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Sample records for protium

  1. Cryogenic distillation facility for isotopic purification of protium and deuterium

    SciTech Connect

    Alekseev, I.; Arkhipov, Ev.; Bondarenko, S.; Fedorchenko, O.; Ganzha, V.; Ivshin, K.; Kravtsov, P. Trofimov, V.; Vasilyev, A.; Vasyanina, T.; Vorobyov, A.; Vznuzdaev, M.; Kammel, P.; Petitjean, C.

    2015-12-15

    Isotopic purification of the protium and deuterium is an important requirement of many physics experiments. A cryogenic facility for high-efficiency separation of hydrogen isotopes with a cryogenic distillation column as the main element is described. The instrument is portable, so that it can be used at the experimental site. It was designed and built at the Petersburg Nuclear Physics Institute, Gatchina, Russia. Fundamental operating parameters have been measured including a liquid holdup in the column packing, the pressure drops across the column and the purity of the product at different operating modes. A mathematical model describes expected profiles of hydrogen isotope concentration along the distillation column. An analysis of ortho-parahydrogen isomeric composition by gas chromatography was used for evaluation of the column performance during the tuning operations. The protium content during deuterium purification (≤100 ppb) was measured using gas chromatography with accumulation of the protium in the distillation column. A high precision isotopic measurement at the Institute of Particle Physics, ETH-Zurich, Switzerland, provided an upper bound of the deuterium content in protium (≤6 ppb), which exceeds all commercially available products.

  2. Cryogenic distillation facility for isotopic purification of protium and deuterium

    NASA Astrophysics Data System (ADS)

    Alekseev, I.; Arkhipov, Ev.; Bondarenko, S.; Fedorchenko, O.; Ganzha, V.; Ivshin, K.; Kammel, P.; Kravtsov, P.; Petitjean, C.; Trofimov, V.; Vasilyev, A.; Vasyanina, T.; Vorobyov, A.; Vznuzdaev, M.

    2015-12-01

    Isotopic purification of the protium and deuterium is an important requirement of many physics experiments. A cryogenic facility for high-efficiency separation of hydrogen isotopes with a cryogenic distillation column as the main element is described. The instrument is portable, so that it can be used at the experimental site. It was designed and built at the Petersburg Nuclear Physics Institute, Gatchina, Russia. Fundamental operating parameters have been measured including a liquid holdup in the column packing, the pressure drops across the column and the purity of the product at different operating modes. A mathematical model describes expected profiles of hydrogen isotope concentration along the distillation column. An analysis of ortho-parahydrogen isomeric composition by gas chromatography was used for evaluation of the column performance during the tuning operations. The protium content during deuterium purification (≤100 ppb) was measured using gas chromatography with accumulation of the protium in the distillation column. A high precision isotopic measurement at the Institute of Particle Physics, ETH-Zurich, Switzerland, provided an upper bound of the deuterium content in protium (≤6 ppb), which exceeds all commercially available products.

  3. Cryogenic distillation facility for isotopic purification of protium and deuterium.

    PubMed

    Alekseev, I; Arkhipov, Ev; Bondarenko, S; Fedorchenko, O; Ganzha, V; Ivshin, K; Kammel, P; Kravtsov, P; Petitjean, C; Trofimov, V; Vasilyev, A; Vasyanina, T; Vorobyov, A; Vznuzdaev, M

    2015-12-01

    Isotopic purification of the protium and deuterium is an important requirement of many physics experiments. A cryogenic facility for high-efficiency separation of hydrogen isotopes with a cryogenic distillation column as the main element is described. The instrument is portable, so that it can be used at the experimental site. It was designed and built at the Petersburg Nuclear Physics Institute, Gatchina, Russia. Fundamental operating parameters have been measured including a liquid holdup in the column packing, the pressure drops across the column and the purity of the product at different operating modes. A mathematical model describes expected profiles of hydrogen isotope concentration along the distillation column. An analysis of ortho-parahydrogen isomeric composition by gas chromatography was used for evaluation of the column performance during the tuning operations. The protium content during deuterium purification (≤100 ppb) was measured using gas chromatography with accumulation of the protium in the distillation column. A high precision isotopic measurement at the Institute of Particle Physics, ETH-Zurich, Switzerland, provided an upper bound of the deuterium content in protium (≤6 ppb), which exceeds all commercially available products.

  4. Inert blanketing of a hydride bed using typical grade protium

    SciTech Connect

    Klein, J.E.

    2015-03-15

    This paper describes the impact of 500 ppm (0.05%) impurities in protium on the absorption rate of a 9.66 kg LaNi{sub 4.25}Al{sub 0.75} (LANA0.75) metal hydride bed. The presence of 500 ppm or less inerts (i.e. non-hydrogen isotopes) can significantly impact hydrogen bed absorption rates. The impact on reducing absorption rates is significantly greater than predicted assuming uniform temperature, pressure, and compositions throughout the bed. Possible explanations are discussed. One possibility considered was the feed gas contained impurity levels higher than 500 ppm. It was shown that a level of 5000 ppm of inerts would have been necessary to fit the experimental result so this possibility wa dismissed. Another possibility is that the impurities in the protium supply reacted with the hydride material and partially poisoned the hydride. If the hydride were poisoned with CO or another impurity, the removal of the over-pressure gas in the bed would not be expected to allow the hydride loading of the bed to continue as the experimental results showed, so this possibility was also dismissed. The last possibility questions the validity of the calculations. It is assumed in all the calculations that the gas phase composition, temperature, and pressure are uniform throughout the bed. These assumptions are less valid for large beds where there can be large temperature, pressure, and composition gradients throughout the bed. Eventually the impact of 0.05% inerts in protium on bed absorption rate is shown and explained in terms of an increase in inert partial pressure as the bed was loaded.

  5. Anti-Inflammatory Activity of Triterpenes Isolated from Protium paniculatum Oil-Resins.

    PubMed

    de Almeida, Patrícia D O; Boleti, Ana Paula de A; Rüdiger, André Luis; Lourenço, Geane A; da Veiga Junior, Valdir Florêncio; Lima, Emerson S

    2015-01-01

    Protium is the main genus of the Burseraceae family and one of the most common genera in South America, with an important species called "breu." Gum and oil-resins of this species are used as tonic and stimulant and for the treatment of ulcers and inflammation. The present study aims to isolate and investigate the anti-inflammatory activity of triterpene compounds isolated from oil-resin of Protium paniculatum. The pentacyclic triterpenes α,β-amyrin, acetylated α,β-amyrin, α,β-amyrone, and brein/maniladiol did not alter the viability of murine J774 macrophages (IC50 > 20 µg/mL), with the exception of mixture of brein/maniladiol which showed moderate cytotoxic activity. Also it was observed that compounds at 10 µg/mL inhibited more than 80% of production of NO(•), although only α,β-amyrin was able to inhibit the production of TNF-α (52.03 ± 2.4%). The compounds inhibited the production of IL-6 and induced the production of IL-10 in murine J774 macrophages stimulated by LPS. α,β-Amyrone inhibited the expression of COX-2 and also inhibited the formation of paw or ear edema in rats and mice, having a quick and immediate effect. This study may provide the basis for future investigations on the therapeutic role of α,β-amyrone in treating inflammation. PMID:27034686

  6. Anti-Inflammatory Activity of Triterpenes Isolated from Protium paniculatum Oil-Resins

    PubMed Central

    de Almeida, Patrícia D. O.; Boleti, Ana Paula de A.; Rüdiger, André Luis; Lourenço, Geane A.; da Veiga Junior, Valdir Florêncio; Lima, Emerson S.

    2015-01-01

    Protium is the main genus of the Burseraceae family and one of the most common genera in South America, with an important species called “breu.” Gum and oil-resins of this species are used as tonic and stimulant and for the treatment of ulcers and inflammation. The present study aims to isolate and investigate the anti-inflammatory activity of triterpene compounds isolated from oil-resin of Protium paniculatum. The pentacyclic triterpenes α,β-amyrin, acetylated α,β-amyrin, α,β-amyrone, and brein/maniladiol did not alter the viability of murine J774 macrophages (IC50 > 20 µg/mL), with the exception of mixture of brein/maniladiol which showed moderate cytotoxic activity. Also it was observed that compounds at 10 µg/mL inhibited more than 80% of production of NO•, although only α,β-amyrin was able to inhibit the production of TNF-α (52.03 ± 2.4%). The compounds inhibited the production of IL-6 and induced the production of IL-10 in murine J774 macrophages stimulated by LPS. α,β-Amyrone inhibited the expression of COX-2 and also inhibited the formation of paw or ear edema in rats and mice, having a quick and immediate effect. This study may provide the basis for future investigations on the therapeutic role of α,β-amyrone in treating inflammation. PMID:27034686

  7. A Low Temperature Distillation System for Separating Mixtures of Protium, Deuterium, and Tritium Isotopes

    SciTech Connect

    Embury, Michael, C.; Watkins, Reed A.; Hinckley, Richard; Post, Jr., Arthur H.

    1985-04-30

    A low temperature (24 K) distillation system for separating mixtures of hydrogen isotopes has been designed, fabricated, and delivered for use as the main component of the Hydrogen Isotope Separation System (HISS) at Mound. The HISS will handle feed mixtures of all six isotopic species of hydrogen (H2, HD, HT, D2, DT, T2) and will enrich the tritium while producing a stackable raffinate. Arther D. Little, Inc. (ADL) was the prime contractor for the distillation system. The design and fabrication techniques used for the HISS distillation system are similar to those used for previous stills which were also designed and built by ADL. The distillation system was tested with mixtures of protium and deuterium at the ADL shop. This system, as well as the feed, product, and raffinate handling systems are presently being installed at Mound where integrated testing is scheduled next calendar year.

  8. Essential Oil from the Resin of Protium heptaphyllum: Chemical Composition, Cytotoxicity, Antimicrobial Activity, and Antimutagenicity

    PubMed Central

    de Lima, Ewelyne Miranda; Cazelli, Didley Sâmia Paiva; Pinto, Fernanda Endringer; Mazuco, Renata Alves; Kalil, Ieda Carneiro; Lenz, Dominik; Scherer, Rodrigo; de Andrade, Tadeu Uggere; Endringer, Denise Coutinho

    2016-01-01

    Background: Protium heptaphyllum (Aubl.) March is popularly used as an analgesic and anti-inflammatory agent. Objective: This study aimed to evaluate the chemical composition of P. heptaphyllum essential oil, its cytotoxicity in a breast cancer cell line (MCF-7), antimicrobial activity, and its antimutagenicity in vivo. Materials and Methods: The chemical composition of the essential oil collected in three 3 years was determined by gas chromatography-mass spectrometry. The cytotoxicity was evaluated using a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. Annexin V conjugated with fluorescein isothiocyanate, caspase-3, and tumor necrosis factor-alpha (TNF-α) assays were performed to evaluate apoptosis and inflammatory events. The antimutagenic activity at doses of 25, 50, and 100 mg/kg was determined using a micronucleus test in murine bone marrow. Results: The essential oil showed a predominance of monoterpene compounds, being the terpinolene, p-cymene-8-ol, and p-cymene, present in the essential oil extracted in the 3 years. The essential oil showed a protection against cyclophosphamide-induced genotoxicity, and the cytotoxicity index polychromatic erythrocytes/normochromatic erythrocytes ratio in animals treated with oil at all doses (1.34 ± 0.33; 1.15 ± 0.1; 1.11 ± 0.13) did not differ from the negative control animal (1.31 ± 0.33), but from the cyclophosphamide group (0.61 ± 0.12). Cytotoxicity, at a concentration of 40.0 μg/mL, and antimicrobial activity were not observed for the essential oil (minimum inhibitory concentration ≥0.5 mg/mL). The essential oil did not change the levels of caspase-3 in the TNF-α level. Conclusion: The essential oil showed antimutagenic activity due to its chemical composition. SUMMARY Terpinolene, p-cymene-8-ol, and p-cymene are the main constituents of the essential oil of P. heptaphyllum collected within 3-yearsThe essential oil of P. heptaphyllum did not show antimicrobial activity (MIC >0.5 mg

  9. ANALYTICAL METHOD FOR MEASURING TOTAL PROTIUM AND TOTAL DEUTERIUM IN A GAS MIXTURE CONTAINING H2, D2,AND HD VIA GAS CHAROMATOGRAPHY

    SciTech Connect

    Sessions, H

    2007-08-07

    The most common analytical method of identifying and quantifying non-radioactive isotopic species of hydrogen is mass spectrometry. A low mass, high resolution mass spectrometer with adequate sensitivity and stability to identify and quantify hydrogen isotopes in the low ppm range is an expensive, complex instrument. A new analytical technique has been developed that measures both total protium (H) and total deuterium (D) in a gas mixture containing H{sub 2}, D{sub 2}, and HD using an inexpensive micro gas chromatograph (GC) with two molecular sieve columns. One column uses D{sub 2} as the carrier gas and the other uses H{sub 2} as the carrier gas. Laboratory tests have shown that when used in this configuration the GC can measure both total protium and total deuterium each with a detection and quantification limit of less than 20 ppm.

  10. Evidence for ecological divergence across a mosaic of soil types in an Amazonian tropical tree: Protium subserratum (Burseraceae).

    PubMed

    Misiewicz, Tracy M; Fine, Paul V A

    2014-05-01

    Soil heterogeneity is an important driver of divergent natural selection in plants. Neotropical forests have the highest tree diversity on earth, and frequently, soil specialist congeners are distributed parapatrically. While the role of edaphic heterogeneity in the origin and maintenance of tropical tree diversity is unknown, it has been posited that natural selection across the patchwork of soils in the Amazon rainforest is important in driving and maintaining tree diversity. We examined genetic and morphological differentiation among populations of the tropical tree Protium subserratum growing parapatrically on the mosaic of white-sand, brown-sand and clay soils found throughout western Amazonia. Nuclear microsatellites and leaf morphology were used to (i) quantify the extent of phenotypic and genetic divergence across habitat types, (ii) assess the importance of natural selection vs. drift in population divergence, (iii) determine the extent of hybridization and introgression across habitat types, (iv) estimate migration rates among populations. We found significant morphological variation correlated with soil type. Higher levels of genetic differentiation and lower migration rates were observed between adjacent populations found on different soil types than between geographically distant populations on the same soil type. PST -FST comparisons indicate a role for natural selection in population divergence among soil types. A small number of hybrids were detected suggesting that gene flow among soil specialist populations may occur at low frequencies. Our results suggest that edaphic specialization has occurred multiple times in P. subserratum and that divergent natural selection across edaphic boundaries may be a general mechanism promoting and maintaining Amazonian tree diversity.

  11. Spatial distribution and fruiting phenology of Protium heptaphyllum (Burseraceae) determine the design of the underground foraging system of Atta sexdens L. (Hymenoptera: Formicidae).

