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Sample records for protium

  1. 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.

  2. 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.

  3. 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.

  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. Two new species and a new combination in Protium (Burseraceae) from Costa Rica

    PubMed Central

    Santamaría-Aguilar, Daniel; Lagomarsino, Laura P.

    2017-01-01

    Abstract Two new species of Protium (Burseraceae) are described and illustrated: Protium aguilarii sp. nov., from the Pacific slope of the Osa Peninsula, Puntarenas Province, Costa Rica; and Protium hammelii sp. nov., from wet forests on the Caribbean slopes of Nicaragua and Costa Rica. In addition, Protium brenesii comb. nov., is proposed as a new combination based on Trichilia brenesii, a name that was based on a specimen collected with flowers in the mountains near San Ramón, Alajuela Province, Costa Rica. It is compared with Protium costaricense, a similar species with which it has been confused for more than 90 years. Finally, illustrations and specimen citations are provided for all the aforementioned taxa, and some others with which they have been confused. PMID:28228688

  6. Two new species and a new combination in Protium (Burseraceae) from Costa Rica.

    PubMed

    Santamaría-Aguilar, Daniel; Lagomarsino, Laura P

    2017-01-01

    Two new species of Protium (Burseraceae) are described and illustrated: Protium aguilariisp. nov., from the Pacific slope of the Osa Peninsula, Puntarenas Province, Costa Rica; and Protium hammeliisp. nov., from wet forests on the Caribbean slopes of Nicaragua and Costa Rica. In addition, Protium brenesiicomb. nov., is proposed as a new combination based on Trichilia brenesii, a name that was based on a specimen collected with flowers in the mountains near San Ramón, Alajuela Province, Costa Rica. It is compared with Protium costaricense, a similar species with which it has been confused for more than 90 years. Finally, illustrations and specimen citations are provided for all the aforementioned taxa, and some others with which they have been confused.

  7. Antitermite activities of coumarin derivatives and scopoletin from Protium javanicum Burm. f.

    PubMed

    Adfa, Morina; Yoshimura, Tsuyoshi; Komura, Kenichi; Koketsu, Mamoru

    2010-07-01

    The antitermite (termiticidal and antifeedant) activity of Protium javanicum Burm. f. extract was investigated. The ethyl acetate fraction was active. Scopoletin (1), quercetin, and stigmasterol were isolated by bioassay-guided fractionation. Scopoletin had the highest activity among the three compounds. In order to investigate the structure-activity relationship (SAR) of the methoxy and hydroxy groups at the C-6 and C-7 positions of the coumarin skeleton, we synthesized several coumarin derivatives whose chemical structures are similar to scopoletin. Scopoletin exhibited the strongest termiticidal activity among the 10 compounds tested, followed by 6-methoxycoumarin (3), 6-hydroxycoumarin (7), and umbelliferone (8). All compounds except coumarin (9) showed antifeedant activity.

  8. 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

  9. 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.

  10. Antibacterial activity of extract and fractions from branches of Protium spruceanum and cytotoxicity on fibroblasts.

    PubMed

    Amparo, Tatiane Roquete; Rodrigues, Ivanildes Vasconcelos; Seibert, Janaína Brandão; Souza, Rafaella Hilda Zaniti; Oliveira, Amanda Ribeiro de; Cabral, Vivette Appolinário Rodrigues; Vieira, Paula Melo de Abreu; Brandão, Geraldo Célio; Okuma, Adriana Akemi; Filho, Sidney Augusto Vieira; Teixeira, Luiz Fernando Medeiros; Souza, Gustavo Henrique Bianco de

    2017-07-20

    The crude ethanol extract (CEE) and fractions from branches of Protium spruceanum were subjected to antibacterial and cytotoxicity assays. Compounds of the most active fraction were identified by GC-MS and LC-MS. CEE was active against 19 bacteria and the ethyl acetate fraction (EAF) showed the lowest minimum bactericidal concentration (MBC 0.3-80.0 mg/mL). Through time-kill assay was observed that EAF induced rapid bactericidal effect against Staphylococcus saprophyticus. The cytotoxicity tests against L929 fibroblasts showed great potential of EAF on the treatment of infections caused by five bacteria (MBC < IC50). The results provide in vitro scientific support to the possible application of branches of P. spruceanum as antimicrobial agent that may contribute for treatment of infections.

  11. Fungal endophytes isolated from Protium heptaphyllum and Trattinnickia rhoifolia as antagonists of Fusarium oxysporum.

    PubMed

    Fierro-Cruz, Juan E; Jiménez, Pedro; Coy-Barrera, Ericsson

    Control of fungal pathogens is mainly addressed by the use of chemically synthesized fungicides which result in environmental pollution, developing resistance after prolonged use. In this context, endophytes have been recognized as potential biocontrollers, and also as a promising source of antifungal metabolites. Therefore, as part of our research on phytopathogen controllers, 355 fungal endophytes were isolated from Protium heptaphyllum and Trattinnickia rhoifolia (Burseraceae), both ethnobotanically important tree species that produce secondary metabolites of agronomic and industrial interest. Endophytes were tested by in vitro dual culture against Fusarium oxysporum, a phytopathogen of agronomic importance. Five endophytes exerted at least 40% inhibition on F. oxysporum growth. Ethyl acetate (EtOAc) extracts were obtained from the most active antagonistic fungi, after growing them in three different liquid media. The extracts were tested against a conidial suspension of F. oxysporum by direct bioautography. Two extracts derived from fungi identified as Chaetomium globosum, F211_UMNG and Meyerozima sp. F281_UMNG showed inhibition of pathogen growth. Isolate C. globosum, F211_UMNG was selected for a chemical analysis by RP-HPLC-DAD-ESI-MS and antifungal molecules such as cladosporin, chaetoatrosin A and chaetoviridin A were annotated and identified based on their MS data. Copyright © 2017 Asociación Argentina de Microbiología. Publicado por Elsevier España, S.L.U. All rights reserved.

  12. Analytical Method for Measuring Total Protium and Total Deuterium in a Gas Mixture Containing H2, D2, and HD Via Gas Chromatography

    SciTech Connect

    SESSIONS, HENRY

    2004-03-24

    A new analytical technique has been developed that measures both total protium (H) and deuterium (D) in a gas mixture containing H2, D2, and HD. This new analytical technique uses a micro gas chromatograph (GC) with two molecular sieve columns. One column uses D2 as the carrier gas and the other uses H2 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 sensitivity of less than 20 ppm. This new analytical technique was developed as a result of a request to provide instrumentation to measure the protium and deuterium concentrations at several process points during initial testing of the new hydrogen tritium thermal cycling absorption process columns.

  13. Chemical Composition, Enantiomeric Distribution, and Antifungal Activity of the Oleoresin Essential Oil of Protium amazonicum from Ecuador.

    PubMed

    Satyal, Prabodh; Powers, Chelsea N; Parducci V, Rafael; McFeeters, Robert L; Setzer, William N

    2017-09-23

    Background:Protium species (Burseraceae) have been used in the treatment of various diseases and conditions such as ulcers and wounds. Methods: The essential oil from the oleoresin of Protium amazonicum was obtained by hydrodistillation and analyzed by GC-MS, GC-FID, and chiral GC-MS. P. amazonicum oleoresin oil was screened for antifungal activity against Candida albicans, Aspergillus niger, and Cryptococcus neoformans. Results: A total of 54 components representing 99.6% of the composition were identified in the oil. The essential oil was dominated by δ-3-carene (47.9%) with lesser quantities of other monoterpenoids α-pinene (4.0%), p-cymene (4.1%), limonene (5.1%), α-terpineol (5.5%) and p-cymen-8-ol (4.8%). Chiral GC-MS revealed most of the monoterpenoids to have a majority of levo enantiomers present with the exceptions of limonene and α-terpineol, which showed a dextro majority. P. amazonicum oleoresin oil showed promising activity against Cryptococcus neoformans, with MIC = 156 μg/mL. Conclusions: This account is the first reporting of both the chemical composition and enantiomeric distribution of the oleoresin essential oil of P. amazonicum from Ecuador. The oil was dominated by (-)-δ-3-carene, and this compound, along with other monoterpenoids, likely accounts for the observed antifungal activity of the oil.

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

    PubMed

    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

    Protium heptaphyllum (Aubl.) March is popularly used as an analgesic and anti-inflammatory agent. 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. 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. 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. The essential oil showed antimutagenic activity due to its chemical composition. 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/mL) against E. coli, S. aureus, E. faecalis, and C. albicansThe essential oil

  15. 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

  16. 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.

  17. 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.

  18. Evidence that both protium and deuterium undergo significant tunneling in the reaction catalyzed by bovine serum amine oxidase

    SciTech Connect

    Grant, K.L.; Klinman, J.P. )

    1989-08-08

    The magnitudes of primary and secondary H/T and D/T kinetic isotope effects have been measured in the bovine serum amine oxidase catalyzed oxidation of benzylamine from 0 to 45{degree}C. Secondary H/T and D/T kinetic effects are small and in the range anticipated from equilibrium isotope effects; Arrhenius preexponential factors (A{sub H}/A{sub T} and A{sub D}/A{sub T}) determined from the temperature dependence of isotope effects also indicate semiclassical behavior. By contrast, primary H/T and D/T isotope effects, 35.2 {plus minus} 0.8 and 3.07 {plus minus} 0.07, respectively, at 25{degree}C, are larger than semiclassical values and give anomalously low preexponential factor rations, A{sub H}/A{sub T} = 0.12 {plus minus} 0.04 and A{sub D}/A{sub T} = 0.51 {plus minus} 0.10. Stopped-flow studies indicate similar isotope effects on cofactor reduction as seen in the steady state, consistent with a single rate-limiting C-H bond cleavage step for V{sub max}/K{sub m}. The comparison of primary and secondary isotope effects allows the authors to rule out appreciable coupling between the primary and secondary hydrogens at C-1 of the substrate. From the properties of primary isotope effects, they conclude that both protium and deuterium undergo significant tunneling in the course of substrate oxidation. These finding represent the first example of quantum mechanical effects in an enzyme-catalyzed proton abstraction reaction.

  19. Attenuation of capsaicin-induced acute and visceral nociceptive pain by alpha- and beta-amyrin, a triterpene mixture isolated from Protium heptaphyllum resin in mice.

    PubMed

    Oliveira, Francisco A; Costa, Charllynton L S; Chaves, Mariana H; Almeida, Fernanda R C; Cavalcante, Italo J M; Lima, Alana F; Lima, Roberto C P; Silva, Regilane M; Campos, Adriana Rolim; Santos, Flavia A; Rao, Vietla S N

    2005-10-21

    The triterpene mixture, alpha- and beta-amyrin, isolated from Protium heptaphyllum resin was evaluated on capsaicin-evoked nociception in mice. Orally administered alpha- and beta-amyrin (3 to 100 mg/kg) significantly suppressed the nociceptive behaviors--evoked by either subplantar (1.6 microg) or intracolonic (149 microg) application of capsaicin. The antinociception produced by alpha- and beta-amyrin against subplantar capsaicin-induced paw-licking behavior was neither potentiated nor attenuated by ruthenium red (1.5 mg/kg, s.c.), a non-specific antagonist of vanilloid receptor (TRPV1), but was greatly abolished in animals pretreated with naloxone (2 mg/kg, s.c.), suggesting an opioid mechanism. However, participation of alpha2-adrenoceptor involvement was unlikely since yohimbine (2 mg/kg, i.p.) pretreatment failed to block the antinociceptive effect of alpha- and beta-amyrin in the experimental model of visceral nociception evoked by intracolonic capsaicin. The triterpene mixture (3 to 30 mg/kg, p.o.) neither altered significantly the pentobarbital sleeping time, nor impaired the ambulation or motor coordination in open-field and rota-rod tests, respectively, indicating the absence of sedative or motor abnormality that could account for its antinociception. Nevertheless, alpha- and beta-amyrin could significantly block the capsaicin (10 mg/kg, s.c.)-induced hyperthermic response but not the initial hypothermia. These results suggest that the triterpene mixture, alpha- and beta-amyrin has an analgesia inducing effect, possibly involving vanilloid receptor (TRPV1) and an opioid mechanism.

  20. Amyrins from Protium heptaphyllum Reduce High-Fat Diet-Induced Obesity in Mice via Modulation of Enzymatic, Hormonal And Inflammatory Responses.

