the composition of the product gas mixture varied with temperature

  20. Coupled transport/reaction model of the properties of bentonite buffer in a repository

    International Nuclear Information System (INIS)

    Liu, Jinsong; Neretnieks, I.

    1996-11-01

    Two mechanisms that can affect the long-term properties of the bentonite buffer surrounding the canister in a final repository of spent nuclear fuel are studied. The two mechanisms are the oxidation of reducing minerals in the buffer by radiolytically generated oxidant, and the low-temperature alteration of Na-montmorillonite in the bentonite buffer to illite. A coupled mass transport with geochemical reaction model is used. Four cases have been considered, which differ in the assumptions of whether the radiolytically generated oxidant first oxidizes uraninite in the spent fuel, or it is directly transported to the bentonite to oxidize the pyrite. The cases also differ in the assumptions of varying initial concentrations of pyrite in the bentonite buffer. The modelling results show that, at low temperatures, the sodium montmorillonite in the bentonite buffer is chemically stable with respect to the chemical conditions of the near field. Alteration to illite and thus an increase in hydraulic conductivity and loss of swelling ability is not likely to occur. The radiolytically generated oxidant can possibly oxidize the reducing minerals in the bentonite buffer. A redox front can be generated. In all the cases considered in this study, the modelling results indicate that slightly less than 1% by weight of pyrite in the bentonite buffer will be able to ensure that the redox front does not penetrate through the bentonite buffer within 1 million years. 31 refs

  1. Radiolytic production and thermal decay kinetics of free radicals in n-alkoxyazoxybenzenes

    International Nuclear Information System (INIS)

    Tria, J.J.

    1977-01-01

    Free radical production and decay over several temperature ranges have been studied by ESR for three members of the series of n-alkoxyazoxybenzenes, those with one, two and seven carbon atoms respectively in the alkoxy chain: p,p'-azoxydianisole (PAA), p,p'-azoxydiphenetole (PAP) and 4,4'-bis-heptyloxyazoxybenzene (HAB). Radical yields per 100 ev absorbed at room temperature were: PAA 0.018, 0.019; PAP 0.033, 0.046; HAB 0.10, 0.14 for powder and single crystal samples respectively. Radicals present at room temperature and above are believed to be formed by loss of hydrogen from the benzene rings and the alkoxy groups, with more of the latter (probably α-alkoxy radicals) occurring as the alkoxy group becomes longer, based on the poorly resolved powder spectra. No cyclohexadienyl radicals or alkoxy radicals were seen. Decay of radicals between room temperature and the first liquid crystal phase transition occurred in a ''stepwise'' manner without radical conversions and was analyzed according to a model due to Waite (Phys. Rev., 107, 463 (1957) for diffusion-controlled reaction of randomly distributed reactants with a significant activation energy for the reaction step. Thermodynamic data are included for PAA powder samples and for toluene-grown single crystals. Reactions are postulated for the higher radical yields in powder samples of the three compounds irradiated at 77 0 K

  2. Maillard Reaction: review

    Directory of Open Access Journals (Sweden)

    Júlia d'Almeida Francisquini

    2017-11-01

    Full Text Available Maillard reaction is an important subject of study in food science and technology and different areas of knowledge are involved such as chemistry, food engineering, nutrition and food technology. The objective of this paper is to present the basic concepts of the Maillard reaction, such as the reaction stages, the main compounds producced and some technological consequences for dairy products.

  3. Radiolytic unsaturation decay in polyethylene. Part II--the effect of irradiation temperature, thermal history and orientation

    International Nuclear Information System (INIS)

    Lyons, Bernard J.

    2004-01-01

    The decay rate of vinyl unsaturation in high-density polyethylenes irradiated at temperatures from about 310 to 450 K, changes significantly in the melting range up to the crystalline melting point as does free radical mobility and the polymer crystallinity. However, orienting the polymer, or slow cooling or quenching from the melt, prior to irradiation, do not alter the decay process or its rate, although they do alter the rate of increase of insoluble gel and of elastic modulus in the molten state. It is suggested that, below ∼340 K, the marked deviations from a first-order decay result from the limited mobility of polymeric free radicals in the crystalline phase and from scavenging, by vinyl groups, segregated into the amorphous phase, of radiolytic hydrogen atoms (H). In the melting range, the mobility of polymeric free radicals increases as the crystallinity decreases, reducing the importance of scavenging, so vinyl decay approximates more closely to a first-order relation. In the melt, the vinyl decay relation is not changed qualitatively by H atom scavenging, but the effective vinyl concentration is lower, so the decay rate drops sharply

  4. Formation of a Colloidal CdSe and ZnSe Quantum Dots via a Gamma Radiolytic Technique

    Directory of Open Access Journals (Sweden)

    Aeshah Salem

    2016-09-01

    Full Text Available Colloidal cadmium selenide (CdSe and zinc selenide (ZnSe quantum dots with a hexagonal structure were synthesized by irradiating an aqueous solution containing metal precursors, poly (vinyl pyrrolidone, isopropyl alcohol, and organic solvents with 1.25-MeV gamma rays at a dose of 120 kGy. The radiolytic processes occurring in water result in the nucleation of particles, which leads to the growth of the quantum dots. The physical properties of the CdSe and ZnSe nanoparticles were measured by various characterization techniques. X-ray diffraction (XRD was used to confirm the nanocrystalline structure, energy-dispersive X-ray spectroscopy (EDX was used to estimate the material composition of the samples, transmission electron microscopy (TEM was used to determine the morphologies and average particle size distribution, and UV-visible spectroscopy was used to measure the optical absorption spectra, from which the band gap of the CdSe and ZnSe nanoparticles could be deduced.

  5. Pulse radiolytic and electrochemical investigations of intramolecular electron transfer in carotenoporphyrins and carotenoporphyrin-quinone triads

    International Nuclear Information System (INIS)

    Land, E.J.; Lexa, D.; Bensasson, R.V.; Gust, D.; Moore, T.A.; Moore, A.L.; Liddell, P.A.; Nemeth, G.A.

    1987-01-01

    Thermodynamic and kinetic aspects of intramolecular electron-transfer reactions in carotenoporphyrin dyads and carotenoid-porphyrin-quinone triads have been studied by using pulse radiolysis and cyclic voltammetry. Rapid (<1 μs) electron transfer from carotenoid radical anions to attached porphyrins has been inferred. Carotenoid cations, on the other hand, do not readily accept electrons from attached porphyrins or pyropheophorbides. Electrochemical studies provide the thermodynamic basis for these observations and also allow estimation of the energetics of photoinitiated two-step electron transfer and two-step charge recombination in triad models for photosynthetic charge separation

  6. Photolytic and radiolytic studies of redox processes in aqueous solutions of acridine yellow

    International Nuclear Information System (INIS)

    Micic, O.I.; Nenadovic, M.T.

    1981-01-01

    Irradiation by visible light of an aqueous solution containing acridine yellow as a sensitizer and EDTA or cysteine as an electron donor leads to the formation of reduced species which can later reduce several different electron acceptors. Methyl viologen, europium(III) salicylate, europium(III) EDTA complex or vanadium(III) salicylate were used as electron acceptors. In the presence of a catalyst reduction of water is accompanied by the evolution of hydrogen. The kinetics and mechanism of redox reactions occurring in such a system have been explored by pulse radiolysis. Optimum conditions for water reduction under continuous illumination are analysed and implications for an energy conversion system discussed. (author)

  7. Radiolytic degradation of diclofenac and 2,6-dichloroaniline in aqueous in solution

    International Nuclear Information System (INIS)

    Homlok, R.; Takacs, E.; Wojnarovits, L.

    2011-01-01

    Complete text of publication follows. The pharmaceutical companies in designing new molecules pay attention to the environmental toxicity of the drug; from the different variants they try to choose the less toxic one. However, metabolites, degradation products may also be toxic for the fauna and flora. For instance, diclofenac (DCF), a non steroid type anti inflammatory drug, is a moderately toxic compound. During its degradation 2,6-dichloroaniline (DCA) forms which is much more toxic than the initial molecule. In this work the radiation induced degradation of DCF and DCA is reported. The purpose of the work is the elimination of these compounds from water. The intermediates are studied using pulse radiolysis, while the degradation is followed by UV-VIS spectroscopy, separation by HPLC and products identification by diode array and MS-MS detection. The effect of dose, irradiation atmosphere, and additives are investigated. The change in chemical oxygen demand, in total organic carbon content and in toxicity of the solutions are also followed as a function of dose. The · OH radicals at both molecules add to the ring and this reaction initiates the degradation. In the case of DCF hydroxylated molecules, DCA, and quinone type compound form. In the presence of oxygen there is an increase in the hydroxylated product yield. Ring opening and mineralization is suggested to proceed through peroxy intermediates. In the case of DCA the hydroxy radical reaction is accompanied by chlorine atom elimination.

  8. Chemical transport reactions

    CERN Document Server

    Schäfer, Harald

    2013-01-01

    Chemical Transport Reactions focuses on the processes and reactions involved in the transport of solid or liquid substances to form vapor phase reaction products. The publication first offers information on experimental and theoretical principles and the transport of solid substances and its special applications. Discussions focus on calculation of the transport effect of heterogeneous equilibria for a gas motion between equilibrium spaces; transport effect and the thermodynamic quantities of the transport reaction; separation and purification of substances by means of material transport; and

  9. Pulse radiolytic investigation of the hypoxanthine-xanthine-uric acid system: evidence for transient species

    International Nuclear Information System (INIS)

    Santamaria, J.; Pasquier, C.; Ferradini, C.; Pucheault, J.

    1984-01-01

    The oxidation in aqueous solutions of hypoxanthine into xanthine and xanthine into uric acid by OH radicals has been investigated using pulse radiolysis and fast kinetic absorption spectrophotometry. After hypoxanthine irradiations the spectrum of transient R 1 has been characterized. This radical is formed with a rate constant k/sub (Hyx+OH) = 6.5 x 10 9 M -1 sec -1 and disappears by disproportionation leading to xanthine and hypoxanthine with a rate constant 2K/sub (R 1 + r 1 / = 1.3 x 10 8 M -1 sec - 1 . After xanthine irradiations a radical intermediate R 2 is formed with a rate constant k/sub(X+ OH)/= 5.2 x 10 8 M -1 sec -1 and disappears through a second-order reaction 2K/sub (R 2 + R 2 )/ = 2.0 x 10 8 M -1 sec -1 . Finally, after aeration only uric acid and xanthine are measured

  10. Valence isomerization of hexamethyl(dewar benzene) radical cation. Pulse radiolytic investigation

    International Nuclear Information System (INIS)

    Gebicki, J.; Marcinek, A.; Mayer, J.

    1989-01-01

    Organic radical ions are important intermediates in a wide variety of electron-transfer reactions. Both the steady-state and time-resolved techniques have been extensively applied to probe various aspects of their chemistry. We have recently established that low-temperature pulse radiolysis can be successfully applied to the kinetic study of radical ion transformations with very low activation barriers. The target of the present investigation is the hexamethyl(Dewar benzene) (HMDB)-hexamethylbenzene (HMDB) system. Studies by the CIDNP technique indicated the presence of two distinguishable radical cations in the system HMDB-HMB. This view has not been supported by a nanosecond spectroscopic observation which failed to reveal any evidence for a radical cation other than HMB sm-bullet+ . The aim of this work is to present spectroscopic evidence for two different radical cations HMDB sm-bullet+ -HMB sm-bullet+ and the activation barrier for their interconversion

  11. A Reaction Involving Oxygen and Metal Sulfides.

    Science.gov (United States)

    Hill, William D. Jr.

    1986-01-01

    Describes a procedure for oxygen generation by thermal decomposition of potassium chlorate in presence of manganese dioxide, reacted with various sulfides. Provides a table of sample product yields for various sulfides. (JM)

  12. Formation and reactions of radical cations of substituted benzenes in aqueous media

    International Nuclear Information System (INIS)

    Holcman, J.

    1977-08-01

    Radical cations of anisole, methylated benzenes, ethylbenzene, isopropylbenzene, tert-butylbenzene and N,N-dimethylaniline were studied in aqueous media by pulse radiolytic technique. Absorption spectra and reaction kinetics of the radical cations were recorded. The radical cations are formed from the corresponding OH adducts by the elimination of OH - , either by a simple dissociation or by an acid catalyzed reaction. The rate constants of the formation of the radical cations and their reactions with water, OH - and Fe 2+ , or the reaction of a proton loss, were measured. The rate constants for the reaction with water and OH - , together with the rate constants for the dissociation of the OH adducts, are correlated with the ionization potential of the parent compound. These correlations offer a possibility of predicting the acid-base properties of radical cations of substituted benzenes, or the estimation of their ionization potential. (author)

  13. The radiolytic and chemical degradation of organic ion exchange resins under alkaline conditions: effect on radionuclide speciation

    International Nuclear Information System (INIS)

    Loon, L. van; Hummel, W.

    1995-10-01

    The formation of water soluble organic ligands by the radiolytic and chemical degradation of several ion exchange resins was investigated under conditions close to those of the near field of a cementitious repository. The most important degradation products were characterised and their role on radionuclide speciation evaluated thoroughly. Irradiation of strong acidic cation exchange resins (Powdex PCH and Lewatite S-100) resulted in the formation of mainly sulphate and dissolved organic carbon. A small part of the carbon (10-20%) could be identified as oxalate. The identity of the remainder is unknown. Complexation studies with Cu 2+ and Ni 2+ showed the presence of two ligands: oxalate and ligand X. Although ligand X could not be identified, it could be characterised by its concentration, a deprotonation constant and a complexation constant for the NiX complex. The influence of oxalate and ligand X on the speciation of radionuclides is examined in detail. For oxalate no significant influence on the speciation of radionuclides is expected. The stronger complexing ligand X may exert some influence depending on its concentration and the values of other parameters. These critical parameters are discussed and limiting values are evaluated. In absence of irradiation, no evidence for the formation of ligands was found. Irradiation of strong basic anion exchange resins (Powdex PAO and Lewatite M-500) resulted in the formation of mainly ammonia, amines and dissolved organic carbon. Up to 50% of the carbon could be identified as methyl-, dimethyl- and trimethylamine. Complexation studies with Eu 3+ showed that the complexing capacity under near field conditions was negligible. The speciation of cations such as Ag, Ni, Cu and Pd can be influenced by the presence of amins. The strongest amine-complexes are formed with Pd and therefore, as an example, the aqueous Pd-ammonia system is examined in great detail. (author) 30 figs., 10 tabs., refs

  14. The radiolytic and chemical degradation of organic ion exchange resins under alkaline conditions: effect on radionuclide speciation

    Energy Technology Data Exchange (ETDEWEB)

    Loon, L. van; Hummel, W. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1995-10-01

    The formation of water soluble organic ligands by the radiolytic and chemical degradation of several ion exchange resins was investigated under conditions close to those of the near field of a cementitious repository. The most important degradation products were characterised and their role on radionuclide speciation evaluated thoroughly. Irradiation of strong acidic cation exchange resins (Powdex PCH and Lewatite S-100) resulted in the formation of mainly sulphate and dissolved organic carbon. A small part of the carbon (10-20%) could be identified as oxalate. The identity of the remainder is unknown. Complexation studies with Cu{sup 2+} and Ni{sup 2+} showed the presence of two ligands: oxalate and ligand X. Although ligand X could not be identified, it could be characterised by its concentration, a deprotonation constant and a complexation constant for the NiX complex. The influence of oxalate and ligand X on the speciation of radionuclides is examined in detail. For oxalate no significant influence on the speciation of radionuclides is expected. The stronger complexing ligand X may exert some influence depending on its concentration and the values of other parameters. These critical parameters are discussed and limiting values are evaluated. In absence of irradiation, no evidence for the formation of ligands was found. Irradiation of strong basic anion exchange resins (Powdex PAO and Lewatite M-500) resulted in the formation of mainly ammonia, amines and dissolved organic carbon. Up to 50% of the carbon could be identified as methyl-, dimethyl- and trimethylamine. Complexation studies with Eu{sup 3+} showed that the complexing capacity under near field conditions was negligible. The speciation of cations such as Ag, Ni, Cu and Pd can be influenced by the presence of amins. The strongest amine-complexes are formed with Pd and therefore, as an example, the aqueous Pd-ammonia system is examined in great detail. (author) 30 figs., 10 tabs., refs.

  15. A novel polymerase chain reaction (PCR) - denaturing gradient gel electrophoresis (DGGE) for the identification of Micrococcaceae strains involved in meat fermentations. Its application to naturally fermented Italian sausages.

    Science.gov (United States)

    Cocolin, L; Manzano, M; Aggio, D; Cantoni, C; Comi, G

    2001-05-01

    A new molecular method consisting of polymerase chain reaction (PCR) amplification and denaturing gradient gel electrophoresis (DGGE) of a small fragment from the 16S rRNA gene identified the Micrococcaceae strains isolated from natural fermented Italian sausages. Lactic acid bacteria, total aerobic mesophilic flora, Enterobacteriaceae and faecal enterococci were also monitored. Micrococcaceaea control strains from international collections were used to optimise the method and 90 strains, isolated from fermented sausages, were identified by biochemical tests and PCR-DGGE. No differences were observed between the methods used. The results reported in this paper prove that Staphylococcus xylosus is the main bacterium involved in fermented sausage production, representing, from the tenth day of ripening, the only Micrococcaceaea species isolated.

  16. Radiolytic degradation and toxicity changes in {gamma}-irradiated solutions of 2,4-dichlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Trojanowicz, M. E-mail: trojan@chem.uw.edu.pl; Drzewicz, P.; Panta, P.; Gluszewski, W.; Nalcz-Jawecki, G.; Sawicki, J.; Sampa, M.H.O.; Oikawa, H.; Borrely, S.I.; Czaplicka, M.; Szewczynska, M

    2002-11-01

    Preliminary investigations of a petroleum industry wastes with high concentrations of phenols and chlorophenols have shown that irradiation with electron beam results in the efficient destruction of specific organic compounds. In this study the degradation of 2,4-dichlorophenol (2,4-DCP) was studied using a {sup 60}Co gamma source. The determination of reaction by-products was carried out with HPLC, ion chromatography with various detectors, GC/MS and total organic carbon analyzer. The toxicity was measured with bioluminescence test Microtox[reg]. Studies of products of 2,4-DCP radiolysis at initial concentration level 20-50 mg/l have shown that with increased radiation dose degradation proceeds with a stepwise dehalogenation, through the formation of dihydroxybenzenes followed by the formation of non-aromatic carboxylic acids. The transient formation of dihydroxybenzenes resulted in an increase in toxicity at low doses up to 1 kGy. Even at a dose of 20 kGy, not more than about 20% mineralization was observed. The efficiency and mechanism of 2,4-DCP degradation is affected by the presence of scavengers of hydroxyl radical and hydrated electrons such as nitrate or bicarbonate.

  17. Radiolytic study of the action of perhydroxyl radicals with ascorbic acid

    International Nuclear Information System (INIS)

    Sadat-Shafaie, T.; Ferradini, C.; Julien, R.; Pucheault, J.

    1979-01-01

    This paper shows that the difficulties encountered up to now about the interpretation of the radiolysis of aerated ascorbic acid (AH 2 ) solutions, were due to a low oxygen concentration. For oxygen-saturated solutions, the yield is about G(-AH 2 ) = G/sub OH/ + G/sub H/ + G/sub eaq-/ according to the mechanism, and formic acid has no influence on it. For lower concentrations of oxygen, in the presence of air, the action of oxygen on AH radical being slow, the yield decreases because of competitive reactions. Formic acid accentuates the decrease. This hypothesis allows a quantitative interpretation of the experimental results which explains the influence of AH 2 concentration (1) by the presence of an oxidation chain by O 2 , initiated by OH and HO 2 radicals; this chain, however, is not important even at the highest concentrations, and (2) by a dilution effect allowing partial disproportionation of HO 2 radicals; the kinetic calculation leads to the value of the rate constant of oxidation of AH 2 by HO 2 : k 8 = 3300 M -1 sec -1

  18. Modeling of bubble growth in complex fluids. Application to radiolytic swelling of nuclear bituminized waste products

    International Nuclear Information System (INIS)

    Marchal, Antoine

    2015-01-01

    The aim of this PhD thesis is to predict the swelling of bitumen barrels in which radioactive salts are mixed. The bitumen exposed to radioactivity undergoes a chemical reaction: the radiolysis. This implies a generation of dihydrogen. The created is solubilized until the concentration reaches a limit value which is called saturation. Over this limit nucleation of bubbles is observed. Then they will grow thank to the contribution of the gas generated by radiolysis and they will be submitted to Archimede's principle so that they will rise in the fluid. The swelling is the result of the competition between generation and evacuation of gas. A model has been built to describe the evolution of a bubble population. Because of it is not possible to solve it analytically, a numerical program was developed. The results show that an increase of the fluid viscosity, the gas generation or the container height lead to an increase of the swelling and that an increase of the diffusion coefficient contributes to a decrease of the swelling. In the particular case of a yield stress fluid, the behavior of the bubble population is modified and the evacuation of gas is done with several shots, at the opposite of the case of a Newtonian fluid for which a stationary evacuation is reached. (author)

  19. Chemical effects of (n, γ) nuclear reaction on (Mo6Cl8)Cl4

    International Nuclear Information System (INIS)

    Fucugauchi, L.A.; Millan, S.; Mondragon, A.; Solache-Rios, M.

    1994-01-01

    The chemical effects of 98 Mo(n, γ) 99 Mo reaction on molybdenum(II) chloride [(Mo 6 Cl 8 )Cl 4 ] have been studied. Retention, thermal and radiolytical annealing were determined. It was found that this molybdenum compound has low retention, a negligible tendency to thermal annealing and a virtual insensitivity to hydrolysis. For practical applications in the enrichment of 99 Mo by the Shilard-Chalmers method, molybdenum(II) chloride [(Mo 6 Cl 8 )Cl 4 ] appears to offer good prospects. (author) 14 refs.; 2 figs

  20. Effects of alpha and gamma radiation on glass reaction in an unsaturated environment

    International Nuclear Information System (INIS)

    Wronkiewicz, D.J.; Young, J.E.; Bates, J.K.

    1990-01-01

    Radiation may effect the long-term performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water. The present study examines (1) the effects of alpha or gamma irradiation in a water vapor environment, and (2) the influence of radiolytic products on glass reaction. Results indicate that nitric and organic acids form in an irradiated water vapor environment and are dissolved in thin films of condensed water. Glass samples exposed to these conditions react faster and have a different assemblage of secondary phases than glasses exposed to nonirradiated water vapor environments. 23 refs., 4 figs., 2 tabs

  1. Alkylation of nitriles with gaseous carbenium ions. The ritter reaction in the dilute gas state

    International Nuclear Information System (INIS)

    Cacace, F.; Ciranni, G.; Giacomello, P.