    PubMed

    da Silva, P S D; Leal, I R; Wirth, R; Tabarelli, M

    2012-08-01

    Leaf-cutting ants have long been recognized to forage via complex trail systems but the nature and the ecological drivers of the different foraging strategies adopted remain a key topic. Here, we described the spatiotemporal use of belowground foraging galleries by Atta sexdens L. in the Brazilian Atlantic forest, and examined the adaptive advantages of this foraging strategy. Protium heptaphyllum adult trees (DBH > 10 cm), seed/seedling clumps and ant gallery entrances were mapped across two 1-ha plots during two consecutive fruiting seasons (2002 and 2004). We recorded 75 ca. 40 cm deep gallery entrances beneath 26 P. heptaphyllum trees at nest distances ranging from 14 to 57 m. Furthermore, gallery abundance and galleries associated with seed/seedling clumps correlated positively with P. heptaphyllum density. Our results indicate that A. sexdens was able to set a permanent system of underground galleries targeting P. heptaphyllum trees and their seeds on the ground. Such network of galleries was spatially arranged according to both the spatial distribution and abundance of P. heptaphyllum trees in a way that most gallery entrances were disposed beneath or in close periphery of P. heptaphyllum crowns. Our findings suggest that underground trail systems shaped by fruit resources represent a foraging strategy clearly more common than existing literature on the subject would suggest. In addition, it reinforces the notion that the spatiotemporal availability of resources combined with predation risk largely influence trail configurations as well as overall foraging strategies adopted by leaf-cutting ants. PMID:23950059

  12. Habitat-specific divergence of phenolic defenses in Protium subserratum (Burseraceae)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The procyanidin (PC) content of leaves from several populations of clay, brown-sand and white-sand ecotypes of P. subserratum at several sites across more than 100 km of Amazonian Peru was examined. Leaves from P. subserratum trees growing in brown-sand (BS), clay soil (CS) and white-sand (WS) habit...

  13. Low-temperature helium embrittlement of tritium-charged stainless steel

    SciTech Connect

    Rawl, D.E. Jr.; Caskey, G.R. Jr.; Donovan, J.A.

    1980-01-01

    Specimens of Type 21-6-0 stainless steel were charged with tritium or protium to determine the effect of hydrogen isotope exposure on ductility. Specimens charged with either tritium or protium showed a 40% loss in ductility when tested immediately after charging. Protium-charged specimens stored 5.5 years at 250/sup 0/K showed no additional loss in ductility. However, tritium-charged specimens suffered an additional loss of 86% in ductility when similarly stored.

  14. The polystyrene microsphere filling with hydrogen isotopes through the fill tube with consequent freezing

    NASA Astrophysics Data System (ADS)

    Izgorodin, V. M.; Solomatina, E. Y.; Pepelyaev, A. P.; Rogozhina, M. A.; Osetrov, E. I.

    2016-09-01

    Process of spherical polystyrene capsules filling with hydrogen isotopes through the fill tube for the purpose of a cryogenic target building is described. The scheme of the stand for researches and a technique of carrying out of experiments is represented. Results of capsules filling and subsequent freezing for protium, deuterium and protium- deuterium mixture are shown.

  15. Effectiveness of passivation techniques on hydrogen desorption in a tritium environment

    NASA Astrophysics Data System (ADS)

    Woodall, Steven Michael

    2009-11-01

    Tritium is a radioactive isotope of hydrogen. It is used as a fuel in fusion reactors, a booster material in nuclear weapons and as a light source in commercial applications. When tritium is used in fusion reactors, and especially when used in the manufacture of nuclear weapons, purity is critical. For U.S. Department of Energy use, tritium is recycled by Savannah River Site in South Carolina and is processed to a minimum purity of 99.5%. For use elsewhere in the country, it must be shipped and stored, while maintaining the highest purity possible. As an isotope of hydrogen it exchanges easily with the most common isotope of hydrogen, protium. Stainless steel bottles are used to transport and store tritium. Protium, present in air, becomes associated in and on the surface of stainless steel during and after the manufacture of the steel. When filled, the tritium within the bottle exchanges with the protium in and on the surface of the stainless steel, slowly contaminating the pure tritium with protium. The stainless steel is therefore passivated to minimize the protium outgrowth of the bottles into the pure tritium. This research is to determine how effective different passivation techniques are in minimizing the contamination of tritium with protium. Additionally, this research will attempt to determine a relationship between surface chemistry of passivated steels and protium contamination of tritium. The conclusions of this research found that passivated bottles by two companies which routinely provide passivated materials to the US Department of Energy provide low levels of protium outgrowth into pure tritium. A bottle passivated with a material to prevent excessive corrosion in a highly corrosive environment, and a clean and polished bottle provided outgrowth rates roughly twice those of the passivated bottles above. Beyond generally high levels of chromium, oxygen, iron and nickel in the passivated bottles, there did not appear to be a strong correlation

  16. Hydrogen isotope transfer in austenitic steels and high-nickel alloy during in-core irradiation

    SciTech Connect

    Polosukhin, B.G.; Sulimov, E.M.; Zyrianov, A.P.; Kalinin, G.M.

    1995-10-01

    The transfer of protium and deuterium in austenitic chromium-nickel steels and in a high-nickel alloy was studied in a specially designed facility. The transfer parameters of protium and deuterium were found to change greatly during in-core irradiation, and the effects of irradiation increased as the temperature decreased. Thus, at temperature T<673K, the relative increase in the permeability of hydrogen isotopes under irradiation can be orders of magnitude higher in these steels. Other radiation effects were also observed, in addition to the changes from the initial values in the effects of protium and deuterium isotopic transfer. 4 refs., 3 figs., 2 tabs.

  17. Parameters important in the oxidation of tritium at a stainless steel surface

    SciTech Connect

    Finn, P.A.; Van Deventer, E.H.

    1988-01-01

    The heterogeneous reaction between oxygen gas and permeating tritium is being studied at the back surface of an oxidized 316-stainless steel tube. The ratio between the reaction products collected at the back surface, tritiated water and molecular tritium, is determined as a function of oxygen level, tritium concentration, protium concentration, flow rate, and temperature. This report describes the results from two sets of runs done at 550/sup 0/C with and without 15 ppm protium in the oxygen/helium gas. At oxygen levels of 1200-2000 ppm, the ratio of tritiated water to molecular tritium was >40, i.e., a 98% conversion. At oxygen levels of 40 ppm, the presence of excess protium in the oxygen/helium resulted in a reduced yield of tritiated water.

  18. Polyimide and polyamide-imide in a tritium atmosphere

    SciTech Connect

    Wylie, K.F.; Hockett, J.E.; Buxton, T.L.

    1981-01-01

    Five different commercial polyamide-imide and polyimide specimens were kept in a tritium atmosphere (96.9 mol %, 101 kPa, initial fill conditions) for three months. Selected physical and mechanical properties of the five plastics were examined. Mass spectrometric data showed the growth of protium and HT impurity in the tritium gas.

  19. Issues Arising from Plasma-Wall Interactions in Inner-Class Tokamaks

    SciTech Connect

    Wampler, William R.

    1999-06-23

    This section reviews physical processes involved in the implantation of energetic hydrogen into plasma facing materials and its subsequent diffusion, release, or immobilization by trapping or precipitation within the material. These topics have also been discussed in previous reviews. The term hydrogen or H is used here generically to refer to protium, deuterium or tritium.

  20. Tritium transport vessel using depleted uranium

    SciTech Connect

    Heung, L.K.

    1995-01-01

    A tritium transport vessel using depleted uranium was tested in the laboratory using deuterium and protium. The vessel contains 0.5 kg of depleted uranium and can hold up to 18 grams of tritium. The conditions for activation, tritium loading and tritium unloading were defined. The safety aspects that included air-ingress, tritium diffusion, temperature and pressure potentials were evaluated.

  1. DEMONSTRATION OF THE NEXT-GENERATION TCAP HYDROGEN ISOTOPE SEPARATION PROCESS

    SciTech Connect

    Heung, L; Henry Sessions, H; Steve Xiao, S; Heather Mentzer, H

    2009-01-09

    The first generation of TCAP hydrogen isotope separation process has been in service for tritium separation at the Savannah River Site since 1994. To prepare for replacement, a next-generation TCAP process has been developed. This new process simplifies the column design and reduces the equipment requirements of the thermal cycling system. An experimental twelve-meter column was fabricated and installed in the laboratory to demonstrate its performance. This new design and its initial test results were presented at the 8th International Conference on Tritium Science and Technology and published in the proceedings. We have since completed the startup and demonstration the separation of protium and deuterium in the experimental unit. The unit has been operated for more than 200 cycles. A feed of 25% deuterium in protium was separated into two streams each better than 99.7% purity.

  2. Investigation of hydrogen isotope exchange reaction rate in mixed gas (H{sub 2} and D{sub 2}) at pressure up to 200 MPa using Raman spectroscopy

    SciTech Connect

    Tikhonov, V.V.; Yukhimchuk, A.A.; Musyayev, R.K.; Gurkin, A.I.

    2015-03-15

    Raman spectroscopy is a relevant method for obtaining objective data on isotopic exchange rate in a gaseous mix of hydrogen isotopes, since it allows one to determine a gaseous mix composition in real time without sampling. We have developed a high-pressure fiber-optic probe to be used for obtaining protium Raman spectra under pressures up to 400 MPa and we have recorded spectral line broadening induced by molecule collisions starting from ∼ 40 MPa. Using this fiber-optic probe we have performed experiments to study isotopic exchange kinetics in a gaseous mix of hydrogen isotopes (protium-deuterium) at pressures up to 200 MPa. Preliminary results show that the dependence of the average isotopic exchange rate related to pressure take unexpected values at the very beginning of the time evolution. More work is required to understand this inconsistency.

  3. Chemical Composition and Biological Activities of Fragrant Mexican Copal (Bursera spp.).

    PubMed

    Gigliarelli, Giulia; Becerra, Judith X; Curini, Massimo; Marcotullio, Maria Carla

    2015-01-01

    Copal is the Spanish word used to describe aromatic resins from several genera of plants. Mexican copal derives from several Bursera spp., Protium copal, some Pinus spp. (e.g., P. pseudostrobus) and a few Fabaceae spp. It has been used for centuries as incense for religious ceremonies, as a food preservative, and as a treatment for several illnesses. The aim of this review is to analyze the chemical composition and biological activity of commercial Mexican Bursera copal. PMID:26703535

  4. Chemical Composition and Biological Activities of Fragrant Mexican Copal (Bursera spp.).

    PubMed

    Gigliarelli, Giulia; Becerra, Judith X; Curini, Massimo; Marcotullio, Maria Carla

    2015-12-12

    Copal is the Spanish word used to describe aromatic resins from several genera of plants. Mexican copal derives from several Bursera spp., Protium copal, some Pinus spp. (e.g., P. pseudostrobus) and a few Fabaceae spp. It has been used for centuries as incense for religious ceremonies, as a food preservative, and as a treatment for several illnesses. The aim of this review is to analyze the chemical composition and biological activity of commercial Mexican Bursera copal.

  5. Insect herbivores, chemical innovation, and the evolution of habit specialization in Amazonian trees.

    PubMed

    Fine, Paul V A; Metz, Margaret R; Lokvam, John; Mesones, Italo; Zuñiga, J Milagros Ayarza; Lamarre, Greg P A; Pilco, Magno Vásquez; Baraloto, Christopher

    2013-08-01

    Herbivores are often implicated in the generation of the extraordinarily diverse tropical flora. One hypothesis linking enemies to plant diversification posits that the evolution of novel defenses allows plants to escape their enemies and expand their ranges. When range expansion involves entering a new habitat type, this could accelerate defense evolution if habitats contain different assemblages of herbivores and/or divergent resource availabilities that affect plant defense allocation. We evaluated this hypothesis by investigating two sister habitat specialist ecotypes of Protium subserratum (Burseraceae), a common Amazonian tree that occurs in white-sand and terra firme forests. We collected insect herbivores feeding on the plants, assessed whether growth differences between habitats were genetically based using a reciprocal transplant experiment, and sampled multiple populations of both lineages for defense chemistry. Protium subserratum plants were attacked mainly by chrysomelid beetles and cicadellid hemipterans. Assemblages of insect herbivores were dissimilar between populations of ecotypes from different habitats, as well as from the same habitat 100 km distant. Populations from terra firme habitats grew significantly faster than white-sand populations; they were taller, produced more leaf area, and had more chlorophyll. White-sand populations expressed more dry mass of secondary compounds and accumulated more flavone glycosides and oxidized terpenes, whereas terra firme populations produced a coumaroylquinic acid that was absent from white-sand populations. We interpret these results as strong evidence that herbivores and resource availability select for divergent types and amounts of defense investment in white-sand and terra firme lineages of Protium subserratum, which may contribute to habitat-mediated speciation in these trees.

  6. Chemodiversity of ursane- and oleanane-type triterpenes in Amazonian Burseraceae oleoresins.

    PubMed

    Rüdiger, André L; Veiga-Junior, Valdir F

    2013-06-01

    The oleoresins exuded from species of the Burseraceae family present high potential due to their biological and pharmacological properties. The evaluation of the chemodiversity of the oleoresins of 23 Amazonian species of Burseraceae provided a profile of the principal constituents, viz., the ursane-type triterpenes α-amyrin (1), α-amyrenone (3), and brein (5) and the oleanane-type triterpenes β-amyrin (2), β-amyrenone (4), and maniladiol (6), and allowed to determine which of these species have the highest biotechnological potential and which ones are rich in other, potentially new, triterpenes or volatile compounds of interest for the cosmetics industry. The oleoresin compositions obtained by GC-FID and GC/MS analyses were submitted to principal component analysis (PCA) and hierarchical clustering on principal components (HCPC), which divided the 23 samples in five clusters. Protium giganteum and Trattinnickia peruviana, constituting the first cluster, presented high oleoresin contents of 3 and 4 (28.8 and 16.3% on average, resp.). The seven species of Burseraceae composing the second cluster were potential producers of new triterpenes and volatile compounds. Dacryodes hopkinsii and five Protium species (third cluster) presented average contents for all the triterpenes analyzed. The highest contents of 5 and 6 (averages of 3.9 and 5.4%, resp.) were observed in P. heptaphyllum ssp. ullei and T. glaziovii (fourth cluster). Finally, the six Protium species forming the fifth cluster showed high contents of 1 and 2 (48.0 and 19.9% on average, resp.). Moreover, this study allowed the description of the triterpene composition of 13 not previously investigated species.

  7. Development of nuclear micro-battery with solid tritium source.

    PubMed

    Lee, Sook-Kyung; Son, Soon-Hwan; Kim, KwangSin; Park, Jong-Wan; Lim, Hun; Lee, Jae-Min; Chung, Eun-Su

    2009-01-01

    A micro-battery powered by tritium is being developed to utilize tritium produced from the Wolsong Tritium Removal Facility. The 3D p-n junction device has been designed and fabricated for energy conversion. Titanium tritide is adopted to increase tritium density and safety. Sub micron films or nano-powders of titanium tritide is applied on silicon semiconductor device to reduce the self absorption of beta rays. Until now protium has been used instead of tritium for safety. Hydrogen was absorbed up to atomic ratio of approximately 1.3 and approximately 1.7 in titanium powders and films, respectively. PMID:19328704

  8. Gas handling systems using titanium-sponge and uranium bulk getters

    SciTech Connect

    Kherani, N.P.; Shmayda, W.T.

    1985-09-01

    A protium gas handling system using titanium and uranium bulk getters was designed, constructed and tested. Numerous process operations were carried out on this system to aid in the design of a tritium gas handling system four times the experimental scale. Experimental results have shown that high percentages of tritium on long-term titanium storage beds can be recovered in a relatively short period of time and be transferred to uranium bed(s) in direct (pump-less) and pump-aided transfers. An optimum storage time after which the rate of interstitial /sup 3/He evolution would be prohibitive to conduct direct tritium transfers is estimated.

  9. Isotope effect on gyro-fluid edge turbulence and zonal flows

    NASA Astrophysics Data System (ADS)

    Meyer, O. H. H.; Kendl, A.

