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Sample records for deuterium isotope effect

  1. Equilibrium deuterium isotope effect of surprising magnitude

    International Nuclear Information System (INIS)

    Goldstein, M.J.; Pressman, E.J.

    1981-01-01

    Seemingly large deuterium isotope effects are reported for the preference of deuterium for the α-chloro site to the bridgehead or to the vinyl site in samples of anti-7-chlorobicyclo[4.3.2]undecatetraene-d 1 . Studies of molecular models did not provide a basis for these large equilibrium deuterium isotope effects. The possibility is proposed that these isotope effects only appear to be large for want of comparison with isotope effects measured for molecules that might provide even greater contrasts in local force fields

  2. Selected bibliography on deuterium isotope effects and heavy water

    International Nuclear Information System (INIS)

    Dave, S.M.; Donde, M.M.

    1983-01-01

    In recent years, there has been a great deal of interest in using deuterium and heavy water not only in nuclear industry but also in various fields of basic as well as applied research in physics, chemistry and biology. As a result, the literature is being enriched with a large number of research papers and technical reports published each year. Thus, to enable the scientists to have an easy reference to these works, an endeavour has been made in this selected bibliography, to enlist the publications related to these fields. Since the interest is concerned mainly with heavy water production processes, deuterium isotope effects etc., several aspects (e.g. nuclear) of deuterium have not been covered here. The material in this bibliography which cites 2388 references has been classified under six broad headings, viz. (1) Production of heavy water, (2) Study of deuterium isotope effects, (3) Analysis and Properties of heavy water, (4) Laser Separation of deuterium, (5) Isotopic exchange reactions, and (6) Miscellaneous. The sources of information used for this compilation are chemical abstracts, nuclear science abstracts, INIS Atomindex and also some scattered search through journals and reports available in the B.A.R.C. library. However, in spite of sincere attempts for a wide coverage, no claim is being made towards the exhaustiveness of this bibliography. (author)

  3. Deuterium secondary isotope kinetic effects in imine formation reactions

    International Nuclear Information System (INIS)

    Amaral, L. do; Rossi, M.H.

    1986-01-01

    The kinetic α-deuterium isotope effects, K D /K H , for reaction mechanisms is studied. The reaction of pH function to m-bromobenzaldehyde, semicarbazide nucleophile, methoxy-amine and hydroxylamine are analysed. (M.J.C.) [pt

  4. Secondary deuterium isotope effects in the hydrolysis of some acetals

    International Nuclear Information System (INIS)

    Paterson, R.V.

    Secondary α-deuterium kinetic isotope effects have been determined in the hydrolyses of some acetals. Benzaldehyde dimethyl acetal and 2-phenyl-1,3-dioxolan show isotope effects in agreement with an A1 mechanism. 2-Phenyl-4,4,5,5-tetramethyl-1,3-dioxolan, which has been shown to undergo hydrolysis by an A2 type mechanism, has an isotope effect in agreement with participation by water in the transition state. Hydrolysis of benzylidene norbornanediols, although complicated by isomerisation, has an isotope effect in agreement with an A2 mechanism. Kinetic isotope effects in acetals which have a neighbouring carboxyl group have also been determined. Hydrolysis of 2-carboxybenzaldehyde dimethyl acetal in aqueous and 82% w/w dioxan-water buffers has isotope effects in agreement with a large degree of carbonium ion character in the transition state. Anderson and Capon proposed nucleophilic participation in the hydrolysis of this acetal in 82% dioxan-water. The isotope effect determined in this study is not in agreement with this finding. Hydrolysis of 2-(2'-carboxyphenyl)-4,4,5,5-tetramethyl-1,3-dioxolan shows an isotope effect larger than the corresponding dioxolan without the carboxyl group in agreement with some carbonium ion character in the transition state. A new synthesis of a deuterated aldehyde is described which might be general for aldehydes which will not form benzoins readily. (author)

  5. Synthesis of seven deuteromethyl-caffeine analogues observation of deuterium isotope effects on CMR analysis

    Energy Technology Data Exchange (ETDEWEB)

    Falconnet, J.B.; Brazier, J.L.; Desage, M.

    1986-03-01

    The synthesis of all 7 N-trideuteromethyl isotopomers of caffeine by reaction of trideuteromethyl iodide (C/sup 2/H/sub 3/I) with the appropriate xanthine molecules is described. The use of proton, deuterium and carbon-13-NMR as a first step in purity assessment revealed /sup 13/C-NMR deuterium isotope effects on the resonance of perdeuteromethyl carbons.

  6. Deuterium isotope effects on the ring inversion equilibrium in cyclohexane: the A value of deuterium and its origin

    International Nuclear Information System (INIS)

    Anet, F.A.L.; Kopelevich, M.

    1986-01-01

    It has been reported recently that the deuterium in cyclohexane-d 1 prefers the equatorial over the axial position by about 200 J/mol (i.e., ca. 50 cal/mol), as shown by three different kinds of NMR measurements. Such an isotope effect is unexpectedly large, and this has led the authors to reinvestigate the problem using Saunder's isotopic perturbation method. The authors thereby established that the free energy difference (the A value for deuterium) is 6.3 +/- 1.5 cal/mol, with deuterium more stable equatorial than axial. This value is supported by molecular mechanics calculations based in part on experimental vibrational frequencies. 17 references, 1 figure

  7. Isotope effect and deuterium excess parameter revolution in ice and snow melt

    International Nuclear Information System (INIS)

    Yin Guan; Ni Shijun; Fan Xiao; Wu Hao

    2003-01-01

    The change of water isotope composition actually is a integrated reaction depending on the change of environment. The ice and snow melt of different seasons in high mountain can obviously influence the change of isotope composition and deuterium excess parameter of surface flow and shallow groundwater. To know the isotopic fractionation caused by this special natural background, explore its forming and evolvement, is unusually important for estimating, the relationship between the environment, climate and water resources in an area. Taking the example of isotope composition of surface flow and shallow groundwater in Daocheng, Sichuan, this paper mainly introduced the changing law of isotope composition and deuterium excess parameter of surface flow and hot-spring on conditions of ice and snow melt with different seasons in high mountain; emphatically discussed the isotope effect and deuterium excess parameter revolution in the process of ice and snow melting and its reason. (authors)

  8. Deuterium isotope effects on 13C chemical shifts of 10-Hydroxybenzo[h]quinolines

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Kamounah, Fadhil S.; Gryko, Daniel T.

    2013-01-01

    Deuterium isotope effects on 13C-NMR chemical shifts are investigated in a series of 10-hydroxybenzo[h]quinolines (HBQ’s) The OH proton is deuteriated. The isotope effects on 13C chemical shifts in these hydrogen bonded systems are rather unusual. The formal four-bond effects are found to be nega...

  9. Deuterium isotope effect on the intramolecular electron transfer in Pseudomonas aeruginosa azurin

    DEFF Research Database (Denmark)

    Farver, O.; Zhang, Jingdong; Chi, Qijin

    2001-01-01

    rather than negative. Isotope effects are, however, also inherent in the nuclear reorganization Gibbs free energy and in the tunneling factor for the electron transfer process. A slightly larger thermal protein expansion in H2O than in D2O (0.001 nm K-1) is sufficient both to account for the activation......Intramolecular electron transfer in azurin in water and deuterium oxide has been studied over a broad temperature range. The kinetic deuterium isotope effect, k(H)/k(D), is smaller than unity (0.7 at 298 K), primarily caused by the different activation entropies in water (-56.5 J K-1 mol(-1...

  10. Solvent-dependent deuterium isotope effects in the 15N NMR spectra of an ammonium ion

    International Nuclear Information System (INIS)

    Wielogorska, E.; Jackowski, K.

    2000-01-01

    Deuterium isotope effects on 15 N NMR chemical shifts and spin-spin coupling constants have been investigated for the 15 N enriched ammonium chloride (conc. 15 NH 4 + ion has been observed in water, methanol, ethanol and dimethylsulfoxide, while the 15 ND 4 + has been monitored in the analogous deuterated liquids. It is shown that the isotope effect in nitrogen chemical shifts ( 1 Δ 15 N( 2/1 H)), significantly different in various solvents, changes from -1.392 ppm in dimethylsulfoxide to -0.071 ppm in ethanol. The 1 J(N,H) and 1 J(N,D) coupling constants have been measured for acidic solutions under conditions of slow proton (or deuterium) exchange. The reduced coupling constants have been estimated to present isotope effects in the spin-spin coupling constants. The latter isotope effects are fairly small. (author)

  11. Kinetic secondary deuterium isotope effect in addition of nucleophile to m-bromobenzaldehyde

    International Nuclear Information System (INIS)

    Amaral, L. do; Rossi, M.H.

    1985-01-01

    The kinetic secondary deuterium isotope effects, KD/KH for hydrated proton catalyzed addition of semicarbazide, methoxyamine and hydroxylamine to m-bromobenzaldehyde is studied. The nature of the nucleophile, addition of the carbonyl group and the chemical reactions are evaluated. (M.J.C.) [pt

  12. Deuterium isotope separation

    International Nuclear Information System (INIS)

    Benson, S.W.

    1979-01-01

    Deuterium-containing molecules are separated and enriched by exposing commercially available ethylene, vinyl chloride, 1,2-dichloroethane or propylene to the radiation of tuned infrared lasers to selectively decompose these compounds into enriched molecular products containing deuterium atoms. The deuterium containing molecules can be easily separated from the starting material by absorption, distillation or other simple chemical separation techniques and methods. After evaporation such deuterium containing molecules can be burned to form water with an enriched deuterium content or pyrolyzed to form hydrogen gas with an enriched deuterium content. (author)

  13. Ionic conductivity in aqueous solutions: deuterium isotope effect

    International Nuclear Information System (INIS)

    Samanta, Alok; Ghosh, Swapan K.

    1997-01-01

    A simple theoretical investigation of the calculation of ionic conductivity in aqueous solution is presented. The dipolar hard sphere model for the solvent which has been successful elsewhere has been employed here and it has been possible to reproduce the experimental results quite accurately for both water and heavy water using only two parameters. In a more detailed theoretical approach one should employ better models for water with proper account of its vibrations, liberations and also hydrogen bonding. It is also of interest to study the temperature effect and the concentration dependence of the conductivity. The time-dependent friction can also be calculated from the present formalism and be used for the study of isotope effect in proton transfer reactions or other aspects of chemical dynamics

  14. Unusually large secondary deuterium isotope effect. Thermal trans-cis isomerization of trans-1-phenylcyclohexene

    International Nuclear Information System (INIS)

    Caldwell, R.A.; Misawa, H.; Healy, E.F.; Dewar, M.J.S.

    1987-01-01

    The magnitudes of secondary deuterium isotope effects (SDIE) are generally in the range of 0.9 < k/sub H//k/sub D/ < 1.25, and are often satisfactorily rationalized by the zero-point energy (ZPE) change on going from reactant to transition state due to C-H rehybridization. They now report a far larger SDIE for the title reaction. Its rationalization on the basis of transition state theory suggests that it more closely resembles a primary isotope effect

  15. Mechanistic studies on the bovine liver mitochondrial dihydroorotate dehydrogenase using kinetic deuterium isotope effects

    International Nuclear Information System (INIS)

    Hines, V.; Johnston, M.

    1989-01-01

    Dihydroorotates deuteriated at both C 5 and C 6 have been prepared and used to probe the mechanism of the bovine liver mitochondrial dihydroorotate dehydrogenase. Primary deuterium isotope effects on k cat are observed with both (6RS)-[5(S)- 2 H]- and (6RS)-[6- 2 H]dihydroorotates (3 and 6, respectively); these effects are maximal at low pH. At pH 6.6, D V = 3.4 for the C 5 -deuteriated dihydroorotate (3), and D V = 2.3 for the C 6 -deuteriated compound (6). The isotope effects approach unity at pH 8.8. Analysis of the pH dependence of the isotope effects on k cat reveals a shift in the rate-determining step of the enzyme mechanism as a function of pH. Dihydroorotate oxidation appears to require general base catalysis; this step is completely rate-determining at low pH and isotopically sensitive. Reduction of the cosubstrate, coenzyme Q 6 , is rate-limiting at high pH and is isotopically insensitive; this step appears to require general acid catalysis. The results of double isotope substitution studies and analysis for substrate isotope exchange with solvent point toward a concerted mechanism for oxidation of dihydroorotate. This finding serves to distinguish further the mammalian dehydrogenase from its parasitic cognate, which catalyzes a stepwise oxidation reaction

  16. Isotope effect in the diffusion of hydrogen and deuterium in polymers

    Energy Technology Data Exchange (ETDEWEB)

    Toi, K.; Takeuchi, K.; Tokuda, T.

    1980-02-01

    Temperature dependences of diffusion and permeation coefficients of hydrogen and deuterium in glassy and rubbery polymer films have been measured. The size of the free volume element in rubbery polymers has been calculated according to the theory of Frisch and Rogers for the quantum isotope effect, but the free volume is too large for precise calculation below the glass-transition temperature. The cooperative movement of segments is also discussed using the ratio of preexponential factors for diffusion mechanisms above and below the glass-transition temperature.

  17. The kinetic isotope effect of hydrogen, deuterium and tritium absorbed and desorbed by titanium

    International Nuclear Information System (INIS)

    Huang Gang; Cao Xiaohua; Long Xinggui

    2008-06-01

    p-t curves of hydrogen, deuterium and tritium absorption at 550-750 degree C and desorption at 350-550 degree C by titanium were investigated. The rate constants of absorption and desorption for hydrogen, deuterium and tritium on each temperature are determined and the activation energy values obtained by this analysis are (55.6 ± 2.4) kJ·mol -1 , (110.2 ± 3.0) kJ·mol -1 and (155.5 ± 3.2) kJ·mol -1 for absorption and (27.1±0.4) KJ·mol -1 , (42.3 ± 1.9) kJ·mol -1 and (62.1±1.6) kJ·mol -1 for desorption respectively. The activation energy value of tritium absorption is highest which shows titanium tritiation is hardest. The activation energy value of tritium desorption is highest and it also can prove that titanium tritide is stablest. There are remarkable kinetic hydrogen isotope effects when titanium absorb and desorb hydrogen, deuterium and tritium. (authors)

  18. New NMR method for measuring the difference between corresponding proton and deuterium chemical shifts: isotope effects on exchange equilibria

    International Nuclear Information System (INIS)

    Saunders, M.; Saunders, S.; Johnson, C.A.

    1984-01-01

    A convenient and accurate method is described for measuring the difference between a proton frequency and the corresponding deuterium frequency in its deuterated analogue relative to a reference system by using the deuterium lock in a Fourier-transform NMR spectrometer. This measurement is a sensitive way of measuring equilibrium isotope effects for hydrogen-deuterium exchange. A value of 1.60 per H-D pair is obtained for the equilibrium 2H 3 O + + 3D 2 O in equilibrium 2D 3 O + + 3H 2 O at 30 0 C in aqueous perchloric acid (HClO 4 ). 7 references, 2 tables

  19. alfa-Deuterium kinetic isotope effects in reactions of methyllithium. Is better aggregation the cause of lower reactivity?

    DEFF Research Database (Denmark)

    Holm, Torkil

    1996-01-01

    The value of kH/kD for alfa deuterium kinetic isotope effects for the reaction of methyllithium and methylmagnesium iodid with a series of substrates are consistently ca. 10-15 % higher for the lithium reagent. This may indicate a pre-equilibrium......The value of kH/kD for alfa deuterium kinetic isotope effects for the reaction of methyllithium and methylmagnesium iodid with a series of substrates are consistently ca. 10-15 % higher for the lithium reagent. This may indicate a pre-equilibrium...

  20. Determination of the mechanism of demethylenation of (methylenedioxy)phenyl compounds by cytochrome P450 using deuterium isotope effects

    International Nuclear Information System (INIS)

    Fukuto, J.M.; Kumagai, Y.; Cho, A.K.

    1991-01-01

    The mechanism of demethylenation of (methylenedioxy)benzene (MDB), (methylenedioxy)amphetamine (MDA), and (methylenedioxy)methamphetamine (MDMA) by purified rabbit liver cytochrome P450IIB4 has been investigated by using deuterium isotope effects. A comparison of the magnitude and direction of the observed kinetic isotope effects indicates that the three compounds are demethylenated by different mechanisms. The different mechanisms of demethylenation have been proposed on the basis of comparisons of the observed biochemical isotope effects with the isotope effects from purely chemical systems

  1. Secondary. cap alpha. -deuterium kinetic isotope effects in solvolyses of ferrocenylmethyl acetate and benzoate in ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Sutic, D. (Univ. of Zagreb, Yugoslavia); Asperger, S.; Borcic, S.

    1982-12-17

    Secondary ..cap alpha..-deuterium kinetic isotope effects (KIE) in solvolyses of ferrocenyldideuteriomethyl acetate and benzoate were determined in 96% (v/v) ethanol, at 25/sup 0/C, as k/sub H//k/sub D/ = 1.24 and 1.26, respectively. The KIEs were also determined in the presence of 0.1 mol dm/sup -3/ lithium perchlorate: the k/sub H//k/ sub D/ values were 1.23 and 1.22 for acetate and benzoate complexes, respectively. The maximum KIE for the C-O bond cleavage of a primary substrate is as large as, or larger than, that of secondary derivatives, which is estimated to be 1.23 per deuterium. The measured KIE of about 12% per D therefore represents a strongly reduced effect relative to its maximum. The solvolyses exhibit ''a special salt effect''. This effect indicates the presence of solvent-separated ion pairs and the return to tight pairs. As the maximum KIE is expected in solvolyses involving transformation of one type of ion pair into another, the strongly reduced ..cap alpha..-D KIE supports the structure involving direct participation of electrons that in the ground state are localized at the iron atom. The alkyl-oxygen cleavage is accompanied by 10-15% acyl-oxygen cleavage.

  2. Kinetic α-deuterium isotope effect as a probe of transition state structure and reaction mechanism in nucleoside hydrolysis

    International Nuclear Information System (INIS)

    Stein, R.L.

    1978-01-01

    Theoretical equilibrium α-deuterium isotope effects were calculated for systems modeling nucleoside and glycoside hydrolyses using a computer program (Burton, G.W., Sims, L.B., Wilson, J.C., and Fry, A.J., J. Amer. Chem. Soc., 99, 3374(1977)) which computes isotope effects directly from the expression of Biegeleisen and Mayer (Biegeleisen, J. and Mayer, M.G., J. Chem. Phys., 17, 675(1949)). For nucleoside hydrolysis proceeding through an oxocarbonium ion intermediate, KH/KD = 1.21 to 1.25; while for nucleoside hydrolysis proceeding through an oxocarbonium ion intermediate KH/KD = 1.15 to 1.19. The models used in the calculations were generated systematically and involved a minimum of subjectivity in the selection of molecular parameters. The isotope effects calculated formed the basis for the interpretation of experimental kinetic α-deuterium isotope effects for nucleoside and glycoside hydrolysis

  3. Kinetic α secondary deuterium isotope effects for O-ethyl S-phenyl benzaldehyde acetal hydrolysis

    International Nuclear Information System (INIS)

    Ferraz, J.P.; Cordes, E.H.

    1979-01-01

    The rate of hydrolysis of O-ethyl S-phenyl benzaldehyde acetal at 25 0 C in 20% dioxane--80% water is independent of pH over the range pH6-12; k/sub obsd/ = 1.9 x 10 -7 s -1 . Under more acidic conditions, the rate increases linearly with the activity of the hydrated proton; k 2 = 2.95 x 10 -2 M -1 s -1 . The kinetic α secondary deuterium isotope effect for acid-catalyzed hydrolysis of O-ethyl S-phenyl benzaldehyde acetal, measured at 25 0 C in 20% aqueous dioxane containing 0.05 M HCl, is k/sub H//k/sub D/ = 1.038 +- 0.008, a value consistent with a transition state in which the C--S bond is stretched rather little. In contrast, the corresponding isotope effect for the pH-independent hydrolysis of this substrate, measured at 42.5 0 C in 20% dioxane, is 1.13 +- 0.02, a value consistent with complete C--S bond cleavage in the transition state and rate-determining diffusion apart of the ion-pair formed as the initial intermediate, in accord with the suggestion of Jensen and Jencks. 1 figure, 4 tables

  4. Secondary deuterium isotope effects and transition state structure in the aromatic claisen rearrangement

    International Nuclear Information System (INIS)

    McMichael, K.D.; Korver, G.L.

    1979-01-01

    Kinetic experiments were carried out simultaneously on separate methyl salicylate solutions of allyl phenyl ether and its deuterated phenyl analogues at 170 to 195 0 C. Gas chromatographic analysis for allyl phenyl ether using an internal standard (anisole) and mechanical integration produced concentration/time data which were fitted to the exponential form of the first-order rate equation by a standard and nonlinear least-square program. At least 15 points were obtained for each run, covering 10 to 85% reaction. The derived isotope effects show no temperature dependence. Averages for 6 runs with each compound are k/sub H//k/sub α-D 2 / = 1.18 and K/sub H//k/sub γ-D 2 / = 0.95. An equilibrium α effect of 1.30 and a γ effect of 0.87 may be calculated for both deuterium atoms at 185 0 C. These results show that the C--H vibration frequencies are approximately (1.18 - 1)/(1.27 - 1) or 57 to 77% of the way from those of allyl phenyl ether to those of the cyclohexadiene intermediate. The C--H frequencies of the γ carbon in the transition state are about (0.95 - 1)/(0.88 - 1) or 22 to 62% of the way to those of the intermediate. The structure of the transition state, as far as these bonding frequencies are concerned, is consistent with the Claisen rearrangement

  5. Partially-deuterated samples of HET-s(218–289) fibrils: assignment and deuterium isotope effect

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Albert A.; Ravotti, Francesco; Testori, Emilie; Cadalbert, Riccardo; Ernst, Matthias, E-mail: maer@ethz.ch [ETH Zürich, Physical Chemistry (Switzerland); Böckmann, Anja, E-mail: a.bockmann@ibcp.fr [Institut de Biologie et Chimie des Protéines, Bases Moléculaires et Structurales des Systèmes Infectieux, Labex Ecofect, UMR 5086 CNRS, Université de Lyon (France); Meier, Beat H., E-mail: beme@ethz.ch [ETH Zürich, Physical Chemistry (Switzerland)

    2017-02-15

    Fast magic-angle spinning and partial sample deuteration allows direct detection of {sup 1}H in solid-state NMR, yielding significant gains in mass sensitivity. In order to further analyze the spectra, {sup 1}H detection requires assignment of the {sup 1}H resonances. In this work, resonance assignments of backbone H{sup N} and Hα are presented for HET-s(218–289) fibrils, based on the existing assignment of Cα, Cβ, C’, and N resonances. The samples used are partially deuterated for higher spectral resolution, and the shifts in resonance frequencies of Cα and Cβ due to the deuterium isotope effect are investigated. It is shown that the deuterium isotope effect can be estimated and used for assigning resonances of deuterated samples in solid-state NMR, based on known resonances of the protonated protein.

  6. High secondary [alpha]-deuterium kinetic isotope effect in the acetolysis and formolysis of dideuterioferrocenylmethyl benzoate

    Energy Technology Data Exchange (ETDEWEB)

    Asperger, S. (Research Center of the Croatian Academy of Sciences and Arts, Zagreb (Croatia)); Kukric, Z.; Sutic, D. (Sarajevo Univ. (Yugoslavia). Faculty of Natural Sciences and Mathematics); Saunders, W.H. Jr. (Rochester Univ., NY (United States). Dept. of Chemistry)

    1992-02-01

    Acetolysis and formolysis of dideuterioferrocenylmethyl benzoate exhibit large secondary deuterium kinetic isotope effects and an abnormal temperature dependence. In the presence of LiClO[sub 4], which prevents the reversion from solvent-separated to contact ion-pairs, K[sub H]/K[sub D] at 25 [sup o]C amount to 1.53 [+-] 0.02 (acetolysis) and 1.48 [+-] 0.03 (formolysis). In the presence of LiClO[sub 4] the ratios of Arrhenius pre-exponential factors, A[sub H]/A[sub D], are significantly less than unity and amount to 0.49 [+-] 0.01 (acetolysis) and 0.38 [+-] 0.04 (formolysis). In the absence of LiClO[sub 4] the A[sub H]/A[sub D] ratios are much smaller (0.02 both in acetolysis and formolysis). We suggest that these surprisingly low values result from a change in rate-determining step over the temperature range, from formation of the solvent-separated ion-pair at low temperatures to reaction of the dissociated carbocation with solvent at the highest temperatures. Whether tunnelling plays any role in these solvolyses is discussed. (Author).

  7. Secondary deuterium isotope effects for acid-catalyzed hydrolysis of inosine and adenosine

    International Nuclear Information System (INIS)

    Romero, R.; Stein, R.; Bull, H.G.; Cordes, E.H.

    1978-01-01

    Kinetic α deuterium isotope effects have been measured for acid-catalyzed hydrolysis of inosine and adenosine. For inosine hydrolysis, values of k/sub H/k/sub D/ follow: in 1.0 M HCl, 1.21 and 1.20 at 25 and 50 0 C, respectively; in 0.1 M HCl, 1.19 and 1.18 at 25 and 50 0 C, respectively. For adenosine hydrolysis, k/sub H/k/sub D/ is 1.23 in 0.1 M HCl at 25 0 C. The values require that the transition states for hydrolysis of both the monocation and dication of inosine and the dication of adenosine have marked oxocarbonium ion character. Detailed mechanisms which accord with this and other experimental observations include (1) a classical Al mechanism in which the C--N bond is largely cleaved in the transition state; (2) a mechanism involving some form of nucleophilic participation by solvent in which bond cleavage is advanced relative to bond formation in the transition state; or (3) complete C--N bond cleavage with rate-determining diffusion apart of oxocarbonium ion and purine base. 53 references, 1 figure, 2 tables

  8. Isotope effects in the diffusion of hydrogen and deuterium in ferromagnetic binary alloys of the Cu3Au type

    International Nuclear Information System (INIS)

    Hirscher, M.; Maier, C.U.; Schwendemann, B.; Kronmueller, H.

    1989-01-01

    The diffusion behaviour of hydrogen and deuterium at low temperatures was investigated in ordered and disordered alloys of Ni 3 Fe, Ni 3 Mn, and Fe 3 Pt by means of magnetic after-effect (MAE) measurements. After hydrogen charging all specimens show characteristic MAE relaxation spectra, which can be described taking into account the different octahedral positions of the hydrogen atoms in the Cu 3 Au structure. The observed isotope effect can qualitatively be explained by a thermally activated tunnelling process of the hydrogen isotopes. (orig.)

  9. Quantitative analysis of deuterium using the isotopic effect on quaternary {sup 13}C NMR chemical shifts

    Energy Technology Data Exchange (ETDEWEB)

    Darwish, Tamim A., E-mail: tamim.darwish@ansto.gov.au [National Deuteration Facility, Australian Nuclear Science and Technology Organisation, Locked Bag 21, Kirrawee DC, NSW 2232 (Australia); Yepuri, Nageshwar Rao; Holden, Peter J. [National Deuteration Facility, Australian Nuclear Science and Technology Organisation, Locked Bag 21, Kirrawee DC, NSW 2232 (Australia); James, Michael [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia)

    2016-07-13

    Quantitative analysis of specifically deuterated compounds can be achieved by a number of conventional methods, such as mass spectroscopy, or by quantifying the residual {sup 1}H NMR signals compared to signals from internal standards. However, site specific quantification using these methods becomes challenging when dealing with non-specifically or randomly deuterated compounds that are produced by metal catalyzed hydrothermal reactions in D{sub 2}O, one of the most convenient deuteration methods. In this study, deuterium-induced NMR isotope shifts of quaternary {sup 13}C resonances neighboring deuterated sites have been utilized to quantify the degree of isotope labeling of molecular sites in non-specifically deuterated molecules. By probing {sup 13}C NMR signals while decoupling both proton and deuterium nuclei, it is possible to resolve {sup 13}C resonances of the different isotopologues based on the isotopic shifts and the degree of deuteration of the carbon atoms. We demonstrate that in different isotopologues, the same quaternary carbon, neighboring partially deuterated carbon atoms, are affected to an equal extent by relaxation. Decoupling both nuclei ({sup 1}H, {sup 2}H) resolves closely separated quaternary {sup 13}C signals of the different isotopologues, and allows their accurate integration and quantification under short relaxation delays (D1 = 1 s) and hence fast accumulative spectral acquisition. We have performed a number of approaches to quantify the deuterium content at different specific sites to demonstrate a convenient and generic analysis method for use in randomly deuterated molecules, or in cases of specifically deuterated molecules where back-exchange processes may take place during work up. - Graphical abstract: The relative intensities of quaternary {sup 13}C {"1H,"2H} resonances are equal despite the different relaxation delays, allowing the relative abundance of the different deuterated isotopologues to be calculated using NMR fast

  10. Method of deuterium isotope separation and enrichment

    International Nuclear Information System (INIS)

    Benson, S.W.