    1982-01-01

    Radiolytically formed carbenium ions, such as sec-C 3 H 7 + , sec-C 4 H 9 + , and t-C 4 H 9 + , react in the gas phase with model aliphatic and aromatic nitriles yielding the corresponding nitrilium ions. The latter undergo efficient condensation with water that eventually leads to the formation of the corresponding N-alkylamides. The mechanism is analogous to the Ritter reaction in solution. The reactivity and selectivity of the gas-phase electrophilic attack on nitriles has been deduced from competition experiments under conditions that largely exclude the effects of solvation, ion pairing, etc., which complicate the interpretation of solution-chemistry measurements. 1 table

  2. Monitoring of gamma radiolytic degradation products of methoxychlor pesticide in water by solid phase micro-extraction using hplc and GC-MS (abstract)

    International Nuclear Information System (INIS)

    Butt, S.B.; Zafar, A.

    2011-01-01

    Monitoring, removal and management of toxic chemicals is an essential area of study regarding sustainable progress. Different approaches are adopted to eliminate these water born toxics from water and waste water. Among these gamma radiolytic is an emerging option. This ionization radiation generates highly reactive radicals that reacts with pollutants and hence eliminates these. A solid-phase micro-extraction (SPME) procedure has been developed for the successful preconcentration of organic pollutant irradiated water. A SPME fused-silica fiber coated with Polyacrylate was used as a probe to extract the organic pollutant after irradiation. In this reference, degradation of priority organic pollutant methoxychlor (1, 1, 1-Trichloro 2, 2-bis (p-methoxyphenyl) ethane, in water by gamma irradiation under varied experimental conditions has been investigated. The degree of gamma radiolytic degradation was monitored by HPLC-UV and GC-MS. For 4 kGy and 5 kGy gamma radiation dose at a rate of 200 kGyh/sup -1/ greater or equal to 95 % and 98 % MXC was degraded respectively. The degradation products were identified by Mass Spectrometry after comparing their MS spectras with the NIST 98 library. The major degradation occurs via dechlorination, dehydro chlorination, by the detachment of methoxyphenyl from MXC and by interaction of other radicals generated by the water radiolysis. (author)

  3. Temperature and radiolytic corrosion effects on the chlorine behaviour in nuclear graphite: consequences for the disposable of irradiated graphite from UNGG reactors

    International Nuclear Information System (INIS)

    Vaudey, C.E.

    2010-10-01

    This work concerns the dismantling of the UNGG reactor which have produced around 23 000 t of graphite wastes that ave to be disposed of according to the French law of June 206. These wastes contain two long-lived radionuclides ( 14 C and 36 Cl) which are the main long term dose contributors. In order to get information about their inventory and their long term behaviour in case of water ingress into the repository, it is necessary to determine their location and speciation in the irradiated graphite after the reactor shutdown. This work concerns the study of 36 Cl. The main objective is to reproduce its behaviour during reactor operation. For that purpose, we have studied the effects of temperature and radiolytic corrosion independently. Our results show a rapid release of around 20% 36 Cl during the first hours of reactor operation whereas a much slower release occurs afterwards. We have put in evidence two types of chlorine corresponding to two different chemical forms (of different thermal stabilities) or to two locations (of different accessibilities). We have also shown that the radiolytic corrosion seems to enhance chlorine release, whatever the irradiation dose. Moreover, the major chemical form of chlorine is inorganic. (author)

  4. The Radiolytic Destruction of Glycine Diluted in H2O and CO2 Ice: Implications for Mars and Other Planetary Environments

    Science.gov (United States)

    Gerakines, Perry A.; Hudson, R. L.

    2013-10-01

    Future missions to Mars and other planetary surfaces will probe under the surfaces of these worlds for signs of organic chemistry. In previous studies we have shown that glycine and other amino acids have radiolytic destruction rates that depend on temperature and on dilution within an H2O ice matrix (Gerakines et al., 2012; Gerakines and Hudson 2013). In the new work presented here, we have examined the destruction of glycine diluted in CO2 ice at various concentrations and irradiated with protons at 0.8 MeV, typical of cosmic rays and solar energetic particles. Destruction rates for glycine were measured by infrared spectroscopy in situ, without removing or warming the ice samples. New results on the half life of glycine in solid CO2 will be compared to those found in H2O ice matrices. The survivability of glycine in icy planetary surfaces rich in H2O and CO2 ice will be discussed, and the implications for planetary science missions will be considered. References: Gerakines, P. A., Hudson, R. L., Moore, M. H., and Bell, J-L. (2012). In-situ Measurements of the Radiation Stability of Amino Acids at 15 - 140 K. Icarus, 220, 647-659. Gerakines, P. A. and Hudson, R. L. (2013). Glycine's Radiolytic Destruction in Ices: First in situ Laboratory Measurements for Mars. Astrobiology, 13, 647-655.

  5. Development of a new simulation code for evaluation of criticality transients involving fissile solution boiling

    International Nuclear Information System (INIS)

    Basoglu, Benan; Yamamoto, Toshihiro; Okuno, Hiroshi; Nomura, Yasushi

    1998-03-01

    In this work, we report on the development of a new computer code named TRACE for predicting the excursion characteristics of criticality excursions involving fissile solutions. TRACE employs point neutronics coupled with simple thermal-hydraulics. The temperature, the radiolytic gas effects, and the boiling phenomena are estimated using the transient heat conduction equation, a lumped-parameter energy model, and a simple boiling model, respectively. To evaluate the model, we compared our results with the results of CRAC experiments. The agreement in these comparisons is quite satisfactory. (author)

  6. Study on the combustion behavior of radiolytically generated hydrogen explosion in small scale annular vessels at the reprocessing plant

    International Nuclear Information System (INIS)

    Kudo, Tatsuya; Tamauchi, Yoshikazu; Arai, Nobuyuki; Dai, Wenbin; Sakaihara, Motohiro; Kanehira, Osamu

    2017-01-01

    Hydrogen is generated by radiolysis of water, etc. in process vessels in reprocessing plant. Usually, the hydrogen is scavenged by compressed air into vessels to prevent hydrogen explosion. When an earthquake beyond design based occurs, for example, the compressed air may stop and the hydrogen starts accumulating in the vessels, and under this condition, an ignition source might set off hydrogen explosion. Therefore, the explosion derived by the radiolytically generated hydrogen is designated as one of severe accidents on Rokkasho Reprocessing Plant in new regulatory requirements. It is important to understand the combustion behavior of hydrogen explosion inside a vessel for consideration of safety measures against the severe accident, because the influences of detonation are not considered in the design basis of vessels. Especially, the investigations about the combustion behavior which considered influence of interior obstacles inside the vessel are not performed yet. In order to investigate the combustion behavior comprehensively, explosion experiment, combustion analysis and structural analysis are carried out using the representative vessels (small scale annular vessel, small scale plate vessel, large scale annular vessel and large scale cylindrical vessel) selected from Rokkasho Reprocessing Plant. In this paper, the results of experiments and analysis of small scale annular vessel (as one of representative vessel, imitated a pulsed column in the reprocessing plant) are reported. As imitated vessels, three vessels are manufactured with different interior obstacle arrangements as follows, A) cylindrical obstacles are faithfully reproduced and are arranged based on the actual vessel, B) cylindrical obstacles are arranged more densely than the actual vessel, and C) there are no obstacles inside the vessel. Experiments of hydrogen explosion are performed under condition of stoichiometric hydrogen-air ratio (premixed hydrogen-air is used). As a result of

  7. Nuclear Reaction Data Centers

    International Nuclear Information System (INIS)

    McLane, V.; Nordborg, C.; Lemmel, H.D.; Manokhin, V.N.

    1988-01-01

    The cooperating Nuclear Reaction Data Centers are involved in the compilation and exchange of nuclear reaction data for incident neutrons, charged particles and photons. Individual centers may also have services in other areas, e.g., evaluated data, nuclear structure and decay data, reactor physics, nuclear safety; some of this information may also be exchanged between interested centers. 20 refs., 1 tab

  8. A comprehensive comparative DFT study on adsorption and reactions involved in vinyl acetate synthesis from acetoxylation of ethylene on pure Pd(100) and Pd-Au(100): Elucidating the role of Au

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yanping [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Dong, Xiuqin [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University (China); Zhang, Minhua, E-mail: mhzhangtj@163.com [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China)

    2016-11-30

    Highlights: • Addition of Au into Pd increases the electron density of Pd d-band. • Addition of Au impairs adsorption of species in both Samanos and Moiseev mechanisms. • Addition of Au is kinetically unfavorable for Samonos mechanism. • Addition of Au hinders Moiseev mechanism without considering surface Os and OHs. • Addition of Au facilitates Moiseev mechanism with the effect of surface Os and OHs. - Abstract: Firstly, with DFT, electronic properties of Pd(100) and Pd-Au(100) were examined and it was found that addition of Au into Pd increases the electron density of Pd d-band. Besides, adsorption of relevant species involved in Samanos mechanism and Moiseev mechanism on Pd(100) and Pd-Au(100) was investigated and it was discovered that addition of Au impairs adsorption of species on metal surfaces. Finally, activation energies of all the reactions on Pd(100) and Pd-Au(100) were compared. Our calculations suggested that the rate-limiting step of the Samanos pathway on Pd(100) and Pd-Au(100) is the dehydrogenation of hydrogenated vinyl acetate. The rate-limiting step of the Moiseev pathway on Pd(100) is the coupling of vinyl with acetate, while that on Pd-Au(100) is the dehydrogenation of ethylene. The activation energies that are only involved in the Samanos mechanism become higher on Pd-Au(100) than on pure Pd(100), suggesting that alloying of Au is kinetically unfavorable for Samonos mechanism. Alloying of Au changes the rate-limiting step of Moiseev pathway, and Moiseev mechanism is preferred on Pd-Au(100).

  9. Reduction reactions of water soluble cyano-cobalt(III)-porphyrins: Metal versus ligand centered processes

    International Nuclear Information System (INIS)

    Mosseri, S.; Neta, P.; Harriman, A.; Hambright, P.

    1990-01-01

    Reduction reactions of dicyano-cobalt(III)-porphyrins [potential in vivo cyanide scavenger drugs] were studied by radiolytic and electrochemical methods using the water soluble tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and tetrakis(N-methyl-4-pyridyl)porphyrin (TMPyP). For [(CN)2CoIIITPPS]-, reduction occurs stepwise to the CoII, CoI, and finally to the phlorin anion. This behavior is similar to that of the cobalt porphyrins in the absence of cyanide, except that the cyanide ligand shifts the reduction potentials to much more negative values. On the other hand, under radiolytic conditions, [(CN)2CoIIITMPyP]- is reduced on the porphyrin macrocycle by one electron to give the CoIII pi-radical anion, which disproportionates into the initial complex and the two-electron ring reduced CoIII phlorin. The radical anion is also formed by intramolecular electron transfer subsequent to the reaction of CoIITMPyP and cyanide. The results are compared with the chemistry of Vitamin B-12

  10. Noncanonical Reactions of Flavoenzymes

    Directory of Open Access Journals (Sweden)

    Pablo Sobrado

    2012-11-01

    Full Text Available Enzymes containing flavin cofactors are predominantly involved in redox reactions in numerous cellular processes where the protein environment modulates the chemical reactivity of the flavin to either transfer one or two electrons. Some flavoenzymes catalyze reactions with no net redox change. In these reactions, the protein environment modulates the reactivity of the flavin to perform novel chemistries. Recent mechanistic and structural data supporting novel flavin functionalities in reactions catalyzed by chorismate synthase, type II isopentenyl diphosphate isomerase, UDP-galactopyranose mutase, and alkyl-dihydroxyacetonephosphate synthase are presented in this review. In these enzymes, the flavin plays either a direct role in acid/base reactions or as a nucleophile or electrophile. In addition, the flavin cofactor is proposed to function as a “molecular scaffold” in the formation of UDP-galactofuranose and alkyl-dihydroxyacetonephosphate by forming a covalent adduct with reaction intermediates.

  11. Radiation-induced chemical reactions of carbon monoxide and hydrogen mixture

    International Nuclear Information System (INIS)

    Sugimoto, S.; Nishii, M.; Sugiura, T.

    1984-01-01

    The radiation chemical reaction of CO-H 2 mixture has been studied in the pressure range from 10 4 to 1.3 x 10 5 Pa using 7 l. reaction vessel made of stainless steel. Various hydrocarbons and oxygen containing compounds such as methane, formaldehyde, acetaldehyde, and methanol have been obtained as radiolytic products. The amounts and the G values of these products depended upon the irradiation conditions such as composition of reactant, total pressure, reaction temperature, and dose. It was found that the irradiation at low dose produced small amounts of trioxane and tetraoxane, which have not yet been reported in literature. The yields of these cyclic ethers increased at high pressure and at low temperature. An experiment was also made on CO-H 2 mixture containing ammonia as a cation scavenger to investigate the precursor of these products. (author)

  12. Step-by-Step Simulation of Radiation of Radiation Chemistry Using Green Functions for Diffusion-Influenced Reactions

    Science.gov (United States)

    Plante, Ianik; Cucinotta, Francis A.

    2011-01-01

    The irradiation of biological systems leads to the formation of radiolytic species such as H(raised dot), (raised dot)OH, H2, H2O2, e(sup -)(sub aq), etc.[1]. These species react with neighboring molecules, which result in damage in biological molecules such as DNA. Radiation chemistry is there for every important to understand the radiobiological consequences of radiation[2]. In this work, we discuss an approach based on the exact Green Functions for diffusion-influenced reactions which may be used to simulate radiation chemistry and eventually extended to study more complex systems, including DNA.

  13. Reaction of H atoms with chelators in highly basic solution: H2 production in high level liquid waste simulants

    International Nuclear Information System (INIS)

    Barnabas, F.; Cerny, E.; Jonah, C.D.; Meisel, D.; Sauer, M.C. Jr.

    1995-01-01

    The rate constants for hydrogen abstraction by H from ethylene-diamine tetracetic acid (EDTA), N-(2-hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), glycolic acid and citric acid were measured at pH 13. The predominant product of these reactions is H 2 . The rate constants obtained are more than an order of magnitude larger than the literature rates that had been measured at pH 1. These measurements are of significance for understanding the radiolytic production of H 2 in nuclear waste storage tanks. (Author)

  14. Radiolytic bubble formation and level changes in simulated high-level waste salts and sludges -- application to Savannah River Site and Hanford Storage tanks

    International Nuclear Information System (INIS)

    Walker, D.D.; Crawford, C.L.; Bibler, N.E.

    1993-01-01

    Radiolytically-produced bubbles of trapped gas are observed in simulated high-level waste (HLW) damp salt cake exposed to Co-60 gamma radiation. As the damp salt cake is irradiated, its volume increases due to the formation of trapped gas bubbles. Based on the increase in volume, the rate of trapped gas generation varies between 0.04 and 0.2 molecules/100 eV of energy deposited in the damp salt cake. The maximum volume of trapped gas observed in experiments is in the range 21--26 vol %. After reaching these volumes, the gas bubbles begin to escape. The generated gas includes hydrogen, oxygen, and nitrous oxide. The ratio in which these components are produced depends on the composition of the waste. Nitrous oxide production increases with the amount of sodium nitrite. Gases trapped by this mechanism may account for some of the observed level changes in Savannah River Site and Hanford waste tanks

  15. Experimental determination and chemical modelling of radiolytic processes at the spent fuel/water interface. Experiments carried out in carbonate solutions in absence and presence of chloride

    Energy Technology Data Exchange (ETDEWEB)

    Bruno, Jordi; Cera, Esther; Grive, Mireia; Duro, Lara [Enviros Spain SL (Spain); Eriksen, Trygve [Royal Inst. of Tech., Stockholm (Sweden). Dept. of Nuclear Chemistry

    2003-01-01

    We report on the recent experimental and modelling results of a research programme that started in 1995. The aim has been to understand the kinetic and thermodynamic processes that control the radiolytic generation of oxidants and reductants at the spent fuel water interface and their consequences for spent fuel matrix stability and radionuclide release. This has been done by carrying out well-controlled dissolution experiments of PWR Ringhals spent fuel fragments in an initially anoxic closed system and by using different solution compositions. Experimental series started with several tests carried out with deionised water as solvent, in a second phase experiments were conducted with 10 mM bicarbonate solutions. New experimental series were set up during the last two years by using the same bicarbonate content in solutions with varying NaCl concentrations in order to ascertain the role of this ligand on the radiolytic products and its consequence for radionuclide release. The selected NaCl concentrations are in the range of 0.1 to 10 mM. Experimental data shows that uranium dissolution at early contact times is controlled by the oxidation of the UO{sub 2} matrix. This process controls the co-dissolution of most of the analysed radionuclides, including Sr, Mo, Tc, Np and surprisingly enough, Cs. In the overall the release rates for U and the matrix associated radionuclides are in the range of 10{sup -6} moles/day with a clear decreasing trend with exposure time and after 2 years the initial release rates have decreased down to 3x10{sup -8} moles/day. The solubility of the released actinides appears to be limited by the formation of An(IV) hydroxide phases, although Np concentrations in solution did not reach solubility levels during the time intervals of the present tests. No secondary solid phase appears to control the solubility of the rest of the elements.

  16. Investigation of the effects of radiolytic-gas bubbles on the long-term operation of solution reactors for medical-isotope production

    Science.gov (United States)

    Souto Mantecon, Francisco Javier

    One of the most common and important medical radioisotopes is 99Mo, which is currently produced using the target irradiation technology in heterogeneous nuclear reactors. The medical isotope 99Mo can also be produced from uranium fission using aqueous homogeneous solution reactors. In solution reactors, 99Mo is generated directly in the fuel solution, resulting in potential advantages when compared with the target irradiation process in heterogeneous reactors, such as lower reactor power, less waste heat, and reduction by a factor of about 100 in the generation of spent fuel. The commercial production of medical isotopes in solution reactors requires steady-state operation at about 200 kW. At this power regime, the formation of radiolytic-gas bubbles creates a void volume in the fuel solution that introduces a negative coefficient of reactivity, resulting in power reduction and instabilities that may impede reactor operation for medical-isotope production. A model has been developed considering that reactivity effects are due to the increase in the fuel-solution temperature and the formation of radiolytic-gas bubbles. The model has been validated against experimental results from the Los Alamos National Laboratory uranyl fluoride Solution High-Energy Burst Assembly (SHEBA), and the SILENE uranyl nitrate solution reactor, commissioned at the Commissariat a l'Energie Atomique, in Valduc, France. The model shows the feasibility of solution reactors for the commercial production of medical isotopes and reveals some of the important parameters to consider in their design, including the fuel-solution type, 235U enrichment, uranium concentration, reactor vessel geometry, and neutron reflectors surrounding the reactor vessel. The work presented herein indicates that steady-state operation at 200 kW can be achieved with a solution reactor consisting of 120 L of uranyl nitrate solution enriched up to 20% with 235U and a uranium concentration of 145 kg/m3 in a graphite

  17. Workgroup Report by the Joint Task Force Involving American Academy of Allergy, Asthma & Immunology (AAAAI); Food Allergy, Anaphylaxis, Dermatology and Drug Allergy (FADDA) (Adverse Reactions to Foods Committee and Adverse Reactions to Drugs, Biologicals, and Latex Committee); and the Centers for Disease Control and Prevention Botulism Clinical Treatment Guidelines Workgroup-Allergic Reactions to Botulinum Antitoxin: A Systematic Review.

    Science.gov (United States)

    Schussler, Edith; Sobel, Jeremy; Hsu, Joy; Yu, Patricia; Meaney-Delman, Dana; Grammer, Leslie C; Nowak-Wegrzyn, Anna

    2017-12-27

    Naturally occurring botulism is rare, but a large number of cases could result from unintentional or intentional contamination of a commercial food. Despeciated, equine-derived, heptavalent botulinum antitoxin (HBAT) is licensed in the United States. Timely treatment reduces morbidity and mortality, but concerns that botulinum antitoxin can induce anaphylaxis exist. We sought to quantify the allergy risk of botulinum antitoxin treatment and the usefulness of skin testing to assess this risk. We conducted a systematic review of (1) allergic reactions to botulinum antitoxin and (2) the predictive value of skin testing (ST) before botulinum antitoxin administration. We searched 5 scientific literature databases, reviewed articles' references, and obtained data from the HBAT manufacturer and from the Centers for Disease Control and Prevention. Anaphylaxis incidence was determined for HBAT and previously employed botulinum antitoxins. We calculated the positive predictive value (PPV) and negative predictive value (NPV) of ST for anaphylaxis related to HBAT and other botulinum antitoxins. Seven articles were included. Anaphylaxis incidence was 1.64% (5/305 patients) for HBAT and 1.16% (8/687 patients) for all other botulinum antitoxins (relative risk, 1.41 [95% confidence interval, .47-4.27]; P = .5). Observed values for both PPV and NPV for HBAT-ST (33 patients) were 100%. Observed PPVs and NPVs of ST for other botulinum antitoxins (302 patients) were 0-56% and 50%-100%, respectively. There were no reports of fatal anaphylaxis. Considering the <2 % rate of anaphylaxis, fatal outcomes, modest predictive value of ST, resource requirements for ST, and the benefits of early treatment, data do not support delaying HBAT administration to perform ST in a mass botulinum toxin exposure. Anaphylactic reactions may occur among 1%-2% of botulinum antitoxin recipients and will require epinephrine and antihistamine treatment and, possibly, intensive care. Published by Oxford

  18. Nuclear reactions

    International Nuclear Information System (INIS)

    Lane, A.M.

    1980-01-01

    In reviewing work at Harwell over the past 25 years on nuclear reactions it is stated that a balance has to be struck in both experiment and theory between work on cross-sections of direct practical relevance to reactors and on those relevant to an overall understanding of reaction processes. The compound nucleus and direct process reactions are described. Having listed the contributions from AERE, Harwell to developments in nuclear reaction research in the period, work on the optical model, neutron capture theory, reactions at doorway states with fine structure, and sum-rules for spectroscopic factors are considered in more detail. (UK)

  19. Photochemical and radiation chemistry investigations of reaction kinetics of dissolved electrons in water and ammonium-water mixtures

    International Nuclear Information System (INIS)

    Telser, T.

    1986-01-01

    In the reaction of hydrated electrons in aqueous alkaline solutions, an intermediate product is observed. In this work, this intermediate product was determined to be a long life photoactive product in double flash experiments, which reacts at a speed constant K = 1x10 9 M -1 s -1 in a reaction of the 2nd order. It is formed in a reaction of the 1st order with reference to the electron concentration (e aq - → X, 2X → H 2 ). The alkaline metal cations of the solution appear as reaction partners of the hydrated electrons. The hydrated metal atoms formed were observed in the UV spectrum as absorpton bands at 270 nm. Pulse radiolytic measurements confirm the conclusions of the photochemical experiments. (RB) [de

  20. Parental involvement

    Directory of Open Access Journals (Sweden)

    Ezra S Simon

    2005-01-01

    Full Text Available Parent-Teacher Associations and other community groups can play a significant role in helping to establish and run refugee schools; their involvement can also help refugee adults adjust to their changed circumstances.