    2016-11-01

    The role of ion polarisation and finite Larmor radius on the isotope effect on turbulent tokamak edge transport and flows is investigated by means of local electromagnetic multi-species gyro-fluid computations. Transport is found to be reduced with the effective plasma mass for protium, deuterium and tritium mixtures. This isotope effect is found for both cold and warm ion models, but significant influence of finite Larmor radius and polarisation effects are identified. Sheared flow reduction of transport through self generated turbulent zonal flows and geodesic acoustic modes in the present model (not including neoclassical flows) is found to play only a minor role on regulating isotopically improved confinement.

  10. Equations of state and phase diagrams of hydrogen isotopes

    SciTech Connect

    Urlin, V. D.

    2013-11-15

    A new form of the semiempirical equation of state proposed for the liquid phase of hydrogen isotopes is based on the assumption that its structure is formed by cells some of which contain hydrogen molecules and others contain hydrogen atoms. The values of parameters in the equations of state of the solid (molecular and atomic) phases as well as of the liquid phase of hydrogen isotopes (protium and deuterium) are determined. Phase diagrams, shock adiabats, isentropes, isotherms, and the electrical conductivity of compressed hydrogen are calculated. Comparison of the results of calculations with available experimental data in a wide pressure range demonstrates satisfactory coincidence.

  11. Hot muonic deuterium and tritium from cold targets

    SciTech Connect

    Marshall, G.M.; Beveridge, J.L. ); Bailey, J.M. ); Beer, G.A.; Knowles, P.E.; Mason, G.R.; Olin, A. ); Brewer, J.H.; Forster, B.M. ); Huber, T.M.; Pippitt, B. ); Jacot-Guillarmod, R.; Schellenberg, L. (Fribourg U

    1992-01-01

    Experiments are described which use a solid hydrogen layer to form muonic hydrogen isotopes in vacuum. The method relies on transfer of the muon from protium to either a deuteron or a triton. The resulting muonic deuterium or muonic tritium will not immediately thermalize because of the very low elastic cross sections, and may be emitted from the surface of the layer. Measurements which detect decay electrons, muonic x-rays, and fusion products have been used to study the processes. A target has been constructed which exploits muonic atom emission in order to study the energy dependence of transfer and muon molecular formation.

  12. Hot muonic deuterium and tritium from cold targets

    SciTech Connect

    Marshall, G.M.; Beveridge, J.L.; Bailey, J.M.; Beer, G.A.; Knowles, P.E.; Mason, G.R.; Olin, A.; Brewer, J.H.; Forster, B.M.; Huber, T.M.; Pippitt, B.; Jacot-Guillarmod, R.; Schellenberg, L.; Kammel, P.; Zmeskal, J.; Kunselman, A.R.; Martoff, C.J.; Petitjean, C.

    1992-12-31

    Experiments are described which use a solid hydrogen layer to form muonic hydrogen isotopes in vacuum. The method relies on transfer of the muon from protium to either a deuteron or a triton. The resulting muonic deuterium or muonic tritium will not immediately thermalize because of the very low elastic cross sections, and may be emitted from the surface of the layer. Measurements which detect decay electrons, muonic x-rays, and fusion products have been used to study the processes. A target has been constructed which exploits muonic atom emission in order to study the energy dependence of transfer and muon molecular formation.

  13. Reaction Rates for the Formation of Deuterium Tritide from Deuterium and Tritium

    SciTech Connect

    McConville, G. T.; Menke, D. A.; Ellefson, R. E.

    1985-04-01

    The rates of formation of DT in a mixture of D2 and T2 have been measured as a function of initial T2 concentration, pressure, temperature,and methane concentration in a stainless steel reaction container which had been treated to inhibit protium ingrowth. An attempt has been made to explain the experimental resuts on the basis of ion-molecule chain reactions. Some of the observations are consistent with a gas-phase ion, ground-state molecule reaction, but some of the more interesting observations require more complicated models. The addition of excited state molecules or heterogeneous catalytic effects are possibilities that will need further experiments for confirmation.

  14. Hydrogen Tunneling in Enzyme Reactions

    NASA Astrophysics Data System (ADS)

    Cha, Yuan; Murray, Christopher J.; Klinman, Judith P.

    1989-03-01

    Primary and secondary protium-to-tritium (H/T) and deuterium-to-tritium (D/T) kinetic isotope effects for the catalytic oxidation of benzyl alcohol to benzaldehyde by yeast alcohol dehydrogenase (YADH) at 25 degrees Celsius have been determined. Previous studies showed that this reaction is nearly or fully rate limited by the hydrogen-transfer step. Semiclassical mass considerations that do not include tunneling effects would predict that kH/kT = (kD/kT)3.26, where kH, kD, and kT are the rate constants for the reaction of protium, deuterium, and tritium derivatives, respectively. Significant deviations from this relation have now been observed for both primary and especially secondary effects, such that experimental H/T ratios are much greater than those calculated from the above expression. These deviations also hold in the temperature range from 0 to 40 degrees Celsius. Such deviations were previously predicted to result from a reaction coordinate containing a significant contribution from hydrogen tunneling.

  15. Hydrogen tunneling in enzyme reactions.

    PubMed

    Cha, Y; Murray, C J; Klinman, J P

    1989-03-10

    Primary and secondary protium-to-tritium (H/T) and deuterium-to-tritium (D/T) kinetic isotope effects for the catalytic oxidation of benzyl alcohol to benzaldehyde by yeast alcohol dehydrogenase (YADH) at 25 degrees Celsius have been determined. Previous studies showed that this reaction is nearly or fully rate limited by the hydrogen-transfer step. Semiclassical mass considerations that do not include tunneling effects would predict that kH/kT = (kD/kT)3.26, where kH, kD, and kT are the rate constants for the reaction of protium, deuterium, and tritium derivatives, respectively. Significant deviations from this relation have now been observed for both primary and especially secondary effects, such that experimental H/T ratios are much greater than those calculated from the above expression. These deviations also hold in the temperature range from 0 to 40 degrees Celsius. Such deviations were previously predicted to result from a reaction coordinate containing a significant contribution from hydrogen tunneling.

  16. Characterization of titanium films in the Tandem Mirror Experiment Upgrade (TMX-U)

    SciTech Connect

    Hsu, W.L.; Bastasz, R.; Bauer, W.; Malinowski, M.E.; Mills, B.E.; Allen, S.L.; Clower, C.A.

    1984-04-01

    Titanium gettering is used extensively in the Tandem Mirror Experiment Upgrade (TMX-U) to achieve good vacuum conditions for the production of a sustained energetic plasma. The gettering films under different operating conditions were analyzed by thermal desorption spectroscopy and Auger electron spectroscopy. A sputter profile of the films showed a Ti deposition rate of approx. =1 nm per evaporation sequence. Large quantities of protium (H/Tiroughly-equal0.2), oxygen (O/Tiroughly-equal0.3), and carbon (C/Tiroughly-equal0.1) were detected in the films regardless of their location and the plasma isotope to which they were exposed. While the Ti films that were exposed to deuterium plasmas showed a substantial increase in deuterium content, deuterium still remained a small fraction of the overall hydrogen concentration (D/Hroughly-equal0.1). Analyses of the results suggest that getter pumping of H/sub 2/O from the background gas in the (TMX-U) vacuum system is the primary source for protium and oxygen measured in the films.

  17. TMED-4 INTERIM REPORT PURE ZR EQUILIBRIUM TEST RESULTS

    SciTech Connect

    Korinko, P.; Morgan, G.

    2010-12-17

    Due to higher than expected permeation rates in the production of tritium in the TVA, a development and testing program was implemented to develop the understanding of why the higher rates were occurring. In addition, improved data are needed for both the design as well as the predictive models. One part of the program was to determine the equilibrium pressure of hydrogen and tritium over NPZ (1). During the course of this testing, some curious results were discovered (2) compared to the published literature data (3). Due to these apparently results, a follow-on task was undertaken to determine the equilibrium pressure of protium and deuterium over pure zirconium. A series of experiments were conducted to determine equilibrium pressures and isotherm data for the zirconium - protium and zirconium - deuterium systems. The data match the published literature data reasonably well with the plateau extending to loadings of about 1.4. There is a significant pressure rise for loadings greater than 1.7.

  18. Tritium storage effects on La-Ni-Al alloys: helium, and tritium trapping

    SciTech Connect

    Walters, R.T.; Mosley, W.C.

    1988-01-01

    The use of La-Ni-Al metal hydrides to process and store tritium presents unique problems to the handling of tritium. All hydrogen isotopes are ''trapped'' in La-Ni-Al alloys as a function of homogeneity and the degree of activation, or number of full cycles the material experiences before being exposed to tritium. To a lesser extent, the mole fraction of aluminum has an effect on the number of cycles needed for full activation. Data is presented which shows the effect of La-rich second phases on the retentium of protium, the x-ray diffraction line broadening as a function of number of cycles, and the observed ''heel'' in the alpha region of the isotherm due to Ni-Al second phases. There also appears to be an increase in solubility of tritium due to the lattice expansion on the metal.

  19. Apparatus for separating and recovering hydrogen isotopes

    DOEpatents

    Heung, Leung K.

    1994-01-01

    An apparatus for recovering hydrogen and separating its isotopes. The apparatus includes a housing bearing at least a fluid inlet and a fluid outlet. A baffle is disposed within the housing, attached thereto by a bracket. A hollow conduit is coiled about the baffle, in spaced relation to the baffle and the housing. The coiled conduit is at least partially filled with a hydride. The hydride can be heated to a high temperature and cooled to a low temperature quickly by circulating a heat transfer fluid in the housing. The spacing between the baffle and the housing maximizes the heat exchange rate between the fluid in the housing and the hydride in the conduit. The apparatus can be used to recover hydrogen isotopes (protium, deuterium and tritium) from gaseous mixtures, or to separate hydrogen isotopes from each other.

  20. Remote network control plasma diagnostic system for Tokamak T-10

    NASA Astrophysics Data System (ADS)

    Troynov, V. I.; Zimin, A. M.; Krupin, V. A.; Notkin, G. E.; Nurgaliev, M. R.

    2016-09-01

    The parameters of molecular plasma in closed magnetic trap is studied in this paper. Using the system of molecular diagnostics, which was designed by the authors on the «Tokamak T-10» facility, the radiation of hydrogen isotopes at the plasma edge is investigated. The scheme of optical radiation registration within visible spectrum is described. For visualization, identification and processing of registered molecular spectra a new software is developed using MatLab environment. The software also includes electronic atlas of electronic-vibrational-rotational transitions for molecules of protium and deuterium. To register radiation from limiter cross-section a network control system is designed using the means of the Internet/Intranet. Remote control system diagram and methods are given. The examples of web-interfaces for working out equipment control scenarios and viewing of results are provided. After test run in Intranet, the remote diagnostic system will be accessible through Internet.

  1. Analysis of LaNi{sub 4.25}Al{sub 0.75} (LANA.75) tritide after five years of tritium exposure

    SciTech Connect

    Wermer, J.R.; Holder, J.S.; Mosley, W.C.

    1993-09-01

    Tritium aging studies have shown that LaNi{sub 4.25}Al{sub 0.75} (LANA .75) tritide storage material undergoes significant degradation with tritium aging. After 5.4 years of dormant storage at full stoichiometry, which is considered a worst-case condition for this material, the performance is still acceptable for SRS tritium processing applications. The isotherms change, decreasing the desorption pressures, increasing the isotherm plateau slopes, and decreasing the total storage capacity. Eventually, the material will degrade with time to the point where it may no longer be useful for tritium processing applications. At the end of life, the tritium heel can be exchanged with protium or deuterium to produce a final material containing very little tritium.

  2. Reaction rates and kinetic isotope effects of H2 + OH → H2O + H.

    PubMed

    Meisner, Jan; Kästner, Johannes

    2016-05-01

    We calculated reaction rate constants including atom tunneling of the reaction of dihydrogen with the hydroxy radical down to a temperature of 50 K. Instanton theory and canonical variational theory with microcanonical optimized multidimensional tunneling were applied using a fitted potential energy surface [J. Chen et al., J. Chem. Phys. 138, 154301 (2013)]. All possible protium/deuterium isotopologues were considered. Atom tunneling increases at about 250 K (200 K for deuterium transfer). Even at 50 K the rate constants of all isotopologues remain in the interval 4 ⋅ 10(-20) to 4 ⋅ 10(-17) cm(3) s(-1), demonstrating that even deuterated versions of the title reaction are possibly relevant to astrochemical processes in molecular clouds. The transferred hydrogen atom dominates the kinetic isotope effect at all temperatures.

  3. Reaction rates and kinetic isotope effects of H2 + OH → H2O + H

    NASA Astrophysics Data System (ADS)

    Meisner, Jan; Kästner, Johannes

    2016-05-01

    We calculated reaction rate constants including atom tunneling of the reaction of dihydrogen with the hydroxy radical down to a temperature of 50 K. Instanton theory and canonical variational theory with microcanonical optimized multidimensional tunneling were applied using a fitted potential energy surface [J. Chen et al., J. Chem. Phys. 138, 154301 (2013)]. All possible protium/deuterium isotopologues were considered. Atom tunneling increases at about 250 K (200 K for deuterium transfer). Even at 50 K the rate constants of all isotopologues remain in the interval 4 ṡ 10-20 to 4 ṡ 10-17 cm3 s-1, demonstrating that even deuterated versions of the title reaction are possibly relevant to astrochemical processes in molecular clouds. The transferred hydrogen atom dominates the kinetic isotope effect at all temperatures.

  4. Large deuterium isotope effects and their use: a historical review.

    PubMed

    Krumbiegel, Peter

    2011-03-01

    Isotope effects are differences in the properties of the isotopes of an element resulting in different reaction rates of a corresponding compound, in equilibrium constants and in the spectra. Shortly after the discovery of stable isotopes of hydrogen, oxygen, and carbon, Jacob Bigeleisen formulated a theory of isotope effects and calculated possible maximum values. Large isotope effects of (2)H (deuterium) against (1)H (protium) were seen to possibly influence interpretations of reaction mechanisms if corresponding labelling is used. Much work was invested to ensure the safety of deuterium use in men in spite of the large isotope effect. On the other hand, large deuterium isotope effects gave rise to several practical applications. Examples are the enhancement of the stability of some technical products against oxidative and against hydrolytic degradation (oils, pharmaceuticals) as well as alterations of the detoxification metabolism of pharmaceuticals in vivo. PMID:21390986

  5. Evaluation of Hydrogen Isotope Exchange Methodology on Adsorbents for Tritium Removal

    DOE PAGES

    Morgan, Gregg A.; Xiao, S. Xin

    2015-03-06

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H2 (when flowed through the molecular sieves) will exchange with the adsorbed water, D2O, leaving H2O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminated water (T2O, HTO,more » and DTO) using D2 (or H2)« less

  6. Evaluation of Hydrogen Isotope Exchange Methodology on Adsorbents for Tritium Removal

    SciTech Connect

    Morgan, Gregg A.; Xiao, S. Xin

    2015-03-06

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H2 (when flowed through the molecular sieves) will exchange with the adsorbed water, D2O, leaving H2O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminated water (T2O, HTO, and DTO) using D2 (or H2)

  7. Evaluation of hydrogen isotope exchange methodology on adsorbents for tritium removal

    SciTech Connect

    Morgan, G.A.; Xin Xiao, S.