    1980-01-01

    A method of deuterium isotope separation and enrichment using infrared laser technology in combination with chemical processes for treating and recycling the unreacted and deuterium-depleted starting materials is described. Organic molecules of the formula RX (where R is an ethyl, isopropyl, t-butyl, or cyclopentenyl group and X is F, Cl, Br or OH) containing a normal abundance of hydrogen and deuterium are exposed to intense laser infrared radiation. An olefin containing deuterium (olefin D) will be formed, along with HX. The enriched olefin D can be stripped from the depleted stream of RX and HX, and can be burned to form enriched water or pyrolyzed to produce hydrogen gas with elevated deuterium content. The depleted RX is decomposed to olefins and RX, catalytically exchanged with normal water to restore the deuterium content to natural levels, and recombined to form RX which can be recycled. (LL)

  11. Deuterium isotope effects and fractionation factors of hydrogen-bonded A:T base pairs of DNA

    International Nuclear Information System (INIS)

    Vakonakis, Ioannis; Salazar, Miguel; Kang, Mijeong; Dunbar, Kim R.; Li Wang, Andy C.

    2003-01-01

    Deuterium isotope effects and fractionation factors of N1...H3-N3 hydrogen bonded Watson-Crick A:T base pairs of two DNA dodecamers are presented here. Specifically, two-bond deuterium isotope effects on the chemical shifts of 13 C2 and 13 C4, 2 Δ 13 C2 and 2 Δ 13 C4, and equilibrium deuterium/protium fractionation factors of H3, Φ, were measured and seen to correlate with the chemical shift of the corresponding imino proton, δ H3 . Downfield-shifted imino protons associated with larger values of 2 Δ 13 C2 and 2 Δ 13 C4 and smaller Φ values, which together suggested that the effective H3-N3 vibrational potentials were more anharmonic in the stronger hydrogen bonds of these DNA molecules. We anticipate that 2 Δ 13 C2, 2 Δ 13 C4 and Φ values can be useful gauges of hydrogen bond strength of A:T base pairs

  12. Deuterium isotope effect on metabolism of N-nitrosodimethylamine in vivo in rat

    International Nuclear Information System (INIS)

    Swann, P.F.; Mace, R.; Angeles, R.M.; Keefer, L.K.

    1983-01-01

    The maximal rates of metabolic oxidation of N-nitrosodimethylamine (NDMA) and N-nitrosodimethylamine-d6 (NDMA-d6) in vivo (VH and VD, respectively) have been measured by following 14CO2 exhalation in rats after intraperitoneal injection of the two 14C-labelled carcinogens at high doses (20 or 40 mg/kg). Complete deuteration of NDMA reduced only slightly the maximal rate of metabolism when the two substrates were administered separately (VH/VD approximately 1.2). However, much larger (approximately 4-fold) deuterium isotope effects were observed when mixtures of NDMA with NDMA-d6 were injected. These results are tentatively interpreted as evidence that C-H bond cleavage is not a rate limiting feature of overall metabolism, but that the complex between NDMA and the principal enzyme(s) metabolizing it in vivo freely equilibrates with unbound substrate. Single, large, intraperitoneal doses of NDMA and NDMA-d6 produced a similar alkylation of rat liver DNA and also of kidney DNA. However, a small oral dose (54 micrograms/kg) of NDMA-d6 produced 1/3 less alkylation of liver DNA and 3 times as much alkylation of kidney DNA as did an equimolar dose of NDMA. The reduction in alkylation of liver DNA correlates well with, and possibly explains, the decreased ability of NDMA-d6 to induce liver tumors in rats. The associated increase in the alkylation of kidney DNA suggests that this change is due to a decrease in the amount of nitrosamine removed from the portal blood on the first pass through the liver

  13. Hydrogen/deuterium isotope effects in water and aqueous solutions of organic molecules and proteins

    International Nuclear Information System (INIS)

    Price, David L.; Fu, Ling; Bermejo, F. Javier; Fernandez-Alonso, Felix; Saboungi, Marie-Louise

    2013-01-01

    Highlights: ► Hydrogen/deuterium substitution has significant effects in hydrogenous materials. ► The effects can involve structure, phase behavior and protein stability. ► The effects must be kept in mind in the interpretation of scattering experiments. ► The effects may be mitigated by an appropriate choice of experimental conditions. - Abstract: It is pointed out that hydrogen/deuterium substitution, frequently used in neutron scattering studies of the structure and dynamics of hydrogenous samples, can have significant effects on structure, phase behavior and protein stability. The effects must be kept in mind in the interpretation of such experiments. In suitable cases, these effects can be mitigated by an appropriate choice of experimental conditions

  14. Deuterium isotopic effects connected with unimolecular and concerted mechanisms. The case of 1-deutero-2-chloro alcohols

    International Nuclear Information System (INIS)

    Jambon, C.

    1962-01-01

    After a bibliographic analysis of the probable causes of isotopic effects and their comparison, with the simplifications provided by the athermal model, a discussion of the isotopic effect of deuterium in organic molecules in terms of structural influences is presented, showing the important role of the C-D bond length which is shorter than the C-H bond length, and of the D atom's Van der Waals radius, shorter than that of the H atom. Kinetic measurements were carried out on some reactions involving the mechanisms proposed: unimolecular ionizations and halogen concentrates. The structural models chosen are: 2-chloro-cyclo-hexanols cis and trans 1-H and 2-D; 2-chloro-cyclo-pentanols cis trans 1-H and 1-D; 1-phenyl-l-chloro-2-propanol threo 2-H and 2-D. (author) [fr

  15. Aspartate beta-decarboxylase from Alcaligenes faecalis: carbon-13 kinetic isotope effect and deuterium exchange experiments

    International Nuclear Information System (INIS)

    Rosenberg, R.M.; O'Leary, M.H.

    1985-01-01

    The authors have measured the 13 C kinetic isotope effect at pH 4.0, 5.0, 6.0, and 6.5 and in D 2 O at pH 5.0 and the rate of D-H exchange of the alpha and beta protons of aspartic acid in D 2 O at pH 5.0 for the reaction catalyzed by the enzyme aspartate beta-decarboxylase from Alcaligenes faecalis. The 13 C kinetic isotope effect, with a value of 1.0099 +/- 0.0002 at pH 5.0, is less than the intrinsic isotope effect for the decarboxylation step, indicating that the decarboxylation step is not entirely rate limiting. The authors have been able to estimate probable values of the relative free energies of the transition states of the enzymatic reaction up to and including the decarboxylation step from the 13 C kinetic isotope effect and the rate of D-H exchange of alpha-H. The pH dependence of the kinetic isotope effect reflects the pKa of the pyridine nitrogen of the coenzyme pyridoxal 5'-phosphate but not that of the imine nitrogen. A mechanism is proposed for the exchange of aspartate beta-H that is consistent with the stereochemistry suggested earlier

  16. Stable Oxygen-18 and Deuterium Isotopes

    DEFF Research Database (Denmark)

    Müller, Sascha

    The application of stable Oxygen-18 (18O) and Deuterium (2H) isotopes, as a tracer for fluxes between different compartments of the water cycle was subject of the present PhD-thesis. During a three year period, temporal data from a wide range of water cycle constituents was collected from...... the Skjern River catchment, Denmark. The presented applications focused on studying the isotopic 'input signal' to the hydrosphere in the form of precipitation, the isotopic 'output signal' with its related dynamic processes at a coastal saltwater-freshwater interface (groundwater isotopes) and the temporal...... development within a given lowland headwater catchment (stream water isotopes). Based on our investigations on the precipitation isotopic composition a local meteoric water line (LMWL) was constructed and expressed as: δ2H=7.4 δ18O + 5.36‰. Moreover, we showed that under maritime temperature climate influence...

  17. Novel PEFC Application for Deuterium Isotope Separation

    Directory of Open Access Journals (Sweden)

    Hisayoshi Matsushima

    2017-03-01

    Full Text Available 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.

  18. Mechanism and activation for allosteric adenosine 5'-monophosphate nucleosidase. Kinetic alpha-deuterium isotope effects for the enzyme-catalyzed hydrolysis of adenosine 5'-monophosphate and nicotinamide mononucleotide

    International Nuclear Information System (INIS)

    Skoog, M.T.

    1986-01-01

    The kinetic alpha-deuterium isotope effect on Vmax/Km for hydrolysis of NMN catalyzed by AMP nucleosidase at saturating concentrations of the allosteric activator MgATP2- is kH/kD = 1.155 +/- 0.012. This value is close to that reported previously for the nonenzymatic hydrolysis of nucleosides of related structure, suggesting that the full intrinsic isotope effect for enzymatic NMN hydrolysis is expressed under these conditions; that is, bond-changing reactions are largely or completely rate-determining and the transition state has marked oxocarbonium ion character. The kinetic alpha-deuterium isotope effect for this reaction is unchanged when deuterium oxide replaces water as solvent, corroborating this conclusion. Furthermore, this isotope effect is independent of pH over the range 6.95-9.25, for which values of Vmax/Km change by a factor of 90, suggesting that the isotope-sensitive and pH-sensitive steps for AMP-nucleosidase-catalyzed NMN hydrolysis are the same. Values of kH/kD for AMP nucleosidase-catalyzed hydrolysis of NMN decrease with decreasing saturation of enzyme with MgATP2- and reach unity when the enzyme is less than half-saturated with this activator. This requires that the rate-determining step changes from cleavage of the covalent C-N bond to one which is isotope-independent. In contrast to the case for NMN hydrolysis, AMP nucleosidase-catalyzed hydrolysis of AMP at saturating concentrations of MgATP2- shows a kinetic alpha-deuterium isotope effect of unity. Thus, covalent bond-changing reactions are largely or completely rate-determining for hydrolysis of a poor substrate, NMN, but make little or no contribution to rate-determining step for hydrolysis of a good substrate, AMP, by maximally activated enzyme. This behavior has several precedents

  19. Deuterium kinetic isotope effects in the 1,4-dimethylenecyclohexane boat cope rearrangement

    International Nuclear Information System (INIS)

    Gajewski, J.J.; Jimenez, J.L.

    1986-01-01

    In order to examine the extent of bond making in the boat-like 3,3-sigmatropic shift transition states, trans-2,3-dimethyl-1,4-dimethylenecyclohexane (T) and its exomethylene tetradeuteria derivative (TXD) were prepared. The 3,3-shift of TXD at 305 0 C results in interconversion of starting material, 5,5,6,6-tetradeuterio-trans-2,3-dimethyl-1,4-dimethylene-cyclohexane (TND), and 2,2,3,3-tetradeuterio-anti-1,4-diethylidenecyclohexane (AD). A kinetic analysis of the first-order rate equations for the three-component system in both protio and deuterio species by numerical integration of the data and simplex minimization of the rate constants with symmetry and the assumption of no equilibrium or kinetic isotope effect on the TND-AD reaction gives a bond making kinetic isotope effect of 1/1.04 (0.04). The equilibrium isotope effects observed are 1/1.16 (0.04) so that the extent of bond formation in this boat-like bicyclo[2.2.2]octyl transition state is roughly 25%, a value to be compared with ca. 67% in chair-like acyclic 3,3-shift transition states. This rules out significant intervention of a bicyclo[2.2.2]octane-1,4-diyl intermediate or transition state. 30 references, 6 figures, 4 tables

  20. Deuterium isotope effects on 13C and 15N chemical shifts of intramolecularly hydrogen-bonded enaminocarbonyl derivatives of Meldrum’s and Tetronic acid

    Science.gov (United States)

    Ullah, Saif; Zhang, Wei; Hansen, Poul Erik

    2010-07-01

    Secondary deuterium isotope effects on 13C and 15N nuclear shieldings in a series of cyclic enamino-diesters and enamino-esters and acyclic enaminones and enamino-esters have been examined and analysed using NMR and DFT (B3LYP/6-31G(d,p)) methods. One-dimensional and two-dimensional NMR spectra of enaminocarbonyl and their deuterated analogues were recorded in CDCl 3 and CD 2Cl 2 at variable temperatures and assigned. 1JNH coupling constants for the derivatives of Meldrum's and tetronic acids reveal that they exist at the NH-form. It was demonstrated that deuterium isotope effects, for the hydrogen bonded compounds, due to the deuterium substitution at the nitrogen nucleus lead to large one-bond isotope effects at nitrogen, 1Δ 15N(D), and two-bond isotope effects on carbon nuclei, 2ΔC(ND), respectively. A linear correlations exist between 2ΔC(ND) and 1Δ 15N(D) whereas the correlation with δNH is divided into two. A good agreement between the experimentally observed 2ΔC(ND) and calculated dσ 13C/dR NH was obtained. A very good correlation between calculated NH bond lengths and observed NH chemical shifts is found. The observed isotope effects are shown to depend strongly on Resonance Assisted Hydrogen bonding.

  1. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    Science.gov (United States)

    Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon

    2014-01-01

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D[subscript 2]O and a catalytic amount of H[subscript 2]SO[subscript 4]. The resulting labeled product is characterized by [superscript 1]H NMR. Students also…

  2. Method of deuterium isotope separation using ethylene and ethylene dichloride

    International Nuclear Information System (INIS)

    Benson, S.W.

    1982-01-01

    Compounds enriched in deuterium may be obtained from ethylene, vinyl chloride, 1,2-dichloroethane, or propylene by laser isotope separation. Normal molecules of these organic compounds are exposed to infrared laser radiation of a suitable wavelength. Substantially all of the deuterium-containing molecules exposed to the laser can be selectively dissociated and the deuterium-containing products separated from the starting material and other reaction products. The deuterium-containing molecules can be burned to form water with an enriched deuterium content, or pyrolized to form hydrogen gas enriched in deuterium

  3. Calculation of carbon-14, chlorine-37, and deuterium kinetic isotope effects in the solvolysis of tert-butyl chloride

    International Nuclear Information System (INIS)

    Burton, G.W.; Sims, L.B.; Wilson, J.C.; Fry, A.

    1977-01-01

    In the solvolysis of tert-butyl chloride, satisfactory α-carbon-14, β-deuterium, and chlorine kinetic isotope effects (KIE) may be calculated for a productlike transition state characterized by bond orders n/sub C Cl/ = 0.2, n/sub C C/ = 1.18, and n/sub C H/ = 0.94, employing a diagonal valence force field, provided that allowance is made for hydrogen-bonded solvation of the developing chloride ion with n/sub Cl H/ approx. 0.05 (approx. 7 kcal/mole hydrogen bonds). The effect of the three solvating molecules appears to be to increase the ''effective'' mass of the incipient chloride ion and to decrease the loss of zero-point energy in going to the transition state. Reaction coordinates more complicated than a simple heterolysis of the carbon-chlorine bond appear to be unnecessary and there is no advantage in employing force fields more complex than a simple valence force field containing only diagonal elements for both the reactant and the transition state model. The structural and bonding features of the proposed transition state are in accord with earlier more qualitative conclusions concerning the polar nature and productlike character of the transition state, and provide a reasonable explanation of the kinetic and equilibrium isotope effects (EIE) for the reaction. An alternative transition state model involving weak solvent nucleophilic assistance provides reasonable calculated values for the KIE, but the EIE strongly suggest the importance of solvation of the leaving group which, together with the hyperconjugation of the β hydrogens, provides a preferred explanation of the tert-butyl solvolysis results

  4. β-Secondary and solvent deuterium kinetic isotope effects and the mechanisms of base- and acid-catalyzed hydrolysis of penicillanic acid

    International Nuclear Information System (INIS)

    Deraniyagala, S.A.; Adediran, S.A.; Pratt, R.F.

    1995-01-01

    β-Secondary and solvent deuterium kinetic isotope effects have been determined at 25 degrees C for the alkaline and acid-catalyzed hydrolysis of penicillanic acid. In order to determine the former isotope effect, [6,6- 2 H 2 ]dideuteriopenicillanic acid has been synthesized. In alkaline solution, the former isotope effect was found to be 0.95 ± 0.01. These values support the B AC 2 mechanism of hydrolysis with rate-determining formation of the tetrahedral intermediate that has been proposed for other β-lactams. The measured β-secondary kinetic isotope for the acid-catalyzed reaction was 1.00 ± 0.01. The data indicates that a likely pathway of acid-catalyzed hydrolysis would be that of an A AC 1 mechanism with an intermediate acylium ion. If this were so, the calculated β-secondary isotope effect per hydrogen coplanar with the breaking C-N bond and corrected for the inductive effect of deuterium would be 1.06 ± 0.01. This suggests an early A AC 1 transition state, which would be reasonable in this case because of destabilization of the N-protonated amide with respect to the acylium ion because of ring strain. The absence of specific participation by solvent in the transition state, as would be expected of an A AC 1 but not an associative mechanism, is supported by the strongly inverse solvent deuterium kinetic isotope effect of 0.25 ± 0.00 in 1 M HCl and 0.22 ± 0.01 in 33.3 wt % H 2 SO 4 . 1 fig., 3 tabs

  5. Mechanism of the reaction catalyzed by dihydrofolate reductase from Escherichia coli: pH and deuterium isotope effects with NADPH as the variable substrate

    International Nuclear Information System (INIS)

    Morrison, J.F.; Stone, S.R.

    1988-01-01

    The variations with pH of the kinetic parameters and primary deuterium isotope effects for the reaction of NADPH with dihydrofolate reductase from Escherichia coli have been determined. The aims of the investigations were to elucidate the chemical mechanism of the reaction and to obtain information about the location of the rate-limiting steps. The V and V/K/sub NADPH/ profiles indicate that a single ionizing group at the active center of the enzyme must be protonated for catalysis, whereas the K/sub i/ profiles show that the binding of NADPH to the free enzyme and of ATP-ribose to the enzyme-dihydrofolate complex is pH independent. From the results of deuterium isotope effects on V/K/sub NADPH/, it is concluded that NADPH behaves as a sticky substrate. It is this stickiness that raises artificially the intrinsic pK value of 6.4 for the Asp-27 residue of the enzyme-dihydrofolate complex to an observed value of 8.9. Thus, the binary enzyme complex is largely protonated at neutral pH. The elevation of the intrinsic pK value of 6.4 for the ternary enzyme-NADPH-dihydrofolate complex to 8.5 is not due to the kinetic effects of substrates. Rather, it is the consequence of the lower, pH-independent rate of product release and the faster pH-dependent catalytic step. The data for deuterium isotope and deuterium solvent isotope effects are consistent with the postulate that, for the reduction of dihydrofolate to tetrahydrofolate, protonation precedes hydride transfer. A scheme is proposed for the indirect transfer of a proton from the enzyme to dihydrofolate

  6. Deuterium isotope effects in condensed-phase thermochemical decomposition reactions of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine

    International Nuclear Information System (INIS)

    Shackelford, S.A.; Coolidge, M.B.; Goshgarian, B.B.; Loving, B.A.; Rogers, R.N.; Janney, J.L.; Ebinger, M.H.

    1985-01-01

    The deuterium isotope effect was applied to condensed-phase thermochemical reactions of HMX and HMX-d 8 by using isothermal techniques. Dissimilar deuterium isotope effects revealed a mechanistic dependence of HMX upon different physical states which may singularly predominate in a specific type of thermal event. Solid-state HMX thermochemical decomposition produces a primary deuterium isotope effect (DIE), indicating that covalent C-H bond rupture is the rate-controlling step in this phase. An apparent inverse DIE is displayed by the mixed melt phase and can be attributed to C-H bond contraction during a weakening of molecular lattice forces as the solid HMX liquefies. The liquid-state decomposition rate appears to be controlled by ring C-N bond cleavage as evidenced by a secondary DIE and higher molecular weight products. These results reveal a dependence of the HMX decomposition process on physical state and lead to a broader mechanistic interpretation which explains the seemingly contradictory data found in current literature reviews. 33 references, 9 figures, 5 tables

  7. Secondary α-deuterium isotope effects as a probe to the relationship between structure and mechanism of pyrolysis of secondary azoalkanes

    International Nuclear Information System (INIS)

    Grizzle, P.L.

    1975-01-01

    This study was carried out to investigate the mechanism of azoalkane thermolysis and the effect of molecular structure on the potential-energy hypersurface for pyrolysis utilizing secondary α-deuterium isotope effects. Since the magnitude of the α-effect for 1,1'-diphenylazoethane is of singular importance in the interpretation of those for related compounds, it has been redetermined. To investigate the effect of molecular structure on the potential-energy hypersurface for thermolysis, α-effects have been determined for 2,2,2',2'-tetramethyl-1,1'-diphenylazoethane and (2,2-dimethyl-1-phenylpropyl)azomethane; the inability to prepare these compounds by conventional methods necessitated the development of a new method for synthesis of secondary azoalkanes. A convenient synthesis of secondary azo compounds is reported. Secondary α-deuterium isotope effects were obtained for the thermal decomposition of 1,1'-diphenylazoethane (III) and 1,1'-diphenylazoethane-1,1'-d 2 (III-d 2 ). The isotope effect is entirely consistent with a simultaneous one-step thermolysis mechanism. Secondary α-deuterium isotope effects and activation parameters were obtained in the thermolysis of 2,2,2',2'-tetramethyl-1,1'-diphenylazopropane (VIII) and (2,2-dimethyl-1-phenylpropyl)azomethane (IX). The data for VIII is considered in terms of both a one- and two-step thermolysis mechanism. The α-effect and activation energy for VIII are not obviously reconcilable with a one-step mechanism. The α-effects, activation energies, and rates of thermolysis for VIII, IX, and (1-phenylethyl)azomethane are most easily rationalized by a two-step mechanism

  8. Deuterium isotope effects on the dipole moment and polarizability of HCl and NH3

    International Nuclear Information System (INIS)

    Scher, C.; Ravid, B.; Halevi, E.A.

    1982-01-01

    A previously described adaptation of the conventional Debye procedure for the direct determination of small dipole moment and polarizability differences between two polar gases is applied to the isotopic pairs DCl-HCl and ND 3 -NH 3 . The dipole moment difference obtained for the first isotopic pair, by using the Debye-Van Vleck equation for electric susceptibility, μ(DCl) - μ(HCl) = 0.005 5 +/- 0.0002 D, is consistent with published spectroscopically determined values of μ 00 (DCl) and μ 00 (HCl), while that obtained by using the classical Debye equation is not. For the second pair, use of the Debye-Van Vleck equation, along with a correction for thermal population of vibrationally excited levels, is shown to be essential and yields μ(ND) 3 - μ(NH 3 ) = +0.013 5 +/- 0.001 D and α(ND 3 ) - α(NH 3 ) = -(2.2 +/- 1.7) x 10 -26 cm 3

  9. Method of deuterium isotope separation and enrichment

    International Nuclear Information System (INIS)

    Benson, S.W.

    1978-01-01

    A method of separating deuterium, i.e., heavy hydrogen, from certain naturally occurring sources using tuned infrared lasers to selectively decompose specified classes of organic molecules (i.e., RX) into enriched molecular products containing deuterium atoms is described. The deuterium containing molecules are easily separated from the starting material by absorption, distillation or other simple chemical separation techniques and methods. After evaporation such deuterium containing molecules can be burned to form water with an enriched deuterium content or pyrolyzed to form hydrogen gas with an enriched deuterium content. The undecomposed molecules and the other reaction products which are depleted of their deuterium containing species can be catalytically treated, preferably using normal water, to restore the natural abundance of deuterium and such restored molecules can then be recycled

  10. Rate-controlling two-proton transfer coupled with heavy-atom motion in the 2-pyridinone-catalyzed mutarotation of tetramethylglucose. Experimental and calculated deuterium isotope effects

    International Nuclear Information System (INIS)

    Engdahl, K.A.; Bivehed, H.; Ahlberg, P.; Saunders, W.H. Jr.

    1983-01-01

    Primary and secondary deuterium isotope effects have been measured by polarimetry, and primary isotope effects have been calculated for the classical bifunctional catalysis: 2-pyridinone-catalyzed mutarotation of 2,3,4,6-tetra-O-methyl-α-D-glucopyranose (α-TMG) in benzene. From the positively curved plot of the specific rate of epimerization vs. the mole fraction of 2 H in the ''pool'' of OH and NH hydrogens, the isotope effects k/sub HH//k/sub DD/ = 3.66 +/- 0.09, k/sub HH//k/sub DH/ = 1.5, and k/sub HH//k/sub HD/ = 2.4 have been calculated. A secondary isotope effect of 1.14 +/- 0.02 has been measured by using α-TMG and (1- 2 H)-2,3,4,6-tetra-O-methyl-α-D-glucopyranose [(l- 2 H)-α-TMG], the synthesis of which is described in detail, together with those for (N- 2 H)-2-pyridinone and (1-O- 2 H)-2,3,4,6-tetra-O-methyl-α-D-glucopyranose [(1-O- 2 H)-α-TMG]. The rate data obtained have also been analyzed by fractionation theory, yielding approximately equal fractionation factors (0.5). The interpretation of the results has been assisted by calculations of the primary deuterium isotope effects using the BEBOVIB IV program. Two models involving small and considerable coupling, respectively, of the transferring protons to heavy-atom motion have been considered. In the favored structure for the transition state of the rate-limiting step, two protons are in transit, and their motion is governed either by a potential with a barrier or by one without. Their motion is considerably coupled to the heavy-atom motion (i.e., the breakage of the ring C-O bond), and tunnel corrections to the isotope effects are found to be negligible

  11. Method of deuterium isotope separation and enrichment

    International Nuclear Information System (INIS)

    Benson, S.W.

    1979-01-01

    A method is described for separating and enriching deuterium containing molecules comprising the steps of: providing a source of organic molecules containing a normal abundance of deuterium atoms, the organic molecules having a structural formula RX, in which R is an organic radical selected from ethyl, isopropyl, t-butyl and 3-cyclopentenyl, and in which X is selected from F, Cl, Br and OH, and wherein R represents 3-cyclopentenyl, X may additionally represent H; exposing the molecules to the radiation of at least one pulsed infrared laser source which has been specifically tuned and focussed to selectively decompose RX molecules containing deuterium to form an enriched olefin specie containing deuterium, and HX; and separating the deuterium enriched olefin specie from the undecomposed deuterium depleted RX molecules and HX. (author)

  12. Inter- and intramolecular deuterium isotope effects on the cytochrome P-450-catalyzed oxidative dehalogenation of 1,1,2,2-tetrachloroethane

    International Nuclear Information System (INIS)

    Hales, D.B.; Ho, B.; Thompson, J.A.

    1987-01-01

    The oxidation of 1,1,2,2-tetrachloroethane to dichloroacetic acid was investigated with rat liver microsomes and purified cytochrome P-450. Deuterium substitution had no effect on Km values, but both the inter- and intramolecular isotope effects (kH/kD) on Vmax were in the range 5.7-6.1. The equivalence of the inter- and intramolecular values indicates that 6.0 may be a good estimate of the intrinsic isotope effect. The intermolecular kH/kD value for the conversion of 1,1,2,2-trichloroethane and its 1- 2 H analog to chloroacetic acid was 5.5. These data, and the finding that 1 atom of 18 O was incorporated into the product when TCEA was oxidized in an 18 O 2 atmosphere, support an oxidative dechlorination mechanism that involves hydrogen atom abstraction by the P-450 intermediate oxo complex

  13. Detection of a deuterium isotope effect in di- and trisubstituted alkylphenylnitrosoureas. An SCE study in Chinese hamster V79-E cells.