  1. Electron transfer reactions

    CERN Document Server

    Cannon, R D

    2013-01-01

    Electron Transfer Reactions deals with the mechanisms of electron transfer reactions between metal ions in solution, as well as the electron exchange between atoms or molecules in either the gaseous or solid state. The book is divided into three parts. Part 1 covers the electron transfer between atoms and molecules in the gas state. Part 2 tackles the reaction paths of oxidation states and binuclear intermediates, as well as the mechanisms of electron transfer. Part 3 discusses the theories and models of the electron transfer process; theories and experiments involving bridged electron transfe

  2. Picosecond pulse radiolysis study of primary reactions in solutions

    International Nuclear Information System (INIS)

    El-Omar, Abdel Karim

    2013-01-01

    Following the discovery of ionizing radiations and their chemical effects, it was important to study and comprehend the formation mechanisms of short lived free radicals and molecular products. In order to perform such studies, researchers and research groups worked on developing tools allowing both formation and detection of those species at short time scales. Nowadays, pulse radiolysis imposed itself as a fundamental and efficient tool allowing scientists to probe chemical effects as well as reaction mechanisms in studied media. The Laboratoire de Chimie Physique d'Orsay 'LCP' is an interdisciplinary laboratory hosting the platform of fast kinetics known as 'ELYSE'. Due to its femtosecond laser and its picosecond electron accelerator, we have the possibility to study chemical effects of ionizing radiations interaction with media at ultrashort times up to ∼5 ps.Knowing that we are interested in primary reactions induced in aqueous media by ionizing radiations, ELYSE represents the essential tool in performing our studies. The obtained results concern:- First direct determination of hydroxyl radical 'HO*' radiolytic yield as function of time at picosecond time scale;- Direct effect of ionizing radiation in highly concentrated aqueous solutions as well as investigation of the ultrafast electron transfer reaction between solute molecules and positive holes 'H 2 O*+' formed upon water radiolysis;- Study at room temperature of electron transfer reaction between solvated electron (electron donor) and organic solutes (electron acceptors) en viscous medium;- Study at room temperature of electron's solvation dynamics in ethylene glycol and 2-propanol. (author)

  3. Low-Temperature Thermal Reactions Between SO2 and H2O2 and Their Relevance to the Jovian Icy Satellites

    Science.gov (United States)

    Loeffler, Mark J.; Hudson, Reggie L.

    2013-01-01

    Here we present first results on a non-radiolytic, thermally-driven reaction sequence in solid H2O +SO2 + H2O2 mixtures at 50-130 K, which produces sulfate (SO(-2)/(4)), and has an activation energy of 53 kJ/mole. We suspect that these results may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto.

  4. Quasielastic reactions

    International Nuclear Information System (INIS)

    Henning, W.

    1979-01-01

    Quasielastic reaction studies, because of their capability to microscopically probe nuclear structure, are still of considerable interest in heavy-ion reactions. The recent progress in understanding various aspects of the reaction mechanism make this aim appear closer. The relation between microscopic and macroscopic behavior, as suggested, for example, by the single proton transfer data to individual final states or averaged excitation energy intervals, needs to be explored. It seems particularly useful to extend measurements to higher incident energies, to explore and understand nuclear structure aspects up to the limit of the energy range where they are important

  5. Reaction Qualifications Revisited

    DEFF Research Database (Denmark)

    Lippert-Rasmussen, Kasper

    2009-01-01

    to a person's effectiveness by causing a favourable reaction in customers, co-workers etc. (for short: recipients) - are involved, this assumption is false. Building on work by Wertheimer, Mason, and Miller, this paper proposes an account of the reaction qualifications that count, from the point of view...... preferences, recipients should not respond to the applicant actually hired on the basis of their (the recipients') racial preferences. My account decomposes the meritocratic ideal into four separate norms, one of which applies to recipients rather than to selectors. Finally, it defends the view that reaction...... qualifications based on antimeritocratic reactions, while not unproblematic, are not entirely irrelevant from the point of view of merit. Notably, selectors need not discount them when no one - including the targets of the objectionable preferences - is unfairly disadvantaged. Because not all problematic...

  6. Reaction Qualifications Revisited

    DEFF Research Database (Denmark)

    Lippert-Rasmussen, Kasper

    2009-01-01

      When, in a competitive sphere, people are selected on the basis of qualifications only, their chances of acquiring positions of advantage may seem to depend entirely upon their abilities, not discriminatory bias. However, if reaction qualifications - i.e. characteristics which contribute...... to a person's effectiveness by causing a favourable reaction in customers, co-workers etc. (for short: recipients) - are involved, this assumption is false. Building on work by Wertheimer, Mason, and Miller, this paper proposes an account of the reaction qualifications that count, from the point of view...... of merit. Specifically, it preserves symmetry between negative evaluations of antimeritocratic bases of selection and negative evaluations of qualifications rooted in comparable antimeritocratic reactions. So if employers should not select among applicants on the basis of their (the employers') racial...

  7. Radiolytic stabilization of poly(methyl methacrylate) using commercial additives; Estabilizacao radiolitica do poli(metacrilato de metila) usando aditivos comerciais

    Energy Technology Data Exchange (ETDEWEB)

    Aquino, Katia Aparecida da Silva

    2000-04-01

    Poly(methyl methacrylate), PMMA, Acrigel, a Brazilian polymer, is used in the manufacture of medical supplies sterelizable by ionizing radiation. However, when PMMA is gamma-irradiated it undergoes main chain scissions, which promote molecular degradation causing reduction in its mechanical properties. Therefore, radiolytic of PMMA is important for it to become commercially radiosterizable. In this work some commercial additives, originally used in photo-and thermo-oxidate stabilization of polymers, were tested. Only two additives, type HALS (Hindered Amine Light Stabilizer), denoted Scavenger, showed a good protective quality. The investigation of radiation-induced main scissions was carried out by viscosimetric method. The most effective additive, added to the polymer system at 0.3 w/w%, promotes a great molecular radioprotection of 93%. That means a reduction of G-value (scissions/100 eV) from 0.611 to 0.053. In addition, the glassy transition temperature (T{sub g}) of PMMA (no additive) significantly changed by radiation does not change when PMMA (with additive) is irradiated. The spectroscopy analysis, FT-IR and NMR ({sup 1}H), showed that the radioprotector added to the system does not change the PMMA structure. (author)

  8. Fabrication of Nonenzymatic Glucose Sensors Based on Multiwalled Carbon Nanotubes with Bimetallic Pt-M (M = Ru and Sn Catalysts by Radiolytic Deposition

    Directory of Open Access Journals (Sweden)

    Sun-Young Kwon

    2012-01-01

    Full Text Available Nonenzymatic glucose sensors employing multiwalled carbon nanotubes (MWNTs with highly dispersed Pt-M (M = Ru and Sn nanoparticles (Pt-M@PVP-MWNTs were fabricated by radiolytic deposition. The Pt-M nanoparticles on the MWNTs were characterized by transmittance electron microscopy, elemental analysis, and X-ray diffraction. They were found to be well dispersed and to exhibit alloy properties on the MWNT support. Electrochemical testing showed that these nonenzymatic sensors had larger currents (mA than that of a bare glassy carbon (GC electrode and one modified with MWNTs. The sensitivity (A mM−1, linear range (mM, and detection limit (mM (S/N = 3 of the glucose sensor with the Pt-Ru catalyst in NaOH electrolyte were determined as 18.0, 1.0–2.5, 0.7, respectively. The corresponding data of the sensor with Pt-Sn catalyst were 889.0, 1.00–3.00, and 0.3, respectively. In addition, these non-enzymatic sensors can effectively avoid interference arising from the oxidation of the common interfering species ascorbic acid and uric acid in NaOH electrolyte. The experimental results show that such sensors can be applied in the detection of glucose in commercial red wine samples.

  9. The application of the pore population balance method to the calculation of the radiolytic weight loss and gas transport property changes of nuclear graphites

    International Nuclear Information System (INIS)

    Johnson, P.A.V.

    1982-01-01

    A pore population balance equation, previously used to describe the physical property changes of porous carbons during thermal oxidation in carbon dioxide, has been modified to treat the radiolytic oxidation of graphite in CO 2 /CO/CH 4 gas mixtures. Good agreement has been obtained between theory and experiment for the variation in the gas transport coefficients B, K and lambda of gilsonite graphite with absorbed radiation dose. Calculations indicate that the addition of blind pores to the transport porosity, and an allowance for the opening of closed pores with burn-off, do not account for the experimental fractional weight loss curve. An excellent fit is obtained, however, if a small volume of cylindrical pores of a mean radius approximately equal to the diffusion length of oxidising species in the coolant are present in the pore size spectrum. Gilsonite graphite therefore behaves as if the pore size distribution function is trimodal, with mean radii at about 0.5μm, 2.48μm and greater than or equal to 10.57μm. (author)

  10. Radiolytic Synthesis of Pt-Ru Catalysts Based on Functional Polymer-Grafted MWNT and Their Catalytic Efficiency for CO and MeOH

    Directory of Open Access Journals (Sweden)

    Dae-Soo Yang

    2011-01-01

    Full Text Available Pt-Ru catalysts based on functional polymer-grafted MWNT (Pt-Ru@FP-MWNT were prepared by radiolytic deposition of Pt-Ru nanoparticles on functional polymer-grafted multiwalled carbon nanotube (FP-MWNT. Three different types of functional polymers, poly(acrylic acid (PAAc, poly(methacrylic acid (PMAc, and poly(vinylphenyl boronic acid (PVPBAc, were grafted on the MWNT surface by radiation-induced graft polymerization (RIGP. Then, Pt-Ru nanoparticles were deposited onto the FP-MWNT supports by the reduction of metal ions using γ-irradiation to obtain Pt-Ru@FP-MWNT catalysts. The Pt-Ru@FP-MWNT catalysts were then characterized by XRD, XPS, TEM ,and elemental analysis. The catalytic efficiency of Pt-Ru@FP-MWNT catalyst was examined for CO stripping and MeOH oxidation for use in a direct methanol fuel cell (DMFC. The Pt-Ru@PVPBAc-MWNT catalyst shows enhanced activity for electro-oxidation of CO and MeOH oxidation over that of the commercial E-TEK catalyst.

  11. Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

    Science.gov (United States)

    Liechty, Derek S.; Lewis, Mark J.

    2010-01-01

    Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

  12. Reaction mechanisms

    International Nuclear Information System (INIS)

    Nguyen Trong Anh

    1988-01-01

    The 1988 progress report of the Reaction Mechanisms laboratory (Polytechnic School, France), is presented. The research topics are: the valence bond methods, the radical chemistry, the modelling of the transition states by applying geometric constraints, the long range interactions (ion - molecule) in gaseous phase, the reaction sites in gaseous phase and the mass spectroscopy applications. The points of convergence between the investigations of the mass spectroscopy and the theoretical chemistry teams, as well as the purposes guiding the research programs, are discussed. The published papers, the conferences, the congress communications and the thesis, are also reported [fr

  13. Involving women.

    Science.gov (United States)

    Agbo, J

    1994-01-01

    I am a primary health care (PHC) coordinator working with the May Day Rural project, a local NGO involved in integrated approaches and programs with rural communities in the Ga District of the Greater-Accra region in Ghana. When we talk about the community development approach we must first and foremost recognize that we are talking about women, because in the developing world frequent childbirths mean that her burden of mortality is higher than a man's; her workload is extremely heavy--whether in gardening, farming, other household duties, caring for the sick, or the rearing of children; she has a key role in PHC and community development, because men are always looking for greener pastures elsewhere, leaving the women behind. Women's concerns are critical in most health care projects and women and children are their main beneficiaries. Why not include women in the management team, project design, implementation and evaluation processes? That is what the May Day Rural project is practicing, encouraging women's participation and creating a relationship of trust. full text

  14. Allergic reactions

    Science.gov (United States)

    ... that don't bother most people (such as venom from bee stings and certain foods, medicines, and pollens) can ... person. If the allergic reaction is from a bee sting, scrape the ... more venom. If the person has emergency allergy medicine on ...

  15. Multiresponse modelling of the caramelisation reaction

    OpenAIRE

    Quintas, Mafalda; Guimarães, Carla; Baylina, João; Brandão, Teresa R. S.; Silva, Cristina L.M.

    2007-01-01

    Multiresponse modelling is a powerful tool for studying complex kinetics of reactions occurring in food products. This modelling technique uses information of reactants and products involved, allowing insightful kinetic parameters estimation and helping in clarifying reaction mechanisms. One example of a complex reaction that occurs in food processing is the caramelisation reaction. Caramelisation is the common name for a group of reactions observed when carbohydrates are exposed to high temp...

  16. 2-Dodecylcyclobutanone, a radiolytic product of palmitic acid, is genotoxic in primary human colon cells and in cells from preneoplastic lesions

    International Nuclear Information System (INIS)

    Knoll, Nadine; Weise, Anja; Claussen, Uwe; Sendt, Wolfgang; Marian, Brigitte; Glei, Michael; Pool-Zobel, Beatrice L.

    2006-01-01

    The irradiation of fat results in the formation of 2-alkylcyclobutanones, a new class of food contaminants. Results of previous in vitro studies with primary human colon cells and in vivo experiments with rats fed with 2-alkylcyclobutanones indicated that these radiolytic derivatives may be genotoxic and enhance the progression of colon tumors. The underlying mechanisms of these effects, however, are not clearly understood. Therefore we performed additional investigations to elucidate the genotoxic potential of 2-dodecylcyclobutanone (2dDCB) that is generated from palmitic acid. In particular, we explored the relative sensitivities of human colon cells, representing different stages of tumor development and healthy colon tissues, respectively. HT29clone19A cells, LT97 adenoma cells and primary human epithelial cells were exposed to 2dDCB (150-2097 μM). We determined cytotoxic effects using trypan blue exclusion. Genotoxicity, reflected as strand breaks, was assessed using the alkaline version of the comet assay and chromosomal abnormalities were investigated by 24-color fluorescence-in-situ-hybridization. 2dDCB was cytotoxic in a time- and dose-dependent manner in LT97 adenoma cells and in freshly isolated primary cells but not in the human colon tumor cell line. Associated with this was a marked induction of DNA damage by 2dDCB in LT97 adenoma cells and in freshly isolated colonocytes, whereas in the HT29clone19A cells no strand breaks were detectable. A long-term incubation of LT97 adenoma cells with lower concentrations of 2dDCB revealed cytogenetic effects. In summary, 2dDCB was clearly genotoxic in healthy human colon epithelial cells and in cells representing preneoplastic colon adenoma. These findings provide additional evidence that this compound may be regarded as a possible risk factor for processes in colon carcinogenesis related to initiation and progression

  17. Radiolytic stabilization of poly(methyl methacrylate) in blends with polystyrene; Estabilizacao radiolitica do poli(metacrilato de metila) em misturas fisicas com poliestireno

    Energy Technology Data Exchange (ETDEWEB)

    Lima, Ivania Soares de

    2002-04-01

    In this work the radiolytic stabilization of poly(methyl methacrylate) was analyzed by three radioprotective agents: polystyrene (PS) and hindered amine light stabilizers (HEALS), respectively, PMMA/PS systems, so a called polymeric blends were prepared with different compositions, where the miscibility of these blends were studied using viscometric, microscopy (SEM) and spectroscopy (FT-IR) techniques. The results show that PMMA/PS blends in the compositions below 10 wt% of PS are miscible, on films casting from solution of toluene and methyl-ethyl-ketone (1;1) mixture. On the other hand, in the composition above 10 wt% of PS, PMMA/PS blends show imminiscibility behavior. These polymer solutions were irradiated with gamma rays ({sup 60} Co) and viscometric, microscopic and spectroscopic experiments show gamma radiation-induced compatibilization on PMMA/PS blends on proportion 50/50 and 30/70 take place. Viscometric interaction parameters of miscible and compatibilized PMMA/PS bends were calculated in the range of - 50 kGy, with the goal to find out the polymeric interactions after irradiation of the films. G values of PMMA, PMMA/PS and PMMA+St systems were calculated in order to analyze the radioprotection of PS and St into PMMA matrix. The results show that (90/10) PMMA/PS and PMMA+1,5%St systems promote protection against the gamma the radiation-induced scissions, effect that leads to polymer degradation. Moreover, a small amount of crosslinking observed in irradiated blends has contributed to stabilize mechanical properties of PMMA films. PMMA+0,3% HALS system irradiated in doses above 60 kGy showed little stabilization of the mechanical properties of PMMA, since it was observed mechanical degradation this system. Based on these results, PS and St showed to be the best radioprotective agents to PMMA. (author)

  18. Role of e{sub aq}{sup −}, ·OH and H· in radiolytic degradation of atrazine: A kinetic and mechanistic approach

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Javed Ali, E-mail: javed_chemistry@yahoo.com [Radiation Chemistry Laboratory, National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120 (Pakistan); Shah, Noor S. [Radiation Chemistry Laboratory, National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120 (Pakistan); Institute of Chemical Sciences, University of Swat, Swat 19130 (Pakistan); Nawaz, Shah; Ismail, M.; Rehman, Faiza [Radiation Chemistry Laboratory, National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120 (Pakistan); Khan, Hasan M., E-mail: hmkhan@upesh.edu.pk [Radiation Chemistry Laboratory, National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120 (Pakistan)

    2015-05-15

    Highlights: • Atrazine was efficiently removed from aqueous solution by γ-ray irradiation. • e{sub aq}{sup −} was found to have more crucial role in removal of atrazine than ·OH. • Atrazine degradation was reduced in the presence of t-BuOH and i-PrOH. • Atrazine showed high stability at neutral pH than at very low and high pH conditions. • Potential degradation mechanism was evaluated by GC–MS analysis. - Abstract: The degradation of atrazine was investigated in aqueous solution by gamma-ray irradiation. 8.11 μM initial atrazine concentration could be completely removed in N{sub 2} saturated solution by applying 3500 Gy radiation dose at a dose rate of 296 Gy h{sup −1}. Significant removal of atrazine (i.e., 39.4%) was observed at an absorbed dose of 1184 Gy in air saturated solution and the removal efficiency was promoted to 50.5 and 65.4% in the presence of N{sub 2}O and N{sub 2} gases, respectively. The relative contributions of hydrated electron, hydroxyl radical and hydrogen radical toward atrazine degradation were determined as ratio of observed dose constant (k{sub obs}) and found to be 5: 3: 1 for k{sub eaq}{sup −}: k{sub ·OH}: k{sub H}·, respectively. The degradation efficiency of atrazine was 69.5, 55.6 and 37.3% at pH 12.1, 1.7 and 5.7, respectively. A degradation mechanism was proposed based on the identified degradation by-products by gas chromatography–mass spectrometry. Taking the relative contributions of oxidative and reductive species to atrazine degradation into account, reductive pathway proved to be a better approach for the radiolytic treatment of atrazine contaminated water.

  19. Radiolytic Preparation of Electrocatalysts with Pt-Co and Pt-Sn Nanoparticles for a Proton Exchange Membrane Fuel Cell

    Directory of Open Access Journals (Sweden)

    Sang Kyum Kim

    2014-01-01

    Full Text Available Nanosized Pt-Sn/VC and Pt-Co/VC electrocatalysts were prepared by a one-step radiation-induced reduction (30 kGy process using distilled water as the solvent and Vulcan XC72 as the supporting material. While the Pt-Co/VC electrodes were compared with Pt/VC (40 wt%, HiSpec 4000, in terms of their electrocatalytic activity towards the oxidation of H2, the Pt-Co/VC electrodes were evaluated in terms of their activity towards the hydrogen oxidation reaction (HOR and compared with Pt/VC (40 wt%, HiSpec 4000, Pt-Co/VC, and Pt-Sn/VC in a single cell. Additionally, the prepared electrocatalyst samples (Pt-Co/VC and Pt-Sn/VC were characterized by transmission electron microscopy (TEM, scanning electron microscope (SEM, thermogravimetric analysis (TGA, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, electrochemical surface area (ECSA, and fuel cell polarization performance.

  20. Giant-Planet Chemistry: Ammonium Hydrosulfide (NH4SH), Its IR Spectra and Thermal and Radiolytic Stabilities

    Science.gov (United States)

    Loeffler, Mark J.; Hudson, Reggie L.; Chanover, Nancy J.; Simon, Amy A.

    2015-01-01

    Here we present our recent studies of proton-irradiated and unirradiated ammonium hydrosulfide, NH4SH, a compound predicted to be an important tropospheric cloud component of Jupiter and other giant planets. We irradiated both crystalline and amorphous NH4SH at 10-160 K and used IR spectroscopy to observe and identify reaction products in the ice, specifically NH3 and long-chained sulfur-containing ions. Crystalline NH4SH was amorphized during irradiation at all temperatures studied with the rate being the fastest at the lowest temperatures. Irradiation of amorphous NH4SH at approximately 10-75 K showed that 60-80% of the NH4 + remained when equilibrium was reached, and that NH4SH destruction rates were relatively constant within this temperature range. Irradiations at higher temperatures produced different dose dependence and were accompanied by pressure outbursts that, in some cases, fractured the ice. The thermal stability of irradiated NH4SH was found to be greater than that of unirradiated NH4SH, suggesting that an irradiated giant-planet cloud precipitate can exist at temperatures and altitudes not previously considered.

  1. Kinetics of the gas-phase tritium oxidation reaction

    International Nuclear Information System (INIS)

    Failor, R.A.

    1989-01-01

    Homogeneous gas-phase kinetics of tritium oxidation (2T 2 + O 2 →2T 2 O) have been studied with a model that accounts explicitly for radiolysis of the major species and the kinetics of the subsequent reactions of ionic, excited-state, and neutral species. Results from model calculations are given for 10 -4 -1.0 mol% T 2 in O 2 (298 K, 1 atm). As the reaction evolves three different mechanisms control T 2 O production, each with a different overall rate expression and a different order with respect to the T 2 concentration. The effects of self-radiolysis of pure T 2 on the tritium oxidation reaction were calculated. Tritium atoms, the primary product of T 2 self-radiolysis, altered the oxidation mechanism only during the first few seconds following the initiation of the T 2 -O 2 reaction. Ozone, an important intermediate in T 2 oxidation, was monitored in-situ by U.V. absorption spectroscopy for 0.01-1.0 mol% T 2 an 1 atm O 2 . The shape of the experimental ozone time profile agreed with the model predictions. As predicted, the measured initial rate of ozone production varied linearly with initial T 2 concentration ([T 2 ] 0.6 o ), but at an initial rate one-third the predicted value. The steady-state ozone concentration ([O 3 ]ss) was predicted to be dependent on [T 2 ] 0.3 o , but the measured value was [T 2 ] 0.6 o , resulting in four times higher [O 3 ]ss than predicted for a 1.0% T 2 -O 2 mixture. Adding H 2 to the T 2 -O 2 mixture, to provide insight into the differences between the radiolytic and chemical behavior of the tritium, produced a greater decrease in [O 3 ]ss than predicted. Adjusting the reaction cell surface-to-volume ratio showed implications of minor surface removal of ozone

  2. Radiation induced chemical changes in foodstuffs model reaction systems and strawberries

    International Nuclear Information System (INIS)

    Breitfellner, F.