    2015-03-15

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H{sub 2} (when flowed through the molecular sieves) will exchange with the adsorbed water, D{sub 2}O, leaving H{sub 2}O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminated water (T{sub 2}O, HTO, and DTO) using D{sub 2} (or H{sub 2}). (authors)

  8. Ammonia production in nitrogen seeded plasma discharges in ASDEX Upgrade

    NASA Astrophysics Data System (ADS)

    Rohde, V.; Oberkofler, M.

    2015-08-01

    In present tokamaks nitrogen seeding is used to reduce the power load onto the divertor tiles. Some fraction of the seeded nitrogen reacts with hydrogen to form ammonia. The behaviour of ammonia in ASDEX Upgrade is studied by mass spectrometry. Injection without plasma shows strong absorption at the inner walls of the vessel and isotope exchange reactions. During nitrogen seeding in H-mode discharges the onset of a saturation of the nitrogen retention is observed. The residual gas consists of strongly deuterated methane and ammonia with almost equal amounts of deuterium and protium. This confirms the role of surface reactions in the ammonia formation. The results are consistent with findings in previous investigations. A numerical decomposition of mass spectra is under development and will be needed for quantitative evaluation of the results obtained.

  9. Hydrogen compatibility handbook for stainless steels

    SciTech Connect

    Caskey, G.R. Jr.

    1983-06-01

    This handbook compiles data on the effects of hydrogen on the mechanical properties of stainless steels and discusses this data within the context of current understanding of hydrogen compatibility of metals. All of the tabulated data derives from continuing studies of hydrogen effects on materials that have been conducted at the Savannah River Laboratory over the past fifteen years. Supplementary data from other sources are included in the discussion. Austenitic, ferritic, martensitic, and precipitation hardenable stainless steels have been studied. Damage caused by helium generated from decay of tritium is a distinctive effect that occurs in addition to the hydrogen isotopes protium and deuterium. The handbook defines the scope of our current knowledge of hydrogen effects in stainless steels and serves as a guide to selection of stainless steels for service in hydrogen.

  10. Reaction rates and kinetic isotope effects of H2 + OH → H2O + H.

    PubMed

    Meisner, Jan; Kästner, Johannes

    2016-05-01

    We calculated reaction rate constants including atom tunneling of the reaction of dihydrogen with the hydroxy radical down to a temperature of 50 K. Instanton theory and canonical variational theory with microcanonical optimized multidimensional tunneling were applied using a fitted potential energy surface [J. Chen et al., J. Chem. Phys. 138, 154301 (2013)]. All possible protium/deuterium isotopologues were considered. Atom tunneling increases at about 250 K (200 K for deuterium transfer). Even at 50 K the rate constants of all isotopologues remain in the interval 4 ⋅ 10(-20) to 4 ⋅ 10(-17) cm(3) s(-1), demonstrating that even deuterated versions of the title reaction are possibly relevant to astrochemical processes in molecular clouds. The transferred hydrogen atom dominates the kinetic isotope effect at all temperatures. PMID:27155636

  11. Pf/Zeolite Catalyst for Tritium Stripping

    SciTech Connect

    Hsu, R.H.

    2001-03-26

    This report described promising hydrogen (protium and tritium) stripping results obtained with a Pd/zeolite catalyst at ambient temperature. Preliminary results show 90-99+ percent tritium stripping efficiency may be obtained, with even better performance expected as bed configuration and operating conditions are optimized. These results suggest that portable units with single beds of the Pd/zeolite catalyst may be utilized as ''catalytic absorbers'' to clean up both tritium gas and tritiated water. A cart-mounted prototype stripper utilizing this catalyst has been constructed for testing. This portable stripper has potential applications in maintenance-type jobs such as tritium line breaks. This catalyst can also potentially be utilized in an emergency stripper for the Replacement Tritium Facility.

  12. Kinetic isotope effects calculated with the instanton method.

    PubMed

    Meisner, Jan; Rommel, Judith B; Kästner, Johannes

    2011-12-01

    The ring-opening reaction of the cyclopropylcarbinyl radical proceeds via heavy-atom tunneling at low temperature. We used instanton theory to calculate tunneling rates and kinetic isotope effects with on-the-fly calculation of energies by density functional theory (B3LYP). The accuracy was verified by explicitly correlated coupled-cluster calculations (UCCSD(T)-F12). At cryogenic temperatures, we found protium/deuterium KIEs up to 13 and inverse KIEs down to 0.2. We also studied an intramolecular tautomerization reaction. A simple and computationally efficient method is proposed to calculate KIEs with the instanton method: the instanton path is assumed to be independent of the atomic masses. This results in surprisingly good estimates of the KIEs for the cyclopropylcarbinyl radical and for the secondary KIEs of the tautomerization. Challenges and capabilities of the instanton method for calculating KIEs are discussed.

  13. Effect of oxide particle distribution on the helium-induced fracture of copper

    SciTech Connect

    Wheeler, D.A.

    1990-12-31

    Long-term exposure to tritium (H{sup 3}) gas can degrade the mechanical properties of copper alloys while similar exposure to protium (H{sup 1}) gas does not cause such degradation. This difference in behavior is attributed to the presence of helium which is generated by the radioactive decay of tritium. The accumulation of helium, which is virtually insoluble in the copper lattice, can cause the nucleation of cavities along grain boundaries and promote intergranular fracture. Permeation studies have shown that oxide particles act as trap sites for diffusing hydrogen isotopes, and thus may affect the susceptibility of copper to helium-induced degradation by altering the initial tritium distribution in the metal lattice. Tensile and metallographic data demonstrate that oxide particles trap both tritium and helium and decrease the susceptibility of copper to helium-induced intergranular fracture. 25 refs, 3 tabs, 12 figs.

  14. Effect of oxide particle distribution on the helium-induced fracture of copper

    SciTech Connect

    Wheeler, D.A.

    1990-01-01

    Long-term exposure to tritium (H[sup 3]) gas can degrade the mechanical properties of copper alloys while similar exposure to protium (H[sup 1]) gas does not cause such degradation. This difference in behavior is attributed to the presence of helium which is generated by the radioactive decay of tritium. The accumulation of helium, which is virtually insoluble in the copper lattice, can cause the nucleation of cavities along grain boundaries and promote intergranular fracture. Permeation studies have shown that oxide particles act as trap sites for diffusing hydrogen isotopes, and thus may affect the susceptibility of copper to helium-induced degradation by altering the initial tritium distribution in the metal lattice. Tensile and metallographic data demonstrate that oxide particles trap both tritium and helium and decrease the susceptibility of copper to helium-induced intergranular fracture. 25 refs, 3 tabs, 12 figs.

  15. NNSA TRITIUM SUPPLY CHAIN

    SciTech Connect

    Wyrick, Steven; Cordaro, Joseph; Founds, Nanette; Chambellan, Curtis

    2013-08-21

    Savannah River Site plays a critical role in the Tritium Production Supply Chain for the National Nuclear Security Administration (NNSA). The entire process includes: • Production of Tritium Producing Burnable Absorber Rods (TPBARs) at the Westinghouse WesDyne Nuclear Fuels Plant in Columbia, South Carolina • Production of unobligated Low Enriched Uranium (LEU) at the United States Enrichment Corporation (USEC) in Portsmouth, Ohio • Irradiation of TPBARs with the LEU at the Tennessee Valley Authority (TVA) Watts Bar Reactor • Extraction of tritium from the irradiated TPBARs at the Tritium Extraction Facility (TEF) at Savannah River Site • Processing the tritium at the Savannah River Site, which includes removal of nonhydrogen species and separation of the hydrogen isotopes of protium, deuterium and tritium.

  16. Temperature Dependence of the Kinetic Isotope Effects in Thymidylate Synthase. A Theoretical Study

    PubMed Central

    Kanaan, Natalia; Ferrer, Silvia; Martí, Sergio; Garcia-Viloca, Mireia; Kohen, Amnon; Moliner, Vicent

    2011-01-01

    In recent years, the temperature dependence of primary kinetic isotope effects (KIE) has been used as indicator for the physical nature of enzyme catalyzed H-transfer reactions. An interactive study where experimental data and calculations examine the same chemical transformation is a critical means to interpret more properly temperature dependence of KIEs. Here, the rate limiting step of the thymidylate synthase catalyzed reaction has been studied by means of hybrid Quantum Mechanics/ Molecular Mechanics (QM/MM) simulations in the theoretical framework of the ensemble-averaged variational transition state theory with multidimensional tunneling (EA-VTST/MT) combined with Grote-Hynes theory. The KIEs were calculated across the same temperature range examined experimentally, revealing a temperature independent behaviour, in agreement with experimental findings. The calculations show that the H-transfer proceeds with ca. 91 % by tunneling in the case of protium and ca. 80% when the transferred protium is replaced by tritium. Dynamic recrossing coefficients are almost invariant with temperature and in all cases far from unity, showing significant coupling between protein motions and the reaction coordinate. In particular, the relative movement of a conserved arginine (Arg166 in E. coli) promotes the departure of a conserved cysteine (Cys146 in E. coli) from the dUMP by polarizing the thioether bond thus facilitating this bond breaking that takes place concomitantly with the hydride transfer. These promoting vibrations of the enzyme, which represent some of the dimensions of the real reaction coordinate, would limit the search through configurational space to efficiently find those decreasing both barrier height and width, thereby enhancing the probability of H-transfer by either tunneling (through barrier) or classical (over-the-barrier) mechanisms. In other words, the thermal fluctuations that are coupled to the reaction coordinate, together with transition state

  17. EFFECTS OF TRITIUM EXPOSURE ON UHMW-PE, PTFE, AND VESPEL

    SciTech Connect

    Clark, E; Kirk Shanahan, K

    2006-05-31

    Samples of three polymers, Ultra-High Molecular Weight Polyethylene (UHMW-PE), polytetrafluoroethylene (PTFE, also known as Teflon{reg_sign}), and Vespel{reg_sign} polyimide were exposed to 1 atmosphere of tritium gas at ambient temperature for varying times up to 2.3 years in closed containers. Sample mass and size measurements (to calculate density), spectra-colorimetry, dynamic mechanical analysis (DMA), and Fourier-transform infrared spectroscopy (FT-IR) were employed to characterize the effects of tritium exposure on these samples. Changes of the tritium exposure gas itself were characterized at the end of exposure by measuring total pressure and by mass spectroscopic analysis of the gas composition. None of the polymers exhibited significant changes of density. The color of initially white UHMW-PE and PTFE dramatically darkened to the eye and the color also significantly changed as measured by colorimetry. The bulk of UHMW-PE darkened just like the external surfaces, however the fracture surface of PTFE appeared white compared to the PTFE external surfaces. The white interior could have been formed while the sample was breaking or could reflect the extra tritium dose at the surface directly from the gas. The dynamic mechanical response of UHMW-PE was typical of radiation effects on polymers- an initial stiffening (increased storage modulus) and reduction of viscous behavior after three months exposure, followed by lowering of the storage modulus after one year exposure and longer. The storage modulus of PTFE increased through about nine months tritium exposure, then the samples became too weak to handle or test using DMA. Characterization of Vespel{reg_sign} using DMA was problematic--sample-to-sample variations were significant and no systematic change with tritium exposure could be discerned. Isotopic exchange and incorporation of tritium into UHMW-PE (exchanging for protium) and into PTFE (exchanging for fluorine) was observed by FT-IR using an attenuated

  18. Leaf hydraulic conductance, measured in situ, declines and recovers daily: leaf hydraulics, water potential and stomatal conductance in four temperate and three tropical tree species.

    PubMed

    Johnson, D M; Woodruff, D R; McCulloh, K A; Meinzer, F C

    2009-07-01

    Adequate leaf hydraulic conductance (Kleaf) is critical for preventing transpiration-induced desiccation and subsequent stomatal closure that would restrict carbon gain. A few studies have reported midday depression of Kleaf (or petiole conductivity) and its subsequent recovery in situ, but the extent to which this phenomenon is universal is not known. The objectives of this study were to measure Kleaf, using a rehydration kinetics method, (1) in the laboratory (under controlled conditions) across a range of water potentials to construct vulnerability curves (VC) and (2) over the course of the day in the field along with leaf water potential and stomatal conductance (gs). Two broadleaf (one evergreen, Arbutus menziesii Pursh., and one deciduous, Quercus garryana Dougl.) and two coniferous species (Pinus ponderosa Dougl. and Pseudotsuga menziesii [Mirbel]) were chosen as representative of different plant types. In addition, Kleaf in the laboratory and leaf water potential in the field were measured for three tropical evergreen species (Protium panamense (Rose), Tachigalia versicolor Standley and L.O. Williams and Vochysia ferruginea Mart) to predict their daily changes in field Kleaf in situ. It was hypothesized that in the field, leaves would close their stomata at water potential thresholds at which Kleaf begins to decline sharply in laboratory-generated VC, thus preventing substantial losses of Kleaf. The temperate species showed a 15-66% decline in Kleaf by midday, before stomatal closure. Although there were substantial midday declines in Kleaf, recovery was nearly complete by late afternoon. Stomatal conductance began to decrease in Pseudotsuga, Pinus and Quercus once Kleaf began to decline; however, there was no detectable reduction in gs in Arbutus. Predicted Kleaf in the tropical species, based on laboratory-generated VC, decreased by 74% of maximum Kleaf in Tachigalia, but only 22-32% in Vochysia and Protium. The results presented here, from the previous

  19. EFFECTS OF GAMMA IRRADIATION ON EPDM ELASTOMERS

    SciTech Connect

    Clark, E.

    2011-09-22

    ethylene propylene diene monomer (EPDM)) have been exposed in closed containers to tritium gas initially at 1 atmosphere pressure. These studies have demonstrated the degradation of properties when exposed to tritium gas. Also, the radiolytic production of significant amounts of hydrogen has been observed for UHMW-PE and EPDM. The study documented in this report exposes two similar formulations of EPDM elastomer to gamma irradiation in a closed container backfilled with deuterium. Deuterium is chemically identical to protium and tritium, but allows the identification of protium that is radiolytically produced from the samples. The goal of this program is to compare and contrast the response of EPDM exposure to two different types of ionizing radiation in a similar chemical environment.

  20. Modeling temperature dependent kinetic isotope effects for hydrogen transfer in a series of soybean lipoxygenase mutants: The effect of anharmonicity upon transfer distance

    PubMed Central

    Meyer, Matthew P.; Klinman, Judith P.

    2010-01-01

    Soybean lipoxygenase-1 (SLO) catalyzes the oxidation of linoleic acid. The rate-limiting step in this transformation is the net abstraction of the pro-S hydrogen atom from the center of the 1,5-pentadienyl moiety in linoleic acid. The large deuterium kinetic isotope effect (KIE) for this step appears in the first order rate constant (Dkcat = 81 ± 5 at T = 25 °C). Furthermore, the KIE and the rate for protium abstraction are weakly temperature dependent (EA,D − EA,H = 0.9 ± 0.2 kcal/mol and EA,H = 2.1 ± 0.2 kcal/mol, respectively). Mutations at a hydrophobic site about 13 Å from the active site Fe(III), Ile553, induce a marked temperature dependence that varies roughly in accordance with the degree to which the residue is changed in bulk from the wild type Ile. While the temperature dependence for these mutants varies from the wild type enzyme, the magnitude of the KIE at 25 °C is on the same order of magnitude. A hydrogen tunneling model [Kuznetsov, A.M., Ulstrup, J. Can. J. Chem. 77 (1999) 1085–1096] is utilized to model the KIE temperature profiles for the wild type SLO and each Ile553 mutant. Hydrogenic wavefunctions are modeled using harmonic oscillators and Morse oscillators in order to explore the effects of anharmonicity upon computed kinetic observables used to characterize this hydrogen transfer. PMID:21132078

  1. Seasonal variations in the stable oxygen isotope ratio of wood cellulose reveal annual rings of trees in a Central Amazon terra firme forest.