    PubMed

    Carvalho, Karine Maria Martins Bezerra; de Melo, Tiago Sousa; de Melo, Karina Moura; Quinderé, Ana Luiza Gomes; de Oliveira, Francisca Tuelly Bandeira; Viana, Ana Flávia Seraine Custódio; Nunes, Paulo Iury Gomes; Quetz, Josiane da Silva; Viana, Daniel de Araújo; da Silva, Armenio André de Carvalho Almeida; Havt, Alexandre; Fonseca, Said Gonçalves da Cruz; Chaves, Mariana Helena; Rao, Vietla Satyanarayana; Santos, Flávia Almeida

    2017-02-01

    Obesity remains a global problem. In search of phytochemicals that have antiobesity potential, this study evaluated α,β-amyrin, a triterpenoid mixture from Protium heptaphyllum, on high-fat diet-induced obesity in mice. Groups of mice (n = 8) were fed a normal diet or a high-fat diet, and were orally treated or not treated with either α,β-amyrin (10 or 20 mg/kg) or sibutramine (10 mg/kg) for 15 weeks. Variables measured at termination were body weight, visceral fat accumulation, adipocyte surface area, peroxisome proliferator-activated receptor gamma, and lipoprotein lipase expressions in adipose tissue, the levels of plasma glucose and insulin, the satiety hormones ghrelin and leptin, the digestive enzymes amylase and lipase, and the inflammatory mediators TNF-α, interleukin-6, and MCP-1. Results showed that α,β-amyrin treatment resulted in lower high-fat diet-induced increases in body weight, visceral fat content, adipocyte surface area, peroxisome proliferator-activated receptor gamma, and lipoprotein lipase expressions, and blood glucose and insulin levels. Additionally, the markedly elevated leptin and decreased ghrelin levels seen in the high-fat diet-fed control mice were significantly modulated by α,β-amyrin treatment. Furthermore, α,β-amyrin decreased serum TNF-α and MCP-1. These results suggest that α,β-amyrin could be beneficial in reducing high-fat diet-induced obesity and associated disorders via modulation of enzymatic, hormonal, and inflammatory responses. Georg Thieme Verlag KG Stuttgart · New York.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  2. Structural stability of 1100{degree}C heated Pd/k during absorption cycling in protium

    SciTech Connect

    Fisher, I.A.

    1993-03-12

    Pd/k is a hydride forming packing material which is used in the Thermal Cycling Absorption Process (TCAP). Palladium is supported on kieselguhr to create a packing material which will provide adequate void space to prevent excessive pressure drops and flow restrictions. The use of unsupported palladium would result in blockage of columns and clogging of filters due to the small particle size of unsupported palladium hydride powder. During pilot scale demonstrations, it was noted that the Pd/k packing material had degraded causing severe flow restrictions within the TCAP column. A solution to the problem involved the heating of Pd/k at 1,110{degree}C to strengthen the packing material, and render it more resistant to breakdown. The 1, 100{degree}C heated Pd/k has been shown to be more resistant to mechanical breakdown than the Pd/k prior to heat treatment. Two primary modes of Pd/k particle degradation have been identified: mechanical breakdown caused by particle fluidization and degradation caused by absorption/desorption cycling. Absorption/desorption cycling causes the palladium particles within the packing to expanded and contract upon formation and decomposition of the hydride, respectively. This expansion and contraction causes large localized stresses within the packing material, which if these stresses can not be accommodated within the packing will cause the material to crack and degrade. The purpose of this report is to document the results of the absorption/desorption cycling of 1,100{degree}C heated Pd/k and compare these results to the results obtained from the absorption/desorption cycling of Pd/k which had not been heated at 1, 100{degree}C.

  3. Structural stability of 1100[degree]C heated Pd/k during absorption cycling in protium. [Palladium supported on kieselguhr

    SciTech Connect

    Fisher, I.A.

    1993-03-12

    Pd/k is a hydride forming packing material which is used in the Thermal Cycling Absorption Process (TCAP). Palladium is supported on kieselguhr to create a packing material which will provide adequate void space to prevent excessive pressure drops and flow restrictions. The use of unsupported palladium would result in blockage of columns and clogging of filters due to the small particle size of unsupported palladium hydride powder. During pilot scale demonstrations, it was noted that the Pd/k packing material had degraded causing severe flow restrictions within the TCAP column. A solution to the problem involved the heating of Pd/k at 1,110[degree]C to strengthen the packing material, and render it more resistant to breakdown. The 1, 100[degree]C heated Pd/k has been shown to be more resistant to mechanical breakdown than the Pd/k prior to heat treatment. Two primary modes of Pd/k particle degradation have been identified: mechanical breakdown caused by particle fluidization and degradation caused by absorption/desorption cycling. Absorption/desorption cycling causes the palladium particles within the packing to expanded and contract upon formation and decomposition of the hydride, respectively. This expansion and contraction causes large localized stresses within the packing material, which if these stresses can not be accommodated within the packing will cause the material to crack and degrade. The purpose of this report is to document the results of the absorption/desorption cycling of 1,100[degree]C heated Pd/k and compare these results to the results obtained from the absorption/desorption cycling of Pd/k which had not been heated at 1, 100[degree]C.

  4. Anti-inflammatory effect of alpha, beta-Amyrin, a pentacyclic triterpene from Protium heptaphyllum in rat model of acute periodontitis.

    PubMed

    Holanda Pinto, S A; Pinto, L M S; Cunha, G M A; Chaves, M H; Santos, F A; Rao, V S

    2008-02-01

    This study was aimed to evaluate the anti-inflammatory potential of triterpene alpha, beta-amyrin in rats on acute phase periodontitis. Periodontitis was induced by ligature placement around the maxillary right second molar tooth. Rats (n = 8/group) were pretreated with alpha, beta-amyrin (5 and 10 mg/kg, p. o.), two hours before the induction of periodontal inflammation. Sham-operated and positive controls (lumiracoxib and dexamethasone) were included. Six hours later, plasma levels of TNF-alpha were analysed. Rats were sacrificed at 24 h, and the gingival tissue analysed for myeloperoxidase (MPO) and thiobarbituric acid-reactive substances (TBARS), as measures of neutrophil influx and lipid-peroxidation, respectively alpha, beta-Amyrin as well as dexamethasone significantly inhibited the periodontitis-associated increases of TNF-alpha, and the gingival MPO and TBARS. alpha, beta-Amyrin effect was more prominent at 5 mg/kg. Lumiracoxib manifested varied influence on the studied parameters. These results provide evidence to show that alpha, beta-Amyrin retards acute inflammation in rat model of periodontitis and warrant further study on its efficacy to prevent chronic periodontitis-associated bone loss.

  5. 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.

  6. 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

  7. The diffusivity of hydrogen isotopes in liquid lithium and in solid yttrium

    NASA Astrophysics Data System (ADS)

    Buxbaum, R. E.; Johnson, E. F.

    1982-12-01

    The separation of tritium from liquid lithium at low concentrations is an important problem for fusion technology. One of the most promising techniques for effecting this separation involves sorbing the tritium on solid yttrium metal. Reliable diffusivity data are essential for a realistic evaluation of this technique. The bodies of relevant experimental diffusivity data, i.e., data on protium diffusion in liquid lithium, protium diffusion in solid yttrium, and the isotope effect in metals, are reviewed.

  8. SAES ST909 Bench Scale Methane Cracking Tests

    SciTech Connect

    Klein, J.E.

    2000-12-15

    Tritium extracted from Commercial Light Water Reactor (CLWR) targets will be primarily hydrogen isotopes (tritium and protium), water, helium-4, and helium-3. Relatively low levels of impurities such as carbon monoxide, carbon dioxide, and methane are also expected in the extraction gas stream. Some methane is expected to have tritium substitution for some of the protium atoms. Tritiated ammonia is expected to form in some part of the extraction process due to the large size of the vacuum extraction furnace and the inevitable in-leakage of nitrogen from the secondary containment modules. These tritiated carbon and nitrogen species need to be processed to reduce tritium emissions from tritium processing facilities.

  9. 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.

  10. 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.

  11. Effects of tritium on material properties

    SciTech Connect

    Caskey, G.R. Jr.

    1985-01-01

    The effecs of tritium on deformation and fracture of metals are reviewed with emphasis on similarities and differences between tritium and the other hydrogen isotopes. Helium generated by radioactive decay of tritium introduces time dependent property changes not observed with protium or deuterium. On-going studies and topics for further investigations are identified. 17 refs., 6 figs., 9 tabs.

  12. 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.

  13. 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.

  14. Theoretical rate constants and kinetic isotope effects in the reaction of methane with H, D, T, and Mu atoms.

    PubMed

    Espinosa-García, J

    2008-03-07

    The rate constants and kinetic isotope effects of the reaction of methane with four isotopes of hydrogen, protium (H), deuterium (D), tritium (T), and muonium (Mu), were studied using variational transition state theory with multidimensional tunneling on an analytical potential energy surface, PES-2002, previously constructed by our group. For the four isotopes, our kinetics results agree reasonably with available experimental measurements, improving previous theoretical results that used different potential energy surfaces and/or theoretical approaches. In the comparison of the reactivity between protium and muonium, which is the most severe test of the surface and theoretical method due to the large mass difference between the two isotopes, some sources of discrepancy between theory and experiment were analyzed. These were the zero-point energy, tunneling effect, and the role of the reactivity from methane excited vibrational states.

  15. Permeability of Molecular Hydrogen and Water Vapor Through Butyl Rubber at Ambient Temperature

    SciTech Connect

    Zeigler, K.

    1992-04-09

    The preparation of the Safety Analysis Report for the 233-H Replacement Tritium Facility (RTF) requires permeation constants of hydrogen isotopes through butyl rubber, to estimate possible worker exposure given a certain level of tritium in the confinement gloveboxes. Literature values of the permeability constants for hydrogen isotopes and water vapor through butyl rubber at ambient temperature (22-25 C) have been converted to common units and are tabulated (Tables I and II). Permeation rates of tritiated species are the same as that of protium species, within experimental error. Thus, molecular protium and normal water vapor data serve to estimate tritium permeation rates. Because of vendor to vendor variability of permeability, especially of water vapor, vendor measurements of water vapor permeability should continue to be used to estimate permeation in SRS processes.

  16. Permeability of Molecular Hydrogen and Water Vapor Through Butyl Rubber at Ambient Temperature

    SciTech Connect

    Clark, Elliot A.

    1992-04-09

    The preparation of the Safety Analysis Report for the 233-H Replacement Tritium Facility (RTF) requires permeation constants of hydrogen isotopes through butyl rubber, to estimate possible worker exposure given a certain level of tritium in the confinement gloveboxes. Literature values of the permeability constants for hydrogen isotopes and water vapor through butyl rubber at ambient temperature (22-25 C) have been converted to common units and are tabulated (Tables I and II). Permeation rates of tritiated species are the same as that of protium species, within experimental error. Thus, molecular protium and normal water vapor data serve to estimate tritium permeation rates. Because of vendor-to-vendor variability of permeability, especially of water vapor, vendor measurements of water vapor permeability should continue to be used to estimate permeation in SRS processes.

  17. Hydrogen transport in iron and steel

    NASA Technical Reports Server (NTRS)

    Louthan, M. R., Jr.; Derrick, R. G.; Donovan, J. A.; Caskey, G. R., Jr.

    1976-01-01

    The permeabilities of protium, deuterium, and tritium in foil specimens of Marz grade iron, 4130 steel, Armco iron, HP-9-4-20, and T-1 steels were studied at hydrogen pressures between 0.02 and 0.5 MPa over the temperature range 260-700 K. The permeability was measured by a pressure-rise method, deuterium counting with a detector, and radioactivity counting. Good agreement is found between the measurement techniques used. It is shown that the permeabilities of protium, deuterium, and tritium in iron and T-1 steel at temperatures as low as 260 K are in good agreement with the equation proposed by Gonzalez (1967). However, the permeabilities of HP-9-4-20 and 4130 steel to hydrogen are typically lower than predicted. The isotope effect on hydrogen permeability of HP-9-4-20, 4130 and T-1 steels, and high-purity iron can be estimated by an inverse square root of mass correction.

  18. 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.

  19. Multiple isotope effects with alternative dinucleotide substrates as a probe of the malic enzyme reaction

    SciTech Connect

    Weiss, P.M.; Urbauer, J.L.; Cleland, W.W. ); Gavva, S.R.; Harris, B.G.; Cook, P.F. )

    1991-06-11

    Deuterium isotope effects and {sup 13}C isotope effects with deuterium- and protium-labeled malate have been obtained for both NAD- and NADP-malic enzymes by using a variety of alternative dinucleotide substrates. With nicotinamide-containing dinucleotides as the oxidizing substrate, the {sup 13}C effect decreases when deuterated malate is the substrate compared to the value obtained with protium-labeled malate. These data are consistent with a stepwise chemical mechanism in which hydride transfer precedes decarboxylation of the oxalacetate intermediate as previously proposed. When dinucleotide substrates such as thio-NAD, 3-nicotinamide rings are used, the {sup 13}C effect increases when deuterated malate is the substrate compared to the value obtained with protium-labeled malate. These data, at face value, are consistent with a change in mechanism from stepwise to concerted for the oxidative decarboxylation portion of the mechanism. However, the increase in the deuterium isotope effect from 1.5 to 3 with a concomitant decrease in the {sup 13}C isotope effect from 1.034 to 1.003 as the dinucleotide substrate is changed suggests that the reaction may still be stepwise with the non-nicotinamide dinucleotides. A more likely explanation is that a {beta}-secondary {sup 13}C isotope effect accompanies hydride transfer as a result of hyperconjugation of the {beta}-carboxyl of malate as the transition state for the hydride transfer step is approached.