    1999-10-01

    In the first part of this work 4-hydroxybenzoic acid (4-HBA) and 4-hydroxybenzoic acid ethyl ester (4-HBAEE) were investigated in order to elucidate the reaction mechanisms leading to final products after reaction with OH-radicals (N 2 O-saturated and aerated aqueous solutions) at various pH. Irradiation of 5*10 -4 mol l -1 solutions of 4-HBA at pH 6.0 leads to formation of 3,4-dihydroxybenzoic acid and hydroquinone. In case of the ester neither hydroxylation nor decarboxylation products are observable. By means of pulse radiolysis it could be shown that water splitting from the ester OH-adducts is 17 times faster than from that of the acid. Therefore the main transients are phenoxyl radicals in case of the ester. At pH 10, where base catalyzed water elimination takes place, no hydroxylation products are observable either. In aerated solutions dihydroxy-compounds are formed with both substrates. In the case of 4-HBA 68 % of the OH-radicals result in 3,4-dihydroxyderivate, for 4-HBAEE these are only 25 %. Comparison of the initial degradation yields demonstrates 4-HBAEE to be 1.6-times more stable towards radiation. The second part of this work deals with radiation induced chemical changes in strawberries. Dose/concentration relationships could be obtained for 7 components, i.e. gallic acid, 4-hydroxybenzoic acid, cinnamic acid, 4-hydroxycinnamic acid, 3,4-dihydroxy-cinnamic acid, (-)-epicatechin and (+)-catechin. Linear dose relationships have been found for 4-HBA (formation) and (+)-catechin (degradation). In addition a specific radiolytically formed compound which can be used as marker for irradiation treatment of strawberries could be detected. There are strong indications that it is a radiolytic product of kaempferol, however, it could not yet be identified exactly. (author)

  3. Pulse radiolytic one-electron reduction of 1,4-amino and hydroxy disubstituted 9,10-anthraquinones

    International Nuclear Information System (INIS)

    Pal, H.; Palit, D.K.; Mukherjee, T.; Mittal, J.P.

    1992-01-01

    The semiquinone radicals produced by one-electron reduction of 1-amino-4-hydroxy-9,10-anthraquinone and 1,4-diamino-9,10-anthraquinone have been studied in aqueous-organic mixed solvent using pulse radiolysis technique. Spectroscopic characteristics, kinetic characteristics of formation and decay, acid/base behaviour and redox characteristics of the semiquinones have been investigated and compared with those of some similar systems studied earlier. It has been shown that the variation of the disproportionation equilibria involving the reduced semiquinone radicals, the parent quinone and the fully reduced hydroquinone with pH of the solutions follow a similar trend as observed in the case of other dihydroxy quinones. Stability of the semiquinones over a broad pH range and their thermodynamic properties have been correlated. (Author)

  4. Effects of mercaptans and disulfides on photochemical and high energy radiation induced reactions. Progress report, November 1, 1974--October 31, 1975

    International Nuclear Information System (INIS)

    Cohen, S.G.

    1975-10-01

    A chain reaction may be formulated at alkaline pH in terms of e - /sub aq/ acting as a source of - OH as a reactant and H. regenerating e - /sub aq/. This may account for radiolytic conversion of CO to formate with high G. 60 Co γ-radiolysis of alkaline aqueous acetonitrile and acetamide gave no evidence of a chain; extensive hydrolysis of methyl acetate is now attributed to non-radiolytic, normal hydrolysis. Aromatic mercaptans are found to retard photoreduction of a benzophenone by aliphatic amines, largely by hydrogen atom-transfer repair reactions. Aliphatic mercaptans accelerate photoreduction, apparently by affecting the reduction to quenching ratio in the intermediate charge-transfer complex. In photoreduction of a benzophenone by 2,3-butylene glycol at pH 3, the glycol is converted, not to 3-hydroxy-2-butanone, but to 2-butanone, and about 4 molecules of this are formed per molecule of ketone reduced. A short chain appears to be established. Mercaptan appears to accelerate the reduction of the ketone and retard the formation of 2-butanone

  5. Quasielastic reactions

    International Nuclear Information System (INIS)

    Hansen, O.

    1983-01-01

    A brief review is presented of the experimental and theoretical situation regarding transfer reactions and inelastic scattering. In the first category there is little (very little) precision data for heavy projectiles and consequently almost no experience with quantitative theoretical analysis. For the inelastic scattering the rather extensive data strongly supports the coupled channels models with collective formfactors. At the most back angles, at intensities about 10 -5 of Rutherford scattering, a second, compound-like mechanism becomes dominant. The description of the interplay of these two opposite mechanisms provides a new challenge for our understanding

  6. Nuclear reactions

    International Nuclear Information System (INIS)

    Corner, J.; Richardson, K.; Fenton, N.

    1990-01-01

    Nuclear reactions' marks a new development in the study of television as an agency of public policy debate. During the Eighties, nuclear energy became a major international issue. The disasters at Three-mile Island and Chernobyl created a global anxiety about its risks and a new sensitivity to it among politicians and journalists. This book is a case-study into documentary depictions of nuclear energy in television and video programmes and into the interpretations and responses of viewers drawn from many different occupational groupings. How are the complex and specialist arguments about benefit, risk and proof conveyed through the different conventions of commentary, interview and film sequence? What symbolic associations does the visual language of television bring to portrayals of the issue? And how do viewers make sense of various and conflicting accounts, connecting what they see and hear on the screen with their pre-existing knowledge, experience and 'civic' expectations. The authors examine some of the contrasting forms and themes which have been used by programme makers to explain and persuade, and then give a sustained analysis of the nature and sources of viewers' own accounts. 'Nuclear Reactions' inquires into the public meanings surrounding energy and the environment, spelling out in its conclusion some of the implications for future media treatments of this issue. It is also a key contribution to the international literature on 'television knowledge' and the processes of active viewing. (author)

  7. Peripheral reactions

    International Nuclear Information System (INIS)

    Greiner, D.

    1978-01-01

    Peripheral collisions, that is, collisions involving a small amount of overlap of nuclear matter, are discussed including inclusive interactions, the magnitude of the peripheral cross section, fragmentation, a compilation of experiments and available data, limiting fragmentation, factorization, some models, fragment momentum distributions, and future research directions

  8. Carbene Reactions

    DEFF Research Database (Denmark)

    Hoffmann, R. W.; Barth, W.; Carlsen, Lars

    1983-01-01

    The gas-phase thermolysis of the norbornadienespirodithiolane S-oxides (5) and (7) led to benzene, ethylene, and carbon disulphide as the major products, possibly involving carbon disulphide oxides as intermediates. Thermolyses of the related sulphones (9) or (14) led to completely different prod...

  9. Extent of reaction in open systems with multiple heterogeneous reactions

    Science.gov (United States)

    Friedly, John C.

    1991-01-01

    The familiar batch concept of extent of reaction is reexamined for systems of reactions occurring in open systems. Because species concentrations change as a result of transport processes as well as reactions in open systems, the extent of reaction has been less useful in practice in these applications. It is shown that by defining the extent of the equivalent batch reaction and a second contribution to the extent of reaction due to the transport processes, it is possible to treat the description of the dynamics of flow through porous media accompanied by many chemical reactions in a uniform, concise manner. This approach tends to isolate the reaction terms among themselves and away from the model partial differential equations, thereby enabling treatment of large problems involving both equilibrium and kinetically controlled reactions. Implications on the number of coupled partial differential equations necessary to be solved and on numerical algorithms for solving such problems are discussed. Examples provided illustrate the theory applied to solute transport in groundwater flow.

  10. Spallation reactions; Reactions de spallation

    Energy Technology Data Exchange (ETDEWEB)

    Cugon, J.

    1996-12-31

    Spallation reactions dominate the interactions of hadrons with nuclei in the GeV range (from {approx} 0.1 to {approx} 10 GeV). They correspond to a sometimes important ejection of light particles leaving most of the time a residue of mass commensurate with the target mass. The main features of the experimental data are briefly reviewed. The most successful theoretical model, namely the intranuclear cascade + evaporation model, is presented. Its physical content, results and possible improvements are critically discussed. Alternative approaches are shortly reviewed. (author). 84 refs.

  11. Medium effects in direct reactions

    International Nuclear Information System (INIS)

    Karakoc, M; Bertulani, C

    2013-01-01

    We discuss medium corrections of the nucleon-nucleon (NN) cross sections and their influence on direct reactions at intermediate energies ≳50 MeV/nucleon. The results obtained with free NN cross sections are compared with those obtained with a geometrical treatment of Pauli-blocking and Dirac-Bruecker methods. We show that medium corrections may lead to sizable modifications for collisions at intermediate energies and that they are more pronounced in reactions involving weakly bound nuclei.

  12. Study of nuclear reactions involving heavy nuclei and intermediate- and high-energy protons and an application in nuclear reactor physics (ADS); Estudo das reacoes nucleares envolvendo nucleos pesados e protons a energias intermediarias e altas de uma aplicacao em fisica de reatores nucleares (ADS)

    Energy Technology Data Exchange (ETDEWEB)

    Matuoka, Paula Fernanda Toledo

    2016-07-01

    In the present work, intermediate- and high-energy nuclear reactions involving heavy nuclei and protons were studied with the Monte Carlo CRISP (Rio - Ilheus - Sao Paulo Collaboration) model. The most relevant nuclear processes studied were intranuclear cascade and fission-evaporation competition. Preliminary studies showed fair agreement between CRISP model calculation and experimental data of multiplicity of evaporated neutrons (E < 20 MeV) from the p(1200 MeV) + {sup 208}Pb reaction and of spallation residues from the p(1000 MeV) + {sup 208}Pb reaction. The investigation of neutron multiplicity from proton-induced fission of {sup 232}Th up to 85 MeV showed that it was being overestimated by CRISP model; on the other hand, fission cross section were being underestimated. This behavior is due to limitations of the intranuclear cascade model for low-energies (around 50 MeV). The p(1200 MeV) + {sup 208}Pb reaction was selected for the study of a spallation neutron source. High-energy neutrons (E > 20 MeV) were emitted mostly in the intranuclear cascade stage, while evaporation presented larger neutron multiplicity. Fission cross section of 209 mb and spallation cross section of 1788 mb were calculated both in agreement with experimental data. The fission process resulted in a symmetric mass distribution. Another Monte Carlo code, MCNP, was used for radiation transport in order to understand the role of a spallation neutron source in a ADS (Accelerator Driven System) nuclear reactor. Initially, a PWR reactor was simulated to study the isotopic compositions in spent nuclear fuel. As a rst attempt, a spallation neutron source was adapted to an industrial size nuclear reactor. The results showed no evidence of incineration of transuranic elements and modifications were suggested. (author)

  13. Nuclear reactions in astrophysics

    International Nuclear Information System (INIS)

    Cardenas, M.

    1976-01-01

    It is revised the nuclear reactions which present an interest in astrophysics regarding the explanation of some problems such as the relative quantity of the elements, the structure and evolution of the stars. The principal object of the study is the determination of the experimental possibilities in the field of astrophysics, of an accelerator Van de Graaff's 700 KeV type. Two hundred nuclear reactions approximately, were found, and nothing or very little has been done in the intervals of energy which are of interest. Since the bombardment energies and the involved sections are low in some cases, there are real possibilities, for the largest number of stars to obtain important statistical data with the above mentioned accelerator, taking some necessary precautions. (author)

  14. Sodium concrete reaction - Structural considerations

    International Nuclear Information System (INIS)

    Ferskakis, G.N.

    1984-01-01

    An overview of the sodium concrete reaction phenomenon, with emphasis on structural considerations, is presented. Available test results for limestone, basalt, and magnetite concrete with various test article configurations are reviewed. Generally, tests indicate reaction is self limiting before all sodium is used. Uncertainties, however, concerning the mechanism for penetration of sodium into concrete have resulted in different theories about a reaction model. Structural behavior may be significant in the progression of the reaction due to thermal-structuralchemical interactions involving tensile cracking, compressive crushing, or general deterioration of concrete and the exposure of fresh concrete surfaces to react with sodium. Structural behavior of test articles and potential factors that could enhance the progression of the reaction are discussed

  15. Chain reaction

    International Nuclear Information System (INIS)

    Balogh, Brian.

    1991-01-01

    Chain Reaction is a work of recent American political history. It seeks to explain how and why America came to depend so heavily on its experts after World War II, how those experts translated that authority into political clout, and why that authority and political discretion declined in the 1970s. The author's research into the internal memoranda of the Atomic Energy Commission substantiates his argument in historical detail. It was not the ravages of American anti-intellectualism, as so many scholars have argued, that brought the experts back down to earth. Rather, their decline can be traced to the very roots of their success after World War II. The need to over-state anticipated results in order to garner public support, incessant professional and bureaucratic specialization, and the sheer proliferation of expertise pushed arcane and insulated debates between experts into public forums at the same time that a broad cross section of political participants found it easier to gain access to their own expertise. These tendencies ultimately undermined the political influence of all experts. (author)

  16. The kinetics of free radical metathetical and addition reactions in silane solutions

    International Nuclear Information System (INIS)

    Aloni, R.

    1976-12-01

    In this work radiolytic technique was employed for the initiation of free radical chainreactions in silane solution. The kinetic analysis of the chain mechanism in various solutions enabled the determination of the Arrhenius parameters for metathesis, addition and unimolecular decomposition reactions which make up the chainpropagation sequence in the systems studied. The following radical reactions were investigated: chlorine atom abstraction from chloromethanes by SiCl 3 and Et 3 Si radicals, and chlorine atom abstraction from chloroethanes by Et 3 Si radicals; unimolecular decomposition reactions and hydrogen atom abstraction, *from the solvent, of chloroethyl radicals in triethylsilane solutions; addition and abstraction reactions of Et 3 Si radicals with chloroolefins. Arrhenius parameters were determined for abstraction of chlorine atom from CH 3 Cl, CH 2 Cl 2 , CHCl 3 and CCl 4 , by SiCl 3 radicals and from CCl 4 , CHCl 3 , CH 2 Cl 2 , CCl 3 CN, C 2 Cl 5 H, sym-C 2 Cl 4 H 2 , asym-C 2 Cl 4 H 2 , 1.1.1-C 2 Cl 3 H 3 , 1.1.1-C 2 Dl 3 F 3 and 1.1-C 2 Cl 2 H 4 by Et 3 Si radicals. (author)

  17. Thermal annealing and recoil reactions of 128I atoms in thermal neutron activated iodate-nitrate mixed crystals

    International Nuclear Information System (INIS)

    Mishra, S.P.; Sharma, R.B.

    1983-01-01

    Recoil reaction of 128 I atoms in neutron irradiated mixed crystals (iodate-nitrate) have been studied by thermal annealing methods. The retention of 128 I (i.e. radioactivity of 128 I retained in the parent chemi cal form) decreases sharply in the beginning and then attains saturation value with the increase in concentration of nitrate. The annealing followed the usual characteristic pattern, viz., a steep rise in retention within the first few minutes and then a saturation value thereafter but these saturation values in case of mixed crystals are lower in comparison to those of pure iodate targets. The process obeys simple first order kinetics and the activation energy obtained are of lower order than those obtained in case of pure targets. The results are discussed in the light of present ideas and the role of nitrate ion and its radiolytic products have also been invoked. (author)

  18. Radiolytic Synthesis of Magnetic Nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Grdanovska, Slavica; Tissot, Chanel; Barkatt, Aaron; Al-Sheikhly, Mohamad [Nuclear Engineering Program – Department of Materials Science and Engineering, University of Maryland, College Park, MD (United States)

    2011-07-01

    Magnetic nanocomposites, in which magnetic nanoparticles are encapsulated in polymeric matrices, have important applications in medicine, electronics and mechanical devices. However, the development of processes leading to magnetic nanocomposites with desirable, predictable and reproducible properties has turned out to be a difficult challenge. To date, most studies have concentrated on a magnetic oxide, primarily magnetite (Fe{sub 3}O{sub 4}), as the encapsulated phase. However, the synthesis of batches of magnetite with homogeneous properties at reasonably low temperature is a delicate operation. Indeed, commercial lots of magnetite powder, despite having bulk Fe{sub 3}O{sub 4} stoichiometry, turn out to have large variations in structure and in magnetic properties. The difficulties in controlling the product are greatly magnified when the particle size is in the nanometer range.

  19. Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

    International Nuclear Information System (INIS)

    Stout, R B

    2001-01-01

    A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

  20. Decomposition reactions of bifenox anion radical involving intramolecular electron transfer

    Czech Academy of Sciences Publication Activity Database

    Hromadová, Magdaléna; Mořkovská, Petra; Pospíšil, Lubomír; Giannarelli, S.

    2005-01-01

    Roč. 582, 1-2 (2005), s. 156-164 ISSN 0022-0728 R&D Projects: GA MŠk OC D15.10; GA ČR GP203/02/P082; GA ČR GA203/03/0821 Institutional research plan: CEZ:AV0Z40400503 Keywords : bifenox * nitro-group reduction * double-layer effect Subject RIV: CG - Electrochemistry Impact factor: 2.223, year: 2005

  1. Non-Covalent Organocatalyzed Domino Reactions Involving Oxindoles: Recent Advances

    Directory of Open Access Journals (Sweden)

    Tecla Gasperi

    2017-09-01

    Full Text Available The ubiquitous presence of spirooxindole architectures with several functionalities and stereogenic centers in bioactive molecules has been appealing for the development of novel methodologies seeking their preparation in high yields and selectivities. Expansion and refinement in the field of asymmetric organocatalysis have made possible the development of straightforward strategies that address these two requisites. In this review, we illustrate the current state-of-the-art in the field of spirooxindole synthesis through the use of non-covalent organocatalysis. We aim to provide a concise overview of very recent methods that allow to the isolation of unique, densely and diversified spirocyclic oxindole derivatives with high structural diversity via the use of cascade, tandem and domino processes.

  2. Investigation of Maillard reaction involvement in the steam ...

    African Journals Online (AJOL)

    read), which permit unrestricted use, distribution, and reproduction in any medium, provided the original work is properly credited. Tropical Journal of Pharmaceutical Research is indexed by Science Citation Index (SciSearch), Scopus,.

  3. Consumers' reaction towards involvement of large retailers in selling ...

    African Journals Online (AJOL)

    ... as to understand factors influencing purchase decision and, (2) Cluster analysis ... 'fair deal', 'fair trade promotion', 'social responsibility' and 'against own label' ... major factors that influence consumers' intention to purchase fair trade coffee ...

  4. A Green Multicomponent Reaction for the Organic Chemistry Laboratory: The Aqueous Passerini Reaction

    Science.gov (United States)

    Hooper, Matthew M.; DeBoef, Brenton

    2009-01-01

    Water is the ideal green solvent for organic reactions. However, most organic molecules are insoluble in it. Herein, we report a laboratory module that takes advantage of this property. The Passerini reaction, a three-component coupling involving an isocyanide, aldehyde, and carboxylic acid, typically requires [similar to] 24 h reaction times in…

  5. Chemical kinetics and reaction mechanism

    International Nuclear Information System (INIS)

    Jung, Ou Sik; Park, Youn Yeol

    1996-12-01

    This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

  6. Impact of radiolysis and radiolytic corrosion on the release of {sup 13}C and {sup 37}Cl implanted into nuclear graphite: Consequences for the behaviour of {sup 14}C and {sup 36}Cl in gas cooled graphite moderated reactors

    Energy Technology Data Exchange (ETDEWEB)

    Moncoffre, N., E-mail: nathalie.moncoffre@ipnl.in2p3.fr [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); Toulhoat, N. [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); CEA/DEN, Centre de Saclay (France); Bérerd, N.; Pipon, Y. [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); Université de Lyon, Université Lyon, IUT Lyon-1 département chimie (France); Silbermann, G. [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); EDF – DPI - DIN – CIDEN, DIE - Division Environnement, Lyon (France); Blondel, A. [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); Andra, Châtenay-Malabry (France); Galy, N. [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); EDF – DPI - DIN – CIDEN, DIE - Division Environnement, Lyon (France); and others

    2016-04-15

    Graphite finds widespread use in many areas of nuclear technology based on its excellent moderator and reflector qualities as well as its strength and high temperature stability. Thus, it has been used as moderator or reflector in CO{sub 2} cooled nuclear reactors such as UNGG, MAGNOX, and AGR. However, neutron irradiation of graphite results in the production of {sup 14}C (dose determining radionuclide) and {sup 36}Cl (long lived radionuclide), these radionuclides being a key issue regarding the management of the irradiated waste. Whatever the management option (purification, storage, and geological disposal), a previous assessment of the radioactive inventory and the radionuclide's location and speciation has to be made. During reactor operation, the effects of radiolysis are likely to promote the radionuclide release especially at the gas/graphite interface. Radiolysis of the coolant is mainly initiated through γ irradiation as well as through Compton electrons in the graphite pores. Radiolysis can be simulated in laboratory using γ irradiation or ion irradiation. In this paper, {sup 13}C, {sup 37}Cl and {sup 14}N are implanted into virgin nuclear graphite in order to simulate respectively the presence of {sup 14}C, {sup 36}Cl and nitrogen, a {sup 14}C precursor. Different irradiation experiments were carried out using different irradiation devices on implanted graphite brought into contact with a gas simulating the coolant. The aim was to assess the effects of gas radiolysis and radiolytic corrosion induced by γ or He{sup 2+} irradiation at the gas/graphite interface in order to evaluate their role on the radionuclide release. Our results allow inferring that radiolytic corrosion has clearly promoted the release of {sup 14}C, {sup 36}Cl and {sup 14}N located at the graphite brick/gas interfaces and open pores.

  7. Chemical behaviour of americium in natural aquatic solutions: Hydrolysis, radiolysis and redox reactions

    International Nuclear Information System (INIS)

    Stadler, S.; Kim, J.I.