    PubMed

    Ohashi, Shinta; Durgante, Flávia M; Kagawa, Akira; Kajimoto, Takuya; Trumbore, Susan E; Xu, Xiaomei; Ishizuka, Moriyoshi; Higuchi, Niro

    2016-03-01

    In Amazonian non-flooded forests with a moderate dry season, many trees do not form anatomically definite annual rings. Alternative indicators of annual rings, such as the oxygen (δ(18)Owc) and carbon stable isotope ratios of wood cellulose (δ(13)Cwc), have been proposed; however, their applicability in Amazonian forests remains unclear. We examined seasonal variations in the δ(18)Owc and δ(13)Cwc of three common species (Eschweilera coriacea, Iryanthera coriacea, and Protium hebetatum) in Manaus, Brazil (Central Amazon). E. coriacea was also sampled in two other regions to determine the synchronicity of the isotopic signals among different regions. The annual cyclicity of δ(18)Owc variation was cross-checked by (14)C dating. The δ(18)Owc showed distinct seasonal variations that matched the amplitude observed in the δ(18)O of precipitation, whereas seasonal δ(13)Cwc variations were less distinct in most cases. The δ(18)Owc variation patterns were similar within and between some individual trees in Manaus. However, the δ(18)Owc patterns of E. coriacea differed by region. The ages of some samples estimated from the δ(18)Owc cycles were offset from the ages estimated by (14)C dating. In the case of E. coriacea, this phenomenon suggested that missing or wedging rings may occur frequently even in well-grown individuals. Successful cross-dating may be facilitated by establishing δ(18)Owc master chronologies at both seasonal and inter-annual scales for tree species with distinct annual rings in each region.

  2. Tritium diffusion in V4Cr-4Ti alloy

    SciTech Connect

    Hashizume, K.; Masuda, J.; Otsuka, K. T.; Tanabe, T.; Hatano, Y.; Nakamura, Y.; Nagasaka, T.; Muroga, T.

    2008-07-15

    Characteristics of the tritium diffusion coefficient DT in V-4Cr-4Ti alloy, including a bending in the Arrhenius plot of DT, are examined. Based on a trap model, the possible trap sources and their binding energies for tritium in the alloy are evaluated using the experimental data of DT in pure V, which are measured with a tritium tracer method, and the literature data of protium diffusion in V-Ti and V-Cr alloys. The result of the evaluation suggests the presence of two trap sources in the alloy. The first would be attributed to a trap at each substitutional alloying atom which is likely to be Ti. The binding energy E{sub B} of 0.08 eV gives the best fit to the observed value of DT above 300 K The bending in the Arrhenius plot below 300 K is caused by a second trap site with a higher E and a lower concentration than those of each alloying atom. The trap is probably formed by the alloying atoms presence to neighboring Ti atoms. The contribution of Cr atom to the trap effect seems to be rather small in this alloy. (authors)

  3. Therapeutic switching: from antidermatophytic essential oils to new leishmanicidal products.

    PubMed

    Houël, Emeline; Gonzalez, German; Bessière, Jean-Marie; Odonne, Guillaume; Eparvier, Véronique; Deharo, Eric; Stien, Didier

    2015-02-01

    This study examined whether the antidermatophytic activity of essential oils (EOs) can be used as an indicator for the discovery of active natural products against Leishmania amazonensis. The aerial parts of seven plants were hydrodistilled. Using broth microdilution techniques, the obtained EOs were tested against three strains of dermatophytes (Trichophyton mentagrophytes, Microsporum gypseum and Microsporum canis). To compare the EOs antifungal and antiparasitic effects, the EOs activities against axenic amastigotes of L. amazonensis were concurrently evaluated. For the most promising EOs, their antileishmanial activities against parasites infecting peritoneal macrophages of BALB/c mice were measured. The most interesting antifungal candidates were the EOs from Cymbopogon citratus, Otacanthus azureus and Protium heptaphyllum, whereas O. azureus, Piper hispidum and P. heptaphyllum EOs exhibited the lowest 50% inhibitory concentration (IC50) values against axenic amastigotes, thus revealing a certain correspondence between both activities. The P. hispidum EO was identified as the most promising product in the results from the infected macrophages model (IC50: 4.7 µg/mL, safety index: 8). The most abundant compounds found in this EO were sesquiterpenes, notably curzerene and furanodiene. Eventually, the evaluation of the antidermatophytic activity of EOs appears to be an efficient method for identifying new potential drugs for the treatment of L. amazonensis. PMID:25742270

  4. EFFECTS OF TRITIUM GAS EXPOSURE ON EPDM ELASTOMER

    SciTech Connect

    Clark, E.

    2009-12-11

    Samples of four formulations of ethylene-propylene diene monomer (EPDM) elastomer were exposed to initially pure tritium gas at one atmosphere and ambient temperature for various times up to about 420 days in closed containers. Two formulations were carbon-black-filled commercial formulations, and two were the equivalent formulations without filler synthesized for this work. Tritium effects on the samples were characterized by measuring the sample volume, mass, flexibility, and dynamic mechanical properties and by noting changes in appearance. The glass transition temperature was determined by analysis of the dynamic mechanical properties. The glass transition temperature increased significantly with tritium exposure, and the unfilled formulations ceased to behave as elastomers after the longest tritium exposure. The filled formulations were more resistant to tritium exposure. Tritium exposure made all samples significantly stiffer and therefore much less able to form a reliable seal when employed as O-rings. No consistent change of volume or density was observed; there was a systematic lowering of sample mass with tritium exposure. In addition, the significant radiolytic production of gas, mainly protium (H{sub 2}) and HT, by the samples when exposed to tritium was characterized by measuring total pressure in the container at the end of each exposure and by mass spectroscopy of a gas sample at the end of each exposure. The total pressure in the containers more than doubled after {approx}420 days tritium exposure.

  5. Screening of Venezuelan medicinal plant extracts for cytostatic and cytotoxic activity against tumor cell lines.

    PubMed

    Taylor, Peter; Arsenak, Miriam; Abad, María Jesús; Fernández, Angel; Milano, Balentina; Gonto, Reina; Ruiz, Marie-Christine; Fraile, Silvia; Taylor, Sofía; Estrada, Omar; Michelangeli, Fabian

    2013-04-01

    There are estimated to be more than 20,000 species of plants in Venezuela, of which more than 1500 are used for medicinal purposes by indigenous and local communities. Only a relatively small proportion of these have been evaluated in terms of their potential as antitumor agents. In this study, we screened 308 extracts from 102 species for cytostatic and cytotoxic activity against a panel of six tumor cell lines using a 24-h sulphorhodamine B assay. Extracts from Clavija lancifolia, Hamelia patens, Piper san-vicentense, Physalis cordata, Jacaranda copaia, Heliotropium indicum, and Annona squamosa were the most cytotoxic, whereas other extracts from Calotropis gigantea, Hyptis dilatata, Chromolaena odorata, Siparuna guianensis, Jacaranda obtusifolia, Tapirira guianensis, Xylopia aromatica, Protium heptaphyllum, and Piper arboreum showed the greatest cytostatic activity. These results confirm previous reports on the cytotoxic activities of the above-mentioned plants as well as prompting further studies on others such as C. lancifolia and H. dilatata that have not been so extensively studied.

  6. Tritium stripping in a nitrogen glovebox using SAES St 198

    SciTech Connect

    Klein, J.E.; Wermer, J.R.

    1994-08-31

    SAES metal getter material St 198 was chosen for glovebox stripper tests to evaluate its effectiveness of removing tritium from a nitrogen atmosphere. The St 198 material is unique from a number of other metal hydride-based getter materials in that it is relatively inert to nitrogen and can thus be used in nitrogen glovebox atmospheres. Six tritium stripper experiments which mock-up the use of a SAES St 198 stripper bed for a full-scale (10,500 liter) nitrogen glovebox have been completed. Experiments consisted of a release of small quantity of protium/deuterium spiked with tritium which were scaled to simulate tritium releases of 0.1 g., 1.0 g., and 10 g. into the glovebox. The tritium spike allows detection using tritium ion chambers. The St 198 stripper system produced a reduction in tritium activity of approximately two orders of magnitude in 24 hours (6--8 atmosphere turn-overs) of stripper operation.

  7. Wood Litter Consumption by three Species of Nasutitermes Termites in an Area of the Atlantic Coastal Forest in Northeastern Brazil

    PubMed Central

    Vasconcellos, Alexandre; Moura, Flávia Maria da Silva

    2010-01-01

    Termites constitute a considerable fraction of the animal biomass in tropical forest, but little quantitative data are available that indicates their importance in the processes of wood decomposition. This study evaluated the participation of Nasutitermes corniger (Motschulsky) (Isoptera: Termitidae), N. ephratae (Holmgren), and N. macrocephalus (Silvestri) in the consumption of the wood litter in a remnant area of Atlantic Coastal Forest in northeastern Brazil. The populations of this species were quantified in nests and in decomposing tree trunks, while the rate of wood consumption was determined in the laboratory using wood test-blocks of Clitoria fairchildiana Howard (Fabales: Fabaceae), Cecropia sp. (Urticales: Cecropiaceae), and Protium heptaphyllum (Aublet) Marchand (Sapindales: Burseraceae). The abundance of the three species of termites varied from 40.8 to 462.2 individuals/m2. The average dry wood consumption for the three species was 9.4 mg/g of termites (fresh weight)/day, with N. macrocephalus demonstrating the greatest consumption (12.1 mg/g of termite (fresh weight)/day). Wood consumption by the three species of Nasutitermes was estimated to be 66.9 kg of dry wood /ha/year, corresponding to approximately 2.9% of the annual production of wood-litter in the study area. This consumption, together with that of the other 18 exclusively wood-feeders termite species known to occur in the area, indicates the important participation of termites in removing wood-litter within the Atlantic Coastal Forest domain. PMID:20673190

  8. Simulation and Analysis of Isotope Separation System for Fusion Fuel Recovery System

    NASA Astrophysics Data System (ADS)

    Senevirathna, Bathiya; Gentile, Charles

    2011-10-01

    This paper presents results of a simulation of the Fuel Recovery System (FRS) for the Laser Inertial Fusion Engine (LIFE) reactor. The LIFE reaction will produce exhaust gases that will need to be recycled in the FRS along with xenon, the chamber's intervention gas. Solids and liquids will first be removed and then vapor traps are used to remove large gas molecules such as lead. The gas will be reacted with lithium at high temperatures to extract the hydrogen isotopes, protium, deuterium, and tritium in hydride form. The hydrogen isotopes will be recovered using a lithium blanket processing system already in place and this product will be sent to the Isotope Separation System (ISS). The ISS will be modeled in software to analyze its effectiveness. Aspen HYSYS was chosen for this purpose for its widespread use industrial gas processing systems. Reactants and corresponding chemical reactions had to be initialized in the software. The ISS primarily consists of four cryogenic distillation columns and these were modeled in HYSYS based on design requirements. Fractional compositions of the distillate and liquid products were analyzed and used to optimize the overall system.

  9. Functional and immunochemical characterization of a mutant of Escherichia coli energy uncoupled for lactose transport

    SciTech Connect

    Herzlinger, D.; Carrasco, N.; Kaback, H.R.

    1985-01-01

    Right-side-out cytoplasmic membrane vesicles from Escherichia coli ML 308-22, a mutant ''uncoupled'' for beta-galactoside/H/sup +/ symport are specifically defective in the ability to catalyze accumulation of methyl 1-thio-beta-D-galactopyranoside (TMG) in the presence of an H/sup +/ electrochemical gradient (interior negative and alkaline). Furthermore, the rate of carrier-mediated efflux under nonenergized conditions is slow and unaffected by ambient pH from pH 5.5 to 7.5, and TMG-induced H/sup +/ influx is only about 15% of that observed in vesicles containing wild-type lac permease (ML 308-225). Alternatively, ML 308-22 vesicles bind p-nitrophenyl alpha-D-galactopyranoside and monoclonal antibody 4B1 to the same extent as ML 308-225 vesicles and catalyze facilitated diffusion and equilibrium exchange as well as ML 308-225 vesicles. When entrance counterflow is studied with external substrate at saturating and subsaturating concentrations, it is apparent that the mutation simulates the effects of deuterium oxide. That is, the mutation has no effect on the rate or extent of counterflow when external substrate is saturating but stimulates the efficiency of counterflow when external substrate is below the apparent K/sub m/. Moreover, although replacement of protium with deuterium stimulates counterflow in ML 308-225 vesicles when external substrate is subsaturating, the isotope has no effect on the mutant vesicles under the same conditions.

  10. Antimicrobial activity of some medicinal plants from the cerrado of the centralwestern region of Brazil

    PubMed Central

    Violante, Ivana Maria Póvoa; Hamerski, Lidilhone; Garcez, Walmir Silva; Batista, Ana Lucia; Chang, Marilene Rodrigues; Pott, Vali Joana; Garcez, Fernanda Rodrigues

    2012-01-01

    Ethanol extracts from six selected species from the Cerrado of the Central-Western region of Brazil, which are used in traditional medicine for the treatment of infectious diseases and other medical conditions, namely Erythroxylum suberosum St. Hil. (Erythroxylaceae), Hyptis crenata Pohl. ex Benth. (Lamiaceae), Roupala brasiliensis Klotz. (Proteaceae), Simarouba versicolor St. Hil. (Simaroubaceae), Guazuma ulmifolia Lam. (Sterculiaceae) and Protium heptaphyllum (Aubl.) March. (Burseraceae), as well as fractions resulting from partition of these crude extracts, were screened in vitro for their antifungal and antibacterial properties. The antimicrobial activities were assessed by the broth microdilution assay against six control fungal strains, Candida albicans, C. glabrata, C. krusei, C. parapsilosis, C. tropicalis and Cryptococcus neoformans, and five control Gram-positive and negative bacterial strains, Escherichia coli, Enterococcus faecalis, Klebsiella pneumoniae, Pseudomonas aeruginosa and Staphylococcus aureus. Toxicity of the extracts and fractions against Artemia salina was also evaluated in this work. All plants investigated showed antimicrobial properties against at least one microorganism and two species were also significantly toxic to brine shrimp larvae. The results tend to support the traditional use of these plants for the treatment of respiratory and gastrointestinal disorders and/or skin diseases, opening the possibility of finding new antimicrobial agents from these natural sources. Among the species investigated, Hyptis crenata, Erythroxylum suberosum and Roupala brasiliensis were considered the most promising candidates for developing of future bioactivity-guided phytochemical investigations. PMID:24031956

  11. Antimicrobial activity of some medicinal plants from the cerrado of the centralwestern region of Brazil.

    PubMed

    Violante, Ivana Maria Póvoa; Hamerski, Lidilhone; Garcez, Walmir Silva; Batista, Ana Lucia; Chang, Marilene Rodrigues; Pott, Vali Joana; Garcez, Fernanda Rodrigues

    2012-10-01

    Ethanol extracts from six selected species from the Cerrado of the Central-Western region of Brazil, which are used in traditional medicine for the treatment of infectious diseases and other medical conditions, namely Erythroxylum suberosum St. Hil. (Erythroxylaceae), Hyptis crenata Pohl. ex Benth. (Lamiaceae), Roupala brasiliensis Klotz. (Proteaceae), Simarouba versicolor St. Hil. (Simaroubaceae), Guazuma ulmifolia Lam. (Sterculiaceae) and Protium heptaphyllum (Aubl.) March. (Burseraceae), as well as fractions resulting from partition of these crude extracts, were screened in vitro for their antifungal and antibacterial properties. The antimicrobial activities were assessed by the broth microdilution assay against six control fungal strains, Candida albicans, C. glabrata, C. krusei, C. parapsilosis, C. tropicalis and Cryptococcus neoformans, and five control Gram-positive and negative bacterial strains, Escherichia coli, Enterococcus faecalis, Klebsiella pneumoniae, Pseudomonas aeruginosa and Staphylococcus aureus. Toxicity of the extracts and fractions against Artemia salina was also evaluated in this work. All plants investigated showed antimicrobial properties against at least one microorganism and two species were also significantly toxic to brine shrimp larvae. The results tend to support the traditional use of these plants for the treatment of respiratory and gastrointestinal disorders and/or skin diseases, opening the possibility of finding new antimicrobial agents from these natural sources. Among the species investigated, Hyptis crenata, Erythroxylum suberosum and Roupala brasiliensis were considered the most promising candidates for developing of future bioactivity-guided phytochemical investigations.