  20. Attempting to monitor the incorporation of deuterium into indole-3-acetic acid and tryptophan in Zea mays grown on deuterium oxide labeled water

    SciTech Connect

    Jensen, P.J.; Bandurski, R.S. )

    1989-04-01

    We are attempting to determine when seedlings of Zea mays sweet corn, var. Silver Queen begin de novo biosynthesis of tryptophan and indole-3-acetic acid (IAA). We wish to use the general precursor, deuterium labeled water, to minimize assumptions as to the biosynthetic route. Protium in positions 2, 4, 5, 6 7 of the indole ring are non-exchangeable. IAA and tryptophan synthesized via the shikimic acid pathway would contain deuterium in one or more of these positions . The protium on the indene nitrogen, the carboxyl, the amino group, or the protium alpha to the carboxyl exchange readily and so are removed prior to analysis by base catalyzed exchange. The IAA, or trypotophan, is then purified by DEAE, Dowex 50, and two HPLC steps. IAA is methylated with diazomethane and analyzed by GC/MS. Trytophan is acetylated with triethylamine-acetic anhydride and then methylated with diazomethane and analyzed by GC/MS. Results of these studies on plants grown for varying lengths of time and under various light and nutrient conditions will be reported.

  1. 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.

  2. 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. Copyright © 2013 Verlag Helvetica Chimica Acta AG, Zürich.

  3. Muon Catalyzed Fusion in Solid HD

    NASA Astrophysics Data System (ADS)

    Porcelli, T. A.; Beer, G. A.; Knowles, P. E.; Maier, M.; Mason, G. R.; Marshall, G. M.; Olin, A.; Douglas, J.; Fujiwara, M. C.; Ellerbusch, B.; Huber, T. M.; Kammel, P.; Kunselman, A. R.; Adamczak, A.; Bailey, J. M.; Faifman, M.; Markushin, V.; Jacot-Guillarmod, R.; Mulhauser, F.; Schaller, L. A.; Kim, S. K.; Petitjean, C.; Zmeskal, J.

    1997-10-01

    Muons were stopped in a solid hydrogen and tritium target, where muonic protium atoms (μ p) were formed. The muons transferred to tritium, forming muonic tritium atoms (μ t) which were then emitted, traversing a vacuum drift region to a solid HD (deuterium hydride) layer, where muonic deuterium tritium (dt μ) molecules formed via a resonant process, leading to fusion. A brief description of the experimental apparatus will be given. Analysis of the data from an experiment at TRIUMF, along with Monte Carlo simulations, will be presented.

  4. Cars spectrometer for the isotopic analysis of hydrogen in the fuel circuits of fusion reactors

    SciTech Connect

    Ivanov, A.A.; Polyakov, G.A.; Voronin, V.B.

    1995-12-01

    The paper describes a coherent anti-Stokes Raman scattering (CARS) spectrometer using vibrational transitions in molecules of hydrogen isotopes. Stokes waves in high-pressure protium and deuterium are generated by stimulated Raman scattering. The concentrations of H{sub 2} and D{sub 2} can be determined to within 5% after storing the data for 10 min using the concentration characteristics of the apparatus. The lowest detectable concentration of H{sub 2} and D{sub 2} are 80 ppm and 6%, respectively, the total pressure was 50 torr, and the repetition rate of the measurements was 5 Hz.

  5. 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.

  6. 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.

  7. 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.

  8. Novel PEFC Application for Deuterium Isotope Separation.

    PubMed

    Matsushima, Hisayoshi; Ogawa, Ryota; Shibuya, Shota; Ueda, Mikito

    2017-03-16

    The use of a polymer electrolyte fuel cell (PEFC) with a Nafion membrane for isotopic separation of deuterium (D) was investigated. Mass analysis at the cathode side indicated that D diffused through the membrane and participated in an isotope exchange reaction. The exchange of D with protium (H) in H₂O was facilitated by a Pt catalyst. The anodic data showed that the separation efficiency was dependent on the D concentration in the source gas, whereby the water produced during the operation of the PEFC was more enriched in D as the D concentration of the source gas was increased.

  9. Novel PEFC Application for Deuterium Isotope Separation

    PubMed Central

    Matsushima, Hisayoshi; Ogawa, Ryota; Shibuya, Shota; Ueda, Mikito

    2017-01-01

    The use of a polymer electrolyte fuel cell (PEFC) with a Nafion membrane for isotopic separation of deuterium (D) was investigated. Mass analysis at the cathode side indicated that D diffused through the membrane and participated in an isotope exchange reaction. The exchange of D with protium (H) in H2O was facilitated by a Pt catalyst. The anodic data showed that the separation efficiency was dependent on the D concentration in the source gas, whereby the water produced during the operation of the PEFC was more enriched in D as the D concentration of the source gas was increased. PMID:28772661

  10. 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.

  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.; 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.

  12. Room-temperature coupling between electrical current and nuclear spins in OLEDs

    NASA Astrophysics Data System (ADS)

    Malissa, H.; Kavand, M.; Waters, D. P.; van Schooten, K. J.; Burn, P. L.; Vardeny, Z. V.; Saam, B.; Lupton, J. M.; Boehme, C.

    2014-09-01

    The effects of external magnetic fields on the electrical conductivity of organic semiconductors have been attributed to hyperfine coupling of the spins of the charge carriers and hydrogen nuclei. We studied this coupling directly by implementation of pulsed electrically detected nuclear magnetic resonance spectroscopy in organic light-emitting diodes (OLEDs). The data revealed a fingerprint of the isotope (protium or deuterium) involved in the coherent spin precession observed in spin-echo envelope modulation. Furthermore, resonant control of the electric current by nuclear spin orientation was achieved with radiofrequency pulses in a double-resonance scheme, implying current control on energy scales one-millionth the magnitude of the thermal energy.

  13. Time-of-flight measurement of resonant molecular formation in muon catalyzed dt fusion

    SciTech Connect

    Marshall, G.M.; Adamczak, A.; Bailey, J.M.

    1995-11-01

    Preliminary results are reported for an experiment at TRIUMF where a time-of-flight technique was tested for measuring the energy dependence of the rate for muon catalyzed dt fusion. Muonic tritium toms were created following transfer of negative muons from muonic protium in a layer of solid hydrogen (protium) containing a small fraction of tritium. The atoms escaped from the solid layer via the Ramsauer-Townsend mechanism, traversed a drift region of 18 mm, and then struck an adjacent layer of deuterium, where the muonic atom could form a molecular system. The time of detection of a fusion product (neutron or alpha) following muon arrival is dependent upon the energy of the muonic tritium atom as it traverses the drift region. By comparison of the time distribution of fusion events with a prediction based on the theoretical energy dependence of the rate, the strength of resonant formation can in principle be determined. The results extracted so far are discussed and the limitations of the method are examined.

  14. Hydrogen exchange in nucleosides and nucleotides. Measurement of hydrogen exchange by stopped-flow and ultraviolet difference spectroscopy.

    PubMed

    Cross, D G

    1975-01-28

    Time-dependent changes in the ultraviolet absorbance of the adenine chromophore are observed in the stopped-flow spectrophotometer when adenosine and its analogs are rapidly transferred from protium oxide to deuterium oxide. These absorbance changes are shown to result from hydrogen exchange in the exocyclic amino groups of the purine ribonucleosides by using derivatives of adenosine in which methyl groups replace exchangeable hydrogens and by showing that the general characteristics of hydrogen exchange in adenosine analogs agree with those found here. A study of the dependence of hydrogen-exchange rate constants on adenosine, AMP, and phosphate concentration showed there is a second-order dependence on AMP concentration which is primarily due to intermolecular catalysis by the phosphate group of the nucleotide. The deuterium oxide perturbation difference spectrum, obtained at equilibrium, was found to contain two components that result from blue shifts of the adenine chromophore absorbance: (1) a shift cause by the substitution of deuterium for protium in the ring (N1) nitrogen and exocyclic nitrogens, and (2) a shift associated with a change in the polarizability of the medium. Since the theory of solvent perturbation, which is used to measure the relative "exposure" of chromophores in macromolecules, assumes that the spectral shifts observed are solely due to (2) above, the use of deuterium oxide as a measure of chromophore exposure to perturbants the size of water must be reexamined.

  15. 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.

  16. Choice of a process design for simultaneous detritiation and upgrading of heavy water for the Advanced Neutron Source

    SciTech Connect

    Miller, A.I.; Spagnolo, D.A.; DeVore, J.R.

    1995-11-01

    Tritium removal and heavy water upgrading are essential components of the heavy water-moderated reactor that is the heart of the Advanced Neutron Source (ANS) to be built at Oak Ridge National Laboratory. The technologies for these two processes, which are closely related, are reviewed in the context of the ANS requirements. The evolution of the design of the Heavy Water Upgrading and Detritiation Facility (HWUDF) for ANS is outlined, and the final conceptual design is presented. The conceptual design of HWUDF has two main component systems: (a) a front-end combined electrolysis and catalytic exchange (CECE) system and (b) a back-end cryogenic distillation (CD) system. The CECE process consists of a countercurrent exchange column for hydrogen-water exchange over a wetproofed catalyst and electrolysis to convert water into hydrogen. It accepts all the tritiated heavy water streams of the reactor and performs an almost total separation into a protium (light hydrogen) stream containing tritium and deuterium at only natural abundance and a deuterium stream containing all the tritium and almost no protium. The tritium-containing deuterium stream is then processed by a CD unit, which removes over 90% of the tritium and concentrates it to >99% tritium for indefinite storage as a metal tritide. Deuterium gas with a small residue of tritium is recombined with oxygen from the electrolytic cells and returned as heavy water to the reactor.

  17. Hydrogen tunneling in enzyme reactions

    SciTech Connect

    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.

  18. Fatigue crack propagation behavior and debris formation in Ti-6Al-4V alloys with different grain size

    NASA Astrophysics Data System (ADS)

    Kim, H. J.; Nakahigashi, J.; Ebara, R.; Endo, M.

    2017-05-01

    Titanium alloy is widely used in applications where high specific strength as well as good heat and corrosion resistance is required. Consequently, there are a number of studies on the fatigue characteristics of titanium alloys. In recent years, grain refinement for metallic materials processed by several methods, such as severe plastic deformation, has been studied to improve the mechanical properties. Grain refinement of titanium alloy by the protium treatment is a new technology, and the fatigue properties of this material have yet to be sufficiently studied. Therefore in this study, tension-compression fatigue tests were conducted for a protium treated Ti-6Al-4V alloy with ultra-fine grains of 0.5 μm in average size as well as for an untreated alloy with conventional grains of 6 μm. Specimens had shallow, sharp notches with the depth of 50 μm and the root radius of 10 μm, which enabled successive observation of the initiation and early propagation behaviors of small fatigue cracks. Substantial amount of oxide debris was formed along the crack during crack propagation. The role of debris was discussed in association with propagation resistance.

  19. Culture-Bound Syndromes of a Brazilian Amazon Riverine population: Tentative correspondence between traditional and conventional medicine terms and possible ethnopharmacological implications.

    PubMed

    Pagani, E; Santos, J de F L; Rodrigues, E

    2017-05-05

    hypothetical correlations between CBS as described by the riverine population studied and some "etic" terms. The main importance of this is to help the proposition of target-oriented pharmacological studies of the natural resources used by these communities. Accordingly, the following plants are suggested to be submitted to further studies for antidepressant and anxiolytic activities: Siparuna guianensis, Mansoa alliacea, Leucas martinicensis, Petiveria alliacea, Annona montana and Alpinia nutans; for anti-seizure activity: Protium amazonicum, Protium aracouchini and Protium heptaphyllum; finally for antispasmodic activity: Leucas martinicensis. Copyright © 2017 Elsevier Ireland Ltd. All rights reserved.

  20. 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

  1. 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.

  2. Apparatus for separating and recovering hydrogen isotopes

    SciTech Connect

    Heung, L.K.

    1994-05-17

    An apparatus is described for recovering hydrogen and separating its isotopes. The apparatus includes a housing bearing with 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. 2 figures.

  3. Performance of a metal hydride store on the "Ross Barlow" hydrogen powered canal boat.

    PubMed

    Bevan, A I; Züttel, A; Book, D; Harris, I R

    2011-01-01

    This project involved the conversion of a British Waterways maintenance craft to a canal boat, powered by a combination of a solid-state hydrogen store, Proton Exchange Membrane (PEM) fuel cell, lead-acid battery pack and a high-efficiency, permanent magnet (NdFeB) electric motor. These replaced the conventional diesel engine thus eliminating water, noise, local and general atmospheric pollution. The "Protium" project applies modern technologies to a traditional mode of transportation. The TiMn2-based metal hydride store exhibited excellent performance as an effective means of storing 4 kg of hydrogen with a suitable desorption flow rate and temperature adequate for the operation of a 1 kW PEM fuel cell in a water-based environment.

  4. 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)

  5. 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)

  6. 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.

  7. INSTRUMENTS AND METHODS OF INVESTIGATION: Dynamic compression of hydrogen isotopes at megabar pressures

    NASA Astrophysics Data System (ADS)

    Trunin, Ryurik F.; Urlin, Vitalii D.; Medvedev, Aleksandr B.