    Science.gov (United States)

    Thust, R; Mendel, J; Bach, B; Schwarz, H

    1985-06-01

    The genotoxicity of 1-methyl-3-phenyl-1-nitrosourea (MPNU), 1-methyl-3-(p-chlorophenyl)-1-nitrosourea (C1-MPNU), 1-ethyl-3-phenyl-1-nitrosourea (EPNU), 1,3-dimethyl-3-phenyl-1-nitrosourea (DMPNU) and their derivatives substituted by deuterium in different positions was studied using sister chromatid exchange (SCE) induction in Chinese hamster V79-E cells. Deuterium substitution in the 1-methyl group of MPNU (MPNU-d3) and C1-MPNU (C1-MPNU-d3) diminished the SCE-inducing capacity by 20-30% and by 30-40% in DMPNU (DMPNU-d3B). There was no altered SCE activity detected when the phenyl group of MPNU (MPNU-d5) or the 3-methyl group of DMPNU (DMPNU-d3A) was deuterium labeled. No isotope effect was detected in deuterated EPNU derivatives, presumably due to the instability of these compounds. It is surmised that the easier delocalization of the positive charge in the deuterated alkyl diazonium ion causes a diminished reactivity and therefore influences the type and amount of DNA alkylation. Furthermore, the experiments with DMPNU and its derivatives revealed that, in contrast to mono- and disubstituted nitrosoureas, the biological activities of these very stable trisubstituted nitrosoureas are strongly influenced by a serum factor in the culture fluid.

  14. Detection of a deuterium isotope effect in di- and trisubstituted alkylphenylnitrosoureas. An SCE study in Chinese hamster V79-E cells

    International Nuclear Information System (INIS)

    Thust, R.; Mendel, J.; Bach, B.; Schwarz, H.

    1985-01-01

    The genotoxicity of 1-methyl-3-phenyl-1-nitrosourea (MPNU), 1-methyl-3-(p-chlorophenyl)-1-nitrosourea (C1-MPNU), 1-ethyl-3-phenyl-1-nitrosourea (EPNU), 1,3-dimethyl-3-phenyl-1-nitrosourea (DMPNU) and their derivatives substituted by deuterium in different positions was studied using sister chromatid exchange (SCE) induction in Chinese hamster V79-E cells. Deuterium substitution in the 1-methyl group of MPNU (MPNU-d3) and C1-MPNU (C1-MPNU-d3) diminished the SCE-inducing capacity by 20-30% and by 30-40% in DMPNU (DMPNU-d3B). There was no altered SCE activity detected when the phenyl group of MPNU (MPNU-d5) or the 3-methyl group of DMPNU (DMPNU-d3A) was deuterium labeled. No isotope effect was detected in deuterated EPNU derivatives, presumably due to the instability of these compounds. It is surmised that the easier delocalization of the positive charge in the deuterated alkyl diazonium ion causes a diminished reactivity and therefore influences the type and amount of DNA alkylation. Furthermore, the experiments with DMPNU and its derivatives revealed that, in contrast to mono- and disubstituted nitrosoureas, the biological activities of these very stable trisubstituted nitrosoureas are strongly influenced by a serum factor in the culture fluid

  15. Deuterium isotopic effects connected with unimolecular and concerted mechanisms. The case of 1-deutero-2-chloro alcohols; Effets isotopiques du deuterium attaches a des mecanismes unimoleculaires et concertes. Cas des deutero-1-chloro-2 alcools

    Energy Technology Data Exchange (ETDEWEB)

    Jambon, C

    1962-07-01

    After a bibliographic analysis of the probable causes of isotopic effects and their comparison, with the simplifications provided by the athermal model, a discussion of the isotopic effect of deuterium in organic molecules in terms of structural influences is presented, showing the important role of the C-D bond length which is shorter than the C-H bond length, and of the D atom's Van der Waals radius, shorter than that of the H atom. Kinetic measurements were carried out on some reactions involving the mechanisms proposed: unimolecular ionizations and halogen concentrates. The structural models chosen are: 2-chloro-cyclo-hexanols cis and trans 1-H and 2-D; 2-chloro-cyclo-pentanols cis trans 1-H and 1-D; 1-phenyl-l-chloro-2-propanol threo 2-H and 2-D. (author) [French] Apres une analyse bibliographique des causes probables d'effets isotopiques et leur comparaison, avec les simplifications qu'apporte le modele athermique, on a entrepris l'etude de la discussion isotopique du deuterium dans des molecules organiques en termes d'influences structurelles, cherchant a degager le role important de la longueur de la liaison C-D plus courte que C-H, et du rayon de Van der Waals de l'atome de D plus petit que celui de H. On a effectue des mesures cinetiques sur quelques reactions invoquant les mecanismes envisages: ionisations unimoleculaires et concentrees d'halogenes. Les modeles structuraux choisis sont: chloro 2 - cyclohexanols cis et trans H 1 et D 1; chloro 2 - cyclopentanols cis et trans H 1 et D 1; phenyl 1 - chloro 1 - propanol 2 threo H 2 et D 2. (auteur)

  16. Deuterium isotopic effects connected with unimolecular and concerted mechanisms. The case of 1-deutero-2-chloro alcohols; Effets isotopiques du deuterium attaches a des mecanismes unimoleculaires et concertes. Cas des deutero-1-chloro-2 alcools

    Energy Technology Data Exchange (ETDEWEB)

    Jambon, C

    1962-07-01

    After a bibliographic analysis of the probable causes of isotopic effects and their comparison, with the simplifications provided by the athermal model, a discussion of the isotopic effect of deuterium in organic molecules in terms of structural influences is presented, showing the important role of the C-D bond length which is shorter than the C-H bond length, and of the D atom's Van der Waals radius, shorter than that of the H atom. Kinetic measurements were carried out on some reactions involving the mechanisms proposed: unimolecular ionizations and halogen concentrates. The structural models chosen are: 2-chloro-cyclo-hexanols cis and trans 1-H and 2-D; 2-chloro-cyclo-pentanols cis trans 1-H and 1-D; 1-phenyl-l-chloro-2-propanol threo 2-H and 2-D. (author) [French] Apres une analyse bibliographique des causes probables d'effets isotopiques et leur comparaison, avec les simplifications qu'apporte le modele athermique, on a entrepris l'etude de la discussion isotopique du deuterium dans des molecules organiques en termes d'influences structurelles, cherchant a degager le role important de la longueur de la liaison C-D plus courte que C-H, et du rayon de Van der Waals de l'atome de D plus petit que celui de H. On a effectue des mesures cinetiques sur quelques reactions invoquant les mecanismes envisages: ionisations unimoleculaires et concentrees d'halogenes. Les modeles structuraux choisis sont: chloro 2 - cyclohexanols cis et trans H 1 et D 1; chloro 2 - cyclopentanols cis et trans H 1 et D 1; phenyl 1 - chloro 1 - propanol 2 threo H 2 et D 2. (auteur)

  17. Deuterium isotope effects during formation of phenols by hepatic monoxygenases. Evidence for an alternative to the arene oxide pathway

    International Nuclear Information System (INIS)

    Tomaszewski, J.E.; Jerina, D.M.; Daly, J.W.

    1975-01-01

    The in vivo and in vitro metabolisms of normal and deuterated aromatic substrates have been investigated in rats. Significant isotope effects (k/ sub H//k/sub D/ equals 1.3-1.75) were associated with in vivo formation of meta-hydroxylated metabolites from 1:1 mixtures of normal and perdeuterio-(arylring) nitrobenzene, methyl phenyl sulfide, and methyl phenyl sulfone. Since isotope effects of this magnitude are incompatible with arene oxides as intermediates in the formation of phenols, the results provide evidence that multiple pathways are responsible for the formation of phenols in mammals. Significant isotope effects were not associated with the formation of the other phenolic isomers of nitrobenzene, methyl phenyl sulfone, or methyl phenyl sulfide or with the formation of phenolic products from anisole, bromobenzene, chlorobenzene, fluorobenzene, benzonitrile, naphthalene, zoxazolamine, acetanilide, biphenyl, diphenylhydantoin, benzene, o- and p-xylene, toluene, and mesitylene. Significant isotope effects might not be observable with the latter substrates if the kinetic parameters for oxidation of substrate change or if the arene oxide pathway greatly predominates. Furthermore, extensive in vivo metabolism of any substrate would make isotope effects unobservable by the procedure employed, namely the analysis of isotope content in metabolites formed from 1:1 mixtures of normal and deuterated substrates. (U.S.)

  18. Pull-push mechanism for the 1,2-hydrogen rearrangement of carbenes. Substituent and deuterium isotope effects for thermal decomposition of 1-phenyl-2-diazopropanes

    International Nuclear Information System (INIS)

    Su, D.T.T.; Thornton, E.R.

    1978-01-01

    Intramolecular and intermolecular deuterium isotope effects have been measured for the thermal carbene H rearrangements of three substituted 1-phenyl-2-diazopropanes-1-d in hexane at 25 0 C. The isotope effects, k/sub H//k/sub D/, vary from ca. 1.2 to 1.5, increasing with electron-withdrawing substituents, for the formation of both cis- and trans-β-methylstyrenes. Product ratios were determined for these compounds as well as the corresponding undeuterated ones, permitting calculation of intermolecular primary and secondary isotope effects. In addition, the competition among the cis and trans products and the product of H migration from the terminal methyl group permitted determination of Hammett rho values of ca. -1 for the competition between benzylic and terminal migration. The results strongly indicate a ''pull-push'' mechanism, which can be pictured roughly as electrophilic attack on the C--H bond by the phantom p orbital of the carbene along with backside nucleophilic attack by the carbene unshared electron pair to push the H away and form the π bond. The data are believed to be consistent only with a nonzero barrier for the carbene hydrogen rearrangement

  19. Metabolism of N-methylformamide in mice: primary kinetic deuterium isotope effect and identification of S-(N-methylcarbamoyl)glutathione as a metabolite

    International Nuclear Information System (INIS)

    Threadgill, M.D.; Axworthy, D.B.; Baillie, T.A.; Farmer, P.B.; Farrow, K.C.; Gescher, A.; Kestell, P.; Pearson, P.G.; Shaw, A.J.

    1987-01-01

    S-(N-Methylcarbamoyl)glutathione has been identified by cesium ion liquid secondary ion mass spectrometry as a biliary metabolite in mice of the experimental antitumor agent and hepatotoxin N-methylformamide. Metabolism of N-methylformamide to urinary methylamine, urinary N-acetyl-S-(N-methylcarbamoyl)-cysteine and biliary S-(N-methylcarbamoyl)glutathione was found to be subject to large intermolecular primary kinetic isotope effects when hydrogen was replaced by deuterium in the formyl group (kH/kD = 5.5 +/- 0.2, 4.5 +/- 1.0 and 7 +/- 2, respectively), as shown by mass spectrometry of derivatives of these metabolites. These values indicate the existence of a common metabolic precursor for each of these metabolites. In particular, methylamine is shown not to arise from simple enzymatic hydrolysis of N-methylformamide but is associated with an oxidative process. Therefore, it is highly likely that N-methylformamide is oxidized and conjugated to form S-(N-methylcarbamoyl)glutathione which is metabolized further to N-acetyl-S-(N-methylcarbamoyl) cysteine. Either of these thiocarbamates could be hydrolyzed to give the parent thiol and the observed metabolic end products, methylamine and carbon dioxide. The presence of deuterium in the formyl moiety of N-methylformamide reduced markedly the hepatotoxicity of the compound, as shown by measurements of the activities of appropriate hepatic enzymes in plasma

  20. Nucleophilic addition to olefins. 7. Kinetic deuterium isotope effects as criterion for an enforced preassociation mechanism in the hydrolysis of substituted benzylidene Meldrum's acids

    International Nuclear Information System (INIS)

    Bernasconi, C.F.; Leonarduzzi, G.D.

    1982-01-01

    The hydrolysis of the title compounds occurs in four steps: (1) nucleophilic attack by water or hydroxide ion to form the addition complex T/sub OH/ - ; (2) carbon protonation of T/sub OH/ - to form T/sub OH/ 0 ; (3) oxygen deprotonation of T/sub OH/ 0 to form T/sub OH/ 0 - ; (4) collapse of the tetrahedral intermediate T/sub OH/ - into the respective benzaldehyde and Meldrum's acid anion. There is also a water-catalyzed collapse of T/sub OH/ 0 which becomes dominant in strongly acidic solution. In basic solution carbon protonation of T/sub OH/ - (step 2) is rate limiting; in strongly acidic media the water-catalyzed collapse of T/sub OH/ 0 is rate limiting for all substrates. In moderatly acidic solution two types of behavior were observed. With the p-nitro derivative step 4 is rate limiting at high, step 3 at low buffer concentrations. The latter situation is equivalent to a diffusion-controlled trapping mechanism in the reverse direction. With the parent and the p-methoxy derivative, collapse of T/sub OH/ 0 - occurs before the protonated base catalyst generated in step 3 can diffuse away; this is equivalent to an enforced preassociation mechanism in the reverse direction and is analogous to the reaction of thiol anions with acetaldehyde studied by Gilbert and Jencks. Our interpretation is strongly supported by (1) α secondary kinetic deuterium isotope effects which are large for the preassociation mechanism but essentially nil for the trapping mechanism and (2) by Bronsted #betta# values around 0.8 in the case of the preassociation mechanism and 1.0 for the trapping mechanism. The mechanism for the water-catalyzed collapse of T/sub OH/ 0 - is probably concerted, a conclusion which is supported by a large positive deviation from the Bronsted plot for base catalysis and by a large α secondary kinetic deuterium isotope effect

  1. Primary and secondary kinetic deuterium isotope effects and transition-state structures for benzylic chlorination and bromination of toluene

    International Nuclear Information System (INIS)

    Hanzlik, R.P.; Schaefer, A.R.; Moon, J.B.; Judson, C.M.

    1987-01-01

    As a chemical model for benzylic hydroxylation effects by cytochrome P-450 enzymes, the chlorination of PhCH 3 , PhCH 2 D, PhCHD 2 , and PhCD 3 in a two-phase system of hypochlorite/CH 2 Cl 2 with a phase-transfer catalyst has been investigated. On the basis of the deuterium content of the product benzyl chlorides, relative rate constants were deduced for all possible H- and D-abstractions with these substrates. From this the primary (P) and secondary (S) KDIEs were found to be 5.90 +/- 0.41 and 1.03 +/- 0.02, respectively, and the rule of the geometric mean was found to be closely obeyed. For the analogous bromination of toluene by N-bromosuccinimide in CCl 4 , P and S were 6.37 +/- 0.43 and 1.05 +/- 0.01. The transition states of these processes must therefore involve extensive C-H bond breaking but relatively little rehybridization toward planarity at the reacting carbon

  2. Biological effects of deuterium - depleted water

    International Nuclear Information System (INIS)

    Stefanescu, I.; Titescu, Gh.; Croitoru, Cornelia; Saros-Rogobete, Irina

    2000-01-01

    Deuterium-depleted water (DDW) is represented by water that has an isotopic content smaller than 145 ppm D/(D + H). DDW production technique consists in the separation of deuterium from water by a continuous distillation process under pressure of about 133.3 mbar. The water used as raw material has a isotopic content of 145 ppm D/(D + H) and can be demineralized water, distillated water or condensed-steam. DDW results as a distillate with an isotopic deuterium content of 15-80 ppm, depending on the level we want to achieve. Beginning with 1996 the Institute of Cryogenics and Isotopic Technologies, DDW producer, co-operated with Romanian specialized institutes for studying the biological effects of DDW. The role of naturally occurring D in living organisms was examined by using DDW instead of natural water. These investigations led to the following conclusions: - DDW caused a tendency towards the increase of the basal tone, accompanied by the intensification of the vasoconstrictor effects of phenylefrine, noradrenaline and angiotensin; the increase of the basal tone and vascular reactivity produced by the DDW persists after the removal of the vascular endothelium; - Animals treated with DDW showed an increase of the resistance both to sublethal and lethal gamma radiation doses, suggesting a radioprotective action by the stimulation of non-specific immune defense mechanisms; - DDW stimulates immuno-defense reactions represented by the opsonic, bactericidal and phagocyte capacity of the immune system together with an increase in the number of poly-morphonuclear neutrophils; - Investigations regarding artificial reproduction of fish with DDW fecundated solutions confirmed favorable influence in embryo growth stage and resistance and following growth stages; - It was studied germination, growth and quantitative character variability in plants; one can remark the favorable influence of DDW on biological processes in plants in various ontogenetic stages. (authors)

  3. Strong isotope effects on the charge transfer in slow collisions of He2+ with atomic hydrogen, deuterium, and tritium

    NARCIS (Netherlands)

    Stolterfoht, N.; Cabrera-Trujillo, R.; Oehrn, Y.; Deumens, E.; Hoekstra, R.; Sabin, J. R.

    2007-01-01

    Probabilities and cross sections for charge transfer by He2+ impact on atomic hydrogen (H), deuterium (D), and tritium (T) at low collision energies are calculated. The results are obtained using an ab initio theory, which solves the time-dependent Schrodinger equation. For the H target, excellent

  4. Deuterium and heavy water

    International Nuclear Information System (INIS)

    Vasaru, G.; Ursu, D.; Mihaila, A.; Szentgyorgyi, P.

    1975-01-01

    This bibliography on deuterium and heavy water contains 3763 references (1932-1974) from 43 sources of information. An author index and a subject index are given. The latter contains a list of 136 subjects, arranged in 13 main topics: abundance of deuterium , catalysts, catalytic exchange, chemical equilibria, chemical kinetics, deuterium and heavy water analysis, deuterium and heavy water properties, deuterium and heavy water separation, exchange reactions, general review, heavy water as moderator, isotope effects, synthesis of deuterium compounds

  5. Low-dose in vivo pharmacokinetic and deuterium isotope effect studies of N-nitrosodimethylamine in rats

    International Nuclear Information System (INIS)

    Mico, B.A.; Swagzdis, J.E.; Hu, H.S.; Keefer, L.K.; Oldfield, N.F.; Garland, W.A.

    1985-01-01

    The rates of elimination of N-nitrosodimethylamine (NDMA) and its fully deuterated analogue (N-nitrosodi[ 2 H6]methylamine, [ 2 H6]NDMA) were studied in vivo to explore the origins of the difference in their carcinogenicity. Male Fischer 344 rats, 7.5 weeks of age, were given nitrosamine bolus doses of 1.35 mumol/kg by tail vein injection and 2.02 or 4.05 mumol/kg by p.o. gavage. Animals were sacrificed at various time points from 2.5 to 180 min after i.v. administration or 5 to 120 min after p.o. dosage, and their blood was analyzed for NDMA by gas chromatography-high resolution mass spectrometry. After i.v. injection, blood nitrosamine concentrations declined in an apparently biexponential manner with a terminal half-life of 10 min for NDMA and 12 min for [ 2 H6]NDMA. The apparent total systemic blood clearances for NDMA and [ 2 H6]NDMA were 39 and 26 ml/min/kg, respectively. The apparent steady-state volumes of distribution were nearly identical (297 and 309 ml/kg, respectively). The areas under the curve after 2.02- and 4.05-mumol/kg p.o. doses were proportional to dose. The apparent bioavailability of NDMA was 8%, while that of [ 2 H6]NDMA was 21%. Isotope effects calculated as the ratios of first-pass metabolism, total systemic clearances, bioavailabilities, and intrinsic hepatic clearances were 1.2, 1.5, 2.6, and 3.2, respectively. The isotope effect determined from blood concentrations measured after simultaneous administration of NDMA and [ 2 H6]NDMA by steady-state infusion (each at 1.5 mumol/kg/h) was 2.6 +/- 0.9 (SD)

  6. Deuterium isotope composition of palaeoinfiltration water trapped in speleothems

    International Nuclear Information System (INIS)

    Rozanski, K.

    1987-05-01

    Analytical and methodological aspects of combined isotope investigations of carbonate cave deposits are thoroughly discussed in the report. Weight is put on isotope analyses of fluid inclusions (D and 18 O content) extracted from speleothems of known age. Dating was done by the 230 Th/ 234 U ratio method. Isotopic analyses of speleothems originating from European caves allowed some important conclusions to be formulated regarding past climatic and environmental conditions prevailing over the European continent during the last 300,000 yrs: a) δD values of fluid inclusions suggest a remarkable constancy of the heavy-isotope content of European palaeoinfiltration waters recharged during interglacial periods, b) a climate-induced, long-term changes in isotopic composition of precipitation and surface air temperature over Europe can be characterized by the deuterium gradient of ca.1 4 deg./oo/deg. C, c) an apparent constancy of the continental gradient in deuterium content of European palaeoinfiltration waters as judged from the fluid inclusion data suggests that atmospheric circulation over Europe did not undergo substantial changes for at least 300,000 years

  7. Deuterium isotope effects on toluene metabolism. Product release as a rate-limiting step in cytochrome P-450 catalysis

    International Nuclear Information System (INIS)

    Ling, K.H.; Hanzlik, R.P.

    1989-01-01

    Liver microsomes from phenobarbital-induced rats oxidize toluene to a mixture of benzyl alcohol plus o-, m- and p-cresol (ca. 69:31). Stepwise deuteration of the methyl group causes stepwise decreases in the yield of benzyl alcohol relative to cresols (ca. 24:76 for toluene-d3). For benzyl alcohol formation from toluene-d3 DV = 1.92 and D(V/K) = 3.53. Surprisingly, however, stepwise deuteration induces stepwise increases in total oxidation, giving rise to an inverse isotope effect overall (DV = 0.67 for toluene-d3). Throughout the series (i.e. d0, d1, d2, d3) the ratios of cresol isomers remain constant. These results are interpreted in terms of product release for benzyl alcohol being slower than release of cresols (or their epoxide precursors), and slow enough to be partially rate-limiting in turnover. Thus metabolic switching to cresol formation causes a net acceleration of turnover

  8. Hydrogen, deuterium, and tritium isotope exchange experiments in JET

    Energy Technology Data Exchange (ETDEWEB)

    Horton, L.D.; Andrew, P.; Bracco, G.; Conroy, S.; Corti, S.; Ehrenberg, J.; Goodall, D.H.J.; Jarvis, O.N.; Lomas, P.; Loughlin, M.; Peacock, A.T.; Saibene, G.; Sadler, G.; Sartori, R.; Stamp, M.F.; Thomas, P.R.; Belle, P. van (JET Joint Untertaking, Abingdon, Oxfordshire (United Kingdom))

    1992-12-01

    Isotope exchange experiments have been performed in JET using hydrogen, deuterium, and, in the recent preliminary tritium experiment (PTE), tritium. The rate of change-over from one isotope to another involves two quite different time constants. We have modelled this behaviour using a multireservoir model which splits the accessible hydrogenic particles into two groups, each having a different rate of exchange of particles with the plasma. By applying this model to the sequence of discharges during and after the PTE, we can determine the parameters in the model. The resulting fit also gives a good representation of hydrogen/deuterium change-over experiments, indicating that the tritium behaves in the same manner as other hydrogen isotopes, at least as far as recycling is concerned. Discrepancies between the model and the actual measurements of tritium recovery after the PTE lead us to conclude that isotope exchange processes resulting from collisions of molecules with the vessel walls play a significant role in spreading tritrium around the machine. (orig.).

  9. Use of azeotropic distillation for isotopic analysis of deuterium in soil water and saturate saline solution

    International Nuclear Information System (INIS)

    Santos, Antonio Vieira dos.

    1995-05-01

    The azeotropic distillation technique was adapted to extract soil water and saturate saline solution, which is similar to the sea water for the Isotopic Determination of Deuterium (D). A soil test was used to determine the precision and the nature of the methodology to extract soil water for stable isotopic analysis, using the azeotropic distillation and comparing with traditional methodology of heating under vacuum. This methodology has been very useful for several kinds of soil or saturate saline solution. The apparatus does not have a memory effect, and the chemical reagents do not affect the isotopic composition of soil water. (author). 43 refs., 10 figs., 12 tabs

  10. Isotopic scaling of transport in deuterium-tritium plasmas

    International Nuclear Information System (INIS)

    Scott, S.D.; Adler, H.; Bell, M.G.; Bell, R.; Budny, R.V.; Bush, C.E.; Chang, Z.; Duong, H.

    1995-01-01

    Both global and thermal energy confinement improve in high-temperature supershot plasmas in the Tokamak Fusion Test Reactor (TFTR) when deuterium beam heating is partially or wholly replaced by tritium beam heating. For the same heating power, the tritium-rich plasmas obtain up to 22% higher total energy, 30% higher thermal ion energy, and 20-25% higher central ion temperature. Kinetic analysis of the temperature and density profiles indicates a favorable isotopic scaling of ion heat transport and electron particle transport, with τ Ei (a/2) ∝ (A) 0.7-0.8 and τ pe (a) ∝ (A) 0.8

  11. Deuterium isotope separation factor between hydrogen and liquid water

    International Nuclear Information System (INIS)

    Rolston, J.H.; den Hartog, J.; Butler, J.P.

    1976-01-01

    The overall deuterium isotope separation factor between hydrogen and liquid water, α, has been measured directly for the first time between 280 and 370 0 K. The data are in good agreement with values of α calculated from literature data on the equilibrium constant for isotopic exchange between hydrogen and water vapor, K 1 , and the liquid-vapor separation factor, α/sub V/. The temperature dependence of α over the range 273-473 0 K based upon these new experimental results and existing literature data is given by the equation ln α = -0.2143 + (368.9/T) + (27,870/T 2 ). Measurements on α/sub V/ given in the literature have been surveyed and the results are summarized over the same temperature range by the equation ln α/sub V/ = 0.0592 - (80.3/T) +

  12. Isotopic scaling of transport in deuterium-tritium plasmas

    International Nuclear Information System (INIS)

    Scott, S.D.; Murakami, M.; Adler, H.; Chang, Z.; Duong, H.; Grisham, L.R.; Fredrickson, E.D.; Grek, B.; Hawryluk, R.J.; Hill, K.W.; Hosea, J.; Jassby, D.L.; Johnson, D.W.; Johnson, L.C.; Loughlin, M.J.; Mansfield, D.K.; McGuire, K.M.; Meade, D.M.; Mikkelsen, D.M.; Murphy, J.; Park, H.K.; Ramsey, A.T.; Schivell, J.; Skinner, C.H.; Strachan, J.D.; Synakowski, E.J.; Taylor, G.; Thompson, M.E.; Wieland, R.; Zarnstorff, M.C.

    1995-01-01

    Both global and thermal energy confinement improve in high-temperature supershot plasmas in the Tokamak Fusion Test Reactor (TFTR) when deuterium beam heating is partially or wholly replaced by tritium beam heating. For the same heating power, the tritium-rich plasmas obtain up to 22% higher total energy, 30% higher thermal ion energy, and 20-25% higher central ion temperature. Kinetic analysis of the temperature and density profiles indicates a favorable isotopic scaling of ion heat transport and electron particle transport, with τ Ei (a/2) ∝ left angle A right angle 0.7-0.8 and τ pe (a) ∝ left angle A right angle 0.8 . (orig.)

  13. Deuterium/hydrogen isotope exchange on beryllium and beryllium nitride; Deuterium/Wasserstoff-Isotopenaustausch an Beryllium und Berylliumnitrid

    Energy Technology Data Exchange (ETDEWEB)

    Dollase, Petra; Eichler, Michael; Koeppen, Martin; Dittmar, Timo; Linsmeier, Christian [Forschungszentrum Juelich GmbH, Institut fuer Energie- und Klimaforschung - Plasmaphysik (Germany)

    2016-07-01

    In the fusion experiments JET and ITER, the first wall is made up of beryllium. The use of nitrogen is discussed for radiative cooling in the divertor. This can react with the surface of the first wall to form beryllium nitride (Be{sub 3}N{sub 2}). The hydrogen isotopes deuterium and tritium, which react in the fusion reaction to helium and a neutron, are used as fuel. Since the magnetic confinement of the plasma is not perfect, deuterium and tritium ions are also found on the beryllium wall and can accumulate there. This should be avoided due to the radioactivity of tritium. Therefore the isotope exchange with deuterium is investigated to regenerate the first wall. We investigate the isotopic exchange of deuterium and protium in order to have not to work with radioactive tritium. The ion bombardment is simulated with an ion source. With voltages up to a maximum of 5 kV, deuterium and protic hydrogen ions are implanted in polycrystalline Be and Be{sub 3}N{sub 2}. The samples are then analyzed in situ using X-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). Subsequently, samples prepared under the same conditions are characterized ex-situ by means of nuclear reaction analysis (NRA). [German] In den Fusionsexperimenten JET und ITER besteht die erste Wand im Hauptraum aus Beryllium (Be). Zur Strahlungskuehlung im Divertor wird der Einsatz von Stickstoff diskutiert. Dieser kann mit der Oberflaeche der ersten Wand zu Berylliumnitrid (Be{sub 3}N{sub 2}) reagieren. Als Brennstoff werden die Wasserstoffisotope Deuterium und Tritium eingesetzt, die in der Fusionsreaktion zu Helium und einem Neutron reagieren. Da der magnetische Einschluss des Plasmas nicht perfekt ist, treffen auch Deuterium- und Tritiumionen auf die Berylliumwand auf und koennen sich dort anreichern. Das soll aufgrund der Radioaktivitaet von Tritium unbedingt vermieden werden. Daher wird zur Regenerierung der ersten Wand der Isotopenaustausch mit Deuterium untersucht. Wir

  14. Effect of Coulomb screening on deuterium-deuterium fusion cross-section

    International Nuclear Information System (INIS)

    Wang Shunjin

    1991-01-01

    The popular Gamow formula for the deuterium-deuterium fusion cross-section is generalized to take into account the Coulomb screening effect. The generalized formula has been used to discuss the fusion process occurring in the metal medium

  15. Determination of the Tautomeric Equilibria of Pyridoyl Benzoyl -Diketones in the Liquid and Solid State through the use of Deuterium Isotope Effects on 1H and 13C NMR Chemical Shifts and Spin Coupling Constants

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Borisov, Eugeny V.; Lindon, John C.