  12. Methods of studying the composition of the low-energy ion beams and the surface of deuterated-metal targets

    NASA Astrophysics Data System (ADS)

    Kuznetsov, S. I.; Dudkin, G. N.; Nechaev, B. A.; Bystritsky, I. D.

    2016-06-01

    To study the reactions between the light nuclei (dd, pd, d3He, d4He) with ultralow collision energies, there is a need to obtain the high-precision experimental results on the purity of the target surface saturated with the hydrogen isotopes (protium, deuterium) and on the number and composition of the accelerated particles falling on the target. To solve this problem, a method has been developed and tested for operational testing the quality of the vacuum system and the cleaning of the metal target surface saturated with deuterium. The paper also presents the measurement results for the true flow of the accelerated ions and neutrals of hydrogen (deuterium), using a multigrid electrostatic energy analyzer. The values of the ion and neutral components of the accelerated particle flow were received for the Hall ion source. The values of the secondary electron emission coefficients were determined for a number of the metal targets (Cu, Ti, Ta, Zr) in the range of the accelerated ion energies of 3-12 keV.

  13. Therapeutic switching: from antidermatophytic essential oils to new leishmanicidal products

    PubMed Central

    Houël, Emeline; Gonzalez, German; Bessière, Jean-Marie; Odonne, Guillaume; Eparvier, Véronique; Deharo, Eric; Stien, Didier

    2015-01-01

    This study examined whether the antidermatophytic activity of essential oils (EOs) can be used as an indicator for the discovery of active natural products against Leishmania amazonensis. The aerial parts of seven plants were hydrodistilled. Using broth microdilution techniques, the obtained EOs were tested against three strains of dermatophytes (Trichophyton mentagrophytes, Microsporum gypseum and Microsporum canis). To compare the EOs antifungal and antiparasitic effects, the EOs activities against axenic amastigotes of L. amazonensis were concurrently evaluated. For the most promising EOs, their antileishmanial activities against parasites infecting peritoneal macrophages of BALB/c mice were measured. The most interesting antifungal candidates were the EOs from Cymbopogon citratus, Otacanthus azureus and Protium heptaphyllum, whereas O. azureus, Piper hispidum and P. heptaphyllum EOs exhibited the lowest 50% inhibitory concentration (IC50) values against axenic amastigotes, thus revealing a certain correspondence between both activities. The P. hispidum EO was identified as the most promising product in the results from the infected macrophages model (IC50: 4.7 µg/mL, safety index: 8). The most abundant compounds found in this EO were sesquiterpenes, notably curzerene and furanodiene. Eventually, the evaluation of the antidermatophytic activity of EOs appears to be an efficient method for identifying new potential drugs for the treatment of L. amazonensis. PMID:25742270

  14. EXPERIMENTAL RESULTS FOR THE ISOTOPIC EXCHANGE OF A 1600 LITER TITANIUM HYDRIDE STORAGE VESSEL

    SciTech Connect

    Klein, J.

    2010-12-14

    Titanium is used as a low pressure tritium storage material. The absorption/desorption rates and temperature rise during air passivation have been reported previously for a 4400 gram prototype titanium hydride storage vessel (HSV). A desorption limit of roughly 0.25 Q/M was obtained when heating to 700 C which represents a significant residual tritium process vessel inventory. To prepare an HSV for disposal, batchwise isotopic exchange has been proposed to reduce the tritium content to acceptable levels. A prototype HSV was loaded with deuterium and exchanged with protium to determine the effectiveness of a batch-wise isotopic exchange process. A total of seven exchange cycles were performed. Gas samples were taken nominally at the beginning, middle, and end of each desorption cycle. Sample analyses showed the isotopic exchange process does not follow the standard dilution model commonly reported. Samples taken at the start of the desorption process were lower in deuterium (the gas to be removed) than those taken later in the desorption cycle. The results are explained in terms of incomplete mixing of the exchange gas in the low pressure hydride.

  15. EVALUATION OF ALTERNATE STAINLESS STEEL SURFACE TREATMENTS FOR MASS SPECTROSCOPY AND OTHER TRITIUM SYSTEMS

    SciTech Connect

    Clark, E.; Mauldin, C.; Neikirk, K.

    2012-02-29

    There are specific components in the SRS Tritium Facilities that are required to introduce as few chemical impurities (such as protium and methane) as possible into the process gas. Two such components are the inlet systems for the mass spectroscopy facilities and hydrogen isotope mix standard containers. Two vendors now passivate stainless steel components for these systems, and both are relatively small businesses whose future viability can be questioned, which creates the need for new sources. Stainless steel containers were designed to evaluate alternate surface treatment vendors for tritium storage and handling for these high purity tritium systems. Five vendors applied their own 'best' surface treatments to two containers each - one was a current vendor, another was a chemical vapor deposited silicon coating, and the other three were electropolishing and chemical cleaning vendors. Pure tritium gas was introduced into all ten containers and the composition was monitored over time. The only observed impurities in the gas were some HT, less CT{sub 4}, and very small amounts of T{sub 2}O in all cases. The currently used vendor treated containers contained the least impurities. The chemical vapor deposited silicon treatment resulted in the highest impurity levels. Sampling one set of containers after about one month of tritium exposure revealed the impurity level to be nearly the same as that after more than a year of exposure - this result suggests that cleaning new stainless steel components by tritium gas contact for about a month may be a worthy operation.

  16. Blister formation on 13Cr2MoNbVB ferritic-martensitic steel exposed to hydrogen plasma

    NASA Astrophysics Data System (ADS)

    Nikitin, A. V.; Tolstolutskaya, G. D.; Ruzhytskyi, V. V.; Voyevodin, V. N.; Kopanets, I. E.; Karpov, S. A.; Vasilenko, R. L.; Garner, F. A.

    2016-09-01

    The influence of pre-irradiation specimen deformation level on surface blister formation and sub-surface cracking of dual-phase 13Cr2MoNbVB ferritic-martensitic steel was studied using glow discharge hydrogen plasma with ion energy of 1 keV to fluences of 2 × 1025 H/m2. Protium was used for most studies, but deuterium was used for measuring the depth dependence of hydrogen diffusion. Formation of blisters was observed in the temperature range 230-340 K. It was found that pre-irradiation deformation caused changes in the threshold fluences of blister formation and also in blister size distribution. Subsurface cracks located on grain boundaries far beyond the implantation zone were formed concurrently with blisters, arising from hydrogen diffusion and trapping at defects. It was observed that cracks as long as 1 mm in length were formed in 95% deformed steel at depths up to 500 μm from surface.

  17. Does Size Really Matter? The Steric Isotope Effect in a Supramolecular Host?Guest Exchange Reaction

    SciTech Connect

    Mugridge, Jeffrey; Bergman, Robert; Raymond, Kenneth

    2010-01-29

    Isotope effects (IEs), which arise from differences in zero point energies (ZPEs) between a parent and isotopically substituted bond, have been used extensively by chemists to probe molecular interactions and reactivity. Due to the anharmonicity of the C-H/D vibrational potential energy function and the lower ZPE of a C-D bond, the average C-D bond length is typically {approx}0.005 {angstrom} shorter than an equivalent C-H bond. It is this difference in size that is often invoked to explain the observation of secondary, inverse kinetic isotope effects (KIEs) in chemical processes which proceed through a sterically strained transition state. This so-called 'steric isotope effect' (SIE) has been observed in processes such as the racemization of ortho-substituted biphenyls[6] and phenanthrenes, ring flipping of cyclophanes, and more recently in the deslipping of rotaxanes, where substitution of the sterically less demanding deuterium for protium results in rate accelerations for these processes. Herein, we use deuterium substitution in a cationic guest molecule to probe the sensitivity limits of the guest exchange process from a highly-charged supramolecular host.

  18. Modeling tritium behavior in Li{sub 2}ZrO{sub 3}.

    SciTech Connect

    Billone, M. C.

    1998-01-13

    Lithium metazirconate (Li{sub 2}ZrO{sub 3}) is a promising tritium breeder material for fusion reactors because of its excellent tritium release characteristics. In particular, for water-cooled breeding blankets (e.g., ITER), Li{sub 2}ZrO{sub 3} is appealing from a design perspective because of its good tritium release at low operating temperatures. The steady-state and transient tritium release/retention database for Li{sub 2}ZrO{sub 3} is reviewed, along with conventional diffusion and first-order surface resorption models which have been used to match the database. A first-order surface resorption model is recommended in the current work both for best-estimate and conservative (i.e., inventory upper-bound) predictions. Model parameters we determined and validated for both types of predictions, although emphasis is placed on conservative design predictions. The effects on tritium retention of ceramic microstructure, protium partial pressure in the purge gas and purge gas flow rate are discussed, along with other mechanisms for tritium retention which may not be dominant in the experiments, but may be important in blanket design analyses. The proposed tritium retention/release model can be incorporated into a transient thermal performance code to enable whole-blanket predictions of tritium retention/release during cyclic reactor operation. Parameters for the ITER driver breeding blanket are used to generate a numerical set of model predictions for steady-state operation.

  19. Quantum states of hydrogen atom on Pd(1 1 0) surface

    NASA Astrophysics Data System (ADS)

    Padama, Allan Abraham B.; Nakanishi, Hiroshi; Kasai, Hideaki

    2015-12-01

    The quantum states of adsorbed hydrogen atom on Pd(1 1 0) surface are investigated in this work. From the calculated potential energy surface (PES) of hydrogen atom on Pd(1 1 0), the wave functions and eigenenergies in the ground and few excited states of protium (H) and deuterium (D) are calculated. Localized wave functions of hydrogen atom exist on pseudo-threefold and long bridge sites of Pd(1 1 0). The short bridge site is a local minimum from the result of PES, however, quantum behavior of hydrogen revealed that its vibration would allow it to hop to other pseudo-threefold site (that crosses the short bridge site) than to stay on the short bridge site. Exchange of ordering of the wave functions between H and D is attributed to the difference in their masses. The calculated eigenenergies are found to be in fair agreement with experimental data based from the identified vibrations of hydrogen with component perpendicular to the surface. The activation barriers measured from the eigenenergies are in better agreement with experimental findings in comparison to the data gathered from PES.

  20. Tritium Superpermeability: Experimental Investigation and Simulation of Tritium Recirculation in 'Prometheus' Setup

    SciTech Connect

    Musyaev, R.K.; Lebedev, B.S.; Grishechkin, S.K.; Yukhimchuk, A.A.; Busnyuk, A.A; Notkin, M.E.; Samartsev, A.A.; Livshits, A.I.

    2005-07-15

    The superpermeability phenomenon was suggested to use in fusion machines to separate the fuel mixture from helium ashes, to arrange in-vessel fuel recirculation contours and effective evacuation of fuel mixture out of machine exhaust. To develop this technology and to simulate tritium recirculation in RFNC-VNIIEF at the 'Prometheus' setup the experiments on superpermeation of hydrogen isotopes through metal membrane were realized.The results of experiments on superpermeation of hydrogen isotopes through cylindrical niobium membrane are presented. As the experiment has shown, membrane pumping rate is inversely proportional to square root of isotope mass and amount to 2.5 l/cm{sup 2}s for protium, 1.8 l/cm{sup 2}s for deuterium and 1.5 l/cm{sup 2}s for tritium. The possibility of effective pumping, separation of hydrogen isotopes from helium and residual gas, compression and recuperation of hydrogen isotopes by means of superpermeable membrane was demonstrated. It follows from results that the separation of D/T from He with employment of the techniques of superpermeable membranes might reduce the total amount of tritium in fuel cycle and substantially enhance the resource of cryogenic pumps evacuating helium.

  1. Tritium handling and processing experience at TSTA

    SciTech Connect

    Anderson, J.L.; Okuno, K.

    1994-06-01

    In 1987, the Japan Atomic Energy Research Institute (JAERI) and the US Department of Energy (DOE) signed a collaborative agreement (Annex IV) for the joint funding and operation of the Tritium Systems Test Assembly (TSTA) at the Los Alamos National Laboratory (LANL) for a five year period ending June, 1992. After this initial five year collaboration, the Annex IV agreement was extended for another two year period ending June, 1994. During the first five years, a number of the integrated process loop tests of TSTA were conducted, as well as off-line testing of TSTA subsystems. During integrated loop testing the vacuum system, fuel cleanup systems, isotope separation system, transfer pumping system and gas analysis system, are interconnected and tested using 100 g-inventories of tritium to demonstrate steady-state operation of a tritium fuel processing cycle for a fusion reactor. These tests have resulted in a number of significant accomplishments and an experience data base on research, development and operation of the fuel processing system. One of the most significant accomplishments during the initial five year period was the continuous operation of the fuel processing loop for 25 days. During this 25-day extended operation, both the JAERI fuel cleanup system (J-FCU) and the original TSTA fuel cleanup system (FCU) were operated under similar conditions of flow, pressure, and impurity content of the DT gas. Both fuel cleanup systems were demonstrated to provide adequate impurity removal for plasma exhaust gas processing. The isotope separation system was operated continuously, producing pure tritium while rejecting protium as an impurity.

  2. Holocene History of the Chocó Rain Forest from Laguna Piusbi, Southern Pacific Lowlands of Colombia

    NASA Astrophysics Data System (ADS)

    Behling, Hermann; Hooghiemstra, Henry; Negret, Alvaro José

    1998-11-01

    A high-resolution pollen record from a 5-m-long sediment core from the closed-lake basin Laguna Piusbi in the southern Colombian Pacific lowlands of Chocó, dated by 11 AMS 14C dates that range from ca. 7670 to 220 14C yr B.P., represents the first Holocene record from the Chocó rain forest area. The interval between 7600 and 6100 14C yr B.P. (500-265 cm), composed of sandy clays that accumulated during the initial phase of lake formation, is almost barren of pollen. Fungal spores and the presence of herbs and disturbance taxa suggest the basin was at least temporarily inundated and the vegetation was open. The closed lake basin might have formed during an earthquake, probably about 4400 14C yr B.P. From the interval of about 6000 14C yr B.P. onwards, 200 different pollen and spore types were identified in the core, illustrating a diverse floristic composition of the local rain forest. Main taxa are Moraceae/Urticaceae, Cecropia,Melastomataceae/Combretaceae, Acalypha, Alchornea,Fabaceae, Mimosa, Piper, Protium, Sloanea, Euterpe/Geonoma, Socratea,and Wettinia.Little change took place during that time interval. Compared to the pollen records from the rain forests of the Colombian Amazon basin and adjacent savannas, the Chocó rain forest ecosystem has been very stable during the late Holocene. Paleoindians probably lived there at least since 3460 14C yr B.P. Evidence of agricultural activity, shown by cultivation of Zea maissurrounding the lake, spans the last 1710 yr. Past and present very moist climate and little human influence are important factors in maintaining the stable ecosystem and high biodiversity of the Chocó rain forest.