    2010-09-01

    We review the results of shock compression of solid protium to the pressure 66 GPa, of liquid deuterium to 110 GPa, and of solid deuterium to 123 GPa in explosive devices of spherical geometry. The results are compared with data obtained by US scientists using traditional energy sources (explosives and light-gas guns), striker acceleration in a strong magnetic field (Z facility at Sandia), and powerful lasers (Nova at Lawrence Livermore National Laboratory (LLNL) and Omega at the Laboratory for Laser Energetics, University of Rochester). Results of density measurements of hydrogen isotopes under quasi-isentropic compression are analyzed. The absence of an anomalous increase in density under shock and quasi-isentropic compression of hydrogen isotopes is demonstrated. On the other hand, both processes exhibit a sharp change in the compression curve slopes, at the respective pressures 45 and 300 GPa.

  8. 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.

  9. 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.

  10. X-ray powder diffraction data for ErH(2-x)Dx

    SciTech Connect

    Browning, Jim

    2008-01-01

    We report X-ray powder diffraction data for ErH2-xD x formed by hydrogen (i.e. protium)-deuterium loading of Er metal. Lattice parameters for the varying hydrogen-deuterium compositions followed Vergard's law behavior. The cubic lattice parameter at room temperature for ErH2-xD x obeys a linear relationship according to the formula a = 5.1287 -1.1120 10-4 x; where a = the lattice parameter of the fluorite-type structure and x = the mole percent of deuterium. Microstrain measurements suggest a possible ordering of hydrogen and deuterium in the composition ErH1D1.

  11. Tritium stripping in a nitrogen glove box using palladium/zeolite and SAES St 198

    SciTech Connect

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

    1995-10-01

    Glove box clean-up experiments were conducted in a nitrogen glove box using palladium deposited on zeolite (Pd/z) and a SAES St 198 getter as tritium stripping materials. Protium/deuterium samples spiked with tritium were released into a 620 liter glove box to simulate tritium releases in a 10,500 liter glove box. The Pd/z and the SAES St 198 stripper beds produced a reduction in tritium activity of approximately two to three orders of magnitude and glove box clean-up was limited by a persistent background tritium activity level. Attempts to significantly reduce the glove box activity to lower levels without purging were unsuccessful. 3 refs., 6 figs., 1 tab.

  12. Tritium stripping in a nitrogen glove box using palladium/zeolite and SAES St 198{trademark}

    SciTech Connect

    Klien, J.E.; Wermer, J.R.

    1995-01-01

    Glove box clean-up experiments were conducted in a nitrogen glove box using palladium deposited on zeolite (Pd/z) and a SAES St 198{trademark} getter as tritium stripping materials. Protium/deuterium samples spiked with tritium were released into a 620 liter glove box to simulate tritium releases in a 10,500 liter glove box. The Pd/z and the SAES St 198{trademark} stripper beds produced a reduction in tritium activity of approximately two to three orders of magnitude and glove box clean-up was limited by a persistent background tritium activity level. Attempts to significantly reduce the glove box activity to lower levels without purging were unsuccessful.

  13. 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.

  14. 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.

  15. Role of internal thermodynamics in determining hydrogen tunneling in enzyme-catalyzed hydrogen transfer reactions.

    PubMed

    Rucker, J; Cha, Y; Jonsson, T; Grant, K L; Klinman, J P

    1992-11-24

    Previous investigations have indicated a role for hydrogen tunneling in the yeast alcohol dehydrogenase catalyzed oxidation of benzyl alcohol [Cha, Y., Murray, C. J., & Klinman, J. P. (1989) Science 243, 1325] and the bovine plasma amine oxidase catalyzed oxidation of benzylamine [Grant, K.L., & Klinman, J. P. (1989) Biochemistry 28,6597]. In the present studies, values of protium to tritium and deuterium to tritium isotope effects and their temperature dependencies have been measured using ring-substituted substrates for yeast alcohol dehydrogenase and bovine plasma amine oxidase, revealing tunneling in each case. The results of these studies indicate that hydrogen tunneling is a general phenomenon and is not limited to enzyme reactions with degenerate energy levels for bound substrates and products. An analysis of internal thermodynamics in the yeast alcohol dehydrogenase reaction shows that tunneling occurs when delta H degrees is endothermic and that the degree of tunneling appears to increase as delta H degrees decreases toward zero.

  16. 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.

  17. Hydrogen Isotope Exchange Properties of Porous Solids Containing Hydrogen

    SciTech Connect

    Heung, L.K.; Staack, G.C.

    2005-07-15

    The use of catalysts to improve the exchange kinetics between hydrogen isotopes in the gas phase and that in the solid phase was investigated. Granules of alumina, silica and molecular sieve were coated with platinum as the catalyst. The granules saturated with water at room humidity were packed in a 2-cm diameter column for isotope exchange tests. Deuterium and protium were alternately fed through the column at a constant rate. Isotope concentration in column effluent was monitored to generate isotope break-through curves. The curves were analyzed to produce information on the kinetics and capacity of the material. The results showed that all materials tested provided some extent of isotope exchange but some were superior both in kinetics and capacity. This paper will present the test results.

  18. 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.

  19. 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.

  20. Proton tunneling in aromatic amine dehydrogenase is driven by a short-range sub-picosecond promoting vibration: consistency of simulation and theory with experiment.

    PubMed

    Johannissen, Linus O; Hay, Sam; Scrutton, Nigel S; Sutcliffe, Michael J

    2007-03-15

    Hydrogen transfer, an essential component of most biological reactions, is a quantum problem. However, the proposed role of compressive motion in promoting enzymatic H-transfer is contentious. Using molecular dynamics simulations and density functional theory (DFT) calculations, we show that, during proton tunneling in the oxidative deamination of tryptamine catalyzed by the enzyme aromatic amine dehydrogenase (AADH), a sub-picosecond promoting vibration is inherent to the iminoquinone intermediate. We show by numerical modeling that this short-range vibration, with a frequency of approximately 165 cm-1, is consistent with "gating" motion in the hydrogen tunneling model of Kuznetsov and Ulstrup (Kuznetsov, A. M.; Ulstrup, J. Can. J. Chem. 1999, 77, 1085) in an enzymatic reaction with an observed protium/deuterium kinetic isotope effect that is not measurably temperature-dependent.

  1. 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.

  2. Development of a laser based detritiation system at Ontario Hydro

    SciTech Connect

    Woodall, K.B.; Bartoszek, F.E.; Morrison, M.D.; Robins, J.R.

    1985-09-01

    A system for separation of tritium from protium based on selective multiphoton dissociation of trifluoromethane is under development. In addition to the selective multiphoton dissociation process, processes have been demonstrated for transfer of tritium from a water feed to the trifluoromethane process gas and for the separation of the tritiated dissociation product from the trifluoromethane after the laser dissociation cell. A simple dissociation cell design employing waveguiding of laser radiation in hollow cylindrical dielectrics has been tested. Work is continuing to integrate the experimental data into a computer model of the complete detritiation system which will allow us to determine if this process can provide the basis for low cost, low inventory tritium separation facilities.

  3. Influence of the isotopic composition of water on the hydration of ions

    SciTech Connect

    Korolev, V.P.; Krestov, G.A.

    1988-01-10

    The differences in the hydration of ions in H/sub 2/O and D/sub 2/O were examined as revealed in the enthalpies of the transfer of ions from H/sub 2/O into D/sub 2/O. Two methods of calculation were examined which reflected extreme points of view on the hydration of cations and anions in H/sub 2/O and D/sub 2/O; the method of resolving the enthalpies of transfer on the basis of the cesium-iodine scale was most effective. The differentiating action of the replacement of protium by deuterium in water on the hydration of ions consisted in the weakening of the positive hydration of cations and the intensification of the positive hydration of anions in D/sub 2/O in comparison with H/sub 2/O.

  4. Isotopic hydrogen analysis via conventional and surface-enhanced fiber optic Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Lascola, Robert; Zeigler, Kristine E.; McWhorter, C. Scott; Villa-Aleman, Eliel; Tovo, Laura L.; Ward, April E.

    2004-12-01

    This report describes laboratory development and process plant applications of Raman spectroscopy for detection of hydrogen isotopes in the Tritium Facilities at the Savannah River Site (SRS), a U.S. Department of Energy complex. Raman spectroscopy provides a lower-cost, in situ alternative to mass spectrometry techniques currently employed at SRS. Using conventional Raman and fiber optics, we have measured, in the production facility glove boxes, process mixtures of protium and deuterium at various compositions and total pressures ranging from 1000 - 4000 torr, with detection limits ranging from 1-2% for as low as 3-second integration times. We are currently investigating fabrication techniques for SERS surfaces in order to measure trace (0.01-0.1%) amounts of one isotope in the presence of the other. These efforts have concentrated on surfaces containing palladium, which promotes hydrogen dissociation and forms metal hydride bonds, essentially providing a chemical enhancement mechanism.

  5. Hydrogen blistering of silicon: Effect of implantation temperature, isotope dependence, and key role of dynamic annealing

    SciTech Connect

    Giguere, Alexandre; Terreault, Bernard

    2007-11-15

    Blistering of (001) Cz-Si crystals (>1 {omega} cm), by either protium (H) or deuterium (D) ions of 5 keV energy, was studied as a function of the sample temperature during implantation in the range of 150-450 K. It was found that the blistering dose thresholds decreased with temperature, and very dramatically so in the case of D ions, revealing new aspects of the giant isotope effect. An optimal implantation temperature for ion cutting was found around 100 deg. C, where the required dose is reduced and the isotope effect is minimized. The results are interpreted in terms of models of the interaction of implanted hydrogen with radiation defects, and they show that dynamic annealing is incomparably more efficient in promoting blistering than purely thermal annealing.

  6. Chemical composition of South American Burseraceae non-volatile oleoresins and preliminary solubility assessment of their commercial blend.

    PubMed

    Siani, A C; Nakamura, M J; Tappin, M R R; Monteiro, S S; Guimarães, A C; Ramos, M F S

    2012-01-01

    Non-volatile oleoresins from neotropical Burseraceae are traditionally used for craft, technological and medicinal purposes. The crude resin is usually sold in popular markets of the forest communities. Adding value to this rainforest raw material requires establishing its composition. To analyse the resin composition from different Burseraceae species and establish a minimally reproducible profile by gas chromatography, in order to parameterise its quality control. Crude oleoresin samples of 10 Protium and Trattinnickia species and a commercial blend were subjected to hydrodistillation to remove volatile compounds. The chloroform-soluble residues were methylated, analysed by GC-FID (flame ionisation detection), and individual components were identified by analysing their mass fragmentation pattern in GC-MS and comparison with data from the literature. The blend solubility was assayed in 30 non-chlorinated solvents at three different proportions. The resins consisted exclusively of triterpenes, showing a common predominance of four major compounds in all the samples, corresponding to α-amyrin, β-amyrin, α-amyrenone and β-amyrenone. This profile was complemented with minor amounts of the tetracyclic β-elemolic and α-elemolic acids, maniladiol, brein and other oxidised trace compounds. The better solvents for the resin were those chemically bearing more than four carbon atoms, as n-butyl acetate, 2-ethoxyethanol and isopropanol. The crude resin blend sold contained around 10% of insoluble material that was constituted by up to 70% inorganic residues mixed with humic acid derivatives, as attested by ash analysis and IR spectroscopy, respectively. The experimental results, complemented by a general inspection of the literature, demonstrated a systematically reproducible triterpene profile in Protium and Trattinnickia species. Copyright © 2012 John Wiley & Sons, Ltd.

  7. 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

  8. 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

  9. Aluminum and Other Coatings for the Passivation of Tritium Storage Vessels

    SciTech Connect

    Spencer, W.; Korinko, P.