    1988-06-01

    Hydrolysis and redox reactions of the Am(III) and Am(V) ions have been investigated in NaClO 4 and NaCl solutions as well as in natural saline groundwaters. The hydrolysis constants of Am(OH) n 3-n species and the solubility product of Am(OH) 3 (s) have been determined in 0.1 M NaClO 4 , 0.1 M NaCl and 0.6 M NaCl solutions. As observed in concentrated NaCl solutions (> 3 M), the α-radiation induces the radiolytic oxidation of the Cl - -ion to produce Cl 2 , HClO, ClO - and other oxidized species, which result in a strongly oxidizing medium. Consequently Am(III) is oxidized to Am(V). Under these conditions the hydrolysis constants of AmO 2 (OH) n 1-n species and the solubility product are also determined. The α-radiation induced radiolysis reactions in NaCl solution and the subsequent oxidation reaction of Am(III) have been systematically investigated by varying pH, NaCl concentration and specific α-activity. Also included in the investigation are a few selected groundwaters of relatively high salinity from the Gorleben aquifer systems. (orig.) [de

  8. Diffusion-controlled reactions modeling in Geant4-DNA

    Energy Technology Data Exchange (ETDEWEB)

    Karamitros, M., E-mail: matkara@gmail.com [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, INCIA, UMR 5287, F-33400 Talence (France); Luan, S. [University of New Mexico, Department of Computer Science, Albuquerque, NM (United States); Bernal, M.A. [Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas, SP (Brazil); Allison, J. [Geant4 Associates International Ltd (United Kingdom); Baldacchino, G. [CEA Saclay, IRAMIS, LIDYL, Radiation Physical Chemistry Group, F-91191 Gif sur Yvette Cedex (France); CNRS, UMR3299, SIS2M, F-91191 Gif sur Yvette Cedex (France); Davidkova, M. [Nuclear Physics Institute of the ASCR, Prague (Czech Republic); Francis, Z. [Saint Joseph University, Faculty of Sciences, Department of Physics, Mkalles, Beirut (Lebanon); Friedland, W. [Helmholtz Zentrum München, German Research Center for Environmental Health, Institute of Radiation Protection, Ingolstädter Landstr. 1, 85764 Neuherberg (Germany); Ivantchenko, V. [Ecoanalytica, 119899 Moscow (Russian Federation); Geant4 Associates International Ltd (United Kingdom); Ivantchenko, A. [Geant4 Associates International Ltd (United Kingdom); Mantero, A. [SwHaRD s.r.l., via Buccari 9, 16153 Genova (Italy); Nieminem, P.; Santin, G. [ESA-ESTEC, 2200 AG Noordwijk (Netherlands); Tran, H.N. [Division of Nuclear Physics and Faculty of Applied Sciences, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); Stepan, V. [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); Nuclear Physics Institute of the ASCR, Prague (Czech Republic); Incerti, S., E-mail: incerti@cenbg.in2p3.fr [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France)

    2014-10-01

    Context Under irradiation, a biological system undergoes a cascade of chemical reactions that can lead to an alteration of its normal operation. There are different types of radiation and many competing reactions. As a result the kinetics of chemical species is extremely complex. The simulation becomes then a powerful tool which, by describing the basic principles of chemical reactions, can reveal the dynamics of the macroscopic system. To understand the dynamics of biological systems under radiation, since the 80s there have been on-going efforts carried out by several research groups to establish a mechanistic model that consists in describing all the physical, chemical and biological phenomena following the irradiation of single cells. This approach is generally divided into a succession of stages that follow each other in time: (1) the physical stage, where the ionizing particles interact directly with the biological material; (2) the physico-chemical stage, where the targeted molecules release their energy by dissociating, creating new chemical species; (3) the chemical stage, where the new chemical species interact with each other or with the biomolecules; (4) the biological stage, where the repairing mechanisms of the cell come into play. This article focuses on the modeling of the chemical stage. Method This article presents a general method of speeding-up chemical reaction simulations in fluids based on the Smoluchowski equation and Monte-Carlo methods, where all molecules are explicitly simulated and the solvent is treated as a continuum. The model describes diffusion-controlled reactions. This method has been implemented in Geant4-DNA. The keys to the new algorithm include: (1) the combination of a method to compute time steps dynamically with a Brownian bridge process to account for chemical reactions, which avoids costly fixed time step simulations; (2) a k–d tree data structure for quickly locating, for a given molecule, its closest reactants. The

  9. A comprehensive survey of nuclear reactions; Panorama des reactions nucleaires

    Energy Technology Data Exchange (ETDEWEB)

    Cugnon, J. [Liege Univ., IFPA, AGO Dept. (Belgium)

    2007-07-01

    The various mechanisms of nuclear reactions are surveyed and classified in different regimes, based on the notions of coherent mechanisms and hard versus soft processes. The emphasis is put on the concepts at the basis of the understanding of these regimes and on the elements of nuclear structure which are involved in these different regimes, as well as the on the possibility of extracting this information. Due to lack of space and for pedagogical reasons, the discussion is limited to nucleon-induced and light-ion-induced reactions. However, a few remarks are given concerning some specific probes, such as weakly bound projectiles or neutron-rich nuclei. (author)

  10. Novel Reagents for Multi-Component Reactions

    Science.gov (United States)

    Wang, Yanguang; Basso, Andrea; Nenajdenko, Valentine G.; Gulevich, Anton V.; Krasavin, Mikhail; Bushkova, Ekaterina; Parchinsky, Vladislav; Banfi, Luca; Basso, Andrea; Cerulli, Valentina; Guanti, Giuseppe; Riva, Renata; Rozentsveig, Igor B.; Rozentsveig, Gulnur N.; Popov, Aleksandr V.; Serykh, Valeriy J.; Levkovskaya, Galina G.; Cao, Song; Shen, Li; Liu, Nianjin; Wu, Jingjing; Li, Lina; Qian, Xuhong; Chen, Xiaopeng; Wang, Hongbo; Feng, Jinwu; Wang, Yanguang; Lu, Ping; Heravi, Majid M.; Sadjadi, Samaheh; Kazemizadeh, Ali Reza; Ramazani, Ali; Kudyakova, Yulia S.; Goryaeva, Marina V.; Burgart, Yanina V.; Saloutin, Victor I.; Mossetti, Riccardo; Pirali, Tracey; Tron, Gian Cesare; Rozhkova, Yulia S.; Mayorova, Olga A.; Shklyaev, Yuriy V.; Zhdanko, Alexander G.; Nenajdenko, Valentine G.; Stryapunina, Olga G.; Plekhanova, Irina V.; Glushkov, Vladimir A.; Shklyaev, Yurii V.

    Ketenimines are a class of versatile and highly reactive intermediates that can participate in a variety of organic reactions, such as nucleophilic additions, radical additions, [2 + 2] and [2 + 4] cycloadditions, and sigmatropic rearrangements. In this presentation, we report on a series of multi-component reactions that involve a ketenimine intermediate. These reactions could furnish diverse heterocyclic compounds, including functionalized iminocoumarin, iminodihydroqunolines, iminothiochromens, pyrrolines, isoquinolines, pyridines, β-lactams, imino-1,2-dihydrocoumarins, and benzimidazoles.

  11. Hypersensitivity Reactions from Excipients in Systemic Glucocorticoid Formulations

    DEFF Research Database (Denmark)

    Calogiuri, Gianfranco; Garvey, Lene H; Romita, Paolo

    2016-01-01

    Glucocorticoids are the most widely used drugs for the treatment of hypersensitivity, however these drugs themselves and the excipients contained in commercial corticosteroid formulations are able to induce severe immediate-type hypersensitivity reactions. Reactions involving excipients have been...

  12. Reactions the private life of atoms

    CERN Document Server

    Atkins, Peter

    2011-01-01

    Through an innovative, closely integrated design of images and text, and his characteristically clear, precise, and economical exposition, Peter Atkins explains the processes involved in chemical reactions. He begins by introducing a 'tool kit' of basic reactions, such as precipitation, corrosion, and catalysis, and concludes by showing how these building blocks are brought together in more complex processes such as photosynthesis.

  13. Concise Synthesis of Macrocycles by Multicomponent Reactions

    NARCIS (Netherlands)

    Abdelraheem, Eman M. M.; Khaksar, Samad; Dömling, Alexander

    2018-01-01

    A short reaction pathway was devised to synthesize a library of artificial 18-27-membered macrocycles. The five-step reaction sequence involves ring opening of a cyclic anhydride with a diamine, esterification, coupling with an amino acid isocyanide, saponification, and, finally, macro-ring closure

  14. Redox reactions in food fermentations

    DEFF Research Database (Denmark)

    Hansen, Egon Bech

    2018-01-01

    involves oxidative steps in the early part of the pathways whereas a multitude of different reactions are used as compensating reductions. Much of the diversity seen between food fermentations arise from the different routes and the different electron acceptors used by microorganisms to counterbalance...... and this contributes to the diversity in flavor, color, texture, and shelf life. The review concludes that these reactions are still only incompletely understood and that they represent an interesting area for fundamental research and also represent a fertile field for product development through a more conscious use...... of the redox properties of strains used to compose food cultures....

  15. A Networks Approach to Modeling Enzymatic Reactions.

    Science.gov (United States)

    Imhof, P

    2016-01-01

    Modeling enzymatic reactions is a demanding task due to the complexity of the system, the many degrees of freedom involved and the complex, chemical, and conformational transitions associated with the reaction. Consequently, enzymatic reactions are not determined by precisely one reaction pathway. Hence, it is beneficial to obtain a comprehensive picture of possible reaction paths and competing mechanisms. By combining individually generated intermediate states and chemical transition steps a network of such pathways can be constructed. Transition networks are a discretized representation of a potential energy landscape consisting of a multitude of reaction pathways connecting the end states of the reaction. The graph structure of the network allows an easy identification of the energetically most favorable pathways as well as a number of alternative routes. © 2016 Elsevier Inc. All rights reserved.

  16. Interfacial reactions in intermetallic matrix composites

    International Nuclear Information System (INIS)

    Cantrell, L.B.; Clevenger, E.M.; Perepezko, J.H.

    1993-01-01

    The thermal stability of advanced composites is dominated by the behavior of internal interfaces. Analysis of these internal interfaces often involves consideration of at least ternary order phase equilibria. Limited thermodynamic data exists for ternary and higher order systems. However, a combined approach based upon the use of binary data to estimate ternary phase equilibria and experimentally determined reaction pathways is effective in the analysis of interface reactions in composite systems. In blended powder samples, thermal analysis was used to find possible reaction temperatures, while X-ray analysis, EDS, and EPMA of diffusion couples were used to assess interdiffusion reaction pathways. The approach is illustrated by compatibility studies between TiAl and TiSi 2 at 1,100 C, and in-situ reactions between B 4 C and TiAl at 1300 C where multiple reaction sequences have been analyzed to provide guidance for the design of in-situ reaction processing of composites

  17. Functional and ultrastructural neuroanatomy of interactive intratectal/tectonigral mesencephalic opioid inhibitory links and nigrotectal GABAergic pathways: involvement of GABAA and mu1-opioid receptors in the modulation of panic-like reactions elicited by electrical stimulation of the dorsal midbrain.

    Science.gov (United States)

    Ribeiro, S J; Ciscato, J G; de Oliveira, R; de Oliveira, R C; D'Angelo-Dias, R; Carvalho, A D; Felippotti, T T; Rebouças, E C C; Castellan-Baldan, L; Hoffmann, A; Corrêa, S A L; Moreira, J E; Coimbra, N C

    2005-12-01

    In the present study, the functional neuroanatomy of nigrotectal-tectonigral pathways as well as the effects of central administration of opioid antagonists on aversive stimuli-induced responses elicited by electrical stimulation of the midbrain tectum were determined. Central microinjections of naloxonazine, a selective mu(1)-opiod receptor antagonist, in the mesencephalic tectum (MT) caused a significant increase in the escape thresholds elicited by local electrical stimulation. Furthermore, either naltrexone or naloxonazine microinjected in the substantia nigra, pars reticulata (SNpr), caused a significant increase in the defensive thresholds elicited by electrical stimulation of the continuum comprised by dorsolateral aspects of the periaqueductal gray matter (dlPAG) and deep layers of the superior colliculus (dlSC), as compared with controls. These findings suggest an opioid modulation of GABAergic inhibitory inputs controlling the defensive behavior elicited by MT stimulation, in cranial aspects. In fact, iontophoretic microinjections of the neurotracer biodextran into the SNpr, a mesencephalic structure rich in GABA-containing neurons, show outputs to neural substrate of the dlSC/dlPAG involved with the generation and organization of fear- and panic-like reactions. Neurochemical lesion of the nigrotectal pathways increased the sensitivity of the MT to electrical (at alertness, freezing and escape thresholds) and chemical (blockade of GABA(A) receptors) stimulation, suggesting a tonic modulatory effect of the nigrotectal GABAergic outputs on the neural networks of the MT involved with the organization of the defensive behavior and panic-like reactions. Labeled neurons of the midbrain tectum send inputs with varicosities to ipsi and contralateral dlSC/dlPAG and ipsilateral substantia nigra, pars reticulata and compacta, in which the anterograde and retrograde tracing from a single injection indicates that the substantia nigra has reciprocal connections with

  18. Who and What Does Involvement Involve?

    DEFF Research Database (Denmark)

    Hansen, Jeppe Oute; Petersen, Anders; Huniche, Lotte

    2015-01-01

    This article gives an account of aspects of a multi-sited field study of involvement of relatives in Danish psychiatry. By following metaphors of involvement across three sites of the psychiatric systema family site, a clinical site and a policy sitethe first author (J.O.) investigated how...... theoretical perspective laid out by Ernesto Laclau and Chantal Mouffe, the aim of this study is to show how the dominant discourse about involvement at the political and clinical sites is constituted by understandings of mentally ill individuals and by political objectives of involvement. The analysis...... the responsibility toward the mental health of the ill individual as well as toward the psychological milieu of the family....

  19. Catalytic Wittig and aza-Wittig reactions

    Directory of Open Access Journals (Sweden)

    Zhiqi Lao

    2016-11-01

    Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.

  20. Free radical reactions of daunorubicin

    International Nuclear Information System (INIS)

    Houee-Levin, C.

    1991-01-01

    Daunorubicin is an antitumor antibiotic activated in vivo by reduction. Its mechanism of action involves DNA and topoisomerase attack, but side effects are cytotoxicity related to free radical formation. Therefore the mechanism of the one-electron reduction of the drug and the reactions of the daunorubicin transients towards compounds of biological interest have been studied by the methods of radiolysis, in order to provide possible explanations of the drug mechanism of action. Their relative importance in cellular conditions is discussed [fr

  1. Eye Involvement in TSC

    Science.gov (United States)

    ... eye involvement. Nonretinal and Retinal Eye Findings Facial angiofibromas may involve the eyelids of individuals with TSC, ... the hamartomas have many blood vessels (as are angiofibromas of the skin). Less than half of the ...

  2. Exchange Reactions. Proceedings of the Symposium on Exchange Reactions

    International Nuclear Information System (INIS)

    1965-01-01

    The mechanisms and kinetics of chemical reactions are of great interest to chemists. The study of exchange reactions in particular helps to shed light on the dynamics of chemical change, providing an insight into the structures and the reactivities of the chemical species involved. The main theme of this meeting was the subject of oxidation-reduction reactions in which the net result is the transfer of one or more electrons between the different oxidation states of the same element. Other studies reported included the transfer of protons, atoms, complex ligands or organic radicals between molecules. Heterogeneous exchange, which is of importance in many cases of catalytic action, was also considered. For a long time isotopic tracers have formed the most convenient means of studying exchange reactions and today a considerable amount of work continues to be done with their aid. Consequently, several papers presented at this Symposium reported on work carried out by purely radiochemical tracer methods. In recognition, however, of the important role which nuclear magnetic resonance and electron spin resonance play in this field, in particular in the study of fast reactions, a number of reports on investigations in which these techniques had been used was included in the programme. By kind invitation of the United States Government the Symposium on Exchange Reactions was held from 31 May to 4 June at the Brookhaven National Laboratory, Upton, Long Island, N.Y., USA. It was attended by 46 participants from nine countries and one inter-governmental organization. The publication of these Proceedings makes the contents of the papers and the discussion available to a wider audience

  3. Study of hydrogen consumption reaction catalyzed by Pd ions in the simulated high-level liquid waste

    International Nuclear Information System (INIS)

    Kodama, Takashi

    2013-01-01

    To ensure the safety for storage of high-level liquid waste (HLLW) in tanks is one of the most important safety issues in a reprocessing plant since almost all radioactive materials under processing are collected in these tanks. Accordingly the behavior of radiolytically formed hydrogen (H 2 ) in these tanks is one of key issues and has been studied by several researchers because it might cause an explosion. They reported that not all of H 2 formed in HLLW comes out in the gas phase because H 2 is consumed by some un-clarified secondary reaction which may be caused by the irradiation and/or by the catalytic effect of certain fission product (FP) in HLLW. In order to clarify such effect, we carried out the experiments using the simulated high level liquid waste (SHLLW) with and without palladium (Pd) group ions under irradiation and non-irradiation conditions. As a result, it was found that H 2 consumption reaction is not caused by radiation as was understood so far but is caused by a catalytic effect of Pd ion in SHLLW. That is, H 2 is reacting with HNO 3 and forming H 2 O and NOx. Using the catalytic reaction rate constant measured in the experiments, the analysis showed that the H 2 concentration in the gas phase of an HLLW tank does not reach its explosion limit of 4% even if the sweeping air stops for a long time. (authors)

  4. Treatment and Managing Reactions

    Science.gov (United States)

    ... of reactions. Learn more here. Milk Egg Peanut Tree Nuts Soy Wheat Fish Shellfish Sesame Other Food ... a severe reaction. Consider wearing an emergency medical identification (e.g., bracelet, other jewelry). What to Read ...

  5. Microfluidic chemical reaction circuits

    Science.gov (United States)

    Lee, Chung-cheng [Irvine, CA; Sui, Guodong [Los Angeles, CA; Elizarov, Arkadij [Valley Village, CA; Kolb, Hartmuth C [Playa del Rey, CA; Huang, Jiang [San Jose, CA; Heath, James R [South Pasadena, CA; Phelps, Michael E [Los Angeles, CA; Quake, Stephen R [Stanford, CA; Tseng, Hsian-rong [Los Angeles, CA; Wyatt, Paul [Tipperary, IE; Daridon, Antoine [Mont-Sur-Rolle, CH

    2012-06-26

    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  6. Preequilibrium Nuclear Reactions

    International Nuclear Information System (INIS)

    Strohmaier, B.

    1988-01-01

    After a survey on existing experimental data on precompound reactions and a description of preequilibrium reactions, theoretical models and quantum mechanical theories of preequilibrium emission are presented. The 25 papers of this meeting are analyzed separately

  7. Managing Your Emotional Reactions

    Science.gov (United States)

    ... Videos for Educators Search English Español Managing Your Emotional Reactions KidsHealth / For Teens / Managing Your Emotional Reactions ... Think about what you might do next time. Emotions 101 The skills we use to manage our ...

  8. Heavy ion transfer reactions

    Indian Academy of Sciences (India)

    array (CLARA), extensive investigations of nuclear structure and reaction dynamics have been carried out. In the present paper aspects of these studies will be presented, focussing more closely on the reaction mechanism, in particular on the ...

  9. Polarization transfer in (d-vector,n-vector) reactions

    International Nuclear Information System (INIS)

    Walter, R.L.; Tornow, W.

    1986-01-01

    The status of the measurements and the role of polarization transfer coefficients for (d/sup →/,n/sup →/) reactions is reviewed. Emphasis is given to reactions, involving light-nuclei systems. The importance of (d/sup →/,n/sup →/) reactions as sources of polarized neutrons is pointed out

  10. Droplet heat transfer and chemical reactions during direct containment heating

    International Nuclear Information System (INIS)

    Baker, L. Jr.

    1986-01-01

    A simplified model of heat transfer and chemical reaction has been adapted to evaluate the expected behavior of droplets containing unreacted Zircaloy and stainless steel moving through the containment atmosphere during postulated accidents involving direct containment heating. The model includes internal and external diffusive resistances to reaction. The results indicate that reactions will be incomplete for many conditions characteristic of direct containment heating sequences

  11. Spallation reactions - physics and applications

    International Nuclear Information System (INIS)

    Kelic, A.; Ricciardi, M.; Schmidt, K-H.

    2009-01-01

    Spallation reactions have become an ideal tool for studying the equation of state and thermal instabilities of nuclear matter. In astrophysics, the interactions of cosmic rays with the interstellar medium have to be understood in detail for deducing their original composition and their production mechanisms. Renewed interest in spallation reactions with protons around 1 GeV came up recently with the developments of spallation neutron sources. The project of an accelerator-driven system (ADS) as a technological solution for incinerating the radioactive waste even intensified the efforts for better understanding the physics involved in the spallation process. Experiments on spallation reactions were performed for determining the production cross sections and properties of particles, fragments and heavy residues. Traditional experiments on heavy residues, performed in direct kinematics, were limited to the direct observation of long-lived radioactive nuclides and did not provide detailed information on the kinematics of the reaction. Therefore, an innovative experimental method has been developed, based on inverse kinematics, which allowed to identify all reaction residues in-flight, using the high resolution magnetic spectrometer FRS of GSL Darmstadt. It also gives direct access to the reaction kinematics. An experimental campaign has been carried out in a Europe-wide collaboration, investigating the spallation of several nuclei ranging from 56 Fe to 238 U Complementary experiments were performed with a full-acceptance detection system, yielding total fission cross sections. Recently, another detection system using the large acceptance ALADIN dipole and the LAND neutron detector was introduced to measure light particles in coincidence with the heavy residues. Another intense activity was dedicated to developing codes, which cover nuclear reactions occurring in an ADS. The first phase of the reaction is successfully described by a sequence of quasi-free nucleon

  12. Thermonuclear reaction rates. III

    International Nuclear Information System (INIS)

    Harris, M.J.; Fowler, W.A.; Caughlan, G.R.; Zimmerman, B.A.

    1983-01-01

    Stellar thermonuclear reaction rates are revised and updated, adding a number of new important reaction rates. Several reactions with large negative Q-values are included, and examples of them are discussed. The importance of the decay rates for Mg-26(p,n) exp 26 Al and Al-26(n,p) exp 26 Mg for stellar studies is emphasized. 19 references

  13. Resonant thermonuclear reaction rate

    International Nuclear Information System (INIS)

    Haubold, H.J.; Mathai, A.M.

    1986-01-01

    Basic physical principles for the resonant and nonresonant thermonuclear reaction rates are applied to find their standard representations for nuclear astrophysics. Closed-form representations for the resonant reaction rate are derived in terms of Meijer's G-function. Analytic representations of the resonant and nonresonant nuclear reaction rates are compared and the appearance of Meijer's G-function is discussed in physical terms

  14. Organizing Patient Involvement

    DEFF Research Database (Denmark)

    Brehm Johansen, Mette

    hospitals. During the last 25 years, patient involvement and quality improvement have become connected in Danish healthcare policy. However, the ideal of involving patients in quality improvement is described in very general terms and with only few specific expectations of how it is to be carried out...... in practice, as I show in the thesis. In the patient involvement literature, the difficulties of getting patient involvement in quality improvement to have in an impact on the planning and development of healthcare services is, for example, ascribed to conceptual vagueness of patient involvement, differences...... in perspectives, values and understandings between patients and healthcare professionals, or the lack of managerial attention and prioritization....

  15. Insights into the mechanisms on chemical reactions: reaction paths for chemical reactions

    International Nuclear Information System (INIS)

    Dunning, T.H. Jr.; Rosen, E.; Eades, R.A.