  3. Fractionation of Hydrogen Isotopes by Sulfate- and Nitrate-Reducing Bacteria

    PubMed Central

    Osburn, Magdalena R.; Dawson, Katherine S.; Fogel, Marilyn L.; Sessions, Alex L.

    2016-01-01

    Hydrogen atoms from water and food are incorporated into biomass during cellular metabolism and biosynthesis, fractionating the isotopes of hydrogen—protium and deuterium—that are recorded in biomolecules. While these fractionations are often relatively constant in plants, large variations in the magnitude of fractionation are observed for many heterotrophic microbes utilizing different central metabolic pathways. The correlation between metabolism and lipid δ2H provides a potential basis for reconstructing environmental and ecological parameters, but the calibration dataset has thus far been limited mainly to aerobes. Here we report on the hydrogen isotopic fractionations of lipids produced by nitrate-respiring and sulfate-reducing bacteria. We observe only small differences in fractionation between oxygen- and nitrate-respiring growth conditions, with a typical pattern of variation between substrates that is broadly consistent with previously described trends. In contrast, fractionation by sulfate-reducing bacteria does not vary significantly between different substrates, even when autotrophic and heterotrophic growth conditions are compared. This result is in marked contrast to previously published observations and has significant implications for the interpretation of environmental hydrogen isotope data. We evaluate these trends in light of metabolic gene content of each strain, growth rate, and potential flux and reservoir-size effects of cellular hydrogen, but find no single variable that can account for the differences between nitrate- and sulfate-respiring bacteria. The emerging picture of bacterial hydrogen isotope fractionation is therefore more complex than the simple correspondence between δ2H and metabolic pathway previously understood from aerobes. Despite the complexity, the large signals and rich variability of observed lipid δ2H suggest much potential as an environmental recorder of metabolism. PMID:27531993

  4. Groundwater and surface-water interactions near White Bear Lake, Minnesota, through 2011

    USGS Publications Warehouse

    Jones, Perry M.; Trost, Jared J.; Rosenberry, Donald O.; Jackson, P. Ryan; Bode, Jenifer A.; O'Grady, Ryan M.

    2013-01-01

    Hugo, Minnesota. Water-quality analyses of pore water from nearshore lake-sediment and well-water samples, seepage-meter measurements, and hydraulic-head differences measured in White Bear Lake also indicated groundwater was potentially flowing into White Bear Lake from shallow glacial aquifers to the east and south. Negative temperature anomalies determined in shallow waters in the water-quality survey conducted in White Bear Lake indicated several shallow-water areas where groundwater may be flowing into the lake from glacial aquifers below the lake. Cool lake-sediment temperatures (less than 18 degrees Celsius) were measured in eight areas along the northeast, east, south, and southwest shores of White Bear Lake, indicating potential areas where groundwater may flow into the lake. Stable isotope analyses of well-water, precipitation, and lake-water samples indicated wells downgradient from White Bear Lake screened in the glacial buried aquifer or open to the Prairie du Chien-Jordan aquifer receive a mixture of surface water and groundwater; the largest surface-water contributions are in wells closer to White Bear Lake. A wide range in oxygen-18/oxygen-16 and deuterium/protium ratios was measured in well-water samples, indicating different sources of water are supplying water to the wells. Well water with oxygen-18/oxygen-16 and deuterium/protium ratios that plot close to the meteoric water line consisted mostly of groundwater because deuterium/protium ratios for most groundwater usually are similar to ratios for rainwater and snow, plotting close to meteoric water lines. Well water with oxygen-18/oxygen-16 and deuterium/protium ratios that plot between the meteoric water line and ratios for the surface-water samples from White Bear Lake consists of a mixture of surface water and groundwater; the percentage of each source varies relative to its ratios. White Bear Lake is the likely source of the surface water to the wells that have a mixture of surface water and

  5. Hydrogen release from 800 MeV proton-irradiated tungsten

    NASA Astrophysics Data System (ADS)

    Oliver, B. M.; Venhaus, T. J.; Causey, R. A.; Garner, F. A.; Maloy, S. A.

    2002-12-01

    Tungsten irradiated in spallation neutron sources, such as those proposed for the accelerator production of tritium (APT) project, will contain large quantities of generated helium and hydrogen gas. Tungsten used in proposed fusion reactors will also be exposed to neutrons, and the generated protium will be accompanied by deuterium and tritium diffusing in from the plasma-facing surface. The release kinetics of these gases during various off-normal scenarios involving loss of coolant and after heat-induced rises in temperature are of particular interest for both applications. To determine the release kinetics of hydrogen from tungsten, tungsten rods irradiated with 800 MeV protons in the Los Alamos Neutron Science Center (LANSCE) to high exposures as part of the APT project have been examined. Hydrogen evolution from the tungsten has been measured using a dedicated mass-spectrometer system by subjecting the specimens to an essentially linear temperature ramp from ˜300 to ˜1500 K. Release profiles are compared with predictions obtained using the Tritium Migration Analysis Program (TMAP4). The measurements show that for high proton doses, the majority of the hydrogen is released gradually, starting at about 900 K and reaching a maximum at about 1400 K, where it drops fairly rapidly. Comparisons with TMAP show quite reasonable agreement using a trap energy of 1.4 eV and a trap density of ˜7%. There is a small additional release fraction occurring at ˜550 K, which is believed to be associated with low-energy trapping at or near the surface, and, therefore, was not included in the bulk TMAP model.

  6. Investigating Inner Sphere Reorganization via Secondary Kinetic Isotope Effects in the C–H Cleavage Reaction Catalyzed by Soybean Lipoxygenase: Tunneling in the Substrate Backbone as well as the Transferred Hydrogen

    PubMed Central

    Meyer, Matthew P.; Klinman, Judith P.

    2011-01-01

    This work describes the application of NMR to the measurement of secondary deuterium (2° 2H) and carbon-13 (13C) kinetic isotope effects (KIES) at positions 9 to 13 within the substrate linoleic acid (LA) of soybean lipoxygenase-1. The KIEs have been measured using linoleic acid labeled with either protium (11,11-h2-LA) or deuterium (11,11-d2-LA) at the reactive C11 position, which has been previously shown to yield a primary deuterium isotope effect of ca. 80. The conditions of measurement yield the intrinsic 2° 2H and 13C KIEs on kcat/Km directly for 11,11-d2-LA, whereas the values for the 2° 2H KIEs for 11,11-h2-LA are obtained after correction for a kinetic commitment. The pattern of the resulting 2° 2H and 13C isotope effects reveals values that lie far above those predicted from changes in local force constants. Additionally, many of the experimental values cannot be modeled by electronic effects, torsional strain, or the simple inclusion of a tunneling correction to the rate. Although previous studies have shown the importance of extensive tunneling for cleavage of the primary hydrogen at C11 of LA, the present findings can only be interpreted by extending the conclusion of non-classical behavior to the secondary hydrogens and carbons that flank the position undergoing C-H bond cleavage. A quantum mechanical method introduced by Buhks et al. [J. Phys. Chem. 85, 3763 (1981)] to model the inner sphere reorganization that accompanies electron transfer has been shown to be able to reproduce the scale of the 2° 2H KIEs. PMID:21192631

  7. Transferring Fungi to a Deuterium-Enriched Medium Results in Assorted, Conditional Changes in Secondary Metabolite Production.

    PubMed

    Wang, Bin; Park, Elizabeth M; King, Jarrod B; Mattes, Allison O; Nimmo, Susan L; Clendinen, Chaevien; Edison, Arthur S; Anklin, Clemens; Cichewicz, Robert H

    2015-06-26

    Deuterium is one of the few stable isotopes that have the capacity to significantly alter a compound's chemical and biological properties. The addition of a single neutron to a protium atom results in the near doubling of its mass, which gives rise to deuterium's characteristic isotope effects. Since the incorporation of deuterium into organic substrates is known to alter enzyme/protein-substrate interactions, we tested the extent to which deuterium enrichment would modify fungal secondary metabolite production. Several fungal cultures were tested, and in all cases their secondary metabolomes were marked by changes in natural product production. Workup of one Aspergillus sp. grown under deuterium-enrichment conditions resulted in the production of several secondary metabolites not previously detected from the fungus. Bioassay testing revealed that in comparison to the inactive crude fungal extract derived from growing the fungus under non-deuterium-enriched conditions, an extract derived from the same isolate cultured in a deuterium-enriched medium inhibited methicillin-resistant Staphylococcus aureus. Using an assortment of NMR and mass spectrometry experiments, we were able to identify the bacterial inhibitor as an isotope-labeled version of pigmentosin A (6). Five additional isotopically labeled metabolites were also obtained from the fungus including brevianamide F (1), stephacidin A (2), notoamide D (3), notoamide L (4), and notoamide C (5). Given the assorted changes observed in the secondary metabolite profiles of this and other fungi grown in deuterium-enriched environments, as well as the fact that 1 and 3-6 had not been previously observed from the Aspergillus sp. isolate used in this study, we propose that deuterium enrichment might offer an effective method for further expanding a fungus's chemical diversity potential. PMID:26061478

  8. Fractionation of Hydrogen Isotopes by Sulfate- and Nitrate-Reducing Bacteria.

    PubMed

    Osburn, Magdalena R; Dawson, Katherine S; Fogel, Marilyn L; Sessions, Alex L

    2016-01-01

    Hydrogen atoms from water and food are incorporated into biomass during cellular metabolism and biosynthesis, fractionating the isotopes of hydrogen-protium and deuterium-that are recorded in biomolecules. While these fractionations are often relatively constant in plants, large variations in the magnitude of fractionation are observed for many heterotrophic microbes utilizing different central metabolic pathways. The correlation between metabolism and lipid δ(2)H provides a potential basis for reconstructing environmental and ecological parameters, but the calibration dataset has thus far been limited mainly to aerobes. Here we report on the hydrogen isotopic fractionations of lipids produced by nitrate-respiring and sulfate-reducing bacteria. We observe only small differences in fractionation between oxygen- and nitrate-respiring growth conditions, with a typical pattern of variation between substrates that is broadly consistent with previously described trends. In contrast, fractionation by sulfate-reducing bacteria does not vary significantly between different substrates, even when autotrophic and heterotrophic growth conditions are compared. This result is in marked contrast to previously published observations and has significant implications for the interpretation of environmental hydrogen isotope data. We evaluate these trends in light of metabolic gene content of each strain, growth rate, and potential flux and reservoir-size effects of cellular hydrogen, but find no single variable that can account for the differences between nitrate- and sulfate-respiring bacteria. The emerging picture of bacterial hydrogen isotope fractionation is therefore more complex than the simple correspondence between δ(2)H and metabolic pathway previously understood from aerobes. Despite the complexity, the large signals and rich variability of observed lipid δ(2)H suggest much potential as an environmental recorder of metabolism.

  9. Effect of administration of water enriched in O2 by injection or electrolysis on transcutaneous oxygen pressure in anesthetized pigs

    PubMed Central

    Charton, Antoine; Péronnet, François; Doutreleau, Stephane; Lonsdorfer, Evelyne; Klein, Alexis; Jimenez, Liliana; Geny, Bernard; Diemunsch, Pierre; Richard, Ruddy

    2014-01-01

    Background Oral administration of oxygenated water has been shown to improve blood oxygenation and could be an alternate way for oxygen (O2) supply. In this experiment, tissue oxygenation was compared in anesthetized pigs receiving a placebo or water enriched in O2 by injection or a new electrolytic process. Methods Forty-two pigs randomized in three groups received either mineral water as placebo or water enriched in O2 by injection or the electrolytic process (10 mL/kg in the stomach). Hemodynamic parameters, partial pressure of oxygen in the arterial blood (PaO2), skin blood flow, and tissue oxygenation (transcutaneous oxygen pressure, or TcPO2) were monitored during 90 minutes of general anesthesia. Absorption and tissue distribution of the three waters administered were assessed using dilution of deuterium oxide. Results Mean arterial pressure, heart rate, PaO2, arteriovenous oxygen difference, and water absorption from the gut were not significantly different among the three groups. The deuterium to protium ratio was also similar in the plasma, skin, and muscle at the end of the protocol. Skin blood flow decreased in the three groups. TcPO2 slowly decreased over the last 60 minutes of the experiment in the three groups, but when compared to the control group, the values remained significantly higher in animals that received the water enriched in O2 by electrolysis. Conclusions In this protocol, water enriched in O2 by electrolysis lessened the decline of peripheral tissue oxygenation. This observation is compatible with the claim that the electrolytic process generates water clathrates which trap O2 and facilitate O2 diffusion along pressure gradients. Potential applications of O2-enriched water include an alternate method of oxygen supply. PMID:25210438

  10. Intermediate partitioning kinetic isotope effects for the NIH shift of 4-hydroxyphenylpyruvate dioxygenase and the hydroxylation reaction of hydroxymandelate synthase reveal mechanistic complexity.

    PubMed

    Shah, Dhara D; Conrad, John A; Moran, Graham R

    2013-09-01

    4-Hydroxyphenylpyruvate dioxygenase (HPPD) and hydroxymandelate synthase (HMS) are similar enzymes that catalyze complex dioxygenation reactions using the substrates 4-hydroxyphenylpyruvate (HPP) and dioxygen. Both enzymes decarboxylate HPP and then hydroxylate the resulting hydroxyphenylacetate (HPA). The hydroxylation reaction catalyzed by HPPD displaces the aceto substituent of HPA in a 1,2-shift to form 2,5-dihydroxyphenylacetate (homogentisate, HG), whereas the hydroxylation reaction of HMS places a hydroxyl on the benzylic carbon forming 3'-hydroxyphenylacetate (S-hydroxymandelate, HMA) without ensuing chemistry. The wild-type form of HPPD and variants of both enzymes uncouple to form both native and non-native products. We have used intermediate partitioning to probe bifurcating steps that form these products by substituting deuteriums for protiums at the benzylic position of the HPP substrate. These substitutions result in altered ratios of products that can be used to calculate kinetic isotope effects (KIE) for the formation of a specific product. For HPPD, secondary normal KIEs indicate that cleavage of the bond in the displacement reaction prior to the shift occurs by a homolytic mechanism. NMR analysis of HG derived from HPPD reacting with enantiomerically pure R-3'-deutero-HPP indicates that no rotation about the bond to the radical occurs, suggesting that collapse of the biradical intermediate is rapid. The production of HMA was observed in HMS and HPPD variant reactions. HMS hydroxylates to form exclusively S-hydroxymandelate. When HMS is reacted with R-3'-deutero-HPP, the observed kinetic isotope effect represents geometry changes in the initial transition state for the nonabstracted proton. These data show evidence of sp(3) hybridization in a HPPD variant and sp(2) hybridization in HMS variants, suggesting that HMS stabilizes a more advanced transition state in order to catalyze H-atom abstraction.