    2016-11-16

    Using a highly sensitive residual gas analyzer, the off gassing of hydrogen, water, and hydrocarbons from surface treated storage vessels containing deuterium was measured. The experimental storage vessels were compared to a low off-gassing, electro-polished 304L canister. Alternative vessels were made out of aluminum, or were coatings on 304L steel. Coatings included powder pack aluminide, electro-plated aluminum, powder pack chromide, dense electro-plated chromium, copper plated, and copper plated with 25 and 50 percent nano-diamond. Vessels were loaded with low pressure deuterium to observe exchange with protium or hydrogen as observed with formation of HD and HDO. Off gas of D2O or possible CD4 was observed at mass 20. The main off gas in all of the studies was H2. The studies indicated that coatings required significant post coating treatment to reduce off gas and enhance the permeation barrier from gases likely added during the coating process. Dense packed aluminum coatings needed heating to drive off water. Electro-plated aluminum, chromium and copper coatings appeared to trap hydrogen from the plating process. Nano-diamond appeared to enhance the exchange rate with hydrogen off gas and its coating process trapped significant amounts of hydrogen. Aluminum caused more protium exchange than chromium treated surfaces. Aluminum coatings released more water but pure aluminum vessels released small amounts of hydrogen, little water, and generally performed well. Chromium coating had residual hydrogen that was difficult to totally outgas but otherwise gave low residuals for water and hydrocarbons. Our studies indicated that simple coating of as received 304L metal will not adequately block hydrogen. The base vessel needs to be carefully out gassed before applying a coating and the coating process will likely add additional hydrogen that must be removed. Initial simple bake out and leak checks up to 350° C for a few hours was found to be inadequate. All of the

  10. Medicinal plants in Brazil: Pharmacological studies, drug discovery, challenges and perspectives.

    PubMed

    Dutra, Rafael C; Campos, Maria M; Santos, Adair R S; Calixto, João B

    2016-10-01

    This review article focuses on pre-clinical and clinical studies with some selected Brazilian medicinal plants in different areas of interest, conducted by research groups in Brazil and abroad. It also highlights the Brazilian market of herbal products and the efforts of Brazilian scientists to develop new phytomedicines. This review is divided into three sections. The section I describes the Brazilian large biodiversity and some attempts of Brazilian scientists to assess the pharmacological profile of most plant extracts or isolated active principles. Of note, Brazilian scientists have made a great effort to study the Brazilian biodiversity, especially among the higher plants. In fact, more than 10,000 papers were published on plants in international scientific journals between 2011 and 2013. This first part also discussed the main efforts to develop new medicines from plants, highlighting the Brazilian phytomedicines market. Despite the large Brazilian biodiversity, notably with the higher plants, which comprise over 45,000 species (20-22% of the total worldwide), and the substantial number of scientific publications on medicinal plants, only one phytomedicine is found in the top 20 market products. Indeed, this market is still only worth about 261 million American dollars. This represents less than 5% of the global Brazilian medicine market. The section II of this review focus on the use of Brazilian plant extract and/or active principles for some selected diseases, namely: central nervous systems disorders, pain, immune response and inflammation, respiratory diseases, gastrointestinal tract and metabolic diseases. Finally, section III discusses in more details some selected Brazilian medicinal plants including: Cordia verbenacea, Euphorbia tirucalli, Mandevilla velutina, Phyllanthus spp., Euterpe oleracea, Vitis labrusca, Hypericum caprifoliatum and Hypericum polyanthemum, Maytenus ilicifolia, Protium kleinii and Protium heptaphylium and Trichilia catigua. Most

  11. 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.

  12. 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

  13. Temperature dependence of the kinetic isotope effects in thymidylate synthase. A theoretical study.

    PubMed

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

    2011-05-04

    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 behavior, in agreement with experimental findings. The calculations show that the H-transfer proceeds with ∼91% by tunneling in the case of protium and ∼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 Escherichia 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

  14. Measurement of low picomolar levels of triamcinolone acetonide in human bronchoalveolar lavage fluid by gas chromatography-electron-capture negative-ion mass spectrometry.

    PubMed

    Hubbard, W C; Liu, M C; Bickel, C; Argenti, D; Heald, D; Schleimer, R P

    2001-03-01

    The intense inherent electron-capture properties of the C21 acetate derivative of triamcinolone acetonide (TAA) under methane chemical ionization mass spectrometric conditions were exploited for the development of a highly sensitive and selective gas chromatography-mass spectrometric (GC-MS) technique for measurement of levels of TAA in human bronchoalveolar lavage (BAL) fluid. After the addition of 3.0 ng of a heptadeuterated analog of TAA and varying concentrations of TAA to 2-ml aliquots of BAL fluid, the deuterium and protium forms of the steroid were extracted with diethyl ether, converted to the C21 acetate derivative, and purified via adsorptive chromatography prior to GC-MS analysis. Standard curves obtained from 2-ml aliquots of BAL fluid were linear over a wide range of concentrations of TAA from 0.0 to 24,600 pg/2-ml aliquots of BAL fluid. Levels as low as 6.0 pg/ml (13.8 pmol x L(-1)) in BAL fluid can be reliably determined in 2-ml aliquots of the biological fluid with <10% error. These findings suggest that the assay method exploiting the intense electron-capture properties of TAA is highly suitable for determination of the deposition pattern and in vivo kinetics of TAA in human airways following inhalation of the steroid.

  15. 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.

  16. Benchmarking Quantum Mechanics/Molecular Mechanics (QM/MM) Methods on the Thymidylate Synthase-Catalyzed Hydride Transfer.

    PubMed

    Świderek, Katarzyna; Arafet, Kemel; Kohen, Amnon; Moliner, Vicent

    2017-03-14

    Given the ubiquity of hydride-transfer reactions in enzyme-catalyzed processes, identifying the appropriate computational method for evaluating such biological reactions is crucial to perform theoretical studies of these processes. In this paper, the hydride-transfer step catalyzed by thymidylate synthase (TSase) is studied by examining hybrid quantum mechanics/molecular mechanics (QM/MM) potentials via multiple semiempirical methods and the M06-2X hybrid density functional. Calculations of protium and tritium transfer in these reactions across a range of temperatures allowed calculation of the temperature dependence of kinetic isotope effects (KIE). Dynamics and quantum-tunneling effects are revealed to have little effect on the reaction rate, but are significant in determining the KIEs and their temperature dependence. A good agreement with experiments is found, especially when computed for RM1/MM simulations. The small temperature dependence of quantum tunneling corrections and the quasiclassical contribution term cancel each other, while the recrossing transmission coefficient seems to be temperature-independent over the interval of 5-40 °C.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. Solvent isotope effects on alkane formation by cyanobacterial aldehyde deformylating oxygenase and their mechanistic implications.

    PubMed

    Waugh, Matthew W; Marsh, E Neil G

    2014-09-02

    The reaction catalyzed by cyanobacterial aldehyde deformylating oxygenase is of interest both because of its potential application to the production of biofuels and because of the highly unusual nature of the deformylation reaction it catalyzes. Whereas the proton in the product alkane derives ultimately from the solvent, the identity of the proton donor in the active site remains unclear. To investigate the proton transfer step, solvent isotope effect (SIE) studies were undertaken. The rate of alkane formation was found to be maximal at pH 6.8 and to be the same in D2O or H2O within experimental error, implying that proton transfer is not a kinetically significant step. However, when the ratio of protium to deuterium in the product alkane was measured as a function of the mole fraction of D2O, a (D2O)SIEobs of 2.19 ± 0.02 was observed. The SIE was invariant with the mole fraction of D2O, indicating the involvement of a single protic site in the reaction. We interpret this SIE as most likely arising from a reactant state equilibrium isotope effect on a proton donor with an inverse fractionation factor, for which Φ = 0.45. These observations are consistent with an iron-bound water molecule being the proton donor to the alkane in the reaction.

  2. Periodicity in the isotope chemistry of hydrogen

    PubMed Central

    Bigeleisen, Jacob

    1981-01-01

    Periodicities and regularities are established among the deuterium to protium isotopic reduced partition function ratios, ln(s/s′)f, of 39 diatomic and 19 polyatomic hydrides. It is shown that ln(s/s′)f for diatomic hydrides can be correlated with the position in the periodic table of the element X in the hydride HX. A similar analysis is made for the contributions from X—H stretching motion in the polyatomic hydrides HnX. It is shown that the contributions from stretching motions to ln(s/s′)f in diatomic and polyatomic molecules are a linear function of the square root of the stretching force constants. The contributions from bending coordinates to ln(s/s′)f depend on both the molecular structure of the hydride and the bending force constant. Simple correlations are established for the bending contributions to ln(s/s′)f for the hydrides of the elements belonging to a common group in the periodic table. Four periodic rules of the isotope chemistry of hydrogen summarize and classify the data on the isotopic partition function ratios and the isotopic differences in free energies of formation of hydrides. PMID:16593077

  3. Hydrogen Isotope Exchange Properties of Porous Solids Containing Hydrogen

    SciTech Connect

    HEUNG, LEUNGK.

    2004-08-18

    Porous solids such as activated alumina, silica and molecular sieves generally contain significant amounts of hydrogen atoms in the form of H2O or OH even at high temperature and low humidity environment. A significant amount of this hydrogen is available for reversible isotopic exchange. This exchange reaction is slow under normal conditions and does not render itself to practical applications. But if the exchange kinetics is improved this reaction has the potential to be used for tritium removal from gas streams or for hydrogen isotopic separation.The use of catalysts to improve the exchange kinetics between hydrogen isotope in the gas phase and that in the solid phase was investigated. Granules of alumina, silica and molecular sieve were coated with platinum or palladium as the catalyst. The granules were packed in a 2-cm diameter column for isotope exchange tests. Gas streams containing different concentrations of deuterium in nitrogen or argon were fed through the protium saturated column. Isotope concentration in column effluent was monitored to generate isotope break-through curves. The curves were analyzed to produce information on the kinetics and capacity of the material. The results showed that all materials tested provided some extent of isotope exchange but some were superior both in kinetics and capacity. This paper will present the test results.

  4. Antiprotozoal activities of Colombian plants.

    PubMed

    Weniger, B; Robledo, S; Arango, G J; Deharo, E; Aragón, R; Muñoz, V; Callapa, J; Lobstein, A; Anton, R

    2001-12-01

    In our search for therapeutical alternatives for antiprotozoal chemotherapy, we collected a selection of 44 plants from western Colombia upon ethnopharmacological and chemotaxonomic considerations. Polar and apolar extracts of these species were examined for antimalarial activity using in vitro tests with two clones of Plasmodium falciparum. Leishmanicidal and trypanocidal activity were determined in vitro using promastigote and amastigote forms of several strains of Leishmania sp. and epimastigotes of Trypanosoma cruzi. Among the selected plants, the 15 following species showed good or very good antiprotozoal activity in vitro: Aspidosperma megalocarpon, Campnosperma panamense, Conobea scoparioides, Guarea polymera, Guarea guidonia, Guatteria amplifolia, Huberodendron patinoi, Hygrophila guianensis, Jacaranda caucana, Marila laxiflora, Otoba novogranatensis, Otoba parviflora, Protium amplium, Swinglea glutinosa and Tabernaemontana obliqua. Cytotoxicity was assessed in U-937 cells and the ratio of cytotoxicity to antiprotozoal activity was determined for the active extracts. Ten extracts from eight species showed selectivity indexes > or = 10. Among the extracts that showed leishmanicidal activity, the methylene chloride extract of leaves from C. scoparioides showed a selectivity index in the same range that the one of the Glucantime control. Several of the active leishmanicidal plants are traditionally used against leishmaniasis by the population of the concerned area.

  5. 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.

  6. The contribution of edaphic heterogeneity to the evolution and diversity of Burseraceae trees in the western Amazon.

    PubMed

    Fine, Paul V A; Daly, Douglas C; Villa Muñoz, Gorky; Mesones, Italo; Cameron, Kenneth M

    2005-07-01

    Environmental heterogeneity in the tropics is thought to lead to specialization in plants and thereby contribute to the diversity of the tropical flora. We examine this idea with data on the habitat specificity of 35 western Amazonian species from the genera Protium, Crepidospermum, and Tetragastris in the monophyletic tribe Protieae (Burseraceae) mapped on a molecular-based phylogeny. We surveyed three edaphic habitats that occur throughout terra firme Amazonia: white-sand, clay, and terrace soils in eight forests across more than 2000 km in the western Amazon. Twenty-six of the 35 species were found to be associated with only one of three soil types, and no species was associated with all three habitats; this pattern of edaphic specialization was consistent across the entire region. Habitat association mapped onto the phylogenetic tree shows association with terrace soils to be the probable ancestral state in the group, with subsequent speciation events onto clay and white-sand soils. The repeated gain of clay association within the clade likely coincides with the emergence of large areas of clay soils in the Miocene deposited during the Andean uplift. Character optimizations revealed that soil association was not phylogenetically clustered for white-sand and clay specialists, suggesting repeated independent evolution of soil specificity is common within the Protieae. This phylogenetic analysis also showed that multiple cases of putative sister taxa with parapatric distributions differ in their edaphic associations, suggesting that edaphic heterogeneity was an important driver of speciation in the Protieae in the Amazon basin.

  7. A review of proton transfer reactions between various carbon-acids and amine bases in aprotic solvents

    NASA Astrophysics Data System (ADS)

    Jarczewski, Arnold; Hubbard, Colin D.

    2003-04-01

    The subject of proton transfer between carbon acids and nitrogen bases in aprotic solvents is reviewed. Equilibrium and rate constants that characterize such reactions are most often determined utilizing UV-visible spectrophotometry. At ambient temperature reaction rates are sufficiently rapid that fast reaction methods, for example, the stopped-flow and temperature-jump techniques are required in many cases. Variation of the properties of the donor and acceptor reaction pairs enables electronic and steric effects upon thermodynamic and kinetic parameters of proton transfer to be assessed. Determination of the kinetic isotope effect (KIE), i.e. k(protium)/ k(deuterium) led to the conclusion that, under certain circumstances and when the KIE is greater than seven, the proton undergoes reaction with a significant degree of quantum mechanical tunneling, consistent with a theoretical prediction advanced several decades earlier. In fact this aspect may be one of the most significant outgrowths of these studies. Many reactions have been characterized (by tunneling) but rarely are the reacting systems experimentally amenable to obtaining all the experimental criteria that support tunneling. Controversy that has arisen regarding treatment of experimental data and resulting conclusions from them is visited in this review. The structural nature of the product state of reaction is formulated based on spectroscopic evidence, in favorable cases, and probable structures of the transition state can be inferred.