    1987-01-01

    We report reaction paths for two prototypical chemical reactions: Li + HF, an electron transfer reaction, and OH + H 2 , an abstraction reaction. In the first reaction we consider the connection between the energetic terms in the reaction path Hamiltonian and the electronic changes which occur upon reaction. In the second reaction we consider the treatment of vibrational effects in chemical reactions in the reaction path formalism. 30 refs., 9 figs

  16. Radiolysis of water at elevated temperatures. Pt. 3: Simulation of radiolytic products at 25 and 2500C under the irradiation with γ-rays and fast neutrons

    International Nuclear Information System (INIS)

    Sunaryo, Geni R.; Katsumura, Yosuke; Ishigure, Kenkichi

    1995-01-01

    The G-values of water decomposition products under the irradiations with γ-rays and fast neutrons up to 250 o C have been determined in previous studies. In order to clarify the characteristics of the determined G-values, computer simulations under the simplified conditions in nuclear reactors have been carried out. The recent G-values for γ-radiolysis reported by recent workers are almost equivalent from the point of simulations. On the contrary, G-values for fast neutron radiolysis give a significant influence to the result, which arises from the higher molecular yields and smaller radical yields of water decomposition in fast neutron radiolysis, and it has been revealed that the dose evaluation in the reaction is inevitably important. In addition, it was pointed out by the simulations that reverse reactions for H 2 + . OH → H . + H 2 O and e aq - + H + → . H, which can be neglected at room temperature, become important at higher temperatures. (author)

  17. SISGR: Physical Chemistry of Reaction Dynamics in Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Blank, David [Univ. of Minnesota, Minneapolis, MN (United States)

    2017-10-30

    Room temperature ionic liquids (RTILs) are liquids made up of atomic and molecular ions. This is in contrast with more common liquids, such as water, that are made up of neutral molecules. The additional charges on the atoms and molecules can alter the properties of these liquids, for example they tend to have a very high vapor pressure and the ability to shield charge in electronic devices. For these and other reasons RTILs have recently been deployed in a number of applications that involve production of free electrons in the liquid, such as batteries, capacitors, nuclear power plants, and solar cells. Electrons tend to be very reactive, and understanding their behaviour in these liquids is important for the future design of ionic liquids to be employed in these environments. This study investigated the behavior of electrons generated in RTILs by pulses of ultraviolet light, including how long they survive, and how reactive they are with the both the surrounding liquid and impurities in the liquid. The ionic liquid studied was one of the most commonly used, called N-alkyl-N-methyl-pyrrolidinium bistriflimide. What the study revealed was that the majority of the electrons initially created, about 96%, had a very short lifetime of less than one picosecond (10-12 second) due to a process called geminate recombination. The study also demonstrated that the electrons are very reactive at the moment they are detached from the molecules in the liquid by light, but that they relax very quickly and lose almost all of their reactivity in much less than one picosecond. The short lifetime and rapid loss of reactivity both serve as important mechanisms that protect the liquid from radiolytic damage.

  18. Probing reaction dynamics with GDR decay

    International Nuclear Information System (INIS)

    Beene, J.R.

    1994-01-01

    The giant dipole resonance (GDR) has been a prolific source of information on the physics of the nucleus. Mostly it has taught us about nuclear structure, but recently experiments have utilized the GDR as a probe of nuclear reaction dynamics. In this report two examples of such investigations are discussed involving very different reactions and probing time scales that differ by a factor of ∼10 3

  19. JOINT INVOLVEMENT IN SYPHILIS

    Directory of Open Access Journals (Sweden)

    T. I. Zlobina

    2016-01-01

    Full Text Available Joint involvement in syphilis has been considered as casuistry in recent years. At the same time, the high incidence of primary syphilis and the notified cases of late neurosyphilis may suggest that joint involvement in this disease is by no means always verified. Traditionally there are two forms of syphilitic arthritis: primary synovial (involving the articular membranes and sac and primary bone (involving the articular bones and cartilages ones. The paper describes the authors' clinical case of the primary bone form of articular syphilis in a 34-year-old man. 

  20. Intramolecular and Transannular Diels-Alder Reactions

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Ascic, Erhad

    2014-01-01

    Few reactions can compete with the Diels-Alder (DA) [4+2] cycloaddition for the rapid and efficient generation of molecular complexity. The DA reaction is atom-economic and stereospecific, as well as diastereo- and regioselective. The intramolecular version (IMDA) of the DA cycloaddition and its...... and dienophile, methods for acceleration of IMDA reactions (such as use of high pressure) and catalysis (using oxophilic or carbophilic metal complexes, Brønsted acids, and enzymes). The use of furans as diene components (IMDAF), intramolecular hetero-DA (IMHDA) and IMDA reactions with inverse electron demand...... are also covered. Applications of IMDA to asymmetric synthesis (from substrate control through to enantioselective catalysis, including organocatalysis) are presented, along with tandem sequences involving IMDA cycloaddition. A theme pervading the whole chapter is the use of IMDA reactions for the total...

  1. Transfer involving deformed nuclei

    International Nuclear Information System (INIS)

    Rasmussen, J.O.; Guidry, M.W.; Canto, L.F.

    1985-03-01

    Results are reviewed of 1- and 2-neutron transfer reactions at near-barrier energies for deformed nuclei. Rotational angular momentum and excitation patterns are examined. A strong tendency to populating high spin states within a few MeV of the yrast line is noted, and it is interpreted as preferential transfer to rotation-aligned states. 16 refs., 12 figs

  2. Enhancing Activity for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Busch, Michael; Halck, Niels Bendtsen

    2014-01-01

    Electrochemical production of hydrogen, facilitated in electrolyzers, holds great promise for energy storage and solar fuel production. A bottleneck in the process is the catalysis of the oxygen evolution reaction, involving the transfer of four electrons. The challenge is that the binding energies...... of all reaction intermediates cannot be optimized individually. However, experimental investigations have shown that drastic improvements can be realized for manganese and cobalt-based oxides if gold is added to the surface or used as substrate. We propose an explanation for these enhancements based...... that the oxygen evolution reaction overpotential decreases by 100–300 mV for manganese oxides and 100 mV for cobalt oxides....

  3. Photogeochemical reactions of manganese under anoxic conditions

    Science.gov (United States)

    Liu, W.; Yee, N.; Piotrowiak, P.; Falkowski, P. G.

    2017-12-01

    Photogeochemistry describes reactions involving light and naturally occurring chemical species. These reactions often involve a photo-induced electron transfer that does not occur in the absence of light. Although photogeochemical reactions have been known for decades, they are often ignored in geochemical models. In particular, reactions caused by UV radiation during an ozone free early Earth could have influenced the available oxidation states of manganese. Manganese is one of the most abundant transition metals in the crust and is important in both biology and geology. For example, the presence of manganese (VI) oxides in the geologic record has been used as a proxy for oxygenic photosynthesis; however, we suggest that the high oxidation state of Mn can be produced abiotically by photochemical reactions. Aqueous solutions of manganese (II) as well as suspensions of rhodochrosite (MnCO3) were irradiated under anoxic condition using a 450 W mercury lamp and custom built quartz reaction vessels. The photoreaction of the homogeneous solution of Mn(II) produced H2 gas and akhtenskite (ɛ-MnO2) as the solid product . This product is different than the previously identified birnessite. The irradiation of rhodochrosite suspensions also produced H2 gas and resulted in both a spectral shift as well as morphology changes of the mineral particles in the SEM images. These reactions offer alternative, abiotic pathways for the formation of manganese oxides.

  4. Parent Involvement Handbook.

    Science.gov (United States)

    Caplan, Arna

    This handbook on parent involvement, designed to be used with preschool programs, was developed by the Jefferson County Public Schools in Lakewood, Colorado. Included are: (1) a general statement about parent involvement in an early childhood program, (2) a description of the Jefferson County Early Childhood Program, (3) a description of the…

  5. The Involved Ostrich

    DEFF Research Database (Denmark)

    Davies, Andrea; Dobscha, Susan; Geiger, Susi

    2008-01-01

    that the transition into parenthood can be difficult for men due to their lack of a physical connection to the pregnancy, a perception that the baby industry is not designed for them, the continuance of male stereotypes in the media, and also the time available to men to become involved in consumption activities......-natal data. Data revealed that men, according to their partner’s perceptions, used consumption as a virtual umbilical cord, although levels of consumption involvement varied from co-involvement for most purchases, to limited involvement, and/or involvement for ‘large’ items, particularly travel systems...... and technical items. This research also revealed that men partook in highly masculinized forms of “nesting,” and in general shunned pregnancy book reading; although some did engage in “research” activities such as searching the internet for product safety information. We conclude from this study...

  6. Nuclear reaction studies

    International Nuclear Information System (INIS)

    Alexander, J.M.; Lacey, R.A.

    1994-01-01

    Research focused on the statistical and dynamical properties of ''hot'' nuclei formed in symmetric heavy-ion reactions. Theses included ''flow'' measurements and the mechanism for multifragment disassembly. Model calculations are being performed for the reactions C+C, Ne+Al, Ar+Sc, Kr+Nb, and Xe+La. It is planned to study 40 Ar reactions from 27 to 115 MeV/nucleon. 2 figs., 41 refs

  7. Knock-out reactions

    International Nuclear Information System (INIS)

    de Forest, T. Jr.

    1977-01-01

    It is pointed out that the primary motivation for performing high energy single nucleon knock-out reactions is based on the concept of quasi-elastic scattering. The validity of and corrections to the partial wave impulse approximation and kinematical invariance of knock-out reactions and tests of the reaction mechanism are treated. The effect of distortions on the momentum distribution in the effective momentum approximation for given parameters are plotted. 12 references

  8. Reaction kinetics of polybutylene terephthalate polycondensation reaction

    NARCIS (Netherlands)

    Darda, P. J.; Hogendoorn, J. A.; Versteeg, G. F.; Souren, F.

    2005-01-01

    The kinetics of the forward polycondensation reaction of polybutylene terephthalate (PBT) has been investigated using thermogravimetric analysis (TGA). PBT - prepolymer with an initial degree of polymerization of 5.5 was used as starting material. The PBT prepolymer was prepared from dimethyl

  9. Reaction rates for neutrino processes

    International Nuclear Information System (INIS)

    Shalitin, D.

    1978-01-01

    Some integrals involved in neutrino processes are evaluated by transformation to a special system of reference - usually to the center of mass system (CM). Rather simple analytic expressions are obtained for reaction rates and, though less simple, for moments. An interesting result thus obtained is for an isotropic interaction (in CM) of a neutrino with a monoenergetic isotropic gas of extreme relativistic electrons: it is found that the probability of the scattered neutrino to have energy in a certain range is independent of this energy. (Auth.)

  10. Thermonuclear reaction listing

    International Nuclear Information System (INIS)

    Fukai, Yuzo

    1993-01-01

    The following 10 elements, including T, are well known as nuclear fusion fuels: p, D, T, 3 He, 4 He, 6 Li, 7 Li, 9 Be, 10 B, 11 B, ( 12 C, 13 C), where 12 C and 13 C are considered only in the calculation of Q value. Accordingly the number of the thermonuclear reactions is 55, and 78, if including carbon elements. The reactions have some branches. For the branches having two and three reaction products, the reaction products, Q value and threshold energy are calculated by using a computer. We have investigated those of the branches having more than three products from the papers of Ajzenberg-Selove and so on. And also, by the same papers, we check whether the above mentioned branch has been observed or not. The results are as follows: (I) the number of reactions which have Q 0 branches only with γ ray production, and Q 0 and neutron production is 36(17), and (IV) that of reactions whose branch with Q > 0 does not produce neutrons is 9(3). The value in the parentheses shows the number of the case of the carbon elements. For 55 thermonuclear reactions induced by lighter nuclides than 11 B, the reaction products, the values of Q and threshold energy, and the papers with reaction cross section data are presented in the tables. (author)

  11. Sleeve reaction chamber system

    Science.gov (United States)

    Northrup, M Allen [Berkeley, CA; Beeman, Barton V [San Mateo, CA; Benett, William J [Livermore, CA; Hadley, Dean R [Manteca, CA; Landre, Phoebe [Livermore, CA; Lehew, Stacy L [Livermore, CA; Krulevitch, Peter A [Pleasanton, CA

    2009-08-25

    A chemical reaction chamber system that combines devices such as doped polysilicon for heating, bulk silicon for convective cooling, and thermoelectric (TE) coolers to augment the heating and cooling rates of the reaction chamber or chambers. In addition the system includes non-silicon-based reaction chambers such as any high thermal conductivity material used in combination with a thermoelectric cooling mechanism (i.e., Peltier device). The heat contained in the thermally conductive part of the system can be used/reused to heat the device, thereby conserving energy and expediting the heating/cooling rates. The system combines a micromachined silicon reaction chamber, for example, with an additional module/device for augmented heating/cooling using the Peltier effect. This additional module is particularly useful in extreme environments (very hot or extremely cold) where augmented heating/cooling would be useful to speed up the thermal cycling rates. The chemical reaction chamber system has various applications for synthesis or processing of organic, inorganic, or biochemical reactions, including the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction.

  12. Tattoo reaction: Case series

    Directory of Open Access Journals (Sweden)

    Muneer Mohamed

    2018-04-01

    Full Text Available Tattoo is going to be a very common practice especially among young people and we are witnessing a gradual increase of numerous potential complications to tattoo placement which are often seen by physicians, but generally unknown to the public. The most common skin reactions to tattoo include a transient acute inflammatory reaction due to trauma of the skin with needles and medical complications such as superficial and deep local infections, systemic infections, allergic contact dermatitis, photodermatitis, granulomatous and lichenoid reactions, and skin diseases localized on tattooed area (eczema, psoriasis, lichen, and morphea. In this series we present three cases of tattoo reaction.

  13. Nuclear Astrophysics and Neutron Induced Reactions: Quasi-Free Reactions and RIBs

    International Nuclear Information System (INIS)

    Cherubini, S.; Spitaleri, C.; Crucilla, V.; Gulino, M.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Puglia, S.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Coc, A.; Kubono, S.; Binh, D. N.; Hayakawa, S.; Wakabayashi, Y.; Yamaguchi, H.; Burjan, V.; Kroha, V.; De Sereville, N.

    2010-01-01

    The use of quasi-free reactions in studying nuclear reactions between charged particles of astrophysical interest has received much attention over the last two decades. The Trojan Horse Method is based on this approach and it has been used to study a number of reactions relevant for Nuclear Astrophysics. Recently we applied this method to the study of nuclear reactions that involve radioactive species, namely to the study of the 18 F+p→ 15 O+α process at temperatures corresponding to the energies available in the classical novae scenario. Quasi-free reactions can also be exploited to study processes induced by neutrons. This technique is particularly interesting when applied to reaction induced by neutrons on unstable short-lived nuclei. Such processes are very important in the nucleosynthesis of elements in the sand r-processes scenarios and this technique can give hints for solving key questions in nuclear astrophysics where direct measurements are practically impossible.

  14. Ozone production in the reaction of T2 and O2 gas: A comparison of experimental results and model predictions

    International Nuclear Information System (INIS)

    Failor, R.A.; Souers, P.C.; Magnotta, F.

    1992-01-01

    Ozone, predicted to be an important intermediate species in T 2 oxidation, was monitored in situ by UV absorption spectroscopy for 0.01-1.0 mol % T 2 in O 2 (1 atm, 298 K). These are the first measurements of a tritium oxidation reaction intermediate. The experimental results were compared with the predictions of the author's comprehensive model of tritium oxidation. The experimentally determined temporal variation in ozone concentration is qualitatively reproduced by the model. As predicted, the measured initial rate of ozone production varied linearly with the initial T 2 concentration ([T 2 ] o ), but with a value one-third of that predicted. The steady-state ozone concentration ([O 3 ] ss ) a factor of 4 larger than predicted for a 1.0% T 2 -O 2 mixture. Addition of H 2 to the T 2 O 2 mixture, to differentiate between the radiolytic and chemical behavior of the tritium, produced a decrease in [O 3 ] ss which was larger than predicted. Changing the reaction cell surface-to-volume ratio showed indications of minor surface removal of ozone. No reasonable variation in model input parameters brought both the predicted initial ozone production rates and steady-state concentrations of ozone into agreement with the experimental results. Though qualitative agreement was achieved, further studies, with emphasis on surface effects, are necessary to explain quantitative differences and gain a greater understanding of the oxidation mechanism. 27 refs., 11 figs., 4 tabs

  15. IDEA and Family Involvement

    Directory of Open Access Journals (Sweden)

    Mehmet Emin Öztürk

    2017-01-01

    Full Text Available Individuals with Disabilities Education Act (IDEA gives many rights to parents with special needs in terms of involvement and participation. Given the importance of family involvement in the special education process, and federal legislation that increasingly mandated and supported such involvement over time, considerable research has focused on the multiple ways that relationships between schools and families in the special education decision making process have played out. Educational professionals should create a positive climate for CLD families so that they feel more comfortable and therefore are able to participate more authentically and meaningfully.

  16. Modeling chemical reactions for drug design.

    Science.gov (United States)

    Gasteiger, Johann

    2007-01-01

    Chemical reactions are involved at many stages of the drug design process. This starts with the analysis of biochemical pathways that are controlled by enzymes that might be downregulated in certain diseases. In the lead discovery and lead optimization process compounds have to be synthesized in order to test them for their biological activity. And finally, the metabolism of a drug has to be established. A better understanding of chemical reactions could strongly help in making the drug design process more efficient. We have developed methods for quantifying the concepts an organic chemist is using in rationalizing reaction mechanisms. These methods allow a comprehensive modeling of chemical reactivity and thus are applicable to a wide variety of chemical reactions, from gas phase reactions to biochemical pathways. They are empirical in nature and therefore allow the rapid processing of large sets of structures and reactions. We will show here how methods have been developed for the prediction of acidity values and of the regioselectivity in organic reactions, for designing the synthesis of organic molecules and of combinatorial libraries, and for furthering our understanding of enzyme-catalyzed reactions and of the metabolism of drugs.

  17. Parental Involvement in Education.

    Science.gov (United States)

    Blackstone, Tessa

    1979-01-01

    Arguments in favor of increased parental involvement, particularly in nursery education, are presented. Opposition to participation from parents and teachers is discussed and specific areas in which cooperation might be possible are suggested along with different levels of participation. (JMF)

  18. Hydrogen evolution reaction catalyst

    Science.gov (United States)

    Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan

    2016-02-09

    Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.

  19. Precompound Reactions: Basic Concepts

    International Nuclear Information System (INIS)

    Weidenmueller, H. A.

    2008-01-01

    Because of the non-zero nuclear equilibration time, the compound-nucleus scattering model fails when the incident energy exceeds 10 or 20 MeV, and precompound reactions become important. Basic ideas used in the quantum-statistical approaches to these reactions are described

  20. Fluorogenic organocatalytic reactions

    NARCIS (Netherlands)

    Raeisolsadati Oskouei, M.

    2017-01-01

    In this thesis, we introduce fluorescence spectroscopy as a new tool to gain insight into the interactions between the substrates and catalyst during organocatalytic reactions. The ultimate goal is to resolve the kinetics of the binding and reaction steps and obtain detailed understanding of the

  1. Applications of Reaction Rate

    Science.gov (United States)

    Cunningham, Kevin

    2007-01-01

    This article presents an assignment in which students are to research and report on a chemical reaction whose increased or decreased rate is of practical importance. Specifically, students are asked to represent the reaction they have chosen with an acceptable chemical equation, identify a factor that influences its rate and explain how and why it…

  2. Chemical burn or reaction

    Science.gov (United States)

    Chemicals that touch skin can lead to a reaction on the skin, throughout the body, or both. ... leave the person alone and watch carefully for reactions affecting the entire body. Note: If a chemical gets into the eyes, the eyes should be ...

  3. Degradations and Rearrangement Reactions

    Science.gov (United States)

    Zhang, Jianbo

    This section deals with recent reports concerning degradation and rearrangement reactions of free sugars as well as some glycosides. The transformations are classified in chemical and enzymatic ways. In addition, the Maillard reaction will be discussed as an example of degradation and rearrangement transformation and its application in current research in the fields of chemistry and biology.

  4. Radiolytical Preparation of a Poly(Vinylbenzyl Sulfonic Acid)-Grafted FEP Membrane and Characterization as Polymer Electrolytes for Direct Methanol Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Nho, Y -C; Shin, J; Sohn, J -Y; Fei, G [Radiation Research Division for Industry and Environment, Korea Atomic Energy Research Institute, 1266 Sinjeong-dong, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of)

    2012-09-15

    In this study, a novel polymer electrolyte membrane, poly(vinylbenzyl sulfonic acid)-grafted poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP-g-PVBSA), has been successfully prepared by simultaneous irradiation grafting of vinylbenzyl chloride(VBC) monomer onto a FEP film and taking subsequent chemical modification steps to modify the benzyl chloride moiety to the benzyl sulfonic acid moiety. The chemical reactions for the sulfonation were carried out via the formation of thiouronium salt with thiourea, base-catalyzed hydrolysis for the formation of thiol, and oxidation with hydrogen peroxide. Each chemical conversion process was confirmed by FTIR, elemental analysis, and SEM-EDX. A chemical stability study performed with Fenton's reagent (3% H{sub 2}O{sub 2} solution containing 4 ppm of Fe{sup 2+}) at 70 deg. C revealed that FEP-g-PVBSA has a higher chemical stability than the poly(styrene sulfonic acid)-grafted membranes (FEP-g-PSSA). An EDX analysis was also used to observe the cross-sectional distribution behaviors of the hydrophilic sulfonic acid groups and hydrophobic fluorine groups. The characteristics of an ion-exchange capacity (IEC), water and methanol uptake, methanol permeability, and proton conductivity as a function of the degree of grafting were also studied. The IECs and water uptakes of membranes with different degrees of grafting (36-102%) were measured to be in the range of 0.8-1.62 meq/g, and 10-30%, respectively. When the degree of grafting reached 60% the proton conductivity was higher than that of a Nafion (registered) 212 membrane (6.1E-02 S/cm). The methanol permeability and uptake of the FEP-g-PVBSA membrane was significantly lower than that of the Nafion (registered) 212 membrane, and even the degree of grafting reached 102%. (author)

  5. Chromatographic studies on thermal and radiolytic degradation of n-dodecane-HNO3 two components system and its purification employing silica gel treatment

    International Nuclear Information System (INIS)

    Kadam, Prashant; Kaushik, C.P.; Ozarde, P.D.; Bindu, M.; Tripathi, S.C.; Jambunathan, U.; Pandit, G.G.

    2005-01-01

    This paper describes the studies carried out to examine the extent of degradation of n-dodecane at elevated temperature for different time periods and the effect of gamma radiolysis at different absorbed dose, in n-dodecane- nitric acid two components system. The studies also involved the identification of the degradation products formed during above process using GC-MS. A large number of degradation products were observed. Formation of degradation products increases with absorbed dose and time of heating. Further purification of degraded dodecane was carried out with silica gel crystals as an adsorbent. Treated dodecane samples were subjected to GC/GC-MS analysis, to confirm the extent of removal degradation products. (author)

  6. Kinetics of hydrogen isotope exchange reactions

    International Nuclear Information System (INIS)

    Gold, V.; McAdam, M.E.

    1975-01-01

    Under the influence of tritium β-radiation, 1,4-dioxan undergoes hydrogen exchange with the solvent water. The inhibition of the reaction by known electron scavengers (Ag + , Cu 2+ , Ni 2+ , Co 2+ , Zn 2+ , H 3 + O) and also by species with high reactivity towards hydroxyl radicals but negligible reactivity towards solvated electrons (N 3 - , Br - , SCN - ) has been examined in detail. γ-irradiation similarly induces hydrogen exchange. The action of scavengers is interpreted as requiring the involvement of two separately scavengeable primary radiolysis products in the sequence of reactions leading to exchange. The presence of electron scavengers, even at high concentration, does not totally inhibit the exchange, and a secondary exchange route, involving a low vacancy state of inhibitor cations, is considered responsible for the 'unscavengeable' portion of the reaction, by providing an alternative exchange route. Analogies are drawn between the exchange reaction and other radiation-induced reactions that are thought to involve spur processes. Some implication of radiation-chemical studies in water-alcohol mixtures are indicated. (author)

  7. Calculation of the energetics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dunning, T.H. Jr.; Harding, L.B.; Shepard, R.L.; Harrison, R.J.