    2015-01-01

    The tautomeric equilibria for 2-pyridoyl-, 3-pyridoyl-, and 4-pyridoyl-benzoyl methane have been investigated using deuterium isotope effects on 1H and 13C chemical shifts both in the liquid and the solid state. Equilibria are established both in the liquid and the solid state. In addition......, in the solution state the 2-bond and 3-bond J(1H–13C) coupling constants have been used to confirm the equilibrium positions. The isotope effects due to deuteriation at the OH position are shown to be superior to chemical shift in determination of equilibrium positions of these almost symmetrical -pyridoyl......-benzoyl methanes. The assignments of the NMR spectra are supported by calculations of the chemical shifts at the DFT level. The equilibrium positions are shown to be different in the liquid and the solid state. In the liquid state the 4-pyridoyl derivative is at the B-form (C-1 is OH), whereas the 2-and 3-pyridoyl...

  16. Isotope effects on nuclear shielding

    International Nuclear Information System (INIS)

    Hansen, P.E.

    1983-01-01

    This review concentrates upon empirical trends and practical uses of mostly secondary isotope effects, both of the intrinsic and equilibrium types. The text and the tables are arranged in the following fashion. The most 'popular' isotope effect is treated first, deuterium isotope effects on 13 C nuclear shielding, followed by deuterium on 1 H nuclear shieldings, etc. Focus is thus on the isotopes producing the effect rather than on the nuclei suffering the effect. After a brief treatment of each type of isotope effect, general trends are dealt with. Basic trends of intrinsic isotope effects such as additivity, solvent effects, temperature effects, steric effects, substituent effects and hyperconjugation are discussed. Uses of isotope effects for assignment purposes, in stereochemical studies, in hydrogen bonding and in isotopic tracer studies are dealt with. Kinetic studies, especially of phosphates, are frequently performed by utilizing isotope effects. In addition, equilibrium isotope effects are treated in great detail as these are felt to be new and very important and may lead to new uses of isotope effects. Techniques used to obtain isotope effects are briefly surveyed at the end of the chapter. (author)

  17. Water containing deuterium electrolysis to obtain gaseous hydrogen isotope in a high state of purity

    International Nuclear Information System (INIS)

    Bellanger, Gilbert

    1992-01-01

    In this paper, the basic concept is to prepare hydrogen in a high state of purity by electrolysing water using a palladium cathode. During electrolysis, hydrogen is at first adsorbed at the palladium surface, and next it diffuses through it till opposite face of its entry where it is desorbed; thus permitting to regain it in a very pure state for storage. The method can be used from water containing deuterium. To improve hydrogen adsorption, surface effect of palladium must be studied. It was found that heat treatment of palladium improved the hydrogen permeation flux. The diffusivity of hydrogen is controlled by Fick and Sieverts equations in which temperature has a significant influence on permeation rates. Anyway, hydrogen desorption does not cause any difficulty. In a second part, we have studied the isotopic separation factor using water containing deuterium. We remarked in fact that it depends on current density, overpotential, diffusivity of hydrogen and deuterium and isotopic composition of electrolyte as expected. In the last part, we realized an original electrolysis model in a glove-box in which are taken into account the results given before and also the technology components employed in processes involving the use of tritium. (author) [fr

  18. Improvement in deuterium recovery from water–isotope mixture by thermal diffusion in the device of branch columns

    International Nuclear Information System (INIS)

    Hsu, Ching-Chun; Yeh, Ho-Ming

    2014-01-01

    Highlights: • Recovery of deuterium by thermal diffusion from water–isotope mixture has been investigated. • The undesirable remixing effect can be reduced by employing the device of branch columns. • Deuterium recoveries were compared with that in a single column of the same total column length. • Considerable recovery improvement is obtainable in the device of branch columns, instead of in a single-column device. - Abstract: Deuterium recovery from water–isotopes mixture using thermal diffusion can be improved by employing the branch column device, instead of single column devices, with the same total column length. The remixing effect due to convection currents in a thermal diffusion column for heavy water enrichment is thus reduced and separation improvement increases when the flow rate or the total column length increases. The improvement in separation can reach about 50% for the numerical example given

  19. Effect of deposited tungsten on deuterium accumulation in beryllium in contact with atomic deuterium

    Energy Technology Data Exchange (ETDEWEB)

    Sharapov, V.M.; Gavrilov, L.E. [Institute of Physical Chemistry, Russian Academy of Sciences, Moscow (Russian Federation); Kulikauskas, V.S.

    1998-01-01

    Usually ion or plasma beam is used for the experiment with beryllium which simulates the interaction of plasma with first wall in fusion devices. However, the use of thermal or subthermal atoms of hydrogen isotopes seems to be useful for that purpose. Recently, the authors have studied the deuterium accumulation in beryllium in contact with atomic deuterium. The experimental setup is shown, and is explained. By means of elastic recoil detection (ERD) technique, it was shown that in the exposure to D atoms at 740 K, deuterium is distributed deeply into the bulk, and is accumulated up to higher concentration than the case of the exposure to molecular deuterium. The depth and concentration of deuterium distribution depend on the exposure time, and those data are shown. During the exposure to atomic deuterium, oxide film grew on the side of a sample facing plasma. In order to understand the mechanism of deuterium trapping, the experiment was performed using secondary ion mass spectrometry (SIMS) and residual gas analysis (RGA). The influence that the tungsten deposit from the heated cathode exerted to the deuterium accumulation in beryllium in contact with atomic deuterium was investigated. These results are reported. (K.I.)

  20. What is the effect of variations optimization of the transition state on α-deuterium secondary kinetic isotope effects? A prototype: CD3H + H right-reversible CD3 + H2

    International Nuclear Information System (INIS)

    Lu, Dahong; Maurice, D.; Truhlar, D.G.

    1990-01-01

    Variational Transition state theory calculations with semiclassical transmission coefficients have been carried out for a prototype case of α-deuterium secondary kinetic isotope effects (KIEs) in a reaction involving the transformation of an sp 3 carbon to sp 2 , in particular for the reactions of CH 4 and CD 3 H with H and D. The authors also study the KIE for the reverse direction and for the reactions of CH 4 and CD 3 H with D. They find that the variational transition states lead to significantly different nontunneling KIEs than the conventional ones, e.g., 1.22 vs. 1.07, and the inclusion of multidimensional tunneling effects increases the discrepancy even more. The origins of these variations and tunneling effects are examined in detail in terms of structures, vibrational frequencies, and the curvature of the reaction path. The conclusions have wide implications for the validity of conventional treatments of kinetic isotope effects. They predict some particularly large secondary KIEs at low temperature, and these predictions can be tested by future experiments

  1. Regioselective photoisomerizations of bridgehead substituted dibenzobarrelenes and benzonorbornadienes. The implication of excited-state secondary deuterium isotope effects of benzo-vinyl bridging

    International Nuclear Information System (INIS)

    Paquette, L.A.; Bay, E.

    1982-01-01

    Replacement of a bridgehead hydrogen by deuterium in substituted dibenzobarrelenes and benzonorbornadienes leads to k/sub H//k/sub D/ values of 1.11-1.27 (cyclopropyl substitution disfavored); these effects are opposite to those seen with other substitutents (except bromine) and demand that bridged radicals be formed reversibly or not at all. Since results demonstrate that the influence of bridgehead substitutents is clearly large, it is possible that pendant functional groups at each of the available sites exert their influence in a direct concerted manner. At least three intriguing studies now become worthy of immediate attention. In the first, benzonorbornadienes that are differently substituted at the bridgehead sites may serve as exceptionally sensitive probes of relative radical stabilization capabilities in the excited state. Direct competition experiments of this sort are unprecedented. Secondly, it becomes important to assess the relative controlling powers of bridgehead/aryl and bridgehead/vinyl substitutent combinations

  2. The study of the deuterium isotopic fractionation through the cell membrane of the plant

    International Nuclear Information System (INIS)

    Berdea, P.; Cuna, Stela; Deliu, C.

    2002-01-01

    The purpose of this study is to prove that there is a water deuterium isotope fractionation when the water passes through the cell membrane. The carrots (Daucus carota) were grown in vitro in a Murashige and Skoog mineral-salt medium and have been exposed to a water solution with a uniform isotopic content. After seven days the cell culture was filtered and the cell water was vacuum extracted. The water from aqueous solution and the cell water were analyzed for hydrogen by isotope ratio mass spectrometry. The procedure was repeated for 14 and 21 day old cell cultures. The measurements have revealed a water deuterium isotopic fractionation between extra-cellular water and cellular water. The deuterium content was found to be higher within the cells by 10 o / oo for non-embryonic cells and 13 o / oo for the embryonic cells. This fractionation is a non-evaporative fractionation between intracellular and extra-cellular water and it represents a new step in the overall fractionation of deuterium water in the plants. The existence of such isotopic fractionation through the cell membrane implies that the relationship between the deuterium content of cellulose nitrate in plant and meteoric water should be revised. Also, this finding is of interest for understanding the balance and dynamics of the hydrogen isotopes in the environment. (authors)

  3. Method to separate deuterium isotopes using ethylene and ethylene dichloride

    International Nuclear Information System (INIS)

    Benson, S.W.

    1979-01-01

    The separation of deuterium by the dissociation of ethylene vinyl chloride, 1,2-dichloro-ethanes or propylene with the help of intensive, matched infrared lasers enables a relatively good yield if operated on a large scale, e.g. in refineries with large through-put. The deuterium from the laser photolysis of ethylene and vinyl chloride is found in the acetylene formed, which has to be separated off and processed. When using dichloroehtane, the deuterium is found in the vinal chloride formed. The methods are briefly described. (UWI) [de

  4. Isotope effects in photochemical rearrangements

    International Nuclear Information System (INIS)

    Sommer, F.

    1983-01-01

    Taking anthracene resp. 9-deuteroanthracene as the initial substance, different substitution products have been prepared. The products originating by direct photolysis have been characterized and their structure has been determined. By comparing the measured kinetic isotope effect and the quantum yield of the nondeuterated and the monodeuterated fluorenes formed it could been demonstrated that the isotope effect mainly is due to the reaction rates and the influence of the deuterium substitution upon the radiationless desactivation against that is small. (HBR) [de

  5. Considerations related to the deuterium-depleted water isotopic analysis for an industrial production pilot plant

    International Nuclear Information System (INIS)

    Varlam, Mihai; Steflea, Dumitru; Irimescu, Rodica

    2000-01-01

    In the last few years, there is a major interest related to the use of Deuterium Depleted Water (DDW) for biological and medical purposes. Therefore, a production installation for DDW was developed and now, it is working in our Institute. The deuterium isotopic concentration for the final product is in the 10 - 40 ppm D / (D + H) range depending on customers' requirements. In order to control and manage the production process and also to validate the final product, a special procedure for deuterium content measurement for DDW by Isotopic Ratio Mass Spectrometry was developed. The main instrumentation is a MAT 250 IRMS with a hydrogen preparation line based on the zinc reduction process. The first concern regarding the analysis procedure for these water samples with very low deuterium concentration has been related to the preparation of an internal standard with a D / (D + H) isotopic value in the measurement range. For this raison, a distinct procedure was developed and applied, so that starting to the well-known VSMOW standard and so, a sequence of 12 samples with decreasing deuterium content was obtained. These samples were measured and 3 / 2 ratio mass signals versus 2 mass signal were plotted and statistically analyzed. Obviously, for each measurement, a H 3+ correction factor was calculated and applied, as a results of an entire statistically elimination procedure and by extrapolation of the linear curve plotted, a value for the primary DDW was determined. Other important problem related to deuterium content determination was to minimize the H 3+ factor correction. As the deuterium content is very low the contribution of this factor to the 3 mass signal becomes very important. Therefore, special operations were developed, considering the behaviour of linear dependence between 3 / 2 mass signal versus 2 mass signal in the lower part. Finally, special attention was given to estimate the lower isotopic concentration analysis limit. (authors)

  6. Absolute measurement of the isotopic ratio of a water sample with very low deuterium content

    International Nuclear Information System (INIS)

    Hagemann, R.; Nief, G.; Roth, E.

    1968-01-01

    The presence of H 3+ ions which are indistinguishable from HD + ions presents the principal difficulty encountered in the measurement of isotopic ratios of water samples with very low deuterium contents using a mass spectrometer. Thus, when the sample contains no deuterium, the mass spectrometer does not indicate zero. By producing, in situ, from the sample to be measured, water vapor with an isotopic ratio very close to zero using a small distilling column, this difficulty is overcome. This column, its operating parameters, as well as the way in which the measurements are made are described. An arrangement is employed in which the isotopic ratios can be measured with a sensitivity better than 0.01 x 10 -6 . The method is applied to the determination of the isotopic ratios of three low deuterium content water samples. The results obtained permit one to assign to the sample with the lowest deuterium content an absolute value equal to 1.71 ± 0.03 ppm. This water sample is a primary standard from which is determined the isotopic ratio of a natural water sample which serves as the laboratory standard. (author) [fr

  7. Isotope effects on chemical equilibria

    International Nuclear Information System (INIS)

    Golding, P.D.

    1974-01-01

    The thermodynamic equilibrium constants of three deuterated substituted acetic acids are reported. The calculation of secondary isotope effects of the second kind for the three isotopic acid pairs has been accomplished by the appropriate comparison of thermodynamic equilibrium constants, and by the comparison of isotopic slopes. The effect of substituent variation on the isotope effects reported here disqualifies the simple inductive model as a legitimate description of secondary isotope effects of the second kind. The correlation of diminishing isotope effect per deuterium atom with increasing acidity is also invalidated by the present results. The syntheses of 9-thia-9,10-dihydrophenanthrene-9-oxide and thioxanthene-10-oxide are described. These compounds have been partially deuterated at their respective methylene positions. Spectral evidence indicates stereoselectivity of the methylene protons in the exchange reactions of both compounds. (author)

  8. Laser separation of hydrogen isotopes: Tritium-from-deuterium recovery

    International Nuclear Information System (INIS)

    Magnotta, F.; Herman, I.P.; Aldridge, F.T.; Maienschein, J.L.

    1984-01-01

    Single-step enrichment factors exceeding 15,000 have been observed in the removal of tritium-from-deuterium by 12 μm laser multiple-photon dissociation of chloroform. The photochemistry and photophysics of this process is discussed along with prospects for implementation of this method in practical heavy water reactor detritiation. 7 refs., 7 figs., 1 tab

  9. Mechanistic positron emission tomography studies: demonstration of a deuterium isotope effect in the monoamine oxidase-catalyzed binding of (/sup 11/C)L-deprenyl in living baboon brain

    Energy Technology Data Exchange (ETDEWEB)

    Fowler, J.S.; Wolf, A.P.; MacGregor, R.R.; Dewey, S.L.; Logan, J.; Schlyer, D.J.; Langstrom, B.

    1988-11-01

    The application of positron emission tomography (PET) to the study of biochemical transformations in the living human and animal body requires the development of highly selective radiotracers whose concentrations in tissue provide a record of a discrete metabolic process. L-N-(11C-methyl)Deprenyl ((11C)L-deprenyl), a suicide inactivator of monoamine oxidase (MAO) type B, has been developed as a radiotracer for mapping MAO B in the living human and animal brain. In this investigation, (11C)L-deprenyl (1) and (11C)L-deprenyl-alpha, alpha-2H2 (2) have been compared in three different baboons by PET measurement of carbon-11 uptake and retention in the brain and the measurement of the amount of unchanged tracer in the arterial plasma over a 90-min time interval. For one baboon, N-(11C-methyl-2H3)L-deprenyl (3) was also studied. Kinetic parameters calculated using a three-compartment model revealed a deuterium isotope effect of 3.8 +/- 1.1. Comparison of the two tracers (1 and 2) in mouse brain demonstrated that deuterium substitution significantly reduced the amount of radioactivity bound to protein. HPLC and GLC analysis of the soluble radioactivity in mouse brain after injection of (11C)L-deprenyl showed the presence of (11C)methamphetamine as a major product along with unidentified labeled products. Sodium dodecyl sulfate-polyacrylamide electrophoresis with carbon-14-labeled L-deprenyl showed that a protein of molecular weight 58,000 was labeled. These results establish that MAO-catalyzed cleavage of the alpha carbon-hydrogen bond on the propargyl group is the rate limiting (or a major rate contributing) step in the retention of carbon-11 in brain and that the in vivo detection of labeled products in brain after the injection of (11C)L-deprenyl provides a record of MAO activity.

  10. Water use patterns of three species in subalpine forest, Southwest China: the deuterium isotope approach

    Science.gov (United States)

    Qing Xu; Harbin Li; Jiquan Chen; Jiquan Cheng; Xiaoli Cheng; Shirong Liu; Shuqing An

    2011-01-01

    Determination of water sources of plant species in a community is critical for understanding the hydrological processes and their importance in ecosystem functions. Such partitioning of plant xylem water into specific sources (i.e. precipitation, groundwater) can be achieved by analyzing deuterium isotopic composition (δD) values for source waters. A subalpine dark...

  11. Catalytic isotope exchange reaction between deuterium gas and water pre-adsorbed on platinum/alumina

    International Nuclear Information System (INIS)

    Iida, Itsuo; Kato, Junko; Tamaru, Kenzi.

    1976-01-01

    The catalytic isotope exchange reaction between deuterium gas and the water pre-adsorbed on Pt/Al 2 O 3 was studied. At reaction temperatures above 273 K, the exchange rate was proportional to the deuterium pressure and independent of the amount of adsorbed water, which suggests that the rate determining step is the supply of deuterium from the gas phase. Its apparent activation energy was 38 kJ mol -1 . Below freezing point of water, the kinetic behaviour was different from that above freezing point. At higher deuterium pressures the rate dropped abruptly at 273 K. Below the temperature the apparent activation energy was 54 kJ mol -1 and the exchange rate depended not on the deuterium pressure but on the amount of the pre-adsorbed water. At lower pressures, however, the kinetic behaviour was the same as the above 273 K, till the rate of the supply of deuterium from the gas phase exceeded the supply of hydrogen from adsorbed water to platinum surface. These results suggest that below 273 K the supply of hydrogen is markedly retarded, the state of the adsorbed water differing from that above 273 K. It was also demonstrated that when the adsorbed water is in the state of capillary condensation, the exchange rate becomes very small. (auth.)

  12. Process and device for stage by stage enrichment of deuterium and/or tritium in a material suitable for isotope exchange of deuterium and tritium with hydrogen

    International Nuclear Information System (INIS)

    Iniotakis, N.; Decken, C.B. von der.

    1983-01-01

    Water containing deuterium and/or tritium is first introduced into a carrier gas flow and reduced for the stage by stage enrichment of deuterium and/or tritium. A hydrogen partial pressure of a maximum of 100 millibar is set in the carrier gas flow. The carrier gas flow is taken along the primary side of an exchange wall suitable for the permeation of hydrogen, and a further carrier gas flow flows on its secondary side, which contains water or hydrogen. Reaction products formed after isotope exchange of deuterium and/or tritium with hydrogen are removed by the secondary carrier gas flow. (orig./HP) [de

  13. Leakage Identification Of Volcanic Product Pollutant Of ijen Crater Using Natural Isotop Deuterium And Oxiren-18

    International Nuclear Information System (INIS)

    Susiati, Heni; Sjarmufni, A.; S.B.S, Yarianto; Suprijadi; Wibagyo

    2001-01-01

    Community surrounding the Asembagus Sugar Fabric guess that the factory has polluted water body of Banyuputih River. Leakage detection of the pollutant has been to prove that guess using variation of natural isotop composition of Deuterium and Oxygen-18. Sampling was carried out at Ijen crater area, Banyupahit River and surrounding the sugar factory and also Belawan Fresh water source. Isotop analysis was done-by mass spectrometer. Based on analysis result have been gotten information that each location have vary of isotop value, Isotop concentration at Ijen crater was relative high so isotop concentration of Banyupahit river was also relative high although rather lower than lien Crater. Based on another interpretation, there are correlation at isotope concentration between Ijen crater and Banyupahit River

  14. Research of catalysts for isotope enrichment of deuterium oxide in water - PX15-03/90 progress report

    International Nuclear Information System (INIS)

    1990-10-01

    The operation results of pre-concentration stages from the Pilot Unity, and the technical information important to the project of development of catalyst for isotope concentration of deuterium oxides (D 2 O) are described. (C.G.C.)

  15. Research of catalysts for isotope enrichment of deuterium oxide in water - PX15-01/89 progress report

    International Nuclear Information System (INIS)

    1989-08-01

    The information about the development of research project for producing concentrate deuterium oxide by isotope enrichment in hydrogen-water contact systems combined with electrolysis are described. (C.G.C.)

  16. Isotopic exchange of cyclic ethers with deuterium over metal catalysts

    International Nuclear Information System (INIS)

    Duchet, J.C.; Cornet, D.

    1976-01-01

    The exchange reaction between deuterium and cyclic ethers (oxolane and α-methyl derivatives) has been investigated using rhodium and palladium catalysts. The first hydrogen undergoing exchange has been found to be located on a β-carbon. This fact, and the poisoning of the exchange of cyclopentane in the presence of ether, suggest that the O atom participates in the exchange mechanism of ethers. It appears, however, that the oxygen--metal bonding occurs only during this simple exchange process; simultaneous adsorption of oxygen and a vicinal carbon causes hydrogenolysis of the O--C bond. In each case multiple exchange is important. In the oxolane molecule two sets of exchangeable hydrogens are distinguished according to their reactivities, as could be expected by analogy with cycloalkanes. However, this distinction is not so clear in the exchange patterns of substituted oxolanes, since intermediate maxima are observed in these cases. It is suggested that the conformational properties of the substituted rings cause a constraint in the formation of 3,4-diadsorbed oxolanes. Thus, multiple exchange, based on α,β-process, and epimerization via the ''roll-over'' mechanism occur preferentially in certain parts of the molecules

  17. Traceability of synthetic drugs by position-specific deuterium isotope ratio analysis

    Energy Technology Data Exchange (ETDEWEB)

    Brenna, Elisabetta [Dipartimento di Chimica, Materiali e di Ingegneria Chimica del Politecnico di Milano and Istituto CNR per la Chimica del Riconoscimento Molecolare, Via Mancinelli 7, Milan I-20131 (Italy)], E-mail: elisabetta.brenna@polimi.it; Fronza, Giovanni [Dipartimento di Chimica, Materiali e di Ingegneria Chimica del Politecnico di Milano (Italy) and Instituto CNR per la Chimica del Riconoscimento Molecolare, Via Mancinelli 7, Milan I-20131 (Italy)], E-mail: giovanni.fronza@polimi.it; Fuganti, Claudio [Dipartimento di Chimica, Materiali e di Ingegneria Chimica del Politecnico di Milano (Italy) and Istituto CNR per la Chimica del Riconoscimento Molecolare, Via Mancinelli 7, Milan I-20131 (Italy)

    2007-10-10

    Samples of fluoxetine of different origin were submitted to natural abundance {sup 2}H NMR spectroscopy. The deuterium content at the various sites of the molecule was found to depend on its synthetic history. Hints on the synthetic procedure can be obtained by comparison with standard compounds, whose synthesis is known. These preliminary results give an idea of the potential of site-specific isotope ratio analysis in the fight against patent infringement and drug counterfeiting.

  18. Traceability of synthetic drugs by position-specific deuterium isotope ratio analysis

    International Nuclear Information System (INIS)

    Brenna, Elisabetta; Fronza, Giovanni; Fuganti, Claudio

    2007-01-01

    Samples of fluoxetine of different origin were submitted to natural abundance 2 H NMR spectroscopy. The deuterium content at the various sites of the molecule was found to depend on its synthetic history. Hints on the synthetic procedure can be obtained by comparison with standard compounds, whose synthesis is known. These preliminary results give an idea of the potential of site-specific isotope ratio analysis in the fight against patent infringement and drug counterfeiting

  19. A general procedure for isotopic (deuterium) labelling of non-steroidal antiinflammatory 2-arylpropionic acids

    International Nuclear Information System (INIS)

    Castell, J.V.; Martinez, L.A.; Universidad Politecnica de Valencia; Miranda, M.A.; Tarrega, Pilar

    1994-01-01

    Alkaline treatment of nonsteroidal antiinflammatory 2-arylpropionic acids in deuterium oxide led in all cases to isotopic exchange of the proton located at the α-position of the side chain. Monodeuteration was observed in the case of carprofen, ibuprofen, ketoprofen, fenoprofen, flurbiprofen and naproxen. Additional exchange of one or two protons of the heterocyclic ring occurred in indoprofen, suprofen and tiaprofenic acid. The isotopic labelling survived under the conditions required to perform in vitro photoallergic studies (photolysis in non-deuterated aqueous media). (Author)

  20. A general procedure for isotopic (deuterium) labelling of non-steroidal antiinflammatory 2-arylpropionic acids

    Energy Technology Data Exchange (ETDEWEB)

    Castell, J.V. (Valencia Univ. Hospital (Spain). Centro de Investigacion); Martinez, L.A. (Valencia Univ. Hospital (Spain). Centro de Investigacion Universidad Politecnica de Valencia (Spain). Dept. de Quimica); Miranda, M.A.; Tarrega, Pilar (Universidad Politecnica de Valencia (Spain). Dept. de Quimica)

    1994-01-01

    Alkaline treatment of nonsteroidal antiinflammatory 2-arylpropionic acids in deuterium oxide led in all cases to isotopic exchange of the proton located at the [alpha]-position of the side chain. Monodeuteration was observed in the case of carprofen, ibuprofen, ketoprofen, fenoprofen, flurbiprofen and naproxen. Additional exchange of one or two protons of the heterocyclic ring occurred in indoprofen, suprofen and tiaprofenic acid. The isotopic labelling survived under the conditions required to perform in vitro photoallergic studies (photolysis in non-deuterated aqueous media). (Author).

  1. Effects of deuterium depleted water on reproduction of Rainbow fish

    International Nuclear Information System (INIS)

    Stefanescu, Ion; Saros-Rogobete, Irina; Titescu, Gheorghe; Caraus, Ion; Pricop, Ferdinand

    2001-01-01

    The paper refers to an isotopic composition used to prepare fecundating solutions for artificial reproduction of fish. The solution is constituted as a mixture of deuterium depleted water and natural water (whose isotopic concentration is of 85-90 ppm D/(D+H)) in which we can add activating and energizing substances. This fecundating solution ensures an improved fecundating level of fish roe, increase life index in the next growth up stages and increase fish resistance at special medium conditions. (authors)

  2. H/D isotope effects in high temperature proton conductors

    DEFF Research Database (Denmark)

    Bonanos, Nikolaos; Huijser, A.; Poulsen, Finn Willy

    2015-01-01

    The atomic mass ratio of ca. 2 between deuterium and hydrogen is the highest for any pair of stable isotopes and results in significant and measurable H/D isotope effects in high temperature proton conductors containing these species. This paper discusses H/D isotope effects manifested in O-H/O-D...

  3. Mechanistic deductions from multiple kinetic and solvent deuterium isotope effects and pH studies of pyridoxal phosphate dependent carbon-carbon lyases: escherichia coli tryptophan indole-lyase

    International Nuclear Information System (INIS)

    Kiick, D.M.; Phillips, R.S.