  8. 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.

  9. Unusually large deuterium discrimination during spore photoproduct formation.

    PubMed

    Ames, David M; Lin, Gengjie; Jian, Yajun; Cadet, Jean; Li, Lei

    2014-06-06

    The deuterium-labeling strategy has been widely used and proved highly effective in mechanistic investigation of chemical and biochemical reactions. However, it is often hampered by the incomplete label transfer, which subsequently obscures the mechanistic conclusion. During the study of photoinduced generation of 5-thyminyl-5,6-dihydrothymine, which is commonly called the spore photoproduct (SP), the Cadet laboratory found an incomplete (~67%) deuterium transfer in SP formation, which contrasts to the exclusive transfer observed by the Li laboratory. Here, we investigated this discrepancy by re-examining the SP formation using d3-thymidine. We spiked the d3-thymidine with varying amounts of unlabeled thymidine before the SP photochemistry is performed. Strikingly, our data show that the reaction is highly sensitive to the trace protiated thymidine in the starting material. As many as 17-fold enrichment is detected in the formed SP, which may explain the previously observed one-third protium incorporation. Although commercially available deuterated reagents are generally satisfactory as mechanistic probes, our results argue that attention is still needed to the possible interference from the trace protiated impurity, especially when the reaction yield is low and large isotopic discrimination is involved.

  10. Unusually Large Deuterium Discrimination during Spore Photoproduct Formation

    PubMed Central

    2015-01-01

    The deuterium-labeling strategy has been widely used and proved highly effective in mechanistic investigation of chemical and biochemical reactions. However, it is often hampered by the incomplete label transfer, which subsequently obscures the mechanistic conclusion. During the study of photoinduced generation of 5-thyminyl-5,6-dihydrothymine, which is commonly called the spore photoproduct (SP), the Cadet laboratory found an incomplete (∼67%) deuterium transfer in SP formation, which contrasts to the exclusive transfer observed by the Li laboratory. Here, we investigated this discrepancy by re-examining the SP formation using d3-thymidine. We spiked the d3-thymidine with varying amounts of unlabeled thymidine before the SP photochemistry is performed. Strikingly, our data show that the reaction is highly sensitive to the trace protiated thymidine in the starting material. As many as 17-fold enrichment is detected in the formed SP, which may explain the previously observed one-third protium incorporation. Although commercially available deuterated reagents are generally satisfactory as mechanistic probes, our results argue that attention is still needed to the possible interference from the trace protiated impurity, especially when the reaction yield is low and large isotopic discrimination is involved. PMID:24820206

  11. Phase transition temperatures of 405-725 K in superfluid ultra-dense hydrogen clusters on metal surfaces

    NASA Astrophysics Data System (ADS)

    Holmlid, Leif; Kotzias, Bernhard

    2016-04-01

    Ultra-dense hydrogen H(0) with its typical H-H bond distance of 2.3 pm is superfluid at room temperature as expected for quantum fluids. It also shows a Meissner effect at room temperature, which indicates that a transition point to a non-superfluid state should exist above room temperature. This transition point is given by a disappearance of the superfluid long-chain clusters H2N(0). This transition point is now measured for several metal carrier surfaces at 405 - 725 K, using both ultra-dense protium p(0) and deuterium D(0). Clusters of ordinary Rydberg matter H(l) as well as small symmetric clusters H4(0) and H3(0) (which do not give a superfluid or superconductive phase) all still exist on the surface at high temperature. This shows directly that desorption or diffusion processes do not remove the long superfluid H2N(0) clusters. The two ultra-dense forms p(0) and D(0) have different transition temperatures under otherwise identical conditions. The transition point for p(0) is higher in temperature, which is unexpected.

  12. Nuclear particle decay in a multi-MeV beam ejected by pulsed-laser impact on ultra-dense hydrogen H(0)

    NASA Astrophysics Data System (ADS)

    Holmlid, Leif

    2015-10-01

    The multi-MeV particles ejected from pulsed laser-induced processes in ultra-dense hydrogen H(0) are observed in vacuum at three different distances up to 2m from the laser target. In previous publications, massive neutral particles with energy of 1-30MeVu-1 were identified. Direct energy spectra of the particles show energies well above 1MeV. The particles studied here interact with metallic collectors and give signals due to several processes like secondary electron emission and lepton pair production (published). Two experimental facts are immediate: (1) the signal per sr at large distance is up to 10 times higher than at short distance, (2) the signal at large distance is faster in real time than at short distance. These results show directly that the signal at long distance is mainly due to a mixture of intermediate particles formed by decay in the beam. The decaying signals have time constants of approximately 12 and 26ns for ultra-dense deuterium D(0) and 52 ns for ultra-dense protium p(0). These decay time constants agree well with those for decay of light mesons. These particles with narrow MeV energy distributions are formed by stepwise decay from particles like HN(0). The main result is that a decaying particle flux is formed by the laser-induced processes. The final muons produced may be useful for muon catalyzed fusion.

  13. Comparison of classical reaction paths and tunneling paths studied with the semiclassical instanton theory.

    PubMed

    Meisner, Jan; Markmeyer, Max N; Bohner, Matthias U; Kästner, Johannes

    2017-08-30

    Atom tunneling in the hydrogen atom transfer reaction of the 2,4,6-tri-tert-butylphenyl radical to 3,5-di-tert-butylneophyl, which has a short but strongly curved reaction path, was investigated using instanton theory. We found the tunneling path to deviate qualitatively from the classical intrinsic reaction coordinate, the steepest-descent path in mass-weighted Cartesian coordinates. To perform that comparison, we implemented a new variant of the predictor-corrector algorithm for the calculation of the intrinsic reaction coordinate. We used the reaction force analysis method as a means to decompose the reaction barrier into structural and electronic components. Due to the narrow energy barrier, atom tunneling is important in the abovementioned reaction, even above room temperature. Our calculated rate constants between 350 K and 100 K agree well with experimental values. We found a H/D kinetic isotope effect of almost 10(6) at 100 K. Tunneling dominates the protium transfer below 400 K and the deuterium transfer below 300 K. We compared the lengths of the tunneling path and the classical path for the hydrogen atom transfer in the reaction HCl + Cl and quantified the corner cutting in this reaction. At low temperature, the tunneling path is about 40% shorter than the classical path.

  14. 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.

  15. The requirements for processing tritium recovered from liquid lithium blankets: The blanket interface

    SciTech Connect

    Clemmer, R.G.; Finn, P.A.; Greenwood, L.R.; Grimm, T.L.; Sze, D.K.; Bartlit, J.R.; Anderson, J.L.; Yoshida, H.; Naruse

    1988-03-01

    We have initiated a study to define a blanket processing mockup for Tritium Systems Test Assembly. Initial evaluation of the requirements of the blanket processing system have been started. The first step of the work is to define the condition of the gaseous tritium stream from the blanket tritium recovery system. This report summarizes this part of the work for one particular blanket concept, i.e., a self-cooled lithium blanket. The total gas throughput, the hydrogen to tritium ratio, the corrosive chemicals, and the radionuclides are defined. The key discoveries are: the throughput of the blanket gas stream (including the helium carrier gas) is about two orders of magnitude higher than the plasma exhaust stream;the protium to tritium ratio is about 1, the deuterium to tritium ratio is about 0.003;the corrosion chemicals are dominated by halides;the radionuclides are dominated by C-14, P-32, and S-35;their is high level of nitrogen contamination in the blanket stream. 77 refs., 6 figs., 13 tabs.

  16. FT-IR and 1H NMR studies of the state of solubilized water in water-in-oil microemulsions stabilized by mixtures of single- and double-tailed cationic surfactants.

    PubMed

    Bumajdad, Ali; Madkour, Metwally; Shaaban, Ehab; El Seoud, Omar A

    2013-03-01

    The structure of solubilized water in water-in-n-heptane aggregates stabilized by mixtures of single- and double-tail quaternary ammonium surfactants, namely didodecyldimethylammonium chloride/dodecyltrimethylammonium chloride (DDAC/DTAC) or didodecyldimethylammonium bromide/dodecyltrimethylammonium bromide (DDAB/DTAB) was studied by two noninvasive techniques, (1)H NMR and FT-IR. In the former, the chemical shift data, δ(obs), were used to calculate the so-called deuterium/protium fractionation factor, φ(M), of the aggregate-solubilized water and were found to be unity. In the FT-IR study, upon increasing water/surfactant molar ratio, W, the frequency, ν(OD), of the HOD species decreases, while its full width at half height and its area increase. The results obtained from both techniques indicate that the water appears to be present as a single nano-phase and the structure varies continuously as a result of increasing W. In addition, the effect of changing the counter-ion (Br(-) or Cl(-)) on (1)H NMR and FT-IR results was investigated. In spite of the known difference in the dissociation of these counter-ions from micellar aggregates, this was found not to affect the state of solubilized water. This report gives further insight into the contradictory scientific debates on the structure of water in the polar nano-cores of microemulsions.

  17. Phase transition temperatures of 405-725 K in superfluid ultra-dense hydrogen clusters on metal surfaces

    SciTech Connect

    Holmlid, Leif; Kotzias, Bernhard

    2016-04-15

    Ultra-dense hydrogen H(0) with its typical H-H bond distance of 2.3 pm is superfluid at room temperature as expected for quantum fluids. It also shows a Meissner effect at room temperature, which indicates that a transition point to a non-superfluid state should exist above room temperature. This transition point is given by a disappearance of the superfluid long-chain clusters H{sub 2N}(0). This transition point is now measured for several metal carrier surfaces at 405 - 725 K, using both ultra-dense protium p(0) and deuterium D(0). Clusters of ordinary Rydberg matter H(l) as well as small symmetric clusters H{sub 4}(0) and H{sub 3}(0) (which do not give a superfluid or superconductive phase) all still exist on the surface at high temperature. This shows directly that desorption or diffusion processes do not remove the long superfluid H{sub 2N}(0) clusters. The two ultra-dense forms p(0) and D(0) have different transition temperatures under otherwise identical conditions. The transition point for p(0) is higher in temperature, which is unexpected.

  18. 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.

  19. Design concept of cryogenic falling liquid film helium separator

    SciTech Connect

    Kinoshita, M.; Yamanishi, T.; Bartlit, J.R.; Sherman, R.H.

    1986-07-01

    A design concept is developed for a cryogenic falling liquid film helium separator by clarifying the differences between this process and a cryogenic distillation column. The process characteristics are greatly improved by the idea of adding an H/sub 2/ gas flow to a point near the upper end of the packed section. The flow rate of tritium lost from the top is kept extremely low with an adequately short packed section, and the column pressure is reduced to 1 atm. The addition causes no appreciable increase in the protium percentage (approx. =1%) in the bottom liquid flow. A design procedure applying the Colburn-Hougen method is proposed for determining specifications of the refrigerated section. It is shown that the presence of noncondensible helium requires a significantly larger heat transfer area mainly because the mass transfer resistance increases enormously as the condensation of hydrogen isotopes proceeds. Control schemes are also proposed: The tritium concentration in the top gas is controlled by the H/sub 2/ gas flow rate. The pressure rise caused by an increase of the helium percentage within the refrigerated section, which cannot readily be eliminated by changing input specifications of the refrigerant gas, is avoided by increasing the top gas flow rate to release more helium from the top.

  20. 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

  1. Chemical and hydrogen isotope evidence for in situ dehydrogenation of biotite in silicic magma chambers

    NASA Astrophysics Data System (ADS)

    Feeley, T. C.; Sharp, Z. D.

    1996-11-01

    To examine the potential for volatile fluxing of magma chambers by in situ degassing of hydrous minerals, we obtained complete chemical analyses for biotite separates from silicic lavas. The separates exhibit unusually low H2O contents that inversely correlate with host lava temperatures, high Fe3+/Fe2+ ratios that inversely correlate with host lava oxygen fugacities, and the highest δ D values yet reported for biotite from any silicic igneous rock (up to -19‰). These results are direct evidence for selective loss of protium (1H) from biotite during dehydrogenation in magma chambers heated from below by intrusion of mafic magma. The maximum PΔV energy generated from dehydrogenation alone can approach 2 × 103 joules per kilogram of magma. This finding provides support for the concept that injection of mafic magma coupled with sudden degassing of hydrous minerals in a volatile-rich magma chamber can increase pressure, and thus enhance the possibility of initiating a volcanic eruption.

  2. Irradiation effects and hydrogen behavior in H2+ and He+ implanted γ-LiAlO2 single crystals

    NASA Astrophysics Data System (ADS)

    Jiang, Weilin; Zhang, Jiandong; Kovarik, Libor; Zhu, Zihua; Price, Lloyd; Gigax, Jonathan; Castanon, Elizabeth; Wang, Xuemei; Shao, Lin; Senor, David J.

    2017-02-01

    Gamma-phase lithium aluminate (γ-LiAlO2) is a breeder material for tritium, a necessary substance for strategic stockpile and fusion power systems. A fundamental study of structural evolution and tritium diffusion in γ-LiAlO2 under displacive irradiation is needed to fully assess the material performance. This study utilizes ion implantation of protium (surrogate for tritium) and helium in γ-LiAlO2 single crystals at elevated temperatures to emulate the irradiation effects. The results show that at 573 K there are two distinct disorder saturation stages to 1 dpa without full amorphization; overlapping implantation of H2+ and He+ ions suggests possible formation of gas bubbles. For irradiation to 1021 H+/m2 (0.36 dpa at peak) at 773 K, amorphization occurs at surface with H diffusion and dramatic Li loss; the microstructure contains bubbles and cubic LiAl5O8 precipitates with sizes up to 200 nm or larger. In addition, significant H diffusion and release are observed during thermal annealing.

  3. 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.

  4. 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.

  5. 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.

  6. Wood litter consumption by three species of Nasutitermes termites in an area of the Atlantic Coastal Forest in northeastern Brazil.

    PubMed

    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/m(2). 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.

  7. 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

  8. 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

  9. 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.

  10. Near Infrared Spectroscopy Facilitates Rapid Identification of Both Young and Mature Amazonian Tree Species

    PubMed Central

    Lang, Carla; Costa, Flávia Regina Capellotto; Camargo, José Luís Campana; Durgante, Flávia Machado; Vicentini, Alberto

    2015-01-01

    Precise identification of plant species requires a high level of knowledge by taxonomists and presence of reproductive material. This represents a major limitation for those working with seedlings and juveniles, which differ morphologically from adults and do not bear reproductive structures. Near-infrared spectroscopy (FT-NIR) has previously been shown to be effective in species discrimination of adult plants, so if young and adults have a similar spectral signature, discriminant functions based on FT-NIR spectra of adults can be used to identify leaves from young plants. We tested this with a sample of 419 plants in 13 Amazonian species from the genera Protium and Crepidospermum (Burseraceae). We obtained 12 spectral readings per plant, from adaxial and abaxial surfaces of dried leaves, and compared the rate of correct predictions of species with discriminant functions for different combinations of readings. We showed that the best models for predicting species in early developmental stages are those containing spectral data from both young and adult plants (98% correct predictions of external samples), but even using only adult spectra it is still possible to attain good levels of identification of young. We obtained an average of 75% correct identifications of young plants by discriminant equations based only on adults, when the most informative wavelengths were selected. Most species were accurately predicted (75–100% correct identifications), and only three had poor predictions (27–60%). These results were obtained despite the fact that spectra of young individuals were distinct from those of adults when species were analyzed individually. We concluded that FT-NIR has a high potential in the identification of species even at different ontogenetic stages, and that young plants can be identified based on spectra of adults with reasonable confidence. PMID:26312996

  11. 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

  12. 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.

  13. Mechanism of the reaction catalyzed by mandelate racemase. 1. Chemical and kinetic evidence for a two-base mechanism

    SciTech Connect

    Powers, V.M.; Koo, C.W.; Kenyon, G.L. ); Gerlt, J.A.; Kozarich, J.W. )

    1991-09-24

    The fate of the {alpha}-hydrogen of mandelate in the reaction catalyzed by mandelate racemase has been investigated by a mass spectroscopic method. The method entails the incubation of (R)- or (S)-({alpha}-{sup 1}H) mandelate in buffered D{sub 2}O to a low extent of turnover (about 5-8%), esterification of the resulting mixture of mandelates with diazomethane, derivatization of the methyl esters with a chiral derivatizing agent, and quantitation of the isotope content of the {alpha}-hydrogen of both substrate and product by gas chromatography/mass spectrometric analysis. No significant substrate-derived {alpha}-protium was found in the product for racemization in either direction. In addition, in the (R) to (S) direction almost no exchange of the {alpha}-hydrogen in the remaining (R) substrate pool occurred, but in the (S) to (R) direction 3.5-5.1% exchange of the {alpha}-hydrogen in the remaining substrate (after 5.1-7.2% net turnover) was found. Qualitatively similar results were obtained in the (S) to (R) direction in H{sub 2}O when (S)-({alpha}-{sup 2}H)mandelate was used as substrate. In other experiments, an overshoot in the progress curve was observed when the racemization of either enantiomer of ({alpha}-{sup 1}H) mandelate in D{sub 2}O was monitored by following the change in ellipticity of the reaction mixture; the magnitude of the overshoot was greater in the (R) to (S) than in the (S) to (R) direction. All of the available data indicate that the reaction catalyzed by mandelate racemase proceeds by a two-base mechanism, in contrast to earlier proposals.

  14. Feeding ecology of Saguinus bicolor bicolor (Callitrichidae: Primates) in a relict forest in Manaus, Brazilian Amazonia.

    PubMed

    Egler, S G

    1992-01-01

    This study is part of a long-term ecological study of habitat and dietary requirements of the pied bare-face tamarin (Saguinus bicolor bicolor). One group was studied for 11 months in an area of secondary forest in a suburb of Manaus, Amazonas, Brazil. Three main vegetation types occurred inside the group's home range (12 ha): capoeira, older secondary forest and campinarana (white sand forest). The tamarins ate fruits (21 species), flowers (1 species), exudates (4 species), and arthropods (insects and spiders). They spent 14.3% of total activity time seeking and eating animal prey, and 9.9% feeding on plant material, mostly fruits. In general, fruits consumed were ripe, small and succulent. Trees used for feeding were low and had small crown diameters. Three plant species (Protium aracouchinni, Myrcia cf. fallax, and Couma utilis) were used intensively during the three seasons covered by the study period. The concentrated use of 3 fruit species, each for an extended period (one fruiting species per season), provided the tamarins with a regular food supply. Tamarins consumed exudates from holes in the bark of trees of the families Anacardiaceae and Vochysiaceae, as well as gum exuded from seed pods of Mimosaceae. Exudates were exploited during the dry season and at the beginning of the wet season. Group travel was primarily based on routes connecting the fruiting trees exploited, with foraging for animal prey occurring during travel. Tamarins searched for arthropods on trunks, branches and leaves and in trunk holes. The foraging and feeding tactics displayed by S. b. bicolor are closely linked to morphological characteristics (small size and weight, claw-like nails) that allowed access to energy-rich resources (arthropods and plant exudates) in different strata of the vegetation.

  15. 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.

  16. Tritium Accountancy Issues of the ITER Fuel Cycle

    SciTech Connect

    Laesser, R.; Murdoch, D.K.; Glugla, M.

    2005-07-15

    Unexpectedly large tritium amounts were trapped in the Plasma Facing Components of JET and TFTR during the respective tritium campaigns. Newly created co-deposited layers of carbon and hydrogen were identified as the main sinks. The first wall of ITER in contrast to JET and TFTR will be covered with beryllium, whereas the divertor tiles will be built of tungsten with the exception of a relatively small area of carbon fibre composites. Due to these three materials the composition of the newly created layers will change as a function of plasma operation. Their possible hydrogen content is not known yet and as a consequence the estimates of potentially trapped tritium differ strongly. To respect safety limits measurements of the mobilisable tritium inventories inside the vacuum vessel are required. The present strategy is to rely on the accountancy of the accessible tritium inside the fuel cycle and to derive the quantity of tritium trapped inside the vessel by difference. The tritium injected into the machine is only measured by mass flow meters and no effort is made to determine the tritium exhausted.Enhancements to determine the tritium and deuterium amounts injected into the torus and first proposals for enabling accountancy of the tritium and deuterium released from the torus cryo-pumps on a shot-by-shot basis are given. Only few additional buffer volumes and a micro gas chromatograph are required as the solutions are simple and inexpensive. These tools could be used already in the H-phase of ITER to obtain an integral value of the hydrogen trapped in the co-deposited layers by simple addition of small concentrations of deuterium to the protium and measuring the injected and released deuterium amounts.

  17. Plant Ontogeny, Spatial Distance, and Soil Type Influence Patterns of Relatedness in a Common Amazonian Tree

    PubMed Central

    Barbosa, Carlos Eduardo A.; Misiewicz, Tracy M.; Fine, Paul V. A.; Costa, Flávia R. C.

    2013-01-01

    The formation of spatial genetic structure (SGS) may originate from different patterns of seed deposition in the landscape, and is mostly determined by seed dispersal limitation. After dispersal, mechanisms such as filtering by environmental factors or attack by herbivores/pathogens throughout plant development stages, and potentially either disrupt or intensify SGS patterns. We investigated how the genotype of Protium subserratum (Burseraceae), a common tree species in the Ducke Reserve, Brazil, is distributed across the landscape. We used seven microsatellite markers to assess the SGS among plants at different life stages and in different environments. By quantifying the patterns of relatedness among plants of different sizes, we inferred the ontogenetic stage in which SGS changes occurred, and compared these effects across soil types. Relatedness among seedlings decreased when distance between seedlings increased, especially for the youngest seedlings. However, this trend was not continued by older plants, as relatedness values were higher among neighboring individuals of the juvenile and adult size class. Contrasting relatedness patterns between seedlings and larger individuals suggests a trade-off between the negative effects of being near closely-related adults (e.g. due to herbivore and pathogen attack) and the advantage of being in a site favorable to establishment. We also found that soil texture strongly influenced density-dependence patterns, as young seedlings in clay soils were more related to each other than were seedlings in bottomland sandy soils, suggesting that the mechanisms that create and maintain patterns of SGS within a population may interact with environmental heterogeneity. PMID:23667502

  18. Deuterium content of water increases depression susceptibility: the potential role of a serotonin-related mechanism.

    PubMed

    Strekalova, Tatyana; Evans, Matthew; Chernopiatko, Anton; Couch, Yvonne; Costa-Nunes, João; Cespuglio, Raymond; Chesson, Lesley; Vignisse, Julie; Steinbusch, Harry W; Anthony, Daniel C; Pomytkin, Igor; Lesch, Klaus-Peter

    2015-01-15

    Environmental factors can significantly affect disease prevalence, including neuropsychiatric disorders such as depression. The ratio of deuterium to protium in water shows substantial geographical variation, which could affect disease susceptibility. Thus the link between deuterium content of water and depression was investigated, both epidemiologically, and in a mouse model of chronic mild stress. We performed a correlation analysis between deuterium content of tap water and rates of depression in regions of the USA. Next, we used a 10-day chronic stress paradigm to test whether 2-week deuterium-depleted water treatment (91 ppm) affects depressive-like behavior and hippocampal SERT. The effect of deuterium-depletion on sleep electrophysiology was also evaluated in naïve mice. There was a geographic correlation between a content of deuterium and the prevalence of depression across the USA. In the chronic stress model, depressive-like features were reduced in mice fed with deuterium-depleted water, and SERT expression was decreased in mice treated with deuterium-treated water compared with regular water. Five days of predator stress also suppressed proliferation in the dentate gyrus; this effect was attenuated in mice fed with deuterium-depleted water. Finally, in naïve mice, deuterium-depleted water treatment increased EEG indices of wakefulness, and decreased duration of REM sleep, phenomena that have been shown to result from the administration of selective serotonin reuptake inhibitors (SSRI). Our data suggest that the deuterium content of water may influence the incidence of affective disorder-related pathophysiology and major depression, which might be mediated by the serotoninergic mechanisms.

  19. Chemical mechanism of the endogenous argininosuccinate lyase activity of duck lens delta2-crystallin.

    PubMed Central

    Wu, C Y; Lee, H J; Wu, S H; Chen, S T; Chiou, S H; Chang, G G

    1998-01-01

    The endogenous argininosuccinate lyase activity of duck delta2-crystallin was specifically inactivated by the histidine-specific reagent, diethyl pyrocarbonate. The protein was protected by l-citrulline or l-arginine from the diethyl pyrocarbonate inactivation. To characterize further the chemical mechanism of the delta2-crystallin-catalysed reaction, deuterium-labelled argininosuccinate was enzymically synthesized from fumarate and l-arginine with delta2-crystallin in 2H2O. The argininosuccinate synthesized contained about 19% of the anhydride form; however, the deuterium was clearly demonstrated to be incorporated enantioselectively. Only the pro-HR atom at C-9 of the succinate moiety was labelled in the [2H]argininosuccinate-9-d synthesized, which indicates an anti-elimination mechanism for the endogenous argininosuccinate lyase activity of delta2-crystallin. The enzymic activity of duck lens delta2-crystallin in the pH range 5.5-8.5 was investigated using both protium- and deuterium-labelled argininosuccinate as the substrate. From the logkcat versus pH plot, two molecular pKa values of 6.18+/-0.02 and 8.75+/-0.03 were detected in the delta2-crystallin-argininosuccinate binary complex. The former must be dehydronated and the latter hydronated to achieve an optimum reaction rate. The logkcat/Km versus pH plot suggested two molecular pKa values of 5.96+/-0.09 and 8.29+/-0.10 for the free delta2-crystallin to be involved in the substrate binding. Small kinetic isotope effects of 1.17+/-0.02 and 1.05+/-0.09 were found for kcat and kcat/Km respectively. Combining results from labelling and kinetic analysis indicates that the endogenous argininosuccinate lyase activity of duck delta2-crystallin is compatible with a stepwise E1cB mechanism, the rate-limiting step probably at the C-N bond-cleavage step. PMID:9657972

  20. 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.

  1. 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

  2. Exploratory study of coal-conversion chemistry. Quarterly report No. 3, November 19, 1981-February 18, 1982. [Dihydronaphthalene, 1,2'-dinaphthylmethane, methoxynaphthalene diphenyl ether

    SciTech Connect

    Ross, D.S.; McMillen, D.F.; Ogier, W.C.; Bunnell, R.; Hum, G.P.

    1982-03-01

    Work in Task A has provided additional data on the rate and mechanisms of radical-induced cleavage of strong C-C and C-0 bonds in coal structures. This work has shown that even resonance-stabilized radicals, which form relatively weak C-C bonds, can displace other resonance-stabilized radicals from methylene-bridged coal structures. Kinetic studies reveal that either the self-disproportionation of 1,2-dihydronaphthalene is much faster than previously reported or that the 1,2-dihydronaphthalene-tetralin disproportionation is much less important as a radical initiation process than thermochemical estimates had suggested. 1,2'-Dinaphthylmethane undergoes radical-induced CH/sub 2/-Ar bond scission ten times faster than diphenyl ether. This factor is shown to be consistent with the thermochemistry of displacement by tetralyl radical. In Task B we studied CO/H/sub 2/O conversion of a second, high volatile bituminous coal, PSOC-233. We found that, as with PSOC-026, the initial pH did affect the conversion rate, increasing with higher pH. We also conducted experiments with several oxygen-containing model compounds in CO/D/sub 2/O at 400/sup 0/C for 20 min. We had shown earlier in preliminary control experiments that simple aromatics, such as toluene, did not incorporate deuterium under these conditions. This quarter we found that anisole (Ph-O-CH/sub 3/) was converted to several products, with benzene as the most prominent. About 60% of the anisole was recovered in several experiments with mass balances at about 85%. There was a net incorporation of deuterium in the product benzene. The corresponding conversion in tetralin under the same conditions was two orders of magnitude slower and yielded phenol as the major product. We conclude that in the aqueous medium a chain process can occur that yields phenyl radical, which can then receive protium from a starting anisole or deuterium from the mineral medium.

  3. Hydraulic redistribution in three Amazonian trees.

    PubMed

    Oliveira, Rafael S; Dawson, Todd E; Burgess, Stephen S O; Nepstad, Daniel C

    2005-09-01

    About half of the Amazon rainforest is subject to seasonal droughts of 3 months or more. Despite this drought, several studies have shown that these forests, under a strongly seasonal climate, do not exhibit significant water stress during the dry season. In addition to deep soil water uptake, another contributing explanation for the absence of plant water stress during drought is the process of hydraulic redistribution; the nocturnal transfer of water by roots from moist to dry regions of the soil profile. Here, we present data on patterns of soil moisture and sap flow in roots of three dimorphic-rooted species in the Tapajós Forest, Amazônia, which demonstrate both upward (hydraulic lift) and downward hydraulic redistribution. We measured sap flow in lateral and tap roots of our three study species over a 2-year period using the heat ratio method, a sap-flow technique that allows bi-directional measurement of water flow. On certain nights during the dry season, reverse or acropetal flow (i.e.,in the direction of the soil) in the lateral roots and positive or basipetal sap flow (toward the plant) in the tap roots of Coussarea racemosa (caferana), Manilkara huberi (maçaranduba) and Protium robustum (breu) were observed, a pattern consistent with upward hydraulic redistribution (hydraulic lift). With the onset of heavy rains, this pattern reversed, with continuous night-time acropetal sap flow in the tap root and basipetal sap flow in lateral roots, indicating water movement from wet top soil to dry deeper soils (downward hydraulic redistribution). Both patterns were present in trees within a rainfall exclusion plot (Seca Floresta) and to a more limited extent in the control plot. Although hydraulic redistribution has traditionally been associated with arid or strongly seasonal environments, our findings now suggest that it is important in ameliorating water stress and improving rain infiltration in Amazonian rainforests. This has broad implications for

  4. 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%.

  5. Floristic composition and similarity of 15 hectares in Central Amazon, Brazil.

    PubMed

    da Silva, Kátia Emidio; Martins, Sebastião Venancio; Ribeiro, Carlos Antonio Alvares Soares; Santos, Nerilson Terra; de Azevedo, Celso Paulo; Matos, Francisca Dionizia de Almeida; do Amaral, Ieda Leão

    2011-12-01

    The Amazon region is one of the most diverse areas in the world. Research on high tropical forest diversity brings up relevant contributions to understand the mechanisms that result and support such diversity. In the present study we describe the species composition and diversity of 15 one-ha plots in the Amazonian terra firme dense forest in Brazil, and compare the floristic similarity of these plots with other nine one-ha plots. The 15 plots studied were randomly selected from permanent plots at the Embrapa Experimental site, Amazonas State in 2005. The diversity was analysed by using species richness and Shannon's index, and by applying the Sorensen's index for similarity and unweighted pair-group average (UPGMA) as clustering method. Mantel test was performed to study whether the differences in species composition between sites could be explained by the geographic distance between them. Overall, we identified 8 771 individuals, 264 species and 51 plant families. Most of the species were concentrated in few families and few had large number of individuals. Families presenting the highest species richness were Fabaceae (Faboideae: 22spp., Mimosoideae: 22spp.), Sapotaceae: 22spp., Lecythidaceae: 15 and Lauraceae: 13. Burseraceae had the largest number of individuals with 11.8% of the total. The ten most abundant species were: Protium hebetatum (1 037 individuals), Eschweilera coriacea (471), Licania oblongifolia (310), Pouteria minima (293), Ocotea cernua (258), Scleronema micranthum (197), Eschweilera collina (176), Licania apelata (172), Naucleopsis caloneura (170) and Psidium araca (152), which represented 36.5% of all individuals. Approximately 49% of species had up to ten individuals and 13% appeared only once in all sampled plots, showing a large occurrence of rare species. Our study area is on a forest presenting a high tree species diversity with Shannon's diversity index of 4.49. The dendrogram showed two groups of plots with low similarity between them

  6. [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

  7. In situ (1)H and (13)C MAS NMR kinetic study of the mechanism of H/D exchange for propane on zeolite H-ZSM-5.

    PubMed

    Arzumanov, Sergei S; Reshetnikov, Sergei I; Stepanov, Alexander G; Parmon, Valentin N; Freude, Dieter

    2005-10-27

    The kinetics of hydrogen (H/D) exchange between Brønsted acid sites of zeolite H-ZSM-5 and variously deuterated propanes (propane-d(8), propane-1,1,1,3,3,3-d(6), propane-2,2-d(2)) have been monitored in situ by (1)H MAS NMR spectroscopy within the temperature range of 503-556 K. The contribution of intramolecular hydrogen transfer to the H/D exchange in the adsorbed propane was estimated by monitoring the kinetics of (13)C-labeled carbon scrambling in propane-2-(13)C in situ with (13)C MAS NMR at 543-573 K. Possible mechanisms of the exchange have been verified on the basis of the analysis of the variation of protium concentration in both the methyl and the methylene groups of propane in dependence of the reaction time. The main route of the exchange consists of a direct exchange of the acidic OH groups of the zeolite with either the methyl groups or the methylene group presumably with a pentacoordinated carbonium ion intermediate. The assumption that the intramolecular H scrambling between the methyl groups and the methylene group of propane via carbenium-ion-type intermediates is the fastest process among the other possible routes does not account for the experimental kinetics of H/D exchange for propanes with different initial contents and locations of deuterium in a propane molecule. The rate constant (k(3)) for intramolecular H/D exchange between the methyl and the methylene groups is 4-5 times lower compared to those of the direct exchange of both the methyl (k(1)) and the methylene (k(2)) groups with Brønsted acid sites of the zeolite, the k(1) being ca. 1.5 times higher than k(2). At lower temperature (473 K), the exchange is slower, and the expected difference between k(1) and k(2) is more essential, k(1) = 3k(2). This accounts for earlier observed regioselectivity of the exchange for propane on H-ZSM-5 at 473 K. Faster direct exchange with the methyl groups compared to that with the methylene groups was attributed to a possible, more spatial

  8. 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

  9. 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

  10. Antinociceptive properties of mixture of alpha-amyrin and beta-amyrin triterpenes: evidence for participation of protein kinase C and protein kinase A pathways.

    PubMed

    Otuki, Michel F; Ferreira, Juliano; Lima, Fabiana V; Meyre-Silva, Cristiane; Malheiros, Angela; Muller, Luciane A; Cani, Graziela S; Santos, Adair R S; Yunes, Rosendo A; Calixto, João B

    2005-04-01

    The mixture of the two pentacyclic triterpenes alpha-amyrin and beta-amyrin, isolated from the resin of Protium kleinii and given by intraperitoneal (i.p.) or oral (p.o.) routes, caused dose-related and significant antinociception against the visceral pain in mice produced by i.p. injection of acetic acid. Moreover, i.p., p.o., intracerebroventricular (i.c.v.), or intrathecal (i.t.) administration of alpha,beta-amyrin inhibited both neurogenic and inflammatory phases of the overt nociception caused by intraplantar (i.pl.) injection of formalin. Likewise, alpha,beta-amyrin given by i.p., p.o., i.t., or i.c.v. routes inhibits the neurogenic nociception induced by capsaicin. Moreover, i.p. treatment with alpha,beta-amyrin was able to reduce the nociception produced by 8-bromo-cAMP (8-Br-cAMP) and by 12-O-tetradecanoylphorbol-13-acetate (TPA) or the hyperalgesia caused by glutamate. On the other hand, in contrast to morphine, alpha,beta-amyrin failed to cause analgesia in thermal models of pain. The antinociception caused by the mixture of compounds seems to involve mechanisms independent of opioid, alpha-adrenergic, serotoninergic, and nitrergic system mediation, since it was not affected by naloxone, prazosin, yohimbine, DL-p-chlorophenylalanine methyl ester, or L-arginine. Interestingly, the i.p. administration of alpha,beta-amyrin reduced the mechanical hyperalgesia produced by i.pl. injection of carrageenan, capsaicin, bradykinin, substance P, prostaglandin E2, 8-Br-cAMP, and TPA in rats. However, the mixture of compounds failed to alter the binding sites of [3H]bradykinin, [3H]resiniferatoxin, or [3H]glutamate in vitro. It is concluded that the mixture of triterpene alpha-amyrin and beta-amyrin produced consistent peripheral, spinal, and supraspinal antinociception in rodents, especially when assessed in inflammatory models of pain. The mechanisms involved in their action are not completely understood but seem to involve the inhibition of protein kinase A- and

  11. 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

  12. Groundwater quality for 75 domestic wells in Lycoming County, Pennsylvania, 2014

    USGS Publications Warehouse

    Gross, Eliza L.; Cravotta, Charles A.

    2017-03-06

    from 5.3 to 9.15 and did not meet the SMCL range of 6.5 to 8.5 in 22 samples, with 17 samples having a pH less than 6.5 and 8 samples having pH greater than 8.5. Generally, the samples that had elevated TDS, chloride, or arsenic concentrations had high pH.Total coliform bacteria were detected in 39 of 75 samples (52 percent), with Escherichia coli detected in 10 of those 39 samples. Radon-222 activities ranged from non-detect to 7,420 picocuries per liter (pCi/L), with a median of 863 pCi/L, and exceeded the proposed drinking-water standard of 300 pCi/L in 50 (67 percent) of the 75 samples; radon-222 activities were higher than the alternative proposed standard of 4,000 pCi/L in 3 samples.Water from 15 of 75 (20 percent) wells had concentrations of methane greater than the reporting level of 0.01 mg/L; detectable methane concentrations ranged from 0.04 to 16.8 mg/L. Two samples had methane concentrations (13.1 and 16.8 mg/L) exceeding the action level of 7 mg/L. Low levels of ethane (up to 0.12 mg/L) were present in the five samples with the highest methane concentrations (near or above 1 mg/L) that were analyzed for hydrocarbon compounds and isotopic composition. The isotopic composition of methane in four of these groundwater samples, from the Catskill and Lock Haven Formations and the Hamilton Group, have sample carbon isotopic ratio delta values (carbon-13/carbon-12) ranging from –42.36 to –36.08 parts per thousand (‰) and hydrogen isotopic ratio delta values (deuterium/protium) ranging from –212.0 to –188.4 ‰, which are consistent with the isotopic compositions reported for mud-gas logging samples from these geologic units and a thermogenic source of the methane. However, the isotopic composition and ratios of methane to ethane in a fifth sample indicate the methane in that sample may be of microbial origin that subsequently underwent oxidation. The fifth sample had the highest concentration of methane, 16.8 mg/L, with an carbon isotopic ratio delta