    1988-01-01

    To calculate the energetics of chemical reactions we must solve the electronic Schroedinger equation for the molecular conformations of importance for the reactive encounter. Substantial changes occur in the electronic structure of a molecular system as the reaction progresses from reactants through the transition state to products. To describe these changes, our approach includes the following three elements: the use of multiconfiguration self-consistent field wave functions to provide a consistent zero-order description of the electronic structure of the reactants, transition state, and products; the use of configuration interaction techniques to describe electron correlation effects needed to provide quantitative predictions of the reaction energetics; and the use of large, optimized basis sets to provide the flexibility needed to describe the variations in the electronic distributions. With this approach we are able to study reactions involving as many as 5--6 atoms with errors of just a few kcal/mol in the predicted reaction energetics. Predictions to chemical accuracy, i.e., to 1 kcal/mol or less, are not yet feasible, although continuing improvements in both the theoretical methodology and computer technology suggest that this will soon be possible, at least for reactions involving small polyatomic species. 4 figs.

  8. Basic radiation chemistry for the ionising energy treatment of food

    International Nuclear Information System (INIS)

    Moore, P.W.

    1985-01-01

    Before we can understand the chemistry involved in the irradiation of complex substances such as food we need to have some appreciation of the reactions involved and the products formed when ionising energy interacts with the simple substances such as water and dilute solutions. Reactions involving hydrated electrons, hydrogen atoms and hydroxyl radicals are examined and methods for minimising radiolytic effects in foods are discussed

  9. Heavy ion transfer reactions

    International Nuclear Information System (INIS)

    Weisser, D.C.

    1977-06-01

    To complement discussions on the role of γ rays in heavy ion induced reactions, the author discusses the role played by particle detection. Transfer reactions are part of this subject and are among those in which one infers the properties of the residual nucleus in a reaction by observing the emerging light nucleus. Inelastic scattering ought not be excluded from this subject, although no particles are transferred, because of the role it plays in multistep reactions and in fixing O.M. parameters describing the entrance channel of the reaction. Heavy ion transfer reaction studies have been under study for some years and yet this research is still in its infancy. The experimental techniques are difficult and the demands on theory rigorous. One of the main products of heavy ion research has been the thrust to re-examine the assumptions of reaction theory and now include many effects neglected for light ion analysis. This research has spurred the addition of multistep processes to simple direct processes and coupled channel calculations. (J.R.)

  10. Enhancing chemical reactions

    Science.gov (United States)

    Morrey, John R.

    1978-01-01

    Methods of enhancing selected chemical reactions. The population of a selected high vibrational energy state of a reactant molecule is increased substantially above its population at thermal equilibrium by directing onto the molecule a beam of radiant energy from a laser having a combination of frequency and intensity selected to pump the selected energy state, and the reaction is carried out with the temperature, pressure, and concentrations of reactants maintained at a combination of values selected to optimize the reaction in preference to thermal degradation by transforming the absorbed energy into translational motion. The reaction temperature is selected to optimize the reaction. Typically a laser and a frequency doubler emit radiant energy at frequencies of .nu. and 2.nu. into an optical dye within an optical cavity capable of being tuned to a wanted frequency .delta. or a parametric oscillator comprising a non-centrosymmetric crystal having two indices of refraction, to emit radiant energy at the frequencies of .nu., 2.nu., and .delta. (and, with a parametric oscillator, also at 2.nu.-.delta.). Each unwanted frequency is filtered out, and each desired frequency is focused to the desired radiation flux within a reaction chamber and is reflected repeatedly through the chamber while reactants are fed into the chamber and reaction products are removed therefrom.

  11. The Reaction of Oxy Hemoglobin with Nitrite

    DEFF Research Database (Denmark)

    Hathazi, Denisa; Scurtu, Florina; Bischin, Cristina

    2018-01-01

    The autocatalytic reaction between nitrite and the oxy form of globins involves free radicals. For myoglobin (Mb), an initial binding of nitrite to the iron-coordinated oxygen molecule was proposed; the resulting ferrous-peroxynitrate species was not detected, but its decay product, the high...... to a simple kinetic model involving a transient met-aqua form, in contrast to the ferryl detected in the case of Mb in a similar reaction sequence. These data are in line with a previous observation of a transient accumulation of ferryl Hb under auto-catalytic conditions at much lower concentrations......-peroxynitrate. Density functional theory (DFT) calculations support this latter assignment. The reaction allows for differentiating between the reactivities of various chemically modified hemoglobins, including candidates for blood substitutes. Polymerization of hemoglobin slows the nitrite-induced oxidation, in sharp...

  12. Recent Experiments Involving Few-Nucleon Systems

    Science.gov (United States)

    Tornow, W.

    2014-08-01

    Recent experimental results are presented for reactions involving A = 3 to A = 6 nuclear systems. The emphasis is on unique data obtained at new experimental facilities. It is shown that the inertial confinement fusion facilities OMEGA and NIF provide a largely unexpected opportunity for experimental few-body physics to both obtain data of unprecedented quality and extend previous measurements to energies not accessible in the past. Whenever possible, data are compared to state-of-the-art theoretical calculations.

  13. Electrical Breakdown Phenomena Involving Material Interfaces

    Science.gov (United States)

    2013-06-01

    create ozone through chemical reactions involving reactive species created by the electrical discharge [3]. The glow discharge breakdown in such...2. REPORT TYPE N/A 3. DATES COVERED - 4. TITLE AND SUBTITLE Investigation Of Pre-Ionization And Atmospheric Pulsed Discharge Plasma 5a...growth of the air discharge in the form of a conductive filament consisting of electrons and ions. This filament is created by temporal pulse that

  14. Recent Experiments Involving Few-Nucleon Systems

    International Nuclear Information System (INIS)

    Tornow, W.

    2014-01-01

    Recent experimental results are presented for reactions involving A = 3 to A = 6 nuclear systems. The emphasis is on unique data obtained at new experimental facilities. It is shown that the inertial confinement fusion facilities OMEGA and NIF provide a largely unexpected opportunity for experimental few-body physics to both obtain data of unprecedented quality and extend previous measurements to energies not accessible in the past. Whenever possible, data are compared to state-of-the-art theoretical calculations. (author)

  15. Students' Reactions to Course Policy Decisions

    Science.gov (United States)

    Bailey, Sarah F.; Jenkins, Jade S.; Barber, Larissa K.

    2016-01-01

    Classroom management involves managing students' requests for course policy changes. Instructors can adhere to the course policies or convey flexibility through making an exception for the student. The current study empirically examines students' emotional reactions (hostility, guilt, and surprise) and fairness perceptions to course policy…

  16. Emotional reactions to harmful intergroup behavior

    NARCIS (Netherlands)

    Gordijn, E.H.; Yzerbyt, V.Y.; Wigboldus, D.H.J.; Dumont, M.

    2006-01-01

    In this paper, we examined reactions to situations in which, although one is not personally involved, one could see oneself connected to either the perpetrators or the victims of unfair behavior. We manipulated participants' similarity and measured their identification to either one of two groups

  17. Emotional reactions to harmful intergroup behavior

    NARCIS (Netherlands)

    Gordijn, Ernestine H.; Yzerbyt, Vincent; Wigboldus, Daniël; Dumont, Muriel

    2006-01-01

    In this paper, we examined reactions to situations in which, although one is not personally involved, one could see oneself connected to either the perpetrators or the victims of unfair behavior We 14 manipulated participants' similarity and measured their identification to either one of two groups

  18. Cardiovascular involvement in myositis

    DEFF Research Database (Denmark)

    Diederichsen, Louise P

    2017-01-01

    PURPOSE OF REVIEW: The purpose of this review is to provide an update on cardiovascular involvement in idiopathic inflammatory myopathy (IIM). Studies from the past 18 months are identified and reviewed. Finally, the clinical impact of these findings is discussed. RECENT FINDINGS: Epidemiological...... on cardiac magnetic resonance (CMR) imaging suggests that CMR should be considered as a potentially viable diagnostic tool to evaluate the possibility of silent myocardial inflammation in IIM with normal routine noninvasive evaluation. SUMMARY: Updated literature on cardiovascular involvement in IIM has...... identified an increased risk for subclinical and clinical cardiovascular disease in these rare inflammatory muscle diseases....

  19. The Reaction Wheel Pendulum

    CERN Document Server

    Block, Daniel J; Spong, Mark W

    2007-01-01

    This monograph describes the Reaction Wheel Pendulum, the newest inverted-pendulum-like device for control education and research. We discuss the history and background of the reaction wheel pendulum and other similar experimental devices. We develop mathematical models of the reaction wheel pendulum in depth, including linear and nonlinear models, and models of the sensors and actuators that are used for feedback control. We treat various aspects of the control problem, from linear control of themotor, to stabilization of the pendulum about an equilibrium configuration using linear control, t

  20. Firefighter Nozzle Reaction

    DEFF Research Database (Denmark)

    Chin, Selena K.; Sunderland, Peter B.; Jomaas, Grunde

    2017-01-01

    to anchor forces, the hose becomes straight. The nozzle reaction is found to equal the jet momentum flow rate, and it does not change when an elbow connects the hose to the nozzle. A forward force must be exerted by a firefighter or another anchor that matches the forward force that the jet would exert...... on a perpendicular wall. Three reaction expressions are derived, allowing it to be determined in terms of hose diameter, jet diameter, flow rate, and static pressure upstream of the nozzle. The nozzle reaction predictions used by the fire service are 56% to 90% of those obtained here for typical firefighting hand...

  1. Integrating reaction and analysis: investigation of higher-order reactions by cryogenic trapping

    Directory of Open Access Journals (Sweden)

    Skrollan Stockinger

    2013-09-01

    Full Text Available A new approach for the investigation of a higher-order reaction by on-column reaction gas chromatography is presented. The reaction and the analytical separation are combined in a single experiment to investigate the Diels–Alder reaction of benzenediazonium-2-carboxylate as a benzyne precursor with various anthracene derivatives, i.e. anthracene, 9-bromoanthracene, 9-anthracenecarboxaldehyde and 9-anthracenemethanol. To overcome limitations of short reaction contact times at elevated temperatures a novel experimental setup was developed involving a cooling trap to achieve focusing and mixing of the reactants at a defined spot in a fused-silica capillary. This trap functions as a reactor within the separation column in the oven of a gas chromatograph. The reactants are sequentially injected to avoid undefined mixing in the injection port. An experimental protocol was developed with optimized injection intervals and cooling times to achieve sufficient conversions at short reaction times. Reaction products were rapidly identified by mass spectrometric detection. This new approach represents a practical procedure to investigate higher-order reactions at an analytical level and it simultaneously provides valuable information for the optimization of the reaction conditions.

  2. Who Involves Whom?

    Science.gov (United States)

    Ward, Clifford

    1979-01-01

    The author reviews the development of a parents' group at the Bradford Grange School (Manchester, United Kingdom) for ESN (educationally subnormal) children. Problems with the initial parents' group are pointed out, successful approaches are considered, and the importance of parent involvement is stressed. (SBH)

  3. PATTERNS AND FACTORS INVOLVED

    African Journals Online (AJOL)

    Between 1*' of July 1996 and 30'h of June 2000 a total of 3583 patients were registered at the accident and emergency unit of Nnamdi. Azikiwe ... The case files of these were reviewed with a view to ascertaining the causes and factors involved in the deaths of these patients. The .... H.I.V/AIDS related complications 23 6.8.

  4. Nucleon induced reactions

    International Nuclear Information System (INIS)

    Gmuca, S.; Antalik, R.; Kristiak, J.

    1988-01-01

    The collection contains full texts of 37 contributions; all fall within the INIS Subject Scope. The topics treated include some unsolved problems of nuclear reactions and relevant problems of nuclear structure at low and intermediate energies. (Z.S.)

  5. Reactor for exothermic reactions

    Science.gov (United States)

    Smith, L.A. Jr.; Hearn, D.; Jones, E.M. Jr.

    1993-03-02

    A liquid phase process is described for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

  6. Statistical nuclear reactions

    International Nuclear Information System (INIS)

    Hilaire, S.

    2001-01-01

    A review of the statistical model of nuclear reactions is presented. The main relations are described, together with the ingredients necessary to perform practical calculations. In addition, a substantial overview of the width fluctuation correction factor is given. (author)

  7. Photon induced reactions

    International Nuclear Information System (INIS)

    Mecking, B.A.

    1982-04-01

    Various aspects of medium energy nuclear reactions induced by real photons are reviewed. Special emphasis is put on high accuracy experiments that will become possible with the next generation of electron accelerators. (orig.)

  8. Transfusion reaction - hemolytic

    Science.gov (United States)

    ... Names Blood transfusion reaction Images Surface proteins causing rejection References Choate JD, Maitta RW, Tormey CA, Wu ... PA: Elsevier Saunders; 2016:chap 177. Hall JE. Blood types; transfusion; tissue and organ transplantation. In: Hall JE, ...

  9. Sequential charged particle reaction

    International Nuclear Information System (INIS)

    Hori, Jun-ichi; Ochiai, Kentaro; Sato, Satoshi; Yamauchi, Michinori; Nishitani, Takeo

    2004-01-01

    The effective cross sections for producing the sequential reaction products in F82H, pure vanadium and LiF with respect to the 14.9-MeV neutron were obtained and compared with the estimation ones. Since the sequential reactions depend on the secondary charged particles behavior, the effective cross sections are corresponding to the target nuclei and the material composition. The effective cross sections were also estimated by using the EAF-libraries and compared with the experimental ones. There were large discrepancies between estimated and experimental values. Additionally, we showed the contribution of the sequential reaction on the induced activity and dose rate in the boundary region with water. From the present study, it has been clarified that the sequential reactions are of great importance to evaluate the dose rates around the surface of cooling pipe and the activated corrosion products. (author)

  10. Cutaneous adverse drug reactions

    African Journals Online (AJOL)

    CADRs).1 ... patient's management is thought to be responsible for the reaction. Some clinical ... In SJS/TEN hypotension, diarrhoea, hypothermia and confusion suggest ... and a pain management team, centred around a good core of experienced ...

  11. Firefighter Nozzle Reaction

    DEFF Research Database (Denmark)

    Chin, Selena K.; Sunderland, Peter B.; Jomaas, Grunde

    2017-01-01

    Nozzle reaction and hose tension are analyzed using conservation of fluid momentum and assuming steady, inviscid flow and a flexible hose in frictionless contact with the ground. An expression that is independent of the bend angle is derived for the hose tension. If this tension is exceeded owing...... to anchor forces, the hose becomes straight. The nozzle reaction is found to equal the jet momentum flow rate, and it does not change when an elbow connects the hose to the nozzle. A forward force must be exerted by a firefighter or another anchor that matches the forward force that the jet would exert...... on a perpendicular wall. Three reaction expressions are derived, allowing it to be determined in terms of hose diameter, jet diameter, flow rate, and static pressure upstream of the nozzle. The nozzle reaction predictions used by the fire service are 56% to 90% of those obtained here for typical firefighting hand...

  12. Reaction-rate formula in out of equilibrium quantum field theory

    OpenAIRE

    Niegawa, A.; Okano, K.; Ozaki, H.

    1999-01-01

    A complete derivation, from first principles, of the reaction-rate formula for a generic reaction taking place in an out of equilibrium quantum-field system is given. It is shown that the formula involves no finite-volume correction. Each term of the reaction-rate formula represents a set of physical processes that contribute to the reaction under consideration.

  13. Oxygen evolution reaction catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Haber, Joel A.; Jin, Jian; Xiang, Chengxiang; Gregoire, John M.; Jones, Ryan J.; Guevarra, Dan W.; Shinde, Aniketa A.

    2016-09-06

    An Oxygen Evolution Reaction (OER) catalyst includes a metal oxide that includes oxygen, cerium, and one or more second metals. In some instances, the cerium is 10 to 80 molar % of the metals in the metal oxide and/or the catalyst includes two or more second metals. The OER catalyst can be included in or on an electrode. The electrode can be arranged in an oxygen evolution system such that the Oxygen Evolution Reaction occurs at the electrode.

  14. Spallation reactions: calculations

    International Nuclear Information System (INIS)

    Bertini, H.W.

    1975-01-01

    Current methods for calculating spallation reactions over various energy ranges are described and evaluated. Recent semiempirical fits to existing data will probably yield the most accurate predictions for these reactions in general. However, if the products in question have binding energies appreciably different from their isotropic neighbors and if the cross section is approximately 30 mb or larger, then the intranuclear-cascade-evaporation approach is probably better suited. (6 tables, 12 figures, 34 references) (U.S.)

  15. Microorganisms involved in MIC

    Energy Technology Data Exchange (ETDEWEB)

    Sorensen, K. [Danish Technological Institute (Denmark)

    2011-07-01

    Microbiologically influenced corrosion (MIC) is a widespread problem that is difficult to detect and assess because of its complex mechanism. This paper presents the involvement of microorganisms in MIC. Some of the mechanisms that cause MIC include hydrogen consumption, production of acids, anode-cathode formation and electron shuttling. A classic bio-corrosive microorganism in the oil and gas industry is sulphate-reducing prokaryotes (SRP). Methanogens also increase corrosion rates in metals. Some of the phylogenetic orders detected while studying SRP and methanogens are archaeoglobales, clostridiales, methanosarcinales and methanothermococcus. There were some implications, such as growth of SRP not being correlated with growth of methanogens; methanogens were included in MIC risk assessment. A few examples are used to display how microorganisms are involved in topside corrosion and microbial community in producing wells. From the study, it can be concluded that, MIC risk assessment includes system data and empirical knowledge of the distribution and number of microorganisms in the system.

  16. Involved Node Radiation Therapy

    DEFF Research Database (Denmark)

    Maraldo, Maja V; Aznar, Marianne C; Vogelius, Ivan R

    2012-01-01

    PURPOSE: The involved node radiation therapy (INRT) strategy was introduced for patients with Hodgkin lymphoma (HL) to reduce the risk of late effects. With INRT, only the originally involved lymph nodes are irradiated. We present treatment outcome in a retrospective analysis using this strategy...... to 36 Gy). Patients attended regular follow-up visits until 5 years after therapy. RESULTS: The 4-year freedom from disease progression was 96.4% (95% confidence interval: 92.4%-100.4%), median follow-up of 50 months (range: 4-71 months). Three relapses occurred: 2 within the previous radiation field......, and 1 in a previously uninvolved region. The 4-year overall survival was 94% (95% confidence interval: 88.8%-99.1%), median follow-up of 58 months (range: 4-91 months). Early radiation therapy toxicity was limited to grade 1 (23.4%) and grade 2 (13.8%). During follow-up, 8 patients died, none from HL, 7...

  17. Reactors also involve people

    International Nuclear Information System (INIS)

    Hurt, H.B.

    1975-01-01

    As the nuclear industry develops it is to be hoped that high quality occupational health programs will evolve along with other sound operational procedures and practices. The immediate involvement of occupational health personnel may well afford a safety factor which will minimize the likelihood of either the selection of personnel not adequate for the full responsibilities of their work or the continuation in responsible positions of personnel who develop handicaps of either a physical or mental nature

  18. Involvement through photography.

    Science.gov (United States)

    Takai, J

    2016-12-01

    As a photographer living in Tokyo, I have been visiting Suetsugi village regularly to take photographs and show the printed photographs to the residents. What is the role of photography? What does it mean to be involved in the life of Suetsugi through photography? This article discusses some of the answers to these questions 5 years after the accident at Fukushima Daiichi nuclear power plant.

  19. Getting involved in research.

    Science.gov (United States)

    Banner, Davina; Grant, Lyle G

    2011-01-01

    The need for quality nursing research to promote evidence-based practice and optimize patient care is well recognized. This is particularly pertinent in cardiovascular nursing, where cardiovascular disease continues to be the leading cause of morbidity and mortality worldwide (World Health Organization, 2007). Across the spectrum of academic, clinical, and health care administration nursing roles, research remains fundamental to bridging theory, practice, and education (LoBiondo-Wood, Haber, Cameron, & Singh, 2009). Despite recognition of the importance of nursing research, the gap between research and practice continues to be an ongoing issue (Funk, Tornquist, & Champagne, 1995; Pettengill, Gillies, & Clark, 1994; Rizzuto, Bostrom, Suterm, & Chenitz, 1994; Rolfe, 1998). Nurses are appropriately situated to contribute to research that improves clinical outcomes and health service delivery. However, the majority of nurses in clinical practice do not have a significant research component structured into their nursing role. In this research column, the authors outline the importance of nurses being engaged in research and present some different levels of involvement that nurses may assume. A continuum of nursing research involvement includes asking researchable questions, being a savvy consumer of research evidence, finding your own level of research involvement, and aspiring to lead.

  20. Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

    KAUST Repository

    Hisatomi, Takashi; Takanabe, Kazuhiro; Domen, Kazunari

    2014-01-01

    Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical

  1. Synthesis of conformationally constrained peptidomimetics using multicomponent reactions

    NARCIS (Netherlands)

    Scheffelaar, R.; Klein Nijenhuis, R.A.; Paravidino, M.; Lutz, M.; Spek, A.L.; Ehlers, A.W.; de Kanter, F.J.J.; Groen, M.B.; Orru, R.V.A.; Ruijter, E.

    2009-01-01

    A novel modular synthetic approach toward constrained peptidomimetics is reported. The approach involves a highly efficient three-step sequence including two multicomponent reactions, thus allowing unprecedented diversification of both the peptide moieties and the turn-inducing scaffold. The

  2. Tandem Wittig-ene reaction approach to kainic acid

    Digital Repository Service at National Institute of Oceanography (India)

    Majik, M.S.; Parameswaran, P.S.; Tilve, S.G.

    The first example of a tandem Wittig-intramolecular ene reaction approach and its application toward the synthesis of kainic acid is reported. The synthetic pathway involves conversion of prenyl bromide into phosphorane 3, followed by one-pot Wittig...

  3. Neutrino magnetic moment contribution to the neutrino-deuteron reaction

    International Nuclear Information System (INIS)

    Tsuji, K.; Nakamura, S.; Sato, T.; Kubodera, K.; Myhrer, F.

    2004-01-01

    We study the effect of the neutrino magnetic moment on the neutrino-deuteron breakup reaction, using a method called the standard nuclear physics approach, which has already been well tested for several electroweak processes involving the deuteron

  4. High School Forum: "Invitations to Enquiry": The Calcite/Acid Reaction.

    Science.gov (United States)

    Herron, J. Dudley, Ed.; Driscoll, D. R.

    1979-01-01

    Describes a high school chemistry experiment which involves the reaction between calcite and hydrochloric and sulfuric acids. This reaction can be carried out as a projected demonstration and on an individual basis. (HM)

  5. Measurement of proton capture reactions in the hot cycles: an evaluation of experimental methods

    Energy Technology Data Exchange (ETDEWEB)

    Leleux, P [Inst. de Physique Nucleaire, Univ. Catholique de Louvain, Louvain-la-Neuve (Belgium)

    1998-06-01

    In the hot cycles, most of the proton capture reactions involve radioactive nuclei in the entrance and exit channels. This paper evaluates the specific methods that were designed to measure such reactions. (orig.)