  11. Fractionation of Hydrogen Isotopes by Sulfate- and Nitrate-Reducing Bacteria.

    PubMed

    Osburn, Magdalena R; Dawson, Katherine S; Fogel, Marilyn L; Sessions, Alex L

    2016-01-01

    Hydrogen atoms from water and food are incorporated into biomass during cellular metabolism and biosynthesis, fractionating the isotopes of hydrogen-protium and deuterium-that are recorded in biomolecules. While these fractionations are often relatively constant in plants, large variations in the magnitude of fractionation are observed for many heterotrophic microbes utilizing different central metabolic pathways. The correlation between metabolism and lipid δ(2)H provides a potential basis for reconstructing environmental and ecological parameters, but the calibration dataset has thus far been limited mainly to aerobes. Here we report on the hydrogen isotopic fractionations of lipids produced by nitrate-respiring and sulfate-reducing bacteria. We observe only small differences in fractionation between oxygen- and nitrate-respiring growth conditions, with a typical pattern of variation between substrates that is broadly consistent with previously described trends. In contrast, fractionation by sulfate-reducing bacteria does not vary significantly between different substrates, even when autotrophic and heterotrophic growth conditions are compared. This result is in marked contrast to previously published observations and has significant implications for the interpretation of environmental hydrogen isotope data. We evaluate these trends in light of metabolic gene content of each strain, growth rate, and potential flux and reservoir-size effects of cellular hydrogen, but find no single variable that can account for the differences between nitrate- and sulfate-respiring bacteria. The emerging picture of bacterial hydrogen isotope fractionation is therefore more complex than the simple correspondence between δ(2)H and metabolic pathway previously understood from aerobes. Despite the complexity, the large signals and rich variability of observed lipid δ(2)H suggest much potential as an environmental recorder of metabolism. PMID:27531993

  12. Preparation of low HD contamination cells for the measurement of the triple point temperature of n-D/sub 2/

    SciTech Connect

    McConville, G.T.; Menke, D.A.; Pavese, F.

    1985-01-01

    An effort is under way to produce deuterium triple point sealed cells for a 18.7 K temperature reference point. Stability with time of impurity content in cells, namely HD, was found to be good from measurements made at IMGC since 1978, but nearly all commercially produced ''chemical pure'' D/sub 2/ contains approximately 0.5% HD. To reduce the HD content in the D/sub 2/ cell, two steps have been taken: (1) The stainless steel cell was chemically etched and then vacuum baked to remove Fe from the surface and to diffuse protium out of the cell. (2) The cell was flushed and filled to 70 bar with D/sub 2/ directly obtained from a thermal diffusion column with HD <70 ppM. Triple point measurements with the cell show an initial drift due to para-ortho conversion of 0.4 mK per hour decreasing to 0.7 mK per hour after 130 hours of conversion. The initial triple point temperature on NBS-IPTS-68 was found to be 18.732 +- 0.001 K; this agrees with the value found in the earlier IMGC cells, filled with commercial D/sub 2/, when the latter are corrected for a 0.4 +- 0.1 HD content, but the conversion in this cell was 10 times faster than in 304 stainless steel IMGC cells. Further measurements have been made using the clean n-D/sub 2/ in an unetched 304 stainless steel cell which has been flushed with D/sub 2/O vapor.

  13. Spectroscopic and Computational Studies of Reduction of the Metal versus the Tetrapyrrole Ring of Coenzyme F430 from Methyl-Coenzyme M Reductase†

    PubMed Central

    Dey, Mishtu; Kunz, Ryan; Van Heuvelen, Katherine M.; Craft, Jennifer L.; Horng, Yih-Chern; Tang, Qun; Bocian, David F.; George, Simon J.; Brunold, Thomas C.; Ragsdale, Stephen W.

    2008-01-01

    Methyl-Coenzyme M reductase (MCR) catalyzes the final step in methane biosynthesis by methanogenic archaea and contains a redox-active nickel tetrahydrocorphin, Coenzyme F430, at its active site. Spectroscopic and computational methods have been used to study a novel form of the Coenzyme, called F330, which is obtained by reducing F430 with sodium borohydride (NaBH4). F330 exhibits a prominent absorption peak at 330 nm, which is blue shifted by 100 nm relative to F430. Mass spectrometric studies demonstrate that the tetrapyrrole ring in F330 has undergone reduction, based on the incorporation of protium (or deuterium), upon treatment of F430 with NaBH4 (or NaBD4). One- and two-dimensional NMR studies show that the site of reduction is the exocyclic ketone group of the tetrahydrocorphin. Resonance Raman studies indicate that elimination of this π-bond increases the overall π-bond order in the conjugative framework. X-ray absorption, magnetic circular dichroism, and computational results show that F330 contains low-spin Ni(II). Thus, conversion of F430 to F330 reduces the hydrocorphin ring but not the metal. Conversely, reduction of F430 with Ti(III) citrate to generate F380 (corresponding to the active MCRred1 state) reduces the Ni(II) to Ni(I), but does not reduce the tetrapyrrole ring system, which is consistent with other studies (Piskorski, R. and Jaun, B. (2003) J. Am. Chem. Soc. 125:13120-5 and Craft, J. L. et al. (2004) J. Biol. Inorg. Chem. 9:77-89). The distinct origins of the absorption band shifts associated with the formation of F330 and F380 are discussed within the framework of our computational results. These studies on the nature of the product(s) of reduction of F430 are of interest in the context of the mechanism of methane formation by MCR and in relation to the chemistry of hydroporphinoid systems in general. The spectroscopic and time dependent DFT calculations add important insight into the electronic structure of the Ni-hydrocorphinate in

  14. Stable isotope dilution assays of alternariol and alternariol monomethyl ether in beverages.

    PubMed

    Asam, Stefan; Konitzer, Katharina; Schieberle, Peter; Rychlik, Michael

    2009-06-24

    Stable isotope dilution assays (SIDAs) for the determination of the most important mycotoxins of the black mold Alternaria, namely, alternariol and alternariol monomethyl ether, have been developed. For this purpose, deuterated alternariol and alternariol methyl ether were synthesized by palladium catalyzed protium-deuterium exchange from the unlabeled toxins. Reaction conditions were chosen in such a manner that the formation of the [(2)H(4)]-isotopologues was favored. The synthesized products were characterized by LC-MS, NMR, and UV-spectroscopy. On the basis of the use of [(2)H(4)]-alternariol and [(2)H(4)]-alternariol methyl ether as internal standards, SIDAs were developed and applied to the determination of alternariol and alternariol methyl ether in beverages using LC-MS/MS. Method validation revealed a high sensitivity, i.e., low limits of detection (alternariol, 0.03 microg/kg; alternariol methyl ether, 0.01 microg/kg) and limits of quantitation (alternariol, 0.09 microg/kg; alternariol methyl ether, 0.03 microg/kg), respectively. Recovery from spiked apple juice was 100.5 +/- 3.4% for alternariol (range 0.1-1 microg/kg) and 107.3 +/- 1.6% for alternariol methyl ether (range 0.05-0.5 microg/kg). Interassay precision (expressed as coefficient of variation, CEV) for alternariol was 4.0% (7.82 +/- 0.31 microg/kg; vegetable juice, naturally contaminated) and 4.6% (1.04 +/- 0.05 microg/kg; grape juice, naturally contaminated). For alternariol methyl ether, a CEV of 2.3% (0.79 +/- 0.02 microg/kg; vegetable juice, naturally contaminated) was obtained. Analysis of fruit juices showed low contamination with alternariol and alternariol methyl ether in general, but higher values of both toxins were found in wine and vegetable juices. The values for alternariol were higher than those for alternariol methyl ether in nearly any case. However, the developed SIDA has proven to be optimally suited for further studies on alternariol and alternariol methyl ether content in

  15. Spectroscopic and computational studies of reduction of the metalversus the tetrapyrrole ring of coenzyme F-430 from methyl-coenzyme Mreductase

    SciTech Connect

    Dey, Mishtu; Kunz, Ryan C.; van Heuvelen, Katherine M.; Craft,Jennifer L.; Horng, Yih-Chern; Tang, Qun; Bocian, David F.; George, SimonJ.; Brunold, Thomas C.; Ragsdale, Stephen W.

    2006-06-30

    Methyl-coenzyme M reductase (MCR) catalyzes the final stepin methane biosynthesis by methanogenic archaea and contains aredox-active nickel tetrahydrocorphin, coenzyme F430, at its active site.Spectroscopic and computational methods have been used to study a novelform of the coenzyme, called F330, which is obtained by reducing F430with sodium borohydride (NaBH4). F330 exhibits a prominent absorptionpeak at 330 nm, which is blue shifted by 100 nm relative to F430. Massspectrometric studies demonstrate that the tetrapyrrole ring in F330 hasundergone reduction, on the basis of the incorporation of protium (ordeuterium), upon treatment of F430 with NaBH4 (or NaBD4). One- andtwo-dimensional NMR studies show that the site of reduction is theexocyclic ketone group of the tetrahydrocorphin. Resonance Raman studiesindicate that elimination of this pibond increases the overall pi-bondorder in the conjugative framework. X-ray absorption, magnetic circulardichroism, and computational results show that F330 contains low-spinNi(II). Thus, conversion of F430 to F330 reduces the hydrocorphin ringbut not the metal. Conversely, reduction of F430 with Ti(III) citrate togenerate F380 (corresponding to the active MCRred1 state) reduces theNi(II) to Ni(I) but does not reduce the tetrapyrrole ring system, whichis consistent with other studies [Piskorski, R., and Jaun, B. (2003) J.Am. Chem. Soc. 125, 13120-13125; Craft, J. L., et al. (2004) J. Biol.Inorg. Chem. 9, 77-89]. The distinct origins of the absorption bandshifts associated with the formation of F330 and F380 are discussedwithin the framework of our computational results. These studies on thenature of the product(s) of reduction of F430 are of interest in thecontext of the mechanism of methane formation by MCR and in relation tothe chemistry of hydroporphinoid systems in general. The spectroscopicand time-dependent DFT calculations add important insight into theelectronic structure of the nickel hydrocorphinate in its Ni(II) and

  16. [Determination of deuterium concentration in foods and influence of water with modified isotopic composition on oxidation parameters and heavy hydrogen isotopes content in experimental animals].

    PubMed

    Basov, A A; Bykov, I M; Baryshev, M G; Dzhimak, S S; Bykov, M I

    2014-01-01

    The article presents the results of the study of the deuterium (D) content in food products as well as the influence of deuterium depleted water (DDW) on the concentration of heavy hydrogen isotopes in the blood and lyophilized tissues of rats. The most significant difference in the content of D was found between potato and pork fat, which indexes the standard delta notation (δ) D in promille, related to the international standard SMOW (Standard Mean Ocean of Water) amounted to -83,2 per thousand and -250,7 per thousand, respectively (p<0,05). Among the investigated samples of water deuterium concentration ranged from -75,5 per thousand (Narzan) to +72,1 per thousand (Kubai), that indicates the ability of some food products to increase the concentration of heavy hydrogen atoms in the body. The data obtained in the experimental modeling of the diet of male Wistar rats in the age of 5-6 mo (weight 235 ± 16 g) using DDW (δD = -743,2 per thousand) instead of drinking water (δD = -37,0 per thousand) with identical mineral composition showed that after 2 weeks significant (p <0,05) formation of isotopic (deuterium-protium, D/H) gradient in the body is possible. Changing the direction of isotopic D/H gradient in laboratory animals in comparison with its physiological indicators (72-127 per thousand, "plasma>tissue") is due to different rates ofisotopic exchange reactions in plasma and tissues (liver, kidney, heart), which can be explained by entering into the composition of a modified diet of organic substrates with more than DDW concentration D, which are involved in the construction of cellular structures and eventually lead to a redistribution of D and change direction of D/H gradient "plasma

  17. Muonium--the second radioisotope of hydrogen: a remarkable and unique radiotracer in the chemical, materials, biological and environmental sciences.

    PubMed

    Rhodes, Christopher J

    2012-01-01

    Muonium (Mu), may be regarded as a radioactive hydrogen atom with a positive muon as its nucleus, and is formed in a range of media which are irradiated with positive muons. This exotic atom can be considered as a second radioisotope of hydrogen, along with tritium. Addition of this light atom (with a mass 1/9th that of a normal hydrogen, protium, atom) to unsaturated organic molecules forms free radicals, in which the muon serves as a radioactive and magnetic probe of their kinetic and structural properties. Suitable examples are chosen to illustrate the very large functionality of organic radicals which have been measured using muons and various methods of muSR, where mu stands for muon, S for spin and R may refer to rotation, resonance or relaxation. The principal techniques illustrated are transverse-field muon spin rotation (TF-muSR), avoided level crossing muon spin resonance (ALC-muSR) and longitudinal-field muon spin relaxation (LF-muSRx). Structural studies of radicals, the determination of mechanisms for radical formation, the measurement of radical stabilisation energies, the determination of the kinetics of reactions of free muonium atoms and of free radicals have all been accomplished using TF-muSR methods. It is further shown that TF-muSR is most useful in measuring radical reaction rates in non-aqueous media, to provide information of relevance to cell membrane damage and repair Muonium may further be used as a mechanistic probe since it determines a true pattern of H-atom reactivity in molecules, against which results from similar radiolysed materials may be compared. [In many solid materials that are exposed to ionising radiation, apparent H-atom adduct radicals are detected but which originate from charge-neutralisation of positive holes (radical cations) and ejected electrons, without free H-atoms being formed. DNA is the superlative example of this. Free H-atoms normally feature in the province of radiolysed aqueous media]. The applications of

  18. HYLIFE-II tritium management system

    SciTech Connect

    Longhurst, G.R.; Dolan, T.J.

    1993-06-01

    The tritium management system performs seven functions: (1) tritium gas removal from the blast chamber, (2) tritium removal from the Flibe, (3) tritium removal from helium sweep gas, (4) tritium removal from room air, (5) hydrogen isotope separation, (6) release of non-hazardous gases through the stack, (7) fixation and disposal of hazardous effluents. About 2 TBq/s (5 MCi/day) of tritium is bred in the Flibe (Li{sub 2}BeF{sub 4}) molten salt coolant by neutron absorption. Tritium removal is accomplished by a two-stage vacuum disengager in each of three steam generator loops. Each stage consists of a spray of 0.4 mm diameter, hot Flibe droplets into a vacuum chamber 4 m in diameter and 7 m tall. As droplets fall downward into the vacuum, most of the tritium diffuses out and is pumped away. A fraction {Phi}{approx}10{sup {minus}5} of the tritium remains in the Flibe as it leaves the second stage of the vacuum disengager, and about 24% of the remaining tritium penetrates through the steam generator tubes, per pass, so the net leakage into the steam system is about 4.7 MBq/s (11 Ci/day). The required Flibe pumping power for the vacuum disengager system is 6.6 MW. With Flibe primary coolant and a vacuum disengager, an intermediate coolant loop is not needed to prevent tritium from leaking into the steam system. An experiment is needed to demonstrate vacuum disengager operation with Flibe. A secondary containment shell with helium sweep gas captures the tritium permeating out of the Flibe ducts, limiting leaks there to about 1 Ci/day. The tritium inventory in the reactor is about 190 g, residing mostly in the large Flibe recirculation duct walls. The total cost of the tritium management system is 92 M$, of which the vacuum disengagers cost = 56%, the blast chamber vacuum system = 15%, the cryogenic plant = 9%, the emergency air cleanup and waste treatment systems each = 6%, the protium removal system = 3%, and the fuel storage system and inert gas system each = 2%.