    1988-01-01

    Analysis of the pH dependence of the kinetic parameters and competitive inhibitor Ki values for tryptophan indole-lyase suggests two enzymic groups must be unprotonated in order to facilitate binding and catalysis of tryptophan. The V/K for tryptophan and the pKi for oxindolyl-L-alanine, a putative transition state analogue and competitive inhibitor, decrease below two pK values of 7.6 and 6.0, while the Ki for L-alanine, also a competitive inhibitor, is 3300-fold larger (20 mM) than that for oxindolyl-L-alanine and increases below a single pK of 7.6. A single pK of 7.6 is also observed in the V/K profile for the alternate substrate, S-methyl-L-cysteine. Therefore, the enzymic group with a pK of 7.6 is responsible for proton abstraction at the 2-position of tryptophan, while the enzymic group with a pK of 6.0 interacts with the indole portion of tryptophan and probably catalyzes formation of the indolenine tautomer of tryptophan (in concert with proton transfer to C-3 of indole from the group with pK 7.6) to facilitate carbon-carbon bond cleavage and elimination of indole. The pH variation of the primary deuterium isotope effects for proton abstraction at the 2-position of tryptophan (DV = 2.5 and D(V/Ktrp) = 2.8) are pH independent, while the Vmax for tryptophan or S-methyl-L-cysteine is the same and also pH independent. Thus, substrates bind only to the correctly protonated form of the enzyme. Further, tryptophan is not sticky, and the pK values observed in both V/K profiles are the correct ones

  4. [Solid state isotope hydrogen exchange for deuterium and tritium in human gene-engineered insulin].

    Science.gov (United States)

    Zolotarev, Yu A; Dadayan, A K; Kozik, V S; Gasanov, E V; Nazimov, I V; Ziganshin, R Kh; Vaskovsky, B V; Murashov, A N; Ksenofontov, A L; Haribin, O N; Nikolaev, E N; Myasoedov, N F

    2014-01-01

    The reaction of high temperature solid state catalytic isotope exchange in peptides and proteins under the action of catalyst-activated spillover hydrogen was studied. The reaction of human gene-engineered insulin with deuterium and tritium was conducted at 120-140° C to produce insulin samples containing 2-6 hydrogen isotope atoms. To determine the distribution of the isotope label over tritium-labeled insulin's amino acid residues, oxidation of the S-S bonds of insulin by performic acid was performed and polypeptide chains isolated; then their acid hydrolysis, amino acid analysis and liquid scintillation counts of tritium in the amino acids were conducted. The isotope label was shown to be incorporated in all amino acids of the protein, with the peptide fragment FVNQHLCGSHLVE of the insulin β-chain showing the largest incorporation. About 45% of the total protein isotope label was incorporated in His5 and His10 of this fragment. For the analysis of isotope label distribution in labeled insulin's peptide fragments, the recovery of the S-S bonds by mercaptoethanol, the enzymatic hydrolysis by glutamyl endopeptidase from Bacillus intermedius and HPLC division of the resulting peptides were carried out. Attribution of the peptide fragments formed due to hydrolysis at the Glu-X bond in the β-chain was accomplished by mass spectrometry. Mass spectrometry analysis data of the deuterium-labeled insulin samples' isotopomeric composition showed that the studied solid state isotope exchange reaction equally involved all the protein molecules. Biological studying of tritium-labeled insulin showed its physiological activity to be completely retained.

  5. Deuterium isotope fractionation between ortho-alkyl substituted phenols and t-butylthiol in oxygen bases

    International Nuclear Information System (INIS)

    Wawer, A.; Jelenska-Kazimierczuk, M.; Szydlowski, J.

    1998-01-01

    Equilibrium isotope effect in the exchange reaction of deuterium between phenol(P), 2-isopropyl phenol (IPP), 2,6-diisopropyl phenol (DIPP), 2,6-diterbutyl phenol (DTBP) and tertbutylthiol (TBT) has been studied in 296 K. The fractionation factors (α) have been measured in cyclohexane and carbon tetrachloride solutions and in a few oxygen bases: acetone, 1,4-dioxane, ethyl formate, ethyl ether, tetrahydrofurane, N,N-dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide. Using chemical shifts of phenol OH protons, the thermodynamic parameters of complex formation with the oxygen bases have been determined. The experimental data show that lnα correlates with the formation enthalpy of the phenol-oxygen base complex in DIPP-TBT-base system but there is no simple correlation in IPP-TBT-base system. Furthermore, it was found that in DTBT-TBT-base system lnα depends linearly on the basicity of the solvent (DN parameters). On the other hand, lnα correlates with acidic parameters of the solvents (AN) in IPP-TBT-base and P-TBT-base systems. All above correlations are explained by taking into account two competition processes: self association of phenol molecules and their solvation by oxygen bases. (author)

  6. [Influence of deuterium depleted water on freeze-dried tissue isotopic composition and morphofunctional body performance in rats of different generations].

    Science.gov (United States)

    Dzhimak, S S; Baryshev, M G; Basov, A A; Timakov, A A

    2014-01-01

    The influence of deuterium depleted water on the body of different rats generations was investigated in physiological conditions. As a result of this study it was established that the most significant and rapid reduction in D/H equilibrium was observed in plasma (by 36.2%), and lyophilized kidney tissues (by 15.8%). Less pronounced deuterium decrease was characteristic of liver tissue (9.3%) and heart (8.5%). Stabilization of the isotopic exchange reaction rate was fixed in the blood and tissues of rats, starting from the second generation. At the same time when deuterium depleted water (40 ppm) was used in dietary intake, the change in morphological and functional parameters in laboratory animals associated with the processes of adaptation to the effects of substress isotopic D/H gradient was also noted. The study shows that modification of:only drinking water intake regime can't significantly change the deuterium content in tissues of metabolically active organs, because of the concurrent deuterium receipt in food substances of plant and animal origin.

  7. Experimental studies on hydrogen isotopic deuterium from gas to liquid phase by catalytic exchange

    International Nuclear Information System (INIS)

    Luo Yangming; Wang Heyi; Liu Jun; Fu Zhonghua; Wang Changbin; Han Jun; Xia Xiulong; Tang Lei

    2005-01-01

    The experimental studies on hydrogen isotopic deuterium from gas to liquid phase were completed by mixed ratio 1:4 of Pt-SDB hydrophobic catalyst and hydrophilic packing. The influencing factors on number of transfer units (NTU) and transformation efficiencies of deuterium were researched. The results show that preferable NTU can be obtained by choosing suitable operational temperature and flux of exchange gas. The transformation rate increases with increasing liquid flux, but it cannot obviously be improved when liquid flux attains some level. The length of catalytic column has an obvious influence on transformation rate and 90% of transformation rate is obtained by 4 m column length at gas flux with 2 m 3 /h, liquid flux with 1-2 kg/h and 45 degree C. (author)

  8. Saturation and isotopic replacement of deuterium in low-Z material

    International Nuclear Information System (INIS)

    Doyle, B.L.; Wampler, W.R.; Brice, D.K.; Picraux, S.T.

    1980-01-01

    The saturation and replacement of hydrogen isotopes implanted into TiC, TiB 2 , VB 2 , B 4 C, B, Si, and C has been examined experimentally and modeled theoretically. The deuterium saturation concentrations for these materials varied from .16 to .57. A new isotopic replacement model is presented which predicts isotopic trapping and exchange on the basis of the depth dependence of the implanted ions and the experimentally determined hydrogen saturation concentration. Our results indicate that, for these materials used as coatings on components in a D-T fueled tokamak, T recovery by ion induced replacement with H or D should be feasible and that T buildup will be at tolerable levels

  9. Cytology is advanced by studying effects of deuterium environment

    Science.gov (United States)

    Bose, S.; Crespi, H. L.; Flaumenhaft, E.; Katz, J. J.

    1967-01-01

    Research of deuterium effects on biological systems shows deuteriation is not incompatible with life. With the successful cultivation of deuteriated bacteria, work is now being done on extraction of deuterio-compounds from bacteria.

  10. Isotopic exchange between deuterium and neohexane on supported platinum and palladium catalysts

    International Nuclear Information System (INIS)

    Eskinazi, V.

    1979-01-01

    The isotopic exchange reaction between neohexane and deuterium on supported Pt/SiO 2 and Pd/SiO 2 catalysts has been investigated in the temperature range 86.5 to 110 0 C. Rates of exchange were studied as functions of percentage of metal atoms exposed, the conditions of catalyst pretreatment, and the reaction temperature. The rates of exchange were not strongly dependent upon percentage exposed; however, the relative yields of d 1 through d 5 in the ethyl moiety or neohexane were dependent on the percentage metal atoms exposed. The Pt/SiO 2 catalysts were found to be more active for exchange than the Pd/SiO 2 catalysts by an order of magnitude. Both the turnover frequencies and the exchange pattern were observed to be influenced by the pretreatment of the catalyst. Maxima in the exchange pattern occurred at d 3 and d 5 in the case of Pt/SiO 2 and at d 5 only in the case of the Pd/SiO 2 catalysts. In order to account for the d 3 maximum observed for Pt catalysts, some extension of the Horiuti-Polanyi mechanism is required. Mechanisms by which the d 3 species might be formed are proposed and discussed. On Pd/SiO 2 catalysts exchange occurs preferentially in the ethyl substituent of the quaternary carbon atom rather than on the three methyl substituents of the quaternary carbon atom. Such preference is not observed on Pt/SiO 2 catalysts; in fact, in some cases, this preference is reversed. Whenever exchange occurs in the three methyl substituents, mostly the d 1 product is obtained. For Pt/SiO 2 catalysts, the exchange pattern appears to be influenced by steric effects, but the data suggest that factors other than steric effects are important on Pd

  11. The H+3 + H2 isotopic system. Origin of deuterium astrochemistry

    International Nuclear Information System (INIS)

    Hugo, Edouard Jean-Marie

    2008-01-01

    Dense cold molecular clouds reckoned to be stellar nurseries are the scene of an extreme molecular deuteration. Despite the cosmic D/H ratio of ∝10 -5 , molecular species in prestellar cores are observed to contain nearly as much deuterium as hydrogen. This astonishing deuterium enrichment promoted by low temperatures is the work of H + 3 . It is the key species which unlocks the deuterium from its HD reservoir via reactions like H + 3 +HD ↔ H 2 D + +H 2 and drags it further to other species in successive reactions. For this reason, the H + 3 +H 2 isotopic system is outstandingly critical for the astrochemistry of cold environments. However, its understanding is yet incomplete and insufficient. This thesis thus focuses on the H + 3 +H 2 isotopic system from a theoretical, experimental and astronomical point of view giving a particular look into the role of nuclear spins. As a first step, the stringent nuclear spin selection rules in associative, dissociative and reactive collisions are investigated. This purely theoretical study zooms into the details of the nuclear spin wavefunctions and shows that their permutation symmetry representation is necessary and sufficient, contrary to their angular momentum representation. Additionally, a new deterministic interpretation of nuclear spins in chemical reactions is proposed. Based on these considerations, a complete set of state-to-state rate coefficients for all H + 3 + H 2 isotopic variants is calculated using a microcanonical model leaned on phase space theory. An experimental study is conducted in parallel with a 22-pole ion trap apparatus in order to inspect the influences of temperature and H 2 ortho-to-para ratio. The good overall agreement between experimental and theoretical results supports the validity and utility of the calculated set of rate coefficients. Furthermore, the potentiality of the 22-pole ion trap apparatus is explored via the Laser Induced Reaction (LIR) technique applied to our system of

  12. Alternatives to isotope ratio mass spectrometry for the measurement of deuterium content of body water

    International Nuclear Information System (INIS)

    Bluck, L.J.C.

    2000-01-01

    The measurement of breast milk intake using the isotope dilution techniques is now well established. The methodology involves the administration of a bolus of tracer followed by observation of the kinetics of its passage though the system. For example in the popular 'dose to the mother' method a dose of labeled water is administered to the mother, and over the following days samples of body fluids are taken and the concentration of tracer determined in order to establish the rate of loss of tracer from her body. Likewise samples are taken from the breast fed infant in order to determine the rates of tracer intake and subsequent loss. Deuterium is the tracer of choice for these experiments since it is non-radioactive, and therefore suitable for use in these vulnerable subject groups, and also because of its relative cheapness. Conventionally isotope ratio mass spectrometry (IRMS) has been used for the determination of the amount of deuterium in the body fluids. However this methodology is expensive (an instrument might typically cost US$ 150,000), and it requires a considerable amount of dedicated technical expertise for its operation. Consequently such instrumentation is not widely available, and this has limited the number and scope of studies using this technique. Recently there have been reports of possible alternative technologies for the determination of deuterium in body water which appear attractive because of the wider general availability of the equipment required. It is the purpose of this report to assess these reported methods for their suitability for breast milk intake measurements

  13. Isotope effects: definitions and consequences for pharmacologic studies

    International Nuclear Information System (INIS)

    Van Langenhove, A.

    1986-01-01

    The use of stable isotope-labeled compounds for pharmacologic studies requires careful consideration of the nature of the stable isotope label (2H, 13C, 15N, 18O) and its position of incorporation in the molecule. When deuterium is used, improper positioning can lead to significant primary isotope effects. Primary isotope effects occur when the breaking of the bond to the heavy isotope is the rate-limiting step in a reaction (or metabolic transformation). A reaction will proceed slower for the molecule with the heavy isotope label because of the mass difference between the light and the heavy isotope. In addition to these primary isotope effects, smaller but nevertheless important secondary isotope effects, physicochemical isotope effects, active hydrogen/deuterium exchange, or isotope effects associated with either the enzyme-catalyzed biotransformation or the mass spectrometric ionization and fragmentation can be operative. In mechanistic studies, isotope effects are used to their advantage; however, in pharmacokinetic studies, the occurrence of isotope effects can lead to grossly misleading biologic and analytic results: the metabolism of the drug will differ when in vivo isotope effects are operative, and isotope effects occurring during the analysis procedure will obscure the true metabolic profile of the drug

  14. Combining Solvent Isotope Effects with Substrate Isotope Effects in Mechanistic Studies of Alcohol and Amine Oxidation by Enzymes*

    Science.gov (United States)

    Fitzpatrick, Paul F.

    2014-01-01

    Oxidation of alcohols and amines is catalyzed by multiple families of flavin-and pyridine nucleotide-dependent enzymes. Measurement of solvent isotope effects provides a unique mechanistic probe of the timing of the cleavage of the OH and NH bonds, necessary information for a complete description of the catalytic mechanism. The inherent ambiguities in interpretation of solvent isotope effects can be significantly decreased if isotope effects arising from isotopically labeled substrates are measured in combination with solvent isotope effects. The application of combined solvent and substrate (mainly deuterium) isotope effects to multiple enzymes is described here to illustrate the range of mechanistic insights that such an approach can provide. PMID:25448013

  15. Effect of helium irradiation on deuterium permeation behavior in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Uemura, Yuki; Sakurada, Shodai; Fujita, Hiroe; Azuma, Keisuke; Zhou, Quilai [Graduate School of Science & Technology, Shizuoka University, 836 Ohya, Suruga, Shizuoka, 422-8529 Japan (Japan); Hatano, Yuji [Hydrogen Isotope Research Center, University of Toyama, 3190 Gofuku, Toyama, 930-8555 Japan (Japan); Yoshida, Naoaki; Watanabe, Hideo [Institute for Applied Mechanics, Kyushu University, 6-1 Kasuga-koen, Kasuga, Fukuoka, 816-8580 Japan (Japan); Oyaizu, Makoto; Isobe, Kanetsugu [National Institutes for Quantum and Radiological Science and Technology, 2166 Obuchi, Rokkasho, Aomori, 039-3212 Japan (Japan); Shimada, Masashi [Idaho National Laboratory, 1955 N. Fremont Avenue, Idaho Falls, ID 83415 (United States); Buchenauer, Dean; Kolasinski, Robert [Sandia National Laboratories, Chemistry, Combustion and Materials Center, Livermore, CA 94550 (United States); Chikada, Takumi [Graduate School of Science & Technology, Shizuoka University, 836 Ohya, Suruga, Shizuoka, 422-8529 Japan (Japan); Oya, Yasuhisa, E-mail: oya.yasuhisa@shizuoka.ac.jp [Graduate School of Science & Technology, Shizuoka University, 836 Ohya, Suruga, Shizuoka, 422-8529 Japan (Japan)

    2017-07-15

    In this study, we measured deuterium (D) gas-driven permeation through tungsten (W) foils that had been pre-damaged by helium ions (He{sup +}). The goal of this work was to determine how ion-induced damage affects hydrogen isotope permeation. At 873 K, the D permeability for W irradiated by 3.0 keV He{sup +} was approximately one order of magnitude lower than that for un-damaged W. This difference diminished with increasing temperature. Even after heating to 1173 K, the permeability returned to less than half of the value measured for un-damaged W. We propose that this is due to nucleation of He bubbles near the surface which potentially serve as a barrier to diffusion deeper into the bulk. Exposure at higher temperatures shows that the D permeability and diffusion coefficients return to levels observed for undamaged material. It is possible that these effects are linked to annealing of defects introduced by ion damage, and whether the defects are stabilized by the presence of trapped He.

  16. Comparison of total body water determinations in lactating women by anthropometry, water displacement, and deuterium isotope dilution

    International Nuclear Information System (INIS)

    Wong, W.; Butte, N.; Lee, L.; Garza, C.; Klein, P.

    1986-01-01

    To expand the limited data on the total body water in lactating women, the authors have determined total body water contents, in eight subjects from anthropometric measurements, water displacement, and isotope dilution of deuterium oxide. On the day of the study, their skinfold thicknesses were measured over the biceps and triceps muscles and at the suprailiac and subscapular areas. Their body densities were measured by water displacement. Deuterium oxide was administered orally at 100 mg/kg of body weight. One predose milk sample was collected from each subject. The milk samples were defatted by centrifugation and the milk water was reduced to hydrogen gas for hydrogen isotope ratio measurements by gas-isotope-ratio mass spectrometry. The results indicated that total body water in lactating women estimated from anthropometric measurements was 49.7 +/- 3.3% of body weight, by water displacement was 54.9 +/- 7.2%, and by isotope dilution was 50.8 +/- 3.7%

  17. Process and device for step by step enrichment of deuterium and/or tritium by isotope exchange

    International Nuclear Information System (INIS)

    Iniotakis, N.; Decken, C.B. von der.

    1984-01-01

    Deuterium and/or tritium are bound to steam by isotope exchange after permeation through an exchange wall. Primary and secondary flows are guided by the counterflow principle. The secondary side has a metal oxide as oxidation catalyst. The plant can consist of several enrichment stages. The various flows and parts of the plant are described. (PW) [de

  18. Isotopic Abundance and Chemical Purity Analysis of Stable Isotope Deuterium Labeled Sudan I

    Directory of Open Access Journals (Sweden)

    CAI Yin-ping;LEI Wen;ZHENG Bo;DU Xiao-ning

    2014-02-01

    Full Text Available It is important that to analysis of the isotopic abundance and chemical purity of Sudan I-D5, which is the internal standard of isotope dilution mass spectrometry. The isotopic abundance of Sudan I-D5 is detected by “mass cluster” classification method and LC-MS. The repeatability and reproducibility experiments were carried out by using different mass spectrometers and different operators. The RSD was less than 0.1%, so the repeatability and reproducibility were satisfactory. The accuracy and precision of the isotopic abundance analysis method was good with the results of F test and t test. The high performance liquid chromatography (HPLC had been used for detecting the chemical purity of Sudan I-D5 as external standard method.

  19. Secondary isotope effects on alpha-cleavage reactions

    International Nuclear Information System (INIS)

    Ingemann, S.; Hammerum, S.

    1980-01-01

    Kinetic deuterium isotope effects on mass spectral reactions have in several instances been utilized to provide structural information and to answer mechanistic questions. Typically, the influence of the deuterium label on the rate of one of a number of competing reactions has been studied. Secondary isotope effects have usually been assumed to be relatively insignificant in comparison with the observed kinetic effects, even though various workers have shown that secondary isotope effects may indeed exert a considerable influence on the rates of competing simple cleavages. Recent studies have provided quantitative data to show that the mere presence of deuterium atoms up to six bonds away may influence the rate of a simple cleavage reaction. In relation to an investigation of rearrangements accompanying simple cleavage reactions, a semi-quantitative measure was needed of the variation of the secondary isotope effect with the number of bonds between the deuterium label and the point of rupture. The influence has therefore been examined of the presence of remote deuterium atoms on a typical simple cleavage reaction, the α-cleavage of aliphatic amines. As a model compound, N-methyldipentylamine was chosen, systematically labelled with deuterium. (author)

  20. The H{sup +}{sub 3} + H{sub 2} isotopic system. Origin of deuterium astrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Hugo, Edouard Jean-Marie

    2008-07-01

    Dense cold molecular clouds reckoned to be stellar nurseries are the scene of an extreme molecular deuteration. Despite the cosmic D/H ratio of {proportional_to}10{sup -5}, molecular species in prestellar cores are observed to contain nearly as much deuterium as hydrogen. This astonishing deuterium enrichment promoted by low temperatures is the work of H{sup +}{sub 3}. It is the key species which unlocks the deuterium from its HD reservoir via reactions like H{sup +}{sub 3}+HD {r_reversible} H{sub 2}D{sup +}+H{sub 2} and drags it further to other species in successive reactions. For this reason, the H{sup +}{sub 3}+H{sub 2} isotopic system is outstandingly critical for the astrochemistry of cold environments. However, its understanding is yet incomplete and insufficient. This thesis thus focuses on the H{sup +}{sub 3}+H{sub 2} isotopic system from a theoretical, experimental and astronomical point of view giving a particular look into the role of nuclear spins. As a first step, the stringent nuclear spin selection rules in associative, dissociative and reactive collisions are investigated. This purely theoretical study zooms into the details of the nuclear spin wavefunctions and shows that their permutation symmetry representation is necessary and sufficient, contrary to their angular momentum representation. Additionally, a new deterministic interpretation of nuclear spins in chemical reactions is proposed. Based on these considerations, a complete set of state-to-state rate coefficients for all H{sup +}{sub 3} + H{sub 2} isotopic variants is calculated using a microcanonical model leaned on phase space theory. An experimental study is conducted in parallel with a 22-pole ion trap apparatus in order to inspect the influences of temperature and H{sub 2} ortho-to-para ratio. The good overall agreement between experimental and theoretical results supports the validity and utility of the calculated set of rate coefficients. Furthermore, the potentiality of the 22-pole

  1. Procedure and equipment for the separation of isotopes for deuterium upgrading and for the production of heavy water

    International Nuclear Information System (INIS)

    Schoell, M.

    1981-01-01

    The invention concerns a simple procedure for the separation of isotopes for the enrichment of deuterium and for the production of heavy water as well as the equipment necessary for carrying out the process. Methane is conducted over bacterial cultures oxidizing methane to water and carbon dioxide. An enrichment of deuterium takes place in non-oxidized methane. The bacterial cultures are placed on carriers that are arranged in oxidation columns as baffle plates. Several oxidation towers of this kind can be arranged in series. (orig./RW) [de

  2. Computational study of substrate isotope effect probes of transition state structure for acetylcholinesterase catalysis

    International Nuclear Information System (INIS)

    Sikorski, R.S.; Malany, S.; Seravalli, J.; Quinn, D.M.

    2002-01-01

    Secondary isotope effects for carbonyl addition reactions of methyl thioacetate, acetone and acetaldehyde have been calculated by ab initio quantum mechanical methods in an effect to interpret measured β-deuterium isotope effects on acetylcholinesterase-catalysed hydrolysis of acetylthiocholine. The calculated β-deuterium isotope effect for equilibrium addition of methanol to methyl thioacetate is D3 K eq = 0.965, and the corresponding effect for addition of methoxide ion to methyl thioacetate wherein three waters are hydrogen bonded to the carbonyl oxyanion is D3 K eq = 1.086. Neither of these calculated isotope effects is an inverse as the experimental β-deuterium isotope effect for acetylcholinesterase-catalysed hydrolysis of acetylthiocholine, D3 K eq = 0.90±0.03. Structural comparisons show that the water-solvated methoxide adduct of methyl thioacetate is more expanded than is the natural methanol addition adduct, and suggest that the degree of which the isotope effect is inverse (i.e. less than) is inversely correlated to the degree of expansion of the adduct. A similar correlation of α-deuterium and β-deuterium secondary isotope effects with the degree of expansion of the adducts is found for equilibrium additions of methanol and methoxide ion to acetylaldehyde. These computational results suggest that the markedly inverse β-deuterium isotope effect for the acetylcholinesterase reaction arises from enzymatic compression of the transition state. (author)

  3. Effect of periodic deuterium ion irradiation on deuterium retention and blistering in Tungsten

    Directory of Open Access Journals (Sweden)

    M. Oya

    2017-08-01

    Full Text Available The effect of periodic irradiation on Deuterium (D retention and blistering in Tungsten (W was investigated. W samples were exposed to D plasma at a fixed fluence while varying the irradiation cycle number (1-shot, 2-shots and 3-shots. Exposure energy and flux were ∼50eV and ∼1 ×1022 D m−2 s−1, respectively. Sample temperatures were 537K and 643K. At 573K, D retention and blister density decreased with increasing number of irradiation cycle. In contrast at 643K, D retention showed no dependence on number of irradiation cycle. Therefore, sample temperature during irradiation is an important parameter in comparing the results of continuous and periodic irradiation, especially in studies involving extremely-high-flux (>1024 D m−2 s−1 irradiation and fluence dependency of D retention.

  4. α-deuterium isotope effects in benzyl halides. 2. Reaction of nucleophiles with substituted benzyl bromides. Evidence for a change in transition-state structure with electron-donating substituents

    International Nuclear Information System (INIS)

    Vitullo, V.P.; Grabowski, J.; Sridharan, S.

    1980-01-01

    Rates and α-D isotope effects have been determined for the following substrates and nucleophiles: p-methoxybenzyl bromide (Et 3 N, SCN - , N 3 - , OH - , S 2 O 3 2- ), benzyl bromide (Et 3 N, SCN - , N 3 - , OH - , S 2 O 3 2- ), and p-nitrobenzyl bromide (Et 3 N, SCN - , N 3 - , S 2 O 3 2- ). In nearly all cases the second-order rate constant for each nucleophile goes through a minimum for the unsubstituted compound while the α-D isotope increases monotonically in the squence p-NO 2 > p-H > p-OCH 3 . These results are consistent with an increasing looseness of the S/sub N/2 transition state as the substituent on the aromatic ring becomes more electron donating. 4 figures, 3 tables

  5. Deuterium in astrophysical ice analogues: Isotope exchange and IR detection sensitivity for HDO

    Science.gov (United States)

    Escribano, R. M.; Galvez, O.; Mate, B.; Herrero, V. J.

    2011-12-01

    Among D-bearing molecules, water is especially interesting from an astrophysical point of view. Although the deuterium content of water in astronomical environments is relatively small as compared with other molecules, it holds most valuable information, still largely undeciphered, on the dynamics of formation and evaporation of ice grain mantels in protostellar regions [1], and is crucial for the understanding of the formation of the Solar System and the Earth [2]. In this work, we have used the OD stretching bands of HDO and D2O molecules in various ice mixtures formed by vapor deposition on a cold substrate (see ref [3] for a description of the experimental set-up) to study the sensitivity of the IR technique for the detection of HDO in ice samples, and to monitor processes of H/D isotope exchange in these solids. It is found that the detection sensitivity is strongly dependent on the ice structure. The OD band is extremely broad and tends to disappear into the absorption continuum of H2O for low temperature amorphous samples. Detectable HDO/H2O ratios with this technique may range from a few per cent for amorphous samples to a few per thousand in crystalline ice. These relatively high upper limits and the appreciable dependence of the band shape on temperature, complicating the interpretation of data from many lines of sight, may question the usefulness of this technique. Isotopic H/D exchange in mixed ices of H2O/D2O is found to start at ~ 120 K and is greatly accelerated at 150 K, as crystallization proceeds in the ice. The process is mainly driven by proton transfer assisted by orientational defect mobility. Annealed amorphous samples are more favourable for isotope exchange than samples directly formed in the crystalline phase. The annealing process seems to lead to polycrystalline ice morphology with a higher defect activity. The present data emphasize the relevance of a depletion mechanism for D atoms in hydroxylic bonds in the solid state, recently

  6. Deuterium - depleted water. Achievements and perspectives

    International Nuclear Information System (INIS)

    Titescu, Gh.; Stefanescu, I.; Saros-Rogobete, I.

    2001-01-01

    Deuterium - depleted water represents water that has an isotopic content lower than 145 ppm D/(D+H) which is the natural isotopic content of water. The research conducted at ICSI Ramnicu Valcea, regarding deuterium - depleted water were completed by the following patents: - technique and installation for deuterium - depleted water production; - distilled water with low deuterium content; - technique and installation for the production of distilled water with low deuterium content; - mineralized water with low deuterium content and technique to produce it. The gold and silver medals won at international salons for inventions confirmed the novelty of these inventions. Knowing that deuterium content of water has a big influence on living organisms, beginning with 1996, the ICSI Ramnicu Valcea, deuterium - depleted water producer, co-operated with Romanian specialized institutes for biological effects' evaluation of deuterium - depleted water. The role of natural deuterium in living organisms was examined by using deuterium - depleted water instead of natural water. These investigations led to the following conclusions: 1. deuterium - depleted water caused a tendency towards the increase of the basal tone, accompanied by the intensification of the vasoconstrictor effects of phenylefrine, noradrenaline and angiotensin; the increase of the basal tone and vascular reactivity produced by the deuterium - depleted water persists after the removal of the vascular endothelium; -2. animals treated with deuterium - depleted water showed an increase of the resistance both to sublethal and to lethal gamma radiation doses, suggesting a radioprotective action by the stimulation of non-specific immune defence mechanism; 3, deuterium - depleted water stimulates immune defence reactions, represented by the opsonic, bactericidal and phagocyte capacity of the immune system, together with increase in the numbers of polymorphonuclear neutrophils; 4. investigations regarding artificial

  7. High-throughput simultaneous determination of plasma water deuterium and 18-oxygen enrichment using a high-temperature conversion elemental analyzer with isotope ratio mass spectrometry.

    Science.gov (United States)

    Richelle, M; Darimont, C; Piguet-Welsch, C; Fay, L B

    2004-01-01

    This paper presents a high-throughput method for the simultaneous determination of deuterium and oxygen-18 (18O) enrichment of water samples isolated from blood. This analytical method enables rapid and simple determination of these enrichments of microgram quantities of water. Water is converted into hydrogen and carbon monoxide gases by the use of a high-temperature conversion elemental analyzer (TC-EA), that are then transferred on-line into the isotope ratio mass spectrometer. Accuracy determined with the standard light Antartic precipitation (SLAP) and Greenland ice sheet precipitation (GISP) is reliable for deuterium and 18O enrichments. The range of linearity is from 0 up to 0.09 atom percent excess (APE, i.e. -78 up to 5725 delta per mil (dpm)) for deuterium enrichment and from 0 up to 0.17 APE (-11 up to 890 dpm) for 18O enrichment. Memory effects do exist but can be avoided by analyzing the biological samples in quintuplet. This method allows the determination of 1440 samples per week, i.e. 288 biological samples per week. Copyright 2004 John Wiley & Sons, Ltd.

  8. Hydrogen isotope exchange reaction rates in tritium, hydrogen and deuterium mixed gases

    International Nuclear Information System (INIS)

    Uda, Tatsuhiko

    1992-01-01

    Hydrogen isotope exchange reaction rates in H 2 +T 2 , D 2 +T 2 and H 2 +D 2 +T 2 mixed gases, as induced by tritium decay and beta radiation, were experimentally measured by laser Raman spectrometry. Initially a glass cell was filled with T 2 gas to a pressure of 30-40 kPa, and an equivalent partial pressure of H 2 and/or D 2 was added. The first-order hydrogen isotope exchange reaction rates were 5.54x10 -2 h -1 for H 2 +T 2 mixed gas and 4.76x10 -2 h -1 for D 2 +T 2 . The actual HT producing rate was nearly equivalent to the rate of DT, but the reverse reaction rate of HT was faster than that of DT. The exchange reaction rates between H, D and T showed the isotope effect, HD>HT>DT. The hydrogen isotope exchange reaction rates observed were about twenty times larger than ion formation rates by beta radiation. This result suggests that a free radical chain reaction in hydrogen isotopes is occurring. (orig.)

  9. Deuterium-depleted water

    International Nuclear Information System (INIS)

    Stefanescu, Ion; Steflea, Dumitru; Saros-Rogobete, Irina; Titescu, Gheorghe; Tamaian, Radu

    2001-01-01

    Deuterium-depleted water represents water that has an isotopic content smaller than 145 ppm D/(D+H) which is the natural isotopic content of water. Deuterium depleted water is produced by vacuum distillation in columns equipped with structured packing made from phosphor bronze or stainless steel. Deuterium-depleted water, the production technique and structured packing are patents of National Institute of Research - Development for Cryogenics and Isotopic Technologies at Rm. Valcea. Researches made in the last few years showed the deuterium-depleted water is a biological active product that could have many applications in medicine and agriculture. (authors)

  10. Deuterium isotope shifts for backbone {sup 1}H, {sup 15}N and {sup 13}C nuclei in intrinsically disordered protein {alpha}-synuclein

    Energy Technology Data Exchange (ETDEWEB)

    Maltsev, Alexander S.; Ying Jinfa; Bax, Ad, E-mail: bax@nih.gov [National Institutes of Health, Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases (United States)

    2012-10-15

    Intrinsically disordered proteins (IDPs) are abundant in nature and characterization of their potential structural propensities remains a widely pursued but challenging task. Analysis of NMR secondary chemical shifts plays an important role in such studies, but the output of such analyses depends on the accuracy of reference random coil chemical shifts. Although uniform perdeuteration of IDPs can dramatically increase spectral resolution, a feature particularly important for the poorly dispersed IDP spectra, the impact of deuterium isotope shifts on random coil values has not yet been fully characterized. Very precise {sup 2}H isotope shift measurements for {sup 13}C{sup {alpha}}, {sup 13}C{sup {beta}}, {sup 13}C Prime , {sup 15}N, and {sup 1}H{sup N} have been obtained by using a mixed sample of protonated and uniformly perdeuterated {alpha}-synuclein, a protein with chemical shifts exceptionally close to random coil values. Decomposition of these isotope shifts into one-bond, two-bond and three-bond effects as well as intra- and sequential residue contributions shows that such an analysis, which ignores conformational dependence, is meaningful but does not fully describe the total isotope shift to within the precision of the measurements. Random coil {sup 2}H isotope shifts provide an important starting point for analysis of such shifts in structural terms in folded proteins, where they are known to depend strongly on local geometry.

  11. APPLICATION OF THE NATURALLY-OCCURRING DEUTERIUM ISOTOPE TO TRACING THE CAPILLARY FRINGE

    Science.gov (United States)

    Naturally-occurring deuterium is a useful tracer of subsurface hydrologic processes. A possible application includes the identification of capillary fringes in the vadose zone. Multiple and discontinuous water tables persist in many temperate regions, under various hydrogeologi...

  12. Relativistic description of the Fermi motion effects on deuterium targets

    International Nuclear Information System (INIS)

    Kusno, D.

    1979-12-01

    A comprehensive analysis of the inconsistencies of the conventional, non-relativistic approach, which has been used so far in the extraction of neutron data from deuterium targets, is given. A new approach dealing with the smearing effects, due to the nucleon's Fermi motion inside the deuteron, is developed as an alternative to the conventional one. This new approach is a spin-less, relativistic, simple and consistent approach. A new covariant model of the elastic electromagnetic form factors of the deuteron in the impulse approximation is also presented. The treatment includes spin and allows for a possibility of determining completely the two elastic structure functions

  13. Use of isotope effects to elucidate enzyme mechanisms

    International Nuclear Information System (INIS)

    Cleland, W.W.

    1982-01-01

    The chemical bond breaking steps are normally not rate limiting for enzymatic reactions. However, comparison of deuterium and tritium isotope effects on the same reaction, especially when coupled with 13 C isotope effects for the same step measured with deuterated as well as unlabeled substrates, allows calculation of the intrinsic isotope effects on the bond breaking steps and thus a determination of the commitments to catalysis for the reactants. The variation in observed isotope effects as a function of reactant concentration can be used to determine kinetic mechanisms, while the pH variation of isotope effects can determine the stickiness of the reactants and which portions of the reactant mechanism are pH dependent. Finally the size of primary and secondary intrinsic isotope effects can be used to determine transition state structure

  14. NMR spectroscopic determination of an equilibrium isotope effect on the hydration of cobalt(II)

    International Nuclear Information System (INIS)

    Evilia, R.F.; Saunders, M.

    1985-01-01

    A recently reported NMR method for the measurement of deuterium equilibrium isotope effects is applied to the hydration of the paramagnetic cobalt(II) ion. An isotope effect of about 1.3% is measured. A substantial difference between the intrinsic shift of H 2 O and D 2 O when coordinated to cobalt is also measured

  15. On the Effect of Planetary Stable Isotope Compositions on Growth and Survival of Terrestrial Organisms.

    Directory of Open Access Journals (Sweden)

    Xueshu Xie

    Full Text Available Isotopic compositions of reactants affect the rates of chemical and biochemical reactions. Usually it is assumed that heavy stable isotope enrichment leads to progressively slower reactions. Yet the effect of stable isotopes may be nonlinear, as exemplified by the "isotopic resonance" phenomenon. Since the isotopic compositions of other planets of Solar system, including Mars and Venus, are markedly different from terrestrial (e.g., deuterium content is ≈5 and ≈100 times higher, respectively, it is far from certain that terrestrial life will thrive in these isotopic conditions. Here we found that Martian deuterium content negatively affected survival of shrimp in semi-closed biosphere on a year-long time scale. Moreover, the bacterium Escherichia coli grows slower at Martian isotopic compositions and even slower at Venus's compositions. Thus, the biological impact of varying stable isotope compositions needs to be taken into account when planning interplanetary missions.

  16. Effects of must concentration techniques on wine isotopic parameters.

    Science.gov (United States)

    Guyon, Francois; Douet, Christine; Colas, Sebastien; Salagoïty, Marie-Hélène; Medina, Bernard

    2006-12-27

    Despite the robustness of isotopic methods applied in the field of wine control, isotopic values can be slightly influenced by enological practices. For this reason, must concentration technique effects on wine isotopic parameters were studied. The two studied concentration techniques were reverse osmosis (RO) and high-vacuum evaporation (HVE). Samples (must and extracted water) have been collected in various French vineyards. Musts were microfermented at the laboratory, and isotope parameters were determined on the obtained wine. Deuterium and carbon-13 isotope ratios were studied on distilled ethanol by nuclear magnetic resonance (NMR) and isotope ratio mass spectrometry (IRMS), respectively. The oxygen-18 ratio was determined on extracted and wine water using IRMS apparatus. The study showed that the RO technique has a very low effect on isotopic parameters, indicating that this concentration technique does not create any isotopic fractionation, neither at sugar level nor at water level. The effect is notable for must submitted to HVE concentration: water evaporation leads to a modification of the oxygen-18 ratio of the must and, as a consequence, ethanol deuterium concentration is also modified.

  17. Mechanism of the flame ionization detector. II. Isotope effects and heteroatom effects

    DEFF Research Database (Denmark)

    Holm, Torkil

    1997-01-01

    The relative molar flame ionization detecton (FID) response (RMR) for a hydrocarbon does not change when deuterium is substituted for hydrogen. The exception is methane for which an inverse deuterium effect of 3..5% is observed for tetradeuteriomethane. [13C]Methane shows an inverse isotope effect...... of 2%. The reason for the small or non-existent isotope effects is that H/2H exchange takes place in the pre-combustion hydrogenolysis in the flame. This was shown by taking samples from the lower part of the flame by means of a fused silica capillary probe. By the same technique the hydrogenolytic...

  18. Effect of noble gas ion pre-irradiation on deuterium retention in tungsten

    NARCIS (Netherlands)

    Cheng, L.; Zhao, Z. H.; De Temmerman, G.; Yuan, Y.; Morgan, T. W.; Guo, L. P.; Wang, B.; Zhang, Y.; Wang, B. Y.; Zhang, P.; Cao, X. Z.; Lu, G. H.

    2016-01-01

    Impurity seeding of noble gases is an effective way of decreasing the heat loads onto the divertor targets in fusion devices. To investigate the effect of noble gases on deuterium retention, tungsten targets have been implanted by different noble gas ions and subsequently exposed to deuterium

  19. Noncovalent Hydrogen Isotope Effects

    Science.gov (United States)

    Buchachenko, A. L.; Breslavskaya, N. N.

    2018-02-01

    Zero-point energies (ZPE) and isotope effects, induced by intermolecular, noncovalent vibrations, are computed and tested by experimental data. The ZPE differences of H- and D-complexes of water with hydrogen, methane, and water molecules are about 100-300 cal/mol; they result to isotope effects IE of 1.20-1.70. Semi-ionic bonds between metal ions and water ligands in M(H2O) 6 2+ complexes are much stronger; their ZPEs are about 12-14 kcal/mol per molecule and result to IE of 1.9-2.1 at 300 K. Protonated (deuterated) water and biwater exhibit the largest ZPE differences and isotope effects; the latter are 25-28 and 12-13 for water and biwater, respectively. Noncovalent IEs contribute markedly into the experimentally measured effects and explain many anomalous and even magic properties of the effects, such as the dependence of IE on the solvents and on the presence of the third substances, enormously large isotope effects at the mild conditions, the difference between IEs measured in the reactions of individual protiated and deuterated compounds and those measured in their mixture. Noncovalent IEs are not negligible and should be taken into account to make correct and substantiated conclusions on the reaction mechanisms. The kinetic equations are derived for the total isotope effects, which include noncovalent IEs as additive factors.

  20. Deuterium-depleted water. Romanian achievements and perspective

    International Nuclear Information System (INIS)

    Stefanescu, Ion; Saros-Rogobete, Irina; Titescu, Gheorghe

    2001-01-01

    Deuterium-depleted water has an isotopic content smaller than 145 ppm D/(D+H) which is the natural isotopic content of water. Beginning with 1996 ICSI Rm. Valcea, deuterium-depleted water producer, co-operated with Romanian specialized institutes for biological effect's evaluation of deuterium-depleted water. These investigations lead to the following conclusions: - Deuterium-depleted water caused a tendency towards the increase of the basal tonus, accompanied by the intensification of the vasoconstrictor effects of phenylefrine, noradrenaline and angiotensin; the increase of the basal tonus and vascular reactivity produced by the deuterium-depleted water persist after the removal of the vascular endothelium; - Animals treated with deuterium-depleted water showed an increase of the resistance both to sublethal and to lethal gamma radiation doses, suggesting a radioprotective action; - Deuterium-depleted water stimulates immune defence reactions and increases the numbers of polymorphonuclear neutrophils; - Investigations regarding artificial reproduction of fish with deuterium-depleted water fecundated solutions confirmed favourable influence in embryo growth stage and resistance in subsequent growth stages; - It was studied germination, growth and quantitative character's variability in plants; one can remark the favourable influence of deuterium-depleted water on biological process in plants in various ontogenetic stages; - The deuterium depletion in seawater produces the diminution of the water spectral energy related to an increased metabolism of Tetraselmis Suecica. (authors)

  1. Isotopic effect giant resonances

    International Nuclear Information System (INIS)

    Buenerd, M.; Lebrun, D.; Martin, P.; Perrin, G.; Saintignon, P. de; Chauvin, J.; Duhamel, G.

    1981-10-01

    The systematics of the excitation energy of the giant dipole, monopole, and quadrupole resonances are shown to exhibit an isotopic effect. For a given element, the excitation energy of the transition decreases faster with the increasing neutron number than the empirical laws fitting the overall data. This effect is discussed in terms of the available models

  2. The effects of deuterium-depleted water on bacteria

    International Nuclear Information System (INIS)

    Butnaru, Gallia; Jurca, Elena M.; Titescu, Gh.; Stefanescu, I.

    2000-01-01

    Due to their adaptability the bacteria are ubiquitous, occurring in a large variety of habitats. Most of them are saprotrophs or parasites. Bacteria are agents causing many diseases in animals and humans. The main purpose of this work was to reveal the deuterium-depleted water bactericidal effect. Nonpathogenic Gram-positive (Bacillus subtilis and Bacillus cereus) and pathogenic Gram-negative (Agrobacterium tumefaciens, Erwinia amylovora and Escherichia coli) bacteria were used. The variant deuterium depleted (DDW) eater was compared with distilled water eater one. The diffusometric method was found the proper way of investigation. The bacteria culture was developed in Petri dishes (diam = 70 mm) at a temperature of 25 deg. C. After 24 h, 48 h and 72 h the clear area was measured. The clear area was one in which the bacteria were killed. The surface was determined by the area of the small disc on the filter paper. The statistical data were determined by variance analysis. The results pointed out a large response to DDW presence. The data were classified in: 1. without response when no clear area occurred; - 2. with response when a clear area of under 5 mm 2 occurred; - 3. strong response when the clear area was higher than 10 mm 2 . The Gram-positive and Gram-negative bacteria behaviours were not in correlation with the DDW bactericidal effect. The Bacillus cereus and Escherichia coli were scored as without response and we presume that they were very tolerant. No clear area was induced by DDW. Bacillus subtilis and Erwinia amylovora showed weak response. After 24 h the killed bacteria were extended on the same area, namely, 2.89 mm 2 . Even if the DDW effect seems to be small it was significantly in comparison with the control case (s d = 2.78 mm 2 > 0.1). After 48 h and 72 h the clear surface remained the same. The Agrobacterium tumefaciens' response was very strong. The bacteria were killed on 22.50 mm 2 after 24 h and on 26.95 mm 2 after 48 h, being very

  3. Alternate substrates and isotope effects as a probe of the malic enzyme reaction

    International Nuclear Information System (INIS)

    Gavva, S.R.

    1988-01-01

    Dissociation constants for alternative dinucleotide substrates and competitive inhibitors suggest that the dinucleotide binding site of the Ascaris suum NAD-malic enzyme is hydrophobic in the vicinity of the nicotinamide ring. Changes in the divalent metal ion activator from Mg 2+ to Mn 2+ or Cd 2+ results in a decrease in the dinucleotide affinity and an increase in the affinity for malate. Primary deuterium and 13 C isotope effects obtained with the different metal ions suggest either a change in the transition state structure for the hydride transfer or decarboxylation steps or both. Deuterium isotope effects are finite whether reactants are maintained at saturating or limiting concentrations with all the metal ions and dinucleotide substrates used. For the native enzyme, primary deuterium isotope effects increase with a concomitant decrease in the 13 C effects when NAD is replaced by an alternate dinucleotide substrate different in redox potential

  4. Kinetic isotope effects and aliphatic diazo-compounds

    International Nuclear Information System (INIS)

    Albery, W.J.; Conway, C.W.; Hall, J.A.

    1976-01-01

    Results are reported for the variation of the rate of decomposition of ethyl diazomalonate (EDM) and diazomalonate anions with pH and for the deuterium solvent isotope effect for EDM. The shape of the pH profile is explained by successive protonations of the anions. Ethyl diazoacetate is observed as an intermediate in the decomposition of EDM. The degree of proton transfer in the EDM transition state is deduced from the solvent isotope effect and the results together with those for other aliphatic diazo-compounds are discussed in terms of the Marcus theory. (author)

  5. Isotopic effects in the muon transfer from pmu and dmu to heavier atoms.

    Science.gov (United States)

    Dupays, Arnaud

    2004-07-23

    The results of accurate hyperspherical calculations of the muon-transfer rates from muonic protium and deuterium atoms to nitrogen, oxygen, and neon are reported. Very good agreement with measured rates is obtained and, for the three systems, the isotopic effect is perfectly reproduced. The transfer rate is higher for deuterium in the cases of nitrogen and neon due to constructive interferences between two transfer paths. The lower transfer rate for deuterium in the case of oxygen results from a large resonant contribution. Copyright 2004 The American Physical Society

  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].

    Science.gov (United States)

    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 (phydrogen 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 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 "plasmaisotopic composition, aimed at reducing the level of heavy non-radioactive atoms will allow the targeted nutritional correction of prooxidant-antioxidant status of the population in areas with adverse environmental conditions, stimulating by created isotopic D/H gradient cytoprotective mechanisms influencing the various components of nonspecific protection, including free radical oxidation processes. And then again, periodic assessment of the isotopic composition of nutrients will monitor the quality of food consumed by the population, and if

  7. Partial molar volumes of hydrogen and deuterium in niobium and vanadium

    International Nuclear Information System (INIS)

    Herro, H.M.

    1979-01-01

    Lattice dilation studies and direct pressure experiments gave comparable values for the partial molar volumes of hydrogen and deuterium in niobium and vanadium. Small isotope effects in the partial molar volume of hydrogen were measured in both metals by the differential isotope method. Hydrogen had a larger partial molar volume than deuterium in niobium, but the reverse was true in vanadium. The isotope effect measured in niobium can be represented as being due to the larger amplitude of vibration of the hydrogen atom than the deuterium atom in the metal lattice. Since hydrogen has a larger mean displacement from the equilibrium position than does deuterium, the average force hydrogen exerts on the metal atoms is greater than the force deuterium exerts. The isotope effect in vanadium is likely a result of anharmonic effects in the lattice and local vibrational modes

  8. Meaning of the Deuterium excess in the interpretation of δ 18O and δ 2H stable isotopes in hydrogeological studies

    International Nuclear Information System (INIS)

    Valencia, Jacinto

    2013-01-01

    An analysis element that helps with information on the interpretation of stable isotopes δ 18 O and deuterium in hydrogeological studies is called deuterium excess δ. In the present study, it has been used to interpret the weather, evaporation, humidity and wind conditions at the time of the precipitation in the Altiplano region of Puno, which have led to leaks of mine under study. The values obtained from the calculation of the deuterium excess δ of the seepage water samples are in the order of +15o/oo, indicating that the characteristics of the rainfall in the region have dominated high land desert climate conditions, different the current, ie, low humidity at the time of precipitation and further filtering these waters have received contribution of close water basin, evaporated and could come from Lake Titicaca. (author).

  9. Effects of hydrogen mixture into helium gas on deuterium removal from lithium titanate

    Energy Technology Data Exchange (ETDEWEB)

    Tsuchiya, Akihito, E-mail: tsuchiya@frontier.hokudai.ac.jp [Laboratory of Plasma Physics and Engineering, Hokkaido University, Kita-13, Nishi-8, Kita-ku, Sapporo 060-8628 (Japan); Hino, Tomoaki; Yamauchi, Yuji; Nobuta, Yuji [Laboratory of Plasma Physics and Engineering, Hokkaido University, Kita-13, Nishi-8, Kita-ku, Sapporo 060-8628 (Japan); Akiba, Masato; Enoeda, Mikio [Japan Atomic Energy Agency, 801-1, Mukoyama, Naka 311-0193 (Japan)

    2013-10-15

    Lithium titanate (Li{sub 2}TiO{sub 3}) pebbles were irradiated with deuterium ions with energy of 1.7 keV and then exposed to helium or helium–hydrogen mixed gas at various temperatures, in order to evaluate the effects of gas exposure on deuterium removal from the pebbles. The amounts of residual deuterium in the pebbles were measured by thermal desorption spectroscopy. The mixing of hydrogen gas into helium gas enhanced the removal amount of deuterium. In other words, the amount of residual deuterium after the helium–hydrogen mixed gas exposure at lower temperature was lower than that after the helium gas exposure. In addition, we also evaluated the pebbles exposed to the helium gas with different hydrogen mixture ratio from 0% to 1%, at 573 K. Although the amount of residual deuterium in the pebbles after the exposure decreased with increasing the hydrogen mixture ratio, the implanted deuterium partly remained after the exposure. These results suggest that the tritium inventory may occur at low temperature region in the blanket during the operation.

  10. Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

    Science.gov (United States)

    Kassem, M. E.; Hamed, A. E.; Abulnasr, L.; Abboudy, S.

    1994-11-01

    Isotopic effects in pure and γ-irradiated triglycine selenate crystals were investigated using the specific heat ( Cp) technique. The obtained results showed an interesting dependence of the critical behavior of Cp on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order (γ-type) to a first order transition. After γ-irradiation, the behavior of Cp around the phase transition region was essentially affected. The transition temperature, Tc, decreased and Δ Cp depressed, and the transition became broad. It was noted that the effect of γ-irradiation is opposite to the isotopic effect.

  11. Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

    International Nuclear Information System (INIS)

    Kassem, M.E.; Hamed, A.E.; Abulnasr, L.; Abboudy, S.

    1994-01-01

    Isotopic effects in pure and γ-irradiated triglycine selenate crystals were investigated using the specific heat (C p ) technique. The obtained results showed an interesting dependence of the critical behavior of C p on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order (λ-type) to a first order transition. After γ-irradiation, the behavior of C p around the phase transition region was essentially affected. The transition temperature, T c , decreased and ΔC p depressed, and the transition became broad. It was noted that the effect of γ-irradiation is opposite to the isotopic effect. (author)

  12. Stable isotope hydrology. Deuterium and oxygen-18 in the water cycle

    International Nuclear Information System (INIS)

    Gat, J.R.; Gonfiantini, R.

    1981-01-01

    This monograph is mainly intended for hydrologists, hydrogeologists and geochemists who want to become acquainted, rapidly but in some detail, with the theoretical background of stable isotope fractionation in natural physico-chemical processes involving fresh water, with the isotopic differences actually encountered in natural waters and with their use for practical hydrological purposes. Throughout the monograph, and in particular in the last chapter, a series of examples are discussed, giving the results obtained with stable isotope techniques in current hydrological and hydrogeological investigations or, more generally, in water resources exploration and assessment. One chapter is also dedicated to the techniques for measuring D/H and 18 O/ 16 O ratios in water

  13. Solvent isotope effects on the rates of alkylation of thiolamine models of papain

    International Nuclear Information System (INIS)

    Wandinger, A.; Creighton, D.J.

    1980-01-01

    As a test of whether it is chemically reasonable to attribute any or all of the observed kinetic solvent deuterium isotope effects reported on papain to the fundamental properties of the tautomerization equilibrium, the magnitudes of the solvent deuterium isotope effects on the rates of alkylation of the tautomeric forms of cysteine and β-mercaptoethylamine were determined for bromo- and chloroacetate, bromo- and chloroacetamide, as well as for methylbromoacetate. These thiolamines are viewed as elementary chemical models of the sulfhydryl group tautomerization equilibrium envisioned in the active site of papain. (Auth.)

  14. Determination of Equine Cytochrome c Backbone Amide Hydrogen/Deuterium Exchange Rates by Mass Spectrometry Using a Wider Time Window and Isotope Envelope.

    Science.gov (United States)

    Hamuro, Yoshitomo

    2017-03-01

    A new strategy to analyze amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) data is proposed, utilizing a wider time window and isotope envelope analysis of each peptide. While most current scientific reports present HDX-MS data as a set of time-dependent deuteration levels of peptides, the ideal HDX-MS data presentation is a complete set of backbone amide hydrogen exchange rates. The ideal data set can provide single amide resolution, coverage of all exchange events, and the open/close ratio of each amide hydrogen in EX2 mechanism. Toward this goal, a typical HDX-MS protocol was modified in two aspects: measurement of a wider time window in HDX-MS experiments and deconvolution of isotope envelope of each peptide. Measurement of a wider time window enabled the observation of deuterium incorporation of most backbone amide hydrogens. Analysis of the isotope envelope instead of centroid value provides the deuterium distribution instead of the sum of deuteration levels in each peptide. A one-step, global-fitting algorithm optimized exchange rate and deuterium retention during the analysis of each amide hydrogen by fitting the deuterated isotope envelopes at all time points of all peptides in a region. Application of this strategy to cytochrome c yielded 97 out of 100 amide hydrogen exchange rates. A set of exchange rates determined by this approach is more appropriate for a patent or regulatory filing of a biopharmaceutical than a set of peptide deuteration levels obtained by a typical protocol. A wider time window of this method also eliminates false negatives in protein-ligand binding site identification. Graphical Abstract ᅟ.

  15. Hydrogen isotope behavior in the first wall of JT-60U after deuterium plasma operation

    International Nuclear Information System (INIS)

    Oya, Y.; Tanabe, T.; Oyaidzu, M.; Shibahara, T.; Sugiyama, K.; Yoshikawa, A.; Onishi, Y.; Hirohata, Y.; Ishimoto, Y.; Yagyu, J.; Arai, T.; Masaki, K.; Okuno, K.; Miya, N.; Tanaka, S.

    2007-01-01

    Retention of hydrogen isotopes in the carbon (isotropic graphite) first wall tiles of JT-60U was studied by secondary ion mass spectrometry and thermal desorption spectroscopy. The surface morphology and erosion/deposition profiles of the tiles were characterized using scanning electron microscope and X-ray photoelectron spectroscopy. The upper area is mainly eroded, while the bottom area of the inboard wall is dominated by deposition. In contrast to the divertor area, hydrogen isotope retention in the eroded wall area was generally larger than that in the deposition dominated area. Measured near surface concentrations of hydrogen isotopes in the wall tiles, as well as the D/H ratios, were a little higher than those in the divertor area. This indicates direct implantation of high-energy D from NBI into the first wall. The lower temperature of the first wall relative to the divertor tiles would reduce desorption and/or replacement of implanted D by subsequent D or H impingement

  16. High resolution conductometry for isotopic assay of deuterium in mixtures of heavy water and light water

    International Nuclear Information System (INIS)

    Ananthanarayanan, R.; Sahoo, P.; Murali, N.

    2014-01-01

    A PC based high resolution conductivity monitoring technique has been deployed for determination of isotopic purity of heavy water in samples containing heavy water and light water mixtures using pulsating sensor based conductivity monitoring instrument. The technique involves accurate determination of conductivities of a series of specially treated heavy water and light water mixtures of various compositions at a constant solution temperature. The shift in conductivity (Δκ), which is the difference between conductivities of composite mixture after and before the formation of a typical complex compound (boric acid–mannitol complex in this case), shows a smooth and reproducible decreasing trend with increase in percentage composition of heavy water. This relation, which is obtained by appropriate calibration, is used in the software program for direct display of isotopic purity of heavy water. The technique is examined for determination of percentage composition of heavy water in the entire range of concentration (0-100 %) with reasonable precision (relative standard deviation, RSD ≤1.5 %). About 1 mL of sample is required for each analysis and analysis is completed within a couple of minutes after pretreatment of sample. The accuracy in measurement is ≤1.75 %. (author)

  17. Isotope mixtures of hydrogen in vanadium

    International Nuclear Information System (INIS)

    Mecking-Schloetensack, P.

    1982-03-01

    The properties of isotope-mixtures of Protium and Deuterium stored in Vanadium have been studied. Protium and Deuterium are existing as interstitial-atoms on tetrahedral sites as well as on octahedral sites in this system. This feature leads to large isotopic-effects between the two isotopes. The dependence of the thermodynamic functions like heat of solution, nonconfigurational entropy, specific heat and ordering temperatures from the composition of the isotope-mixture has been determined. (orig.)

  18. Electromigration of hydrogen and deuterium in vanadium, niobium, and tantalum

    International Nuclear Information System (INIS)

    Jensen, C.L.

    1977-10-01

    The electric mobility and effective valence of hydrogen and deuterium in vanadium, niobium, tantalum and three niobium-tantalum alloys were measured. A resistance technique was used to directly determine the electric mobility of hydrogen and deuterium at 30 0 C while a steady-state method was used to measure the effective valence. The use of mass spectrographic techniques on a single specimen which contained both hydrogen and deuterium greatly increased the precision with which the isotope effect in the effective valence could be measured

  19. Nuclear effect study on nucleon structure functions, in comparison with antineutrino interactions on neon and deuterium

    International Nuclear Information System (INIS)

    Vallee, C.

    1984-03-01

    We have studied the nuclear effects on high energy antineutrino charged current interactions by comparing the data which were taken in the Bubble Chamber BEBC filled with Neon and Deuterium. On the one hand, the study of nuclear reinteractions gave us the possibility to estimate the formation time of hadrons. On the other hand, the comparison of structure functions does not show any significant difference between Neon and Deuterium. Though this result does not contradict the effects observed with charged leptons by the EMC and SLAC experiments, it is strongly incompatible with certain theoretical interpretations which implied a stronger effect in antineutrino interactions [fr

  20. Low temperature isotope effects of hydrogen diffusion in metallic glasses

    International Nuclear Information System (INIS)

    Hofmann, A.; Kronmueller, H.

    1989-01-01

    Snoek-like relaxation peaks of Hydrogen and Deuterium in amorphous Fe 80 B 20 , Fe 40 Ni 40 P 14 B 6 and Fe 91 Zr 9 are detected. At low H, D concentrations the peaks are near 200 K and show small isotope effects of the average activation energies (anti Q H ≅ 0.6 eV, anti Q D - anti Q H ≤ 10 meV). For higher H, D-contents the peaks shift to lower temperatures around to 120 K and show distinct isotope effects in the activation energies (anti Q H ≅ 0.3 eV, anti Q D - anti Q H ≅ 30 meV) and in the amplitude of the low temperature tails of the relaxation peaks. This points to isotope mass dependent deviations from the Arrhenius law due to nonthermal tunneling processes. (orig.)

  1. Kinetic isotope effect in the thermolysis of methylenecyclobutane

    International Nuclear Information System (INIS)

    Chickos, J.S.

    1979-01-01

    The intramolecular kinetic isotope effect for the thermolysis of equilibrated methylenecyclobutane-d 2 was investigated at 515 0 C as a function of pressure. A high-pressure value of k/sub H/k/sub D/ (ethylene/ethylene-d 2 ) = 0.9 was obtained at 13 cm of N 2 pressure. This value decreased to 0.86 at 70 μm total pressure. No intermolecular kinetic isotope effect was measured for the formation of ethylene from labeled and unlabeled methylenecyclobutane. The pressure and temperature dependence of the intramolecular kinetic isotope effect was used as evidence in establishing the inverse nature of the effect. The isotope effect observed was explained in terms of competing equilibrium and kinetic isotope effects in which the equilibrium isotope effects dominate. It was concluded on the bases of these results that an acyclic intermediate is involved in the fragmentation of methylenecyclobutane to ethylene and allene. The results also support the notion that deuterium prefers to accumulate at the methylene group with the greatest p character in the carbon--hydrogen bond. 1 figure, 4 tables

  2. Solvent effects and secondary isotope effects for probing diradical character in the thermal decarboxylation of β-peroxylactones

    International Nuclear Information System (INIS)

    Adam, W.; Cueto, O.; Guedes, L.N.; Rodriguez, L.O.

    1978-01-01

    The lack of solvent effects in the activation parameters and product distribution and the lack of secondary deuterium isotope effects at the α-carbon and β-alkyl migrant substantiates that the thermal decarboxylation of β-peroxy lactones proceeds via a 1,5-diradical

  3. Isotope effect on the zero point energy shift upon condensation

    International Nuclear Information System (INIS)

    Kornblum, Z.C.

    1977-01-01

    The various isotope-dependent and independent atomic and molecular properties that pertain to the isotopic difference between the zero point energy (ZPE) shifts upon condensation have been derived. The theoretical development of the change of the ZPE associated with the internal molecular vibrations, due to the condensation of the gaseous molecules, has been presented on the basis of Wolfsberg's second-order perturbation treatment of the isotope-dependent London dispersion forces between liquid molecules. The isotope effect on the ZPE shift is related to the difference between the sums of the integrated intensities of the infrared absorption bands of the two gaseous isotopic molecules. Each intensity sum is expressed, in part, in terms of partial derivatives of the molecular dipole moment with respect to atomic cartesian coordinates. These derivatives are related to the isotope-independent effective charges of the atoms, which are theoretically calculated by means of a modified CNDO/2 computer program. The effective atomic charges are also calculated from available experimental infrared intensity data. The effects of isotopic substitutions of carbon-13 for carbon-12 and/or deuterium for protium, in ethylene, methane, and the fluorinated methanes, CH 3 F, CH 2 F 2 , CHF 3 , and CF 4 , on the ZPE shift upon condensation are calculated. These results compare well with the Bigeleisen B-factors, which are experimentally obtained from vapor pressure measurements of the isotopic species. Each of the following molecular properties will tend to increase the isotopic difference between the ZPE shifts upon condensation: (1) large number of highly polar bonds, (2) high molecular weight, (3) non-polar (preferably) or massive molecule, (4) non-hydrogenous molecule, and (5) closely packed liquid molecules. These properties will result in stronger dispersion forces in the liquid phase between the lighter molecules than between the isotopically heavier molecules

  4. Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 2. Assessing Charge Site Location and Isotope Scrambling

    Science.gov (United States)

    Khakinejad, Mahdiar; Ghassabi Kondalaji, Samaneh; Donohoe, Gregory C.; Valentine, Stephen J.

    2016-03-01

    Ion mobility spectrometry (IMS) coupled with gas-phase hydrogen deuterium exchange (HDX)-mass spectrometry (MS) and molecular dynamic simulations (MDS) has been used for structural investigation of anions produced by electrospraying a sample containing a synthetic peptide having the sequence KKDDDDDIIKIIK. In these experiments the potential of the analytical method for locating charge sites on ions as well as for utilizing collision-induced dissociation (CID) to reveal the degree of deuterium uptake within specific amino acid residues has been assessed. For diffuse (i.e., more elongated) [M - 2H]2- ions, decreased deuterium content along with MDS data suggest that the D4 and D6 residues are charge sites, whereas for the more diffuse [M - 3H]3- ions, the data suggest that the D4, D7, and the C-terminus are deprotonated. Fragmentation of mobility-selected, diffuse [M - 2H]2- ions to determine deuterium uptake at individual amino acid residues reveals a degree of deuterium retention at incorporation sites. Although the diffuse [M - 3H]3- ions may show more HD scrambling, it is not possible to clearly distinguish HD scrambling from the expected deuterium uptake based on a hydrogen accessibility model. The capability of the IMS-HDX-MS/MS approach to provide relevant details about ion structure is discussed. Additionally, the ability to extend the approach for locating protonation sites on positively-charged ions is presented.

  5. Clumped isotope effects during OH and Cl oxidation of methane

    DEFF Research Database (Denmark)

    Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan Albrecht

    2017-01-01

    A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH was produ......A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH...... effects for singly substituted species were consistent with previous experimental studies. For doubly substituted methane, 13CH3D, the observed kinetic isotope effects closely follow the product of the kinetic isotope effects for the 13C and deuterium substituted species (i.e., 13,2KIE = 13KIE × 2KIE...... reactions. In a closed system, however, this effect is overtaken by the large D/H isotope effect, which causes the residual methane to become anti-clumped relative to the initial methane. Based on these results, we demonstrate that oxidation of methane by OH, the predominant oxidant for tropospheric methane...

  6. Isotope effect on the zero point energy shift upon condensation

    International Nuclear Information System (INIS)

    Kornblum, Z.C.; Ishida, T.

    1977-07-01

    The various isotope-dependent and independent atomic and molecular properties that pertain to the isotopic difference between the zero point energy (ZPE) shifts upon condensation were derived. The theoretical development of the change of the ZPE associated with the internal molecular vibrations, due to the condensation of the gaseous molecules, is presented on the basis of Wolfsberg's second-order perturbation treatment of the isotope-dependent London dispersion forces between liquid molecules. The isotope effect on the ZPE shift is related to the difference between the sums of the integrated intensities of the infrared absorption bands of the two gaseous isotopic molecules. The effective atomic charges are also calculated from available experimental infrared intensity data. The effects of isotopic substitutions of carbon-13 for carbon-12 and/or deuterium for protium, in ethylene, methane, and the fluorinated methanes, CH 3 F, CH 2 F 2 , CHF 3 , and CF 4 , on the ZPE shift upon condensation are calculated. These results compare well with the Bigeleisen B-factors, which are experimentally obtained from vapor pressure measurements of the isotopic species. Each of the following molecular properties will tend to increase the isotopic difference between the ZPE shifts upon condensation: (1) large number of highly polar bonds, (2) high molecular weight, (3) non-polar (preferably) or massive molecule, (4) non-hydrogenous molecule, and (5) closely packed liquid molecules. These properties will result in stronger dispersion forces in the liquid phase between the lighter molecules than between the isotopically heavier molecules. 36 tables, 9 figures

  7. The effects of environmental deuterium on normal and neoplastic cultured cell development

    International Nuclear Information System (INIS)

    Bild, W.; Schuller, T.; Zhihai, Qin; Blankenstein, T.; Nastasa, V.; Haulica, I.

    2000-01-01

    The powdered culture media (RPMI - 1640) were reconstituted either with normal distilled water (150 ppm deuterium) either with deuterium - depleted water (DDW) in various concentrations (30, 60, 90 ppm) and sterilized by filtration with 0.2 μm filters. The cell lines used were NIH (normal mouse fibroblasts), RAG (mouse renal carcinoma) and TS/A (mouse mammary adenocarcinoma). In auxiliary tests, BAIBC mouse splenocytes in direct culture were used, stimulated for growth with concanavalin A or LPS (bacterial lipopolysaccharide). The estimation of the growth was made using the MTT assay or direct counting with trypan blue exclusion. The following results were obtained: Deuterium - depleted water had a stimulating effect on cell growth, the most important stimulating action being from the 90 ppm deuterium-water. The growth curves show, in a first phase, a stimulation of the rapid -growing neoplastic cells, followed by a slower growth of the normal cells. Amiloride 100 mM blocking of the Na + /K + membrane pump did not affect the cell growth curves, while the lansoprazole 100 mM blocking of the K + /H + ATP-ase brought the growth curves at the level of those with normal water. This might show an eventual involvement of the K + /H + antiport in the stimulating effects of the DDW. (authors)

  8. D/H isotope effects in π-complexes of deuterated hexamethylbenzenes with the nitrosonium cation

    International Nuclear Information System (INIS)

    Borodkin, G.I.; Elanov, I.R.; Shakirov, M.M.; Shubin, V.G.

    1993-01-01

    The isotope effects of deuterium, manifested in the 13 C NMR spectra of complexes of deuterated hexamethylbenzenes C 6 (CD 3 ) n ·(CH 3 ) 6-n with the nitrosonium cation, have been studied. The small values observed for the isotopic perturbation are evidence of π-bonding of the NO + group to the hexamethylbenzene molecule. The applicability of an additive scheme of calculation of isotope effects for the ring carbon atoms of the complexes, based on the increment of replacement of the CH 3 group by CD 3 in hexamethylbenzene, has been demonstrated

  9. The effect of charge exchange with neutral deuterium on carbon emission in JET divertor plasmas

    International Nuclear Information System (INIS)

    Maggi, C.; Horton, L.; Summers, H.

    1999-11-01

    High density, low temperature divertor plasma operation in tokamaks results in large neutral deuterium concentrations in the divertor volume. In these conditions, low energy charge transfer reactions between neutral deuterium and the impurity ions can in principle enhance the impurity radiative losses and thus help to reduce the maximum heat load to the divertor target. A quantitative study of the effect of charge exchange on carbon emission is presented, applied to the JET divertor. Total and state selective effective charge exchange recombination rate coefficients were calculated in the collisional radiative picture. These coefficients were coupled to divertor and impurity transport models to study the effect of charge exchange on the measured carbon spectral emission in JET divertor discharges. The sensitivity of the effect of charge exchange to the assumptions in the impurity transport model was also investigated. A reassessment was made of fundamental charge exchange cross section data in support of this study. (author)

  10. Deuterium isotope differences in 2-propanone (CH3)2CO/(CD3)2CO: a high-pressure sound-speed, density, and heat capacities study

    International Nuclear Information System (INIS)

    Szydlowski, J.; Gomes de Azevedo, R.; Rebelo, L.P.N.; Esperanca, J.M.S.S.; Guedes, H.J.R.

    2005-01-01

    A new high-pressure, non-intrusive ultrasonic microcell [J. Chem. Thermodyn. 36 (2004) 211-222] was used to carry out sound-speed measurements in deuteriated 2-propanone (acetone-d 6 ) in broad ranges of temperature (288 6 . (p, ρ, T) data for acetone-d 6 were also determined but in a narrower T, p range (298 to 333 K; 0.1 to 60 MPa). In this interval, several thermodynamic properties were thus determined, such as: isentropic (κ s ) and isothermal (κ T ) compressibility, isobaric thermal expansivity (α p ), isobaric (c p ) and isochoric (c v ) specific heat capacity, and the thermal pressure coefficient (γ v ). Comparisons with our data for acetone-h 6 enabled us to establish the magnitude and sign of deuterium isotope effects for identical properties. These effects are a consequence of distinct vibrational mode frequencies in an isotope-invariant force constants' field. Molar heat capacities and their isotope effects were theoretically determined by employing an Einstein-like model for the vibrational frequencies of acetone-h 6 and acetone-d 6

  11. The deuterium depleted water effects on germination, growth and respiration processes in Zea Mays culture

    International Nuclear Information System (INIS)

    Stefanescu, Ioan; Fleancu, Monica; Giosanu, Daniela; Iorga-Siman, Ion

    2002-01-01

    The aim of this paper is to study the influence of deuterium depleted water (DDW) on the germination, growth and respiration processes in Zea Mays culture. The DDW is produced by the Institute of Cryogenics and Isotope Separation, Rm. Valcea (Romania). We used moist seeds in three experimental lots: L-1 (control), using distillated water (because the quality of DDW, excepting the deuterium content, is similar to that of distillated water); L-2, using a mixture of DDW and H 2 O in 1:1 proportion; L-3, germination in light water (DDW). Reported to the control lot, the germinative energy was higher in L-2 and L-3, but it was no significant difference between faculty of germination of variants. The length of main root was higher in L-2 and L-3 as compared to control lot. The intensity process of respiration was stimulated when DDW was used in both cases (L-2 or L-3). So, we can remark a favorable influence of light water on some biological processes in Zea mays plants (authors)

  12. Thermodynamic isotope effects of D2 and T2 reaction with uranium

    International Nuclear Information System (INIS)

    Huang Gang; Long Xinggui; Liang Jianhua; Yang Benfu; Liu Wenke

    2010-01-01

    The p-c-T curves of deuterium and tritium absorption by uranium and p-t curves of desorption were measured. The balance pressure of absorption and desorption on different temperatures were got and then the thermodynamic parameters were determined according to the Van't Hoff equation. It shows that the balance pressure of deuterium absorption is lower than that of tritium absorption on the same temperature and atom ratio. It has the same phenomena for desorption but there are obvious hysteresis effect for reversible process of absorption and desorption. There are a little thermodynamic isotope effects when deuterium and tritium absorption and desorption by uranium estimating from enthalpy and entropy values. (authors)

  13. A measurement of hydrogen transport in deuterium discharges using the dynamic response of the effective mass

    International Nuclear Information System (INIS)

    Dudok de Wit, T.; Duval, B.P.; Joye, B.; Lister, J.B.

    1992-02-01

    Particle tagging in a tokamak provides an attractive method for studying transport mechanisms. The injection of test particles at the plasma edge and the subsequent measurement of the evolution of their concentration at the centre can be used to quantify the underlying transport mechanisms. This has been carried out on the TCA tokamak by injecting hydrogen into a deuterium discharge, and simultaneously measuring the temporal evolution of the effective mass and the edge ionisation rate. (author) 3 figs., 9 refs

  14. Effect of laser spot size on fusion neutron yield in laser–deuterium cluster interactions

    International Nuclear Information System (INIS)

    Chen Guanglong; Lu Haiyang; Wang Cheng; Liu Jiansheng; Li Ruxin; Ni Guoquan; Xu Zhizhan

    2008-01-01

    The effect of the laser spot size on the neutron yield of table-top nuclear fusion from explosions of a femtosecond intense laser pulse heated deuterium clusters is investigated by using a simplified model, in which the cluster size distribution and the energy attenuation of the laser as it propagates through the cluster jet are taken into account. It has been found that there exists a proper laser spot size for the maximum fusion neutron yield for a given laser pulse and a specific deuterium gas cluster jet. The proper spot size, which is dependent on the laser parameters and the cluster jet parameters, has been calculated and compared with the available experimental data. A reasonable agreement between the calculated results and the published experimental results is found

  15. Evaluation of the isotope separation rate of deuterium exchange reaction between H2 and H2O with platinum catalyst

    International Nuclear Information System (INIS)

    Kitamoto, Asashi; Takashima, Yoichi; Shimizu, Masami.

    1983-01-01

    The high performance catalysts of hydrophobic carrier with fully dispersed platinum were used to measure the isotope separation performance of hydrogen by the chemical exchange method. The continuous injection of oxygen on the order of 10 3 ppm was effective in regenerating catalyst activity and in maintaining high performance for a long time. The separation performance in a trickle bed column should be evaluated by using two parameters, ksub(g) and ksub(l). These two parameters were unified to the overall transfer coefficient ksub(fg), which may be sufficient in the estimation of overall performance or the design of a separation plant by the chemical exchange method. When one wants to increase the transfer rate in a chemical exchange column, the improvement of ksub(l) rather than ksub(g) may be more effective in increasing the overall transfer rate (its coefficient is expressed by ksub(fg) in this paper). (author)

  16. Quantum tunneling observed without its characteristic large kinetic isotope effects.

    Science.gov (United States)

    Hama, Tetsuya; Ueta, Hirokazu; Kouchi, Akira; Watanabe, Naoki

    2015-06-16

    Classical transition-state theory is fundamental to describing chemical kinetics; however, quantum tunneling is also important in explaining the unexpectedly large reaction efficiencies observed in many chemical systems. Tunneling is often indicated by anomalously large kinetic isotope effects (KIEs), because a particle's ability to tunnel decreases significantly with its increasing mass. Here we experimentally demonstrate that cold hydrogen (H) and deuterium (D) atoms can add to solid benzene by tunneling; however, the observed H/D KIE was very small (1-1.5) despite the large intrinsic H/D KIE of tunneling (≳ 100). This strong reduction is due to the chemical kinetics being controlled not by tunneling but by the surface diffusion of the H/D atoms, a process not greatly affected by the isotope type. Because tunneling need not be accompanied by a large KIE in surface and interfacial chemical systems, it might be overlooked in other systems such as aerosols or enzymes. Our results suggest that surface tunneling reactions on interstellar dust may contribute to the deuteration of interstellar aromatic and aliphatic hydrocarbons, which could represent a major source of the deuterium enrichment observed in carbonaceous meteorites and interplanetary dust particles. These findings could improve our understanding of interstellar physicochemical processes, including those during the formation of the solar system.

  17. Kinetic formulae for muon-catalyzed fusion of hydrogen isotopes and their application to the description of the data for pure deuterium

    International Nuclear Information System (INIS)

    Gula, A.

    1987-01-01

    The data on the time distributions of muon-catalyzed fusion (μCF) events in pure deuterium targets published before 1987 are analysed using the kinetic formalism developed by the author and collaborators in a series of papers. The formalism enables one to describe these time distributions in an arbitrary mixture of hydrogen isotopes with strict inclusion of registration efficiency and dead time. The kinetic formulae for such distributions can be readily obtained using a prescription based on the theory of signal-flow graphs even for very complicated kinetic situations, thus, allowing one to avoid the simplifying assumptions which have been usually made in earlier analyses. Practically all important processes forming the muon-catalysis chain can be strictly taken into account in the approximation of constant transition rates. Consecutive μCF cycles can be described separately, which provides a useful tool in data analysis. The developed formalism is applied to the existing data for pure deuterium. First cycle-by-cycle time distributions reported for room temperature by the Gatchina group are analysed. 93 refs., 14 figs. (author)

  18. Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

    Energy Technology Data Exchange (ETDEWEB)

    Kassem, M.E.; Hamed, A.E.; Abulnasr, L.; Abboudy, S. [Alexandria Univ. (Egypt). Dept. of Physics

    1994-11-01

    Isotopic effects in pure and {gamma}-irradiated triglycine selenate crystals were investigated using the specific heat (C{sub p}) technique. The obtained results showed an interesting dependence of the critical behavior of C{sub p} on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order ({lambda}-type) to a first order transition. After {gamma}-irradiation, the behavior of C{sub p} around the phase transition region was essentially affected. The transition temperature, T{sub c}, decreased and {Delta}C{sub p} depressed, and the transition became broad. It was noted that the effect of {gamma}-irradiation is opposite to the isotopic effect. (author).

  19. Isotope effect and isotope separation. A chemist's view

    International Nuclear Information System (INIS)

    Ishida, Takanobu

    2002-01-01

    What causes the isotope effects (IE)? This presentation will be centered around the equilibrium isotope effects due to the differences in the nuclear masses. The occurrence of the equilibrium constant, K, of isotope exchange reactions which differ from the values predicted by the classical theory of statistical mechanics, K cl , is explored. The non-classical K corresponds to the unit-stage separation factor, α, that is different from unity and forms a basis of an isotope separation process involving the chemical exchange reaction. Here, the word 'chemical exchange' includes not only the isotope exchange chemical reactions between two or more chemical species but also the isotope exchanges involving the equilibria between liquid and vapor phases and liquid-gas, liquid solution-gas, liquid-liquid, and solid-liquid phases. In Section I, origins of the isotope effect phenomena will be explored and, in the process, various quantities used in discussions of isotope effect that have often caused confusions will be unambiguously defined. This Section will also correlate equilibrium constant with separation factor. In Section II, various forms of temperature-dependence of IE and separation factor will be discussed. (author)

  20. Transient effects during erosion of WN by deuterium ions studied with the quartz crystal microbalance technique

    Energy Technology Data Exchange (ETDEWEB)

    Berger, Bernhard M., E-mail: berger@iap.tuwien.ac.at [Institute of Applied Physics, TU Wien, Fusion@ÖAW, Wiedner Hauptstr. 8-10, 1040 Vienna (Austria); Stadlmayr, Reinhard [Institute of Applied Physics, TU Wien, Fusion@ÖAW, Wiedner Hauptstr. 8-10, 1040 Vienna (Austria); Meisl, Gerd [Max-Planck-Institut für Plasmaphysik, Boltzmannstraße 2, 85748 Garching (Germany); Čekada, Miha [Jožef Stefan Institute, Jamova 39, 1000 Ljubljana (Slovenia); Eisenmenger-Sittner, Christoph [Institute of Solid State Physics, TU Wien, Wiedner Hauptstr. 8-10, 1040 Vienna (Austria); Schwarz-Selinger, Thomas [Max-Planck-Institut für Plasmaphysik, Boltzmannstraße 2, 85748 Garching (Germany); Aumayr, Friedrich, E-mail: aumayr@iap.tuwien.ac.at [Institute of Applied Physics, TU Wien, Fusion@ÖAW, Wiedner Hauptstr. 8-10, 1040 Vienna (Austria)

    2016-09-01

    Transient effects during erosion of polycrystalline tungsten-nitride (WN) films by mono-energetic deuterium projectiles are studied using a quartz crystal microbalance technique. The evolution of the mass removal rate of a 360 nm thin WN film under 500 eV/D and 1000 eV/D bombardment is investigated at a temperature of 465 K in situ and in real-time as a function of the deuterium fluence. The measurements are performed at a typical flux of 10{sup 18} m{sup −2} s{sup −1}. A strong dependency of the observed mass change rate on the deuterium fluence is found. The mass loss is initially higher than for pure tungsten (W) and drops with fluence, finally reaching the same steady state value as for pure W sputtering. Steady state surface conditions are obtained at a fluence of about 0.2 × 10{sup 23} D/m{sup 2} for 500 eV/D and 0.6 × 10{sup 23} D/m{sup 2} for 1000 eV/D. SDTrimSP simulations indicate a preferential removal of N and a corresponding W enrichment of the surface.

  1. Non-linear Isotope Effects

    DEFF Research Database (Denmark)

    Schmidt, Johan Albrecht

    ’s stratosphere is nearly mass dependent, and only a small fraction of the observed anomalous oxygen-17 excess can be attributed to N2O photolysis. In contrast, stratospheric photolysis produces a significant inverse clumped isotope effect.(ii) Stratospheric OCS photolysis significantly enrich the remaining OCS...

  2. Tritium conductivity and isotope effect in proton-conducting perovskites

    International Nuclear Information System (INIS)

    Mukundan, R.; Brosha, E.L.; Birdsell, S.A.; Costello, A.L.; Garzon, F.H.; Willms, R.S.

    1999-01-01

    The tritium ion conductivities of SrZr 0.9 Yb 0.1 O 2.95 and BaCe 0.9 Yb 0.1 O 2.95 have been measured by ac impedance analysis. The high tritium conductivity of these perovskites could potentially lead to their application as an electrochemical membrane for the recovery of tritium from tritiated gas streams. The conductivities of these perovskites, along with SrCe 0.95 Yb 0.05 O 2.975 , were also measured in hydrogen- and deuterium-containing atmospheres to illustrate the isotope effect. For the strontium zirconate and barium cerate samples, the impedance plot consists of two clearly resolved arcs, a bulk and a grain boundary arc, in the temperature range 50--350 C. However, for the strontium cerate sample, the clear resolution of the bulk conductivity was not possible and only the total conductivity was measurable. Thus, the isotope effect was clearly established only for the strontium zirconate and barium cerate samples. The decrease in bulk conductivity with increasing isotope mass was found to be a result of an increase in the activation energy for conduction accompanied by a decrease in the pre-exponential factor. Since the concentration of the mobile species (H+, D+, or T+) should remain relatively constant at T < 350 C, this increase in activation energy is directly attributable to the increased activation energy for the isotope mobility

  3. Extensive Turnover of Compatible Solutes in Cyanobacteria Revealed by Deuterium Oxide (D_2O) Stable Isotope Probing

    International Nuclear Information System (INIS)

    Baran, Richard; Lau, Rebecca; Bowen, Benjamin P.; Diamond, Spencer; Jose, Nick

    2017-01-01

    In diverse environments on a global scale cyanobacteria are important primary producers of organic matter. Moreover, while mechanisms of CO_2 fixation are well understood, the distribution of the flow of fixed organic carbon within individual cells and complex microbial communities is less well characterized. To obtain a general overview of metabolism, we describe the use of deuterium oxide (D_2O) to measure deuterium incorporation into the intracellular metabolites of two physiologically diverse cyanobacteria: a terrestrial filamentous strain (Microcoleus vaginatus PCC 9802) and a euryhaline unicellular strain (Synechococcus sp. PCC 7002). D_2O was added to the growth medium during different phases of the diel cycle. Incorporation of deuterium into metabolites at nonlabile positions, an indicator of metabolite turnover, was assessed using liquid chromatography mass spectrometry. Expectedly, large differences in turnover among metabolites were observed. Some metabolites, such as fatty acids, did not show significant turnover over 12–24 h time periods but did turn over during longer time periods. Unexpectedly, metabolites commonly regarded to act as compatible solutes, including glutamate, glucosylglycerol, and a dihexose, showed extensive turnover compared to most other metabolites already after 12 h, but only during the light phase in the cycle. We observed extensive turnover and found it surprising considering the conventional view on compatible solutes as biosynthetic end points given the relatively slow growth and constant osmotic conditions. Our suggests the possibility of a metabolic sink for some compatible solutes (e.g., into glycogen) that allows for rapid modulation of intracellular osmolarity. To investigate this, uniformly "1"3C-labeled Synechococcus sp. PCC 7002 were exposed to "1"2C glucosylglycerol. Following metabolite extraction, amylase treatment of methanol-insoluble polymers revealed "1"2C labeling of glycogen. Overall, our work shows that D_2

  4. Helium effects on tungsten surface morphology and deuterium retention

    International Nuclear Information System (INIS)

    Ueda, Y.; Peng, H.Y.; Lee, H.T.; Ohno, N.; Kajita, S.; Yoshida, N.; Doerner, R.; De Temmerman, G.; Alimov, V.; Wright, G.

    2013-01-01

    Recent experimental results on tungsten surface morphology, especially nano-structure (fuzz), induced by helium plasma exposure at temperatures between 1000 K and 2000 K are reviewed. This structure was firstly reported in 2006. In this review, most of experimental results reported so far including characteristics and formation conditions of the nano-structure in both linear plasma devices and magnetic confinement devices, erosion and arcing by steady-state plasma exposure and ELM-like pulsed heat or pulsed plasma exposure by a laser and a plasma gun are summarized. In addition, He effects on D retention under simultaneous D/He irradiation on tungsten are presented

  5. Deuterium, carbon and nitrogen isotopic analysis of natural and synthetic caffeines. Authentication of coffees and coffee extracts

    International Nuclear Information System (INIS)

    Danho, D.; Naulet, N.; Martin, G.J.

    1992-01-01

    Isotope ratio mass spectrometry (IRMS) was used to determine the δ( 13 C) and δ( 15 N) values of a series of caffeine samples extracted from coffee beans or obtained by synthesis, 2 H NMR spectra were recorded in order to compute the site-specific isotope ratios of caffeine. The set of the five isotope ratios measured for the 26 different samples was studied by multi-variate analysis (principal component and discriminant analyse) and it is shown that the synthetic samples are clearly distinguishable from the natural caffeines which in turn can be classified with complete accuracy as of either American or African origin

  6. Introduction to Body Composition Assessment Using the Deuterium Dilution Technique with Analysis of Urine Samples by Isotope Ratio Mass Spectrometry

    International Nuclear Information System (INIS)

    2010-01-01

    The IAEA has fostered the more widespread use of a stable isotope technique to assess body composition in different population groups to address priority areas in public health nutrition in Member States. It has done this by supporting national and regional nutrition projects through its technical cooperation programme and coordinated research projects over many years. This publication was developed by an international group of experts to provide practical hands-on guidance in the use of this technique in settings where analysis of stable isotope ratios in biological samples is to be made by isotope ratio mass spectrometry. The publication is targeted at new users of this technique, for example nutritionists, analytical chemists and other professionals. More detailed information on the theoretical background and the practical applications of state of the art methodologies to monitor changes in body composition can be found in IAEA Human Health Series No. 3, Assessment of Body Composition and Total Energy Expenditure in Humans by Stable Isotope Techniques

  7. Direct in vivo characterization of delta 5 desaturase activity in humans by deuterium labeling: Effect of insulin

    International Nuclear Information System (INIS)

    el Boustani, S.; Causse, J.E.; Descomps, B.; Monnier, L.; Mendy, F.; Crastes de Paulet, A.

    1989-01-01

    The conversion of dihomogamma linolenic acid (DHLA) into arachidonic acid (AA) was compared in normal subjects and diabetic patients before and after treatment with insulin. The kinetics of the incorporation of deuterium-labeled DHLA and its conversion product, deuterium-labeled AA, was determined in plasma triglycerides, plasma phospholipids, and platelet lipids of subjects after ingestion of 2 g of the labeled precursor. Analysis was performed by gas liquid chromatography-mass spectrometry using multiple ion detection. In normal subjects, the deuterium-labeled DHLA concentration rose to 24 to 69 mg/L in plasma triglycerides four to nine hours after ingestion and to 20 to 34 mg/L in plasma phospholipids about four hours later. Deuterium-labeled AA appeared at 12 hours, rose to 2.4 to 3.8 mg/L between 48 and 72 hours in plasma phospholipids, but remained at the limit of detection in plasma triglycerides and was undetectable in platelet lipids. In diabetic patients both before and after insulin treatment, the deuterium-labeled DHLA concentration in plasma triglycerides and in plasma phospholipids followed the same pattern as in normal subjects. However, the deuterium-labeled arachidonic acid concentration was below 1 mg/L in plasma phospholipids before insulin. After insulin treatment the patients recovered normal DHLA metabolism because deuterium-labeled AA rose in phospholipids to a mean value of 3.5 mg/L, which is in the same range as that observed in normal subjects (3.2 mg/L). The present data provide direct evidence for the conversion of DHLA into AA in humans. The effect of insulin and the data from the literature of animal studies suggest insulin dependence of delta 5 desaturase in humans

  8. The hydrogen and deuterium concentrations in chondrites

    International Nuclear Information System (INIS)

    Robert, F.; Merlivat, L.

    1978-01-01

    Water and isotopic concentration of H 2 O + are reported. It shows a correlation between the water, the deuterium concentrations and the petrologic types of chondrites. The Chainpur meteorite has been divided into several mineralogical fractions and the results are reported. The results of Orgueil are also reported. The correlation shows that as the sulfate content increases, the water and deuterium contents decrease. The terrestrial contamination is discussed and possible deuterium variation models are presented

  9. The effect of Fe and C in modifying deuterium pickup in Zr-2.5Nb: a response surface analysis

    International Nuclear Information System (INIS)

    Ploc, R.A.

    2001-03-01

    A Response Surface Analysis of the effect of iron and carbon in Zr-2.5Nb-Fe/C drop-castings has shown that iron and carbon have at least a quadratic, synergistic relationship on oxidation and deuterium pickup. Tests were performed in the Halden test reactor and associated autoclave for 208 days at 598 K (325 o C). The synergism explains why pressure tube data have limited value when attempting to deduce the effect of impurity elements on pick up. Out- and in-reactor pick up were similar in trend and magnitude except for the in-reactor deuterium pickup, which was about one-quarter of that out-reactor. Minimum in-reactor deuterium ingress is predicted for 30 ppm (wt) carbon and approximately 1,100 ppm (wt) of iron. Out-reactor optimal values are similar but with slightly higher iron values. (author)

  10. Determination of dew absorption by coffee plant through deuterium concentrations in leaf water

    Energy Technology Data Exchange (ETDEWEB)

    Leopoldo, P R [Faculdade de Ciencias Medicas e Biologicas de Botucatu (Brazil); Salati, E; Matsui, E [Centro de Energia Nuclear na Agricultura, Piracicaba (Brazil)

    1975-12-01

    The effect of dew falling on leaves on the water metabolism of the coffee plant (Coffea arabica) is examined. The use of natural stable isotopes variations in plant physiological studies is demonstrated. Water extracted from leaf samples is analysed by mass spectrometry. Analyses of deuterium concentrations in water extracted from plant leaves, dew and nutrient solutions are made. Determination of changes in deuterium concentration in the water of leaves from plants exposed to dew, compared with leaves not exposed to dew, is carried out. Results show that during daytime there is an enrichment in deuterium in water contained in the leaves, while at night the opposite occurs.

  11. Determination of dew absorption by coffee plant through deuterium concentrations in leaf water

    International Nuclear Information System (INIS)

    Leopoldo, P.R.; Salati, E.; Matsui, E.

    1975-01-01

    The effect of dew falling on leaves on the water metabolism of the coffee plant (Coffea arabica) is examined. The use of natural stable isotopes variations in plant physiological studies is demonstrated. Water extracted from leaf samples is analysed by mass spectrometry. Analyses of deuterium concentrations in water extracted from plant leaves, dew and nutrient solutions are made. Determination of changes in deuterium concentration in the water of leaves from plants exposed to dew, compared with leaves not exposed to dew, is carried out. Results show that during daytime there is an enrichment in deuterium in water contained in the leaves, while at night the opposite occurs [pt

  12. The cumulative effect of deuterium depleted water and pesticides used in fruit trees

    International Nuclear Information System (INIS)

    Cinca, Lidia; Butnaru, Gallia; Titescu, Gh.

    2007-01-01

    Full text: The molds as well as Monillia laxa damages on fruit trees represents 10 - 45% of the harmful agents affecting the trees. The pest utilization at a rate of 3 to 10 times will entail both a strong environment polluting effect and a fruit / food contamination. In our work we wanted to reveal the Deuterium Depleted Water (DDW) effect in enhancing the pest efficiency or to replace it at all. our results pointed out a significant increase of pest efficiency when DDW replaced neutral CuSO 4 at the first treatment. The DDW treatment (3 times) showed a similar effect as pest treatment (first - 20% neutral CuSO 4 ; second - 50% All Cupral and third 0.1% Carbendazin). The fruit yield was 44 and 42 kg/tree at the DDW and classical pest treatment, respectively. In conclusion, the difference was of no significance. (authors)

  13. Stable isotope oxygen-18 and deuterium analysis in surface and groundwater of the Jequitibá Creek Basin, Sete Lagoas, MG

    Energy Technology Data Exchange (ETDEWEB)

    Linhares, Giovanna Maria Gardini; Moreira, Rubens Martins; Pimenta, Rafael Colombo; Scarpelli, Raquel Pazzini; Santos, Elizangela Augusta dos, E-mail: giovannagardini@gmail.com, E-mail: rubens@cdtn.br, E-mail: colombopimenta@gmail.com, E-mail: raquelscarpelli@gmail.com, E-mail: elizangela.augusta@gmail.com [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2017-07-01

    Groundwater is an important source of public and industrial supplies, and inadequate exploitation of water reflects negatively on its quality and production of wells, especially when located in karstic aquifers. The study area includes the Maize and Sorghum National Research / Embrapa, located in the karst region of Sete Lagoas, within of the Jequitibá creek sub-basin, an affluent of the Velhas River. The evaluation of the content of stable isotopes of hydrogen ({sup 2}H), or deuterium, and oxygen ({sup 18}O) of surface waters (lagoons) and groundwater (production and monitoring wells) collected from the study area allowed to know directly the origin of these waters, active climatic processes and interactions between different aquifers and surface bodies, as possible mixtures of water from different sources. The collected samples were analyzed by isotopic ratio mass spectrometry, IRMS Advantege - Thermo Science, from the Center for the Development of Nuclear Technology (CDTN). The mean values found for δ{sup 18}O and δ{sup 2}H in the waters of the monitoring wells were -6.40‰ and -43.21‰, respectively. For the production wells, mean values for δ{sup 18}O and δ{sup 2}H of -5.87 ‰ and -40.09‰, respectively, were obtained. When compared to GMWL, the collected groundwater originates attributed to the precipitations. The lagoon waters had mean values for δ{sup 18}O and δ{sup 2}H of -3.73‰ and -30.08‰. The water collected in the crystalline fissured aquifer presented mean values δ{sup 18}O and δ{sup 2}H of -6.91‰ and -40.26 ‰ respectively, in its rockier portion, and -6.09‰ and -43.05‰. (author)

  14. Stable isotope oxygen-18 and deuterium analysis in surface and groundwater of the Jequitibá Creek Basin, Sete Lagoas, MG

    International Nuclear Information System (INIS)

    Linhares, Giovanna Maria Gardini; Moreira, Rubens Martins; Pimenta, Rafael Colombo; Scarpelli, Raquel Pazzini; Santos, Elizangela Augusta dos

    2017-01-01

    Groundwater is an important source of public and industrial supplies, and inadequate exploitation of water reflects negatively on its quality and production of wells, especially when located in karstic aquifers. The study area includes the Maize and Sorghum National Research / Embrapa, located in the karst region of Sete Lagoas, within of the Jequitibá creek sub-basin, an affluent of the Velhas River. The evaluation of the content of stable isotopes of hydrogen ( 2 H), or deuterium, and oxygen ( 18 O) of surface waters (lagoons) and groundwater (production and monitoring wells) collected from the study area allowed to know directly the origin of these waters, active climatic processes and interactions between different aquifers and surface bodies, as possible mixtures of water from different sources. The collected samples were analyzed by isotopic ratio mass spectrometry, IRMS Advantege - Thermo Science, from the Center for the Development of Nuclear Technology (CDTN). The mean values found for δ 18 O and δ 2 H in the waters of the monitoring wells were -6.40‰ and -43.21‰, respectively. For the production wells, mean values for δ 18 O and δ 2 H of -5.87 ‰ and -40.09‰, respectively, were obtained. When compared to GMWL, the collected groundwater originates attributed to the precipitations. The lagoon waters had mean values for δ 18 O and δ 2 H of -3.73‰ and -30.08‰. The water collected in the crystalline fissured aquifer presented mean values δ 18 O and δ 2 H of -6.91‰ and -40.26 ‰ respectively, in its rockier portion, and -6.09‰ and -43.05‰. (author)

  15. DeUterium industrial production - tome 8

    International Nuclear Information System (INIS)

    Chagas, T.P.

    1987-01-01

    Some selected bibliographical references about processes for deuterium industrial production are presented, as follow: isotope exchange H 2 S-H 2 O and NH 3 -H 2 , eletrolysis and distillation. (E.G.) [pt

  16. Producing deuterium-enriched products

    International Nuclear Information System (INIS)

    1980-01-01

    A method of producing an enriched deuterium product from a gaseous feed stream of mixed hydrogen and deuterium, comprises: (a) combining the feed stream with gaseous bromine to form a mixture of the feed stream and bromine and exposing the mixture to an electrical discharge effective to form deuterium bromide and hydrogen bromide with a ratio of D/H greater than the ratio of D/H in the feed stream; and (b) separating at least a portion of the hydrogen bromide and deuterium bromide from the mixture. (author)

  17. The effect of deuterium substitution on the vapor pressure of acetonitrile

    International Nuclear Information System (INIS)

    Jancso, G.; Jakli, Gy.; Koritsanszky, T.

    1980-01-01

    The vapor pressure difference between CH 3 CN and CD 3 CN was measured by differential capacitance manometry between -40 and +80 deg C. The vapor pressure isotope effects (VPIE) derived from the results may be expressed by the equation: ln(psub(H)/Psub(D))=871.761/T 2 -13.577/T+0.006874. The experimental data were interpreted within the framework of the statistical theory of isotope effects in condensed systems. The largest contribution to the VPIE arises from the shifts in the CH stretching vibrations resulting from condensation which were found to be temperature dependent in good agreement with the available spectroscopic information. (author)

  18. Anomalous H/D isotope effect on 35Cl NQR frequencies and H/D isotope effect on 1H MAS NMR spectra in pyrrolidinium p-chlorobenzoate

    International Nuclear Information System (INIS)

    Nakano, Ryo; Honda, Hisashi; Nakata, Eiichi; Takamizawa, Satoshi; Noro, Sumiko; Kimura, Taiki; Kyo, Shin-shin; Ishimaru, Shin'ichi; Miyake, Ryosuke

    2010-01-01

    An anomalous isotope effect was observed in the 35 Cl NQR frequency of pyrrolidinium p-chlorobenzoate (C 4 H 8 NH 2 + ·ClC 6 H 4 COO - ) by deuterium substitution of hydrogen atoms which form two kinds of N-H...O type hydrogen bonds. Large negative frequency shifts of the 35 Cl resonance lines, reaching 309 kHz at 77 K and 267 kHz at 293 K, were obtained upon deuteration, although the Cl atom in the molecule formed no hydrogen bonds in the crystal. 1 H MAS NMR lines showed significant changes by the deuterium substitution, while in contrast, small shifts of 13 C CP/MAS NMR signals were obtained. Our measurements of 1 H NMR spin-lattice relaxation times (T 1 ) suggested that the H/D isotope shifts detected from the 35 Cl NQR frequencies and 1 H NMR spectra are due to structural changes rather than molecular dynamics. Single-crystal X-ray diffraction measurements showed two remarkable H/D isotope differences in the molecular arrangements, (1) the N-H length along the crystallographic a axis became 1 pm shorter, and (2) the dihedral angle between benzene and the pyrrolidine ring changed by 1.1(2)deg upon deuteration. Using density functional theory estimations, the anomalous 35 Cl NQR frequency shifts and 1 H MAS NMR line-shape changes could be explained by the dihedral angle change rather than the N-H length difference. (author)

  19. Isotopic equilibrium constants of the deuterium exchange between HDO and H2S, H2Se and H2Te

    International Nuclear Information System (INIS)

    Marx, D.

    1959-11-01

    We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH 2 + OHD ↔ SHD + OH 2 ; SeH 2 + OHD ↔ SeHD + OH 2 ; TeH 2 + OHD ↔ TeHD + OH 2 . In gaseous phase, statistical thermodynamics leads to the expression: K (Z OHD x Z RH 2 )/(Z OH 2 x Z RHD ) x e W/T (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [fr

  20. Development of positron annihilation spectroscopy for investigating deuterium decorated voids in neutron-irradiated tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, C.N., E-mail: chase.taylor@inl.gov [Fusion Safety Program, Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Shimada, M.; Merrill, B.J. [Fusion Safety Program, Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Akers, D.W. [Experimental Programs, Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Hatano, Y. [Hydrogen Isotope Research Center, University of Toyama, Toyama 930-8555 (Japan)

    2015-08-15

    The present work is a continuation of a recent research to develop and optimize positron annihilation spectroscopy (PAS) for characterizing neutron-irradiated tungsten. Tungsten samples were exposed to neutrons in the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory and damaged to 0.025 and 0.3 dpa. Subsequently, they were exposed to deuterium plasmas in the Tritium Plasma Experiment (TPE) at Idaho National Laboratory. The implanted deuterium was desorbed through sample heating to 900 °C, and Doppler broadening (DB)-PAS was performed both before and after heating. Results show that deuterium impregnated tungsten is identified as having a smaller S-parameter. The S-parameter increases after deuterium desorption. Microstructural changes also occur during sample heating. These effects can be isolated from deuterium desorption by comparing the S-parameters from the deuterium-free back face with the deuterium-implanted front face. The application of using DB-PAS to examine deuterium retention in tungsten is examined.

  1. Development of positron annihilation spectroscopy for investigating deuterium decorated voids in neutron-irradiated tungsten

    Science.gov (United States)

    Taylor, C. N.; Shimada, M.; Merrill, B. J.; Akers, D. W.; Hatano, Y.

    2015-08-01

    The present work is a continuation of a recent research to develop and optimize positron annihilation spectroscopy (PAS) for characterizing neutron-irradiated tungsten. Tungsten samples were exposed to neutrons in the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory and damaged to 0.025 and 0.3 dpa. Subsequently, they were exposed to deuterium plasmas in the Tritium Plasma Experiment (TPE) at Idaho National Laboratory. The implanted deuterium was desorbed through sample heating to 900 °C, and Doppler broadening (DB)-PAS was performed both before and after heating. Results show that deuterium impregnated tungsten is identified as having a smaller S-parameter. The S-parameter increases after deuterium desorption. Microstructural changes also occur during sample heating. These effects can be isolated from deuterium desorption by comparing the S-parameters from the deuterium-free back face with the deuterium-implanted front face. The application of using DB-PAS to examine deuterium retention in tungsten is examined.

  2. Preparation of deuterated heterocyclic five-membered ring compounds (furan, thiophene, pyrrole, and derivatives) by base-catalyzed hydrogen isotope exchange with deuterium oxide

    International Nuclear Information System (INIS)

    Heinrich, K.H.; Herrmann, M.; Moebius, G.; Sprinz, H.

    1984-01-01

    Several deuterated heterocyclic compounds of the type of furan,thiophene and pyrrole were prepared by base-catalyzed proton exchange with deuterium oxide at temperatures above 423 K in a closed system. The determination of deuterium and its distribution within the molecules was carried out by mass spectrometry and 1 H nmr spectrometry. (author)

  3. Natural abundance deuterium nuclear magnetic resonance spectroscopy: Study of the biosynthesis of monoterpenes

    International Nuclear Information System (INIS)

    Leopold, M.F.

    1990-01-01

    Deuterium NMR spectroscopy at natural abundance (D NMR-na) is a new technique for exploring the biosynthesis of small molecules such as monoterpenes. The analysis of relative site-specific deuterium integration values is an effective means of measuring isotope effects, and examining the regio- and stereochemistry of biosynthetic reactions. The deuterium integration values of linalyl acetate and limonene isolated from the same source were consistent and showed that proton abstraction from the postulated α-terpinyl cation intermediate to form limonene is regioselective from the methyl derived from the Cs methyl of the precursor, geranyl diphosphate. This regiochemistry was observed in limonene samples from different sources and the measured primary kinetic isotope effect ranged from 0.25 to in excess of 100 (no deuterium was removed within experimental error). Various α- and β-pinene samples were isolated and D NMR-na analysis showed evidence of isotopically sensitive partitioning of the pinylcation in the formation of these products. This spectral analysis supported published radiolabeling studies but did not require synthesis of substrates or enzyme purification. The formation of 3-carene occurs without isomerization of the double bond which was previously postulated. The olefinic deuterium of the bicyclic compound was traced to the depleted deuterium at C 2 of isopentyl diphosphate by D NMR-na data and this supported unpublished radiolabeling studies. Study of irregular monoterpenes, chrysanthemyl acetate and lyratyl acetate, showed partitioning of dimethylallyl diphosphate (DMAPP) by chrysanthemyl cyclase. The α-secondary kinetic isotope effect of 1.06-1.12, obtained from relative deuterium integration values, suggested that S N 1 ionization of one molecule of DMAPP is the first step in the condensation reaction

  4. Theoretical Study of H/D Isotope Effects on Nuclear Magnetic Shieldings Using an ab initio Multi-Component Molecular Orbital Method

    Directory of Open Access Journals (Sweden)

    Masanori Tachikawa

    2013-05-01

    Full Text Available We have theoretically analyzed the nuclear quantum effect on the nuclear magnetic shieldings for the intramolecular hydrogen-bonded systems of σ-hydroxy acyl aromatic species using the gauge-including atomic orbital technique combined with our multi-component density functional theory. The effect of H/D quantum nature for geometry and nuclear magnetic shielding changes are analyzed. Our study clearly demonstrated that the geometrical changes of hydrogen-bonds induced by H/D isotope effect (called geometrical isotope effect: GIE is the dominant factor of deuterium isotope effect on 13C chemical shift.

  5. Hydrogen isotope effect on storage behavior of U{sub 2}Ti and UZr{sub 2.3}

    Energy Technology Data Exchange (ETDEWEB)

    Jat, Ram Avtar; Sawant, S.G.; Rajan, M.B.; Dhanuskar, J.R. [Product Development Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Kaity, Santu [Radiometallurgy Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Parida, S.C., E-mail: sureshp@barc.gov.in [Product Development Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India)

    2013-11-15

    U{sub 2}Ti and UZr{sub 2.3} alloys were prepared by arc melting method, vacuum annealed and characterized by XRD, SEM and EDX methods. Hydrogen isotope effect on the storage behavior of these alloys were studied by measuring the hydrogen/deuterium desorption pressure–composition–temperature (PCT) profiles in the temperature range of 573–678 K using a Sievert’s type volumetric apparatus. It was observed that, in the temperature and pressure range of investigation, all the isotherms show a single desorption plateau. The PCT data reveals that both U{sub 2}Ti and UZr{sub 2.3} alloys had normal isotope effects on hydrogen/deuterium desorption at all experimental temperatures. Thermodynamic parameters for dehydrogenation and dedeuteration reactions of the corresponding hydrides and deuterides of the above alloys were deduced from the PCT data.

  6. Deuterium-depleted water. Short history and news

    International Nuclear Information System (INIS)

    Stefanescu, Ioan; Tamaian, Radu; Titescu, Gheorghe

    2002-01-01

    Deuterium-depleted water represents water that has an isotopic content lower than 144 ppm D/(D+H) which is the natural isotopic content of water. DDW is a non-toxic product. Knowing that deuterium content of water has a significant influence on living organisms, since 1996 NIR-DCIT ICSTI at Rm. Valcea cooperated with Romanian specialized instititutes for biological effects' evaluation of DDW. The investigations lead to the conclusion that DDW caused a tendency towards the increase of the basal tone, accompanied by the intensification of the vasoconstrictor effects. Animals teated with DDW showed an increase of the resistance both to sub lethal and to lethal gamma radiation doses. DDW stimulates immune defense reactions. Investigations regarding artificial reproduction of fish with DDW fecundated solutions confirmed favorable influence in embryo growth stage and resistance in next growth stages. One can remark the favourable influence of DDW on biological process in plants in various ontogenetic stages. (authors)

  7. Isotope effect study of κ-(BEDT-TTF)2Cu(NCS)2: Labeling in the anion

    International Nuclear Information System (INIS)

    Kini, A.M.; Wang, H.H.; Schlueter, J.A.

    1995-01-01

    Since the initial discovery of organic superconductivity in 1979, a large number of organic superconductors have now been synthesized. However, the mechanism of electron-pairing in these novel superconductors has remained largely unresolved. Isotope effect studies constitute an important experimental tool for the investigation of whether or not the electron-pairing mechanism in organic superconductors is phonon-mediated, as in conventional superconductors. Recent isotope effect studies in the authors' laboratory, involving seven different isotopically labeled BEDT-TTF (or ET) derivatives, have demonstrated the following: (1) intramolecular phonon modes involving C double-bond C and Csingle bondS stretching vibrations in the ET donor molecule are not the dominant mediators of electron-pairing, and (2) in κ-(ET) 2 Cu(NCS) 2 , there exist two competing isotope effects--a normal mass effect, i.e., lowering of T c upon isotopic labeling, when the ET molecular mass is increased by concurrent 13 C and 34 S labeling, in addition to an inverse isotope effect upon deuterium