  6. Global Controllability of Chemical Reactions

    OpenAIRE

    Drexler, Dániel András; Tóth, János

    2015-01-01

    Controllability of chemical reactions is an important problem in chemical engineering science. In control theory, analysis of the controllability of linear systems is well-founded, however the dynamics of chemical reactions is usually nonlinear. Global controllability properties of chemical reactions are analyzed here based on the Lie-algebra of the vector fields associated to elementary reactions. A chemical reaction is controllable almost everywhere if all the reaction rate coefficients can...

  7. Introduction to chemical reaction engineering

    International Nuclear Information System (INIS)

    Kim, Yeong Geol

    1990-10-01

    This deals with chemical reaction engineering with thirteen chapters. The contents of this book are introduction on reaction engineering, chemical kinetics, thermodynamics and chemical reaction, abnormal reactor, non-isothermal reactor, nonideal reactor, catalysis in nonuniform system, diffusion and reaction in porosity catalyst, design catalyst heterogeneous reactor in solid bed, a high molecule polymerization, bio reaction engineering, reaction engineering in material process, control multi-variable reactor process using digital computer.

  8. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  9. Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

    KAUST Repository

    Hisatomi, Takashi

    2014-10-16

    Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical processes in particulate semiconductors. This review article presents a brief introduction to photocatalysis, followed by kinetic aspects of the photocatalytic water-splitting reaction.Graphical Abstract: [Figure not available: see fulltext.

  10. Three key points along an intrinsic reaction coordinate

    Indian Academy of Sciences (India)

    Unknown

    Abstract. The concept of the reaction force is presented and discussed in detail. For typical processes with energy barriers, it has a universal form which defines three key points along an intrinsic reaction co- ordinate: the force minimum, zero and maximum. We suggest that the resulting four zones be interpreted as involving ...

  11. Heterogeneous Catalysis: Deuterium Exchange Reactions of Hydrogen and Methane

    Science.gov (United States)

    Mirich, Anne; Miller, Trisha Hoette; Klotz, Elsbeth; Mattson, Bruce

    2015-01-01

    Two gas phase deuterium/hydrogen exchange reactions are described utilizing a simple inexpensive glass catalyst tube containing 0.5% Pd on alumina through which gas mixtures can be passed and products collected for analysis. The first of these exchange reactions involves H[subscript 2] + D[subscript 2], which proceeds at temperatures as low as 77…

  12. Stereodynamics: From elementary processes to macroscopic chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Kasai, Toshio [Department of Chemistry, National Taiwan University, Taipei 106, Taiwan (China); Graduate School of Science, Department of Chemistry, Osaka University, Toyonaka, 560-0043 Osaka (Japan); Che, Dock-Chil [Graduate School of Science, Department of Chemistry, Osaka University, Toyonaka, 560-0043 Osaka (Japan); Tsai, Po-Yu [Department of Chemistry, National Taiwan University, Taipei 106, Taiwan (China); Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan (China); Lin, King-Chuen [Department of Chemistry, National Taiwan University, Taipei 106, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan (China); Palazzetti, Federico [Scuola Normale Superiore, Pisa (Italy); Dipartimento di Chimica Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Aquilanti, Vincenzo [Dipartimento di Chimica Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Istituto di Struttura della Materia, Consiglio Nazionale delle Ricerche, Roma (Italy); Instituto de Fisica, Universidade Federal da Bahia, Salvador (Brazil)

    2015-12-31

    This paper aims at discussing new facets on stereodynamical behaviors in chemical reactions, i.e. the effects of molecular orientation and alignment on reactive processes. Further topics on macroscopic processes involving deviations from Arrhenius behavior in the temperature dependence of chemical reactions and chirality effects in collisions are also discussed.

  13. Kinetics of elementary atom and radical reactions: Progress report

    International Nuclear Information System (INIS)

    Gordon, R.J.

    1986-01-01

    Our research program is concerned with the kinetics of elementary gas phase reactions and energy transfer involving polyatomic molecules. We report here on three ongoing projects: The reaction of oxygen atoms with hydrogen molecules, the electronic relaxation of NH radicals, and the vibrational relaxation of highly excited SF 6 molecules. 10 refs., 5 figs

  14. Desensitizing Children's Emotional Reactions to the Mass Media.

    Science.gov (United States)

    Wilson, Barbara J.

    1989-01-01

    Assesses effectiveness of two desensitization strategies for reducing children's emotional reactions to mass media. Examines children having passive exposure, modeled exposure, or no exposure to lizards before watching a horror movie involving lizards. Finds that modeled exposure decreases emotional reactions and negative interpretations, whereas…

  15. Substitution and protonation reactions of nitrilotriaceta tochromium(lll) ions

    CSIR Research Space (South Africa)

    Visser, HG

    1994-04-01

    Full Text Available The reaction of NH4[Cr(NTA)(H2O)2] (NTA = nitrilotriacetic acid) with H+ has been studied at different temperatures and a rate constant of 1.27(3) x 10(-2) S-1 was obtained at 25.1-degrees-C. It is proposed that the reaction involves the formation...

  16. NMR reaction monitoring in flow synthesis

    Directory of Open Access Journals (Sweden)

    M. Victoria Gomez

    2017-02-01

    Full Text Available Recent advances in the use of flow chemistry with in-line and on-line analysis by NMR are presented. The use of macro- and microreactors, coupled with standard and custom made NMR probes involving microcoils, incorporated into high resolution and benchtop NMR instruments is reviewed. Some recent selected applications have been collected, including synthetic applications, the determination of the kinetic and thermodynamic parameters and reaction optimization, even in single experiments and on the μL scale. Finally, software that allows automatic reaction monitoring and optimization is discussed.

  17. NMR reaction monitoring in flow synthesis.

    Science.gov (United States)

    Gomez, M Victoria; de la Hoz, Antonio

    2017-01-01

    Recent advances in the use of flow chemistry with in-line and on-line analysis by NMR are presented. The use of macro- and microreactors, coupled with standard and custom made NMR probes involving microcoils, incorporated into high resolution and benchtop NMR instruments is reviewed. Some recent selected applications have been collected, including synthetic applications, the determination of the kinetic and thermodynamic parameters and reaction optimization, even in single experiments and on the μL scale. Finally, software that allows automatic reaction monitoring and optimization is discussed.

  18. Reaction between uranium hexafluoride and trimethylsilylhalides

    Energy Technology Data Exchange (ETDEWEB)

    Brown, D; Berry, J A [UKAEA Atomic Energy Research Establishment, Harwell. Chemistry Div.; Holloway, J H; Staunton, G M [Leicester Univ. (UK). Dept. of Chemistry

    1938-07-01

    Reactions involving 1.1:1 molar ratios of uranium hexafluoride to either trimethylsilylchloride or trimethylsilylbromide in halocarbon solutions yield ..beta..-UF/sub 5/ at room temperature. With 2 mol equivalents of trimethylsilylchloride the product is UF/sub 4/. The reactions appear to proceed via the intermediate formation of unstable brown uranium(VI) chloride and bromide fluorides. Calculations show that UClF/sub 5/ and UCl/sub 2/F/sub 4/ are thermodynamically unstable with respect to the loss of chlorine at room temperature.

  19. Theoretical studies of chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Schatz, G.C. [Argonne National Laboratory, IL (United States)

    1993-12-01

    This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

  20. Department of Nuclear Reactions: Overview

    International Nuclear Information System (INIS)

    Rusek, K.

    2000-01-01

    Full text: During last year the physicists of the Department of Nuclear Reactions were involved in many experiments and projects: -Low energy nuclear reactions: For the first time a heavy ion beam from the Warsaw Cyclotron C-200 was used to investigate elastic and inelastic scattering of 12 C ions from 12 C target. The experiment is a part of a long range programme devoted to study the energy dependence of the nucleus-nucleus interactions. -Multifragmentation of relativistic heavy ions: Multifragmentation reactions induced by 12 C on different heavy targets and at different energies were studied in experiments performed at Gesellschaft fuer Schwerionenforschung by the ALADIN Collaboration. These asymmetric systems were investigated in order to study the interplay between preequilibrium and equilibrium phenomena in the nuclear liquid - gas phase transition. -The structure of nucleons: A novel, two-structure description of the Roper resonance was proposed on the basis of the α-p scattering data reanalysed by means of a T-matrix formalism. -Atomic physics: Emission of the X-rays by fast heavy ions (S, Ti, Fe) as they traverse the matter (thin carbon or other light element foil) was investigated in a series of experiments performed at University of Erlangen. It was demonstrated, that the characteristic K α X-rays emitted by a heavy ion can serve as a tool for Z-value control of the ion. -Material research: Semiconductor heterostructures were investigated by means of Rutherford Back Scattering and Channeling methods using the 2 MeV α particles from the Van de Graaff accelerator ''Lech'' at the Department. The following reports present the results and major successes which were achieved in 1999. (author)

  1. Involvement Without Participation?

    DEFF Research Database (Denmark)

    Olsén, Peter

    2012-01-01

    The article presents a case study of a knowledge-intensive company that launched a 2-year project to improve their psychosocial working environment. All parties agreed on the project, and the methods used aimed to promote the involvement of the employees. Surprisingly, the psychosocial working...... environment did not improve; on the contrary, it deteriorated. The article highlights cultural and structural obstacles to the process, including an inadequate understanding of organisational learning and a narrow focus on market and competition. The endeavours did not consistently increase delegation...

  2. Inflammatory reaction in chondroblastoma

    International Nuclear Information System (INIS)

    Yamamura, Sigeki; Sato, Keiji; Sugiura, Hideshi; Iwata, Hisashi

    1996-01-01

    The objective of this study was to evaluate the inflammatory reaction accompanying chondroblastoma and to define the value of the finding in clinical practice. We reviewed the clinical, radiographic, and magnetic resonance (MR) findings in six patients with histologically proven chondroblastoma. In all cases, MR imaging showered marrow and soft tissue edema. In four of six cases, periosteal reaction related to intra-osseous edema was more clearly demonstrated on MR imaging than on radiographs. Follow-up MR studies after surgery were available in three patients and all showed disappearance of inflammatory responses such as marrow and soft tissue edema, and reactive synovitis. We propose that these inflammatory reactions of chondroblastomas are inportant signs for detecting residual tumor in recurrences after surgery, as well as for making a precise diagnosis. The MR changes may also be valuable in demonstrating eradication of the tumor. (orig./MG)

  3. Inflammatory reaction in chondroblastoma

    Energy Technology Data Exchange (ETDEWEB)

    Yamamura, Sigeki [Dept. of Orthopedic Surgery, Nagoya Univ. School of Medicine (Japan); Sato, Keiji [Dept. of Orthopedic Surgery, Nagoya Univ. School of Medicine (Japan); Sugiura, Hideshi [Dept. of Orthopedic Surgery, Nagoya Univ. School of Medicine (Japan); Iwata, Hisashi [Dept. of Orthopedic Surgery, Nagoya Univ. School of Medicine (Japan)

    1996-05-01

    The objective of this study was to evaluate the inflammatory reaction accompanying chondroblastoma and to define the value of the finding in clinical practice. We reviewed the clinical, radiographic, and magnetic resonance (MR) findings in six patients with histologically proven chondroblastoma. In all cases, MR imaging showered marrow and soft tissue edema. In four of six cases, periosteal reaction related to intra-osseous edema was more clearly demonstrated on MR imaging than on radiographs. Follow-up MR studies after surgery were available in three patients and all showed disappearance of inflammatory responses such as marrow and soft tissue edema, and reactive synovitis. We propose that these inflammatory reactions of chondroblastomas are inportant signs for detecting residual tumor in recurrences after surgery, as well as for making a precise diagnosis. The MR changes may also be valuable in demonstrating eradication of the tumor. (orig./MG)

  4. Multi-step direct reactions

    International Nuclear Information System (INIS)

    Koning, A.J.

    1992-07-01

    In recent years a variety of statistical theories has been developed concerning multistep direct (MSD) nuclear reactions. In addition, dominant in applications is a whole class of semiclassical models that may be subsumed under the heading of 'generalized exciton models'; these are basically MSD-type extensions on top of compound-like concepts. In this report the relation between their underlying statistical MSD-postulates are highlighted. A command framework is sketched that enables to generate the various MSD theories through assigning statistical properties to different parts of the nuclear Hamiltonian. Then it is shown that distinct forms of nuclear randomness are embodied in the mentioned theories. All these theories appear to be very similar at a qualitative level. In order to explain the high energy-tails and forward-peaked angular distribution typical for particles emitted in MSD reactions, it is imagined that the incident continuum particle stepwise looses its energy and direction in a sequence of collisions, thereby creating new particle-hole pairs in the target system. At each step emission may take place. The statistical aspect comes in because many continuum states are involved in the process. These are supposed to display chaotic behavior, the associated randomness assumption giving rise to important simplifications in the expression for MSD emission cross sections. This picture suggests that mentioned MSD models can be interpreted as a variant of essentially one and the same theory. 113 refs.; 25 figs.; 9 tabs

  5. Electrodeposition of Pd based binary catalysts on Carbon paper via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Direct alcohol fuel cells (DAFCs) continue to extensive attention as potential power sources for portable and stationary applications. The oxygen reduction reaction (ORR) involving the four electron transfer remains a challenge for DAFCs due to its...

  6. Low Energy Nuclear Reactions: 2007 Update

    Science.gov (United States)

    Krivit, Steven B.

    2007-03-01

    This paper presents an overview of low energy nuclear reactions, a subset of the field of condensed matter nuclear science. Condensed matter nuclear science studies nuclear effects in and/or on condensed matter, including low energy nuclear reactions, an entirely new branch of science that gained widespread attention and notoriety beginning in 1989 with the announcement of a previously unrecognized source of energy by Martin Fleischmann and Stanley Pons that came to be known as cold fusion. Two branches of LENR are recognized. The first includes a set of reactions like those observed by Fleischmann and Pons that use palladium and deuterium and yield excess heat and helium-4. Numerous mechanisms have been proposed to explain these reactions, however there is no consensus for, or general acceptance of, any of the theories. The claim of fusion is still considered speculative and, as such, is not an ideal term for this work. The other branch is a wide assortment of nuclear reactions that may occur with either hydrogen or deuterium. Anomalous nuclear transmutations are reported that involve light as well as heavy elements. The significant questions that face this field of research are: 1) Are LENRs a genuine nuclear reaction? 2) If so, is there a release of excess energy? 3) If there is, is the energy release cost-effective?

  7. Knockout reactions: experimental aspects

    Energy Technology Data Exchange (ETDEWEB)

    Cortina Gil, D. [Santiago de Compostela Univ. (Spain)

    2007-07-01

    The availability of radioactive beams has given rise to intense activity in the field of direct reactions. The removal of one(two)-nucleon (referred to as nucleon knockout in this text) from a fast exotic projectile has been extensively investigated. This lecture provides a general overview of the experimental results achieved using this technique. The sensitivity of the method to different experimental aspects is illustrated with a few examples. Special attention is given to the application of nucleon-knockout reactions as a general purpose spectroscopic tool. (author)

  8. Reactions to dietary tartrazine.

    OpenAIRE

    David, T J

    1987-01-01

    Double blind challenges with tartrazine and benzoic acid were performed in hospital in 24 children whose parents gave a definite history of a purely behavioural immediate adverse reaction to one of these substances. The patients, whose ages ranged from 1.6 to 12.4 years, were on a diet that avoided these items, and in all there was a clear history that any lapse of the diet caused an obvious adverse behavioural reaction within two hours. In no patient was any change in behaviour noted either ...

  9. Nuclear fission and reactions

    International Nuclear Information System (INIS)

    Anon.

    1975-01-01

    The nuclear fission research programs are designed to elucidate basic features of the fission process. Specifically, (1) factors determining how nucleons of a fissioning nucleus are distributed between two fission fragments, (2) factors determining kinetic energy and excitation energies of fragments, and (3) factors controlling fission lifetimes. To these ends, fission studies are reported for several heavy elements and include investigations of spontaneous and neutron-induced fission, heavy ion reactions, and high energy proton reactions. The status of theoretical research is also discussed. (U.S.)

  10. Modeling of Reaction Calorimeter

    OpenAIRE

    Farzad, Reza

    2014-01-01

    The purpose of this project was to model the reaction calorimeter in order to calculate the heat of absorption which is the most important parameter in this work. Reaction calorimeter is an apparatus which is used in measuring the heat of absorption of CO2 as well as the total pressure in vapor phase based on vapor-liquid equilibrium state. Mixture of monoethanolamine (MEA) and water was used as a solvent to absorb the CO2.Project was divided in to three parts in order to make the programming...

  11. Introduction to nuclear reactions

    International Nuclear Information System (INIS)

    Satchler, G.R.

    1980-01-01

    This introduction to nuclear reaction phenomena is aimed primarily but not exclusively at readers at the undergraduate student level. An overview of the subject is presented in the first two chapters entitled - Some background information and Introduction to nuclear reactions. The third chapter reviews scattering theory with emphasis on the underlying physical ideas and also provides schematic entrees to the more advanced topics. The physical models which have been developed to account for the various aspects of nuclear phenomena are described in more detail in chapter 4. References and exercises are appended to each chapter. (U.K.)

  12. Knockout reactions: experimental aspects

    International Nuclear Information System (INIS)

    Cortina Gil, D.

    2007-01-01

    The availability of radioactive beams has given rise to intense activity in the field of direct reactions. The removal of one(two)-nucleon (referred to as nucleon knockout in this text) from a fast exotic projectile has been extensively investigated. This lecture provides a general overview of the experimental results achieved using this technique. The sensitivity of the method to different experimental aspects is illustrated with a few examples. Special attention is given to the application of nucleon-knockout reactions as a general purpose spectroscopic tool. (author)

  13. Involvement in Physical Activity

    Directory of Open Access Journals (Sweden)

    James Gavin

    2013-04-01

    Full Text Available A total of 1,096 adolescents participated in 123 focus groups regarding the perceived outcomes of their involvement in sports and physical activity (PA. The groups, segmented by grade level, sex, and school types, were conducted in both public and private high schools in Montreal, Quebec. We sought to understand, through the participants’ own words, their perception of the outcome matrix of involvement in sports and PA. Focus group questions emphasized changes that adolescents associated with such engagement. In particular, participants were asked how sports and PA might influence behaviors, emotional states, personal characteristics, and other outcomes. Twelve themes were identified in the responses: Positive Health and Physical Changes (18.5%, Activity-Related Positive Emotions (15.6%, and Personal Learning (11.3% were most prevalent in the discussions. A cluster of deeper personal changes thematically described as Self-Identity, Autonomy, and Positive Character Development accounted for another 16.5% of the responses. Relatively few commentaries emphasized negative effects (7.1%. Converting the proportions of qualitative data into a quantitative index allowed us to analyze potential differences in emphasis according to sex, age, and school type. Though a few significant findings emerged, the larger pattern was of a uniform perceptual map across the variables for this adolescent sample. Implications drawn from this investigation highlight the need to clearly articulate concrete pathways to positive nonphysical changes (e.g., mood states, autonomy, positive character development from engagements in sports and PA.

  14. Public interest group involvement

    International Nuclear Information System (INIS)

    Shelley, P.

    1986-01-01

    Including public interest groups in the siting process for nuclear waste disposal facilities is of great importance. Controversial sitings often result in litigation, but involving public interest groups early in the process will lessen the change of this. They act as surrogates for the general public and should be considered as members of the team. It is important to remember though, that all public interest groups are different. In choosing public panels such as public advisory committees, members should not be chosen on the basis of some quota. Opposition groups should not be excluded. Also, it is important to put the right person in charge of the committee. The goal of public involvement is to identify the conflicts. This must be done during the decision process, because conflicts must be known before they can be eliminated. Regarding litigation, it is important to ease through and around legal battles. If the siting process has integrity and a good faith effort has been shown, the court should uphold the effort. In addition, it is important to be negotiable and to eliminate shortcuts

  15. PEG-400 as an efficient and recyclable reaction medium for the synthesis of polyhydroquinolines via Hantzsch reaction

    Directory of Open Access Journals (Sweden)

    Shitole Nana Vikram

    2013-01-01

    Full Text Available Polyhydroquinoline derivatives have been prepared efficiently in a one-pot synthesis via Hantzsch condensation using PEG-400 as reaction medium. The present method does not involve any hazardous organic solvents or toxic catalysts. The present methodology offers several advantages such as simple procedure, excellent yields with shorter reaction times and purification of products by non-chromatographic methods.

  16. Reaction mechanism of reductive decomposition of FGD gypsum with anthracite

    International Nuclear Information System (INIS)

    Zheng, Da; Lu, Hailin; Sun, Xiuyun; Liu, Xiaodong; Han, Weiqing; Wang, Lianjun

    2013-01-01

    Highlights: • The reaction mechanism was different if the molar ratio of C/CaSO 4 was different. • The yield of CaO rises with an increase in temperature. • The optimal ratio of C/CaSO 4 = 1.2:1. • The decomposition process is mainly apparent solid–solid reaction with liquid-phase involved. - Abstract: The process of decomposition reaction between flue gas desulfurization (FGD) gypsum and anthracite is complex, which depends on the reaction conditions and atmosphere. In this study, thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA-FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and the experiment in a tubular reactor were used to characterize the decomposition reaction in a nitrogen atmosphere under different conditions. The reaction mechanism analysis showed that the decomposition reaction process and mechanism were different when the molar proportion of C/CaSO 4 was changed. The experiment results showed that appropriate increase in the C/CaSO 4 proportion and higher temperatures were suitable for the formation of the main production of CaO, which can help us to understand the solid state reaction mechanism better. Via kinetic analysis of the reaction between anthracite and FGD gypsum under the optimal molar ratio of C/CaSO 4 , the mechanism model of the reaction was confirmed and the decomposition process was a two-step reaction which was in accordance with apparent solid–solid reaction

  17. Rates of Thermonuclear Reactions in Dense Plasmas

    International Nuclear Information System (INIS)

    Tsytovich, V.N.; Bornatici, M.

    2000-01-01

    in the solar interior are calculated numerically. It is shown that the corrections to reactions involving 8 B and 7 Be may exceed 100%. The results obtained are discussed in connection with the solar neutrino problem. The range of applicability of the approach is also discussed

  18. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    International Nuclear Information System (INIS)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C; Pace, Molly; Kim, Young Jin; Jardine, Philip M.; Watson, David B.

    2007-01-01

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M. partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M. species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions

  19. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

    Science.gov (United States)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

    2007-06-16

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  20. (MIRC) reaction w

    Indian Academy of Sciences (India)

    Sudesh Kumari

    eco-friendly solvents, high yields and easy work-up procedure. Keywords. Ethylene glycol; 4-hydroxycoumarin; ... ability and also compatibility with most organic and inorganic compounds. Because of these properties it is ..... phenyl amino)-2H-chromen-2-one (8a) was isolated from the reaction mixture to confirm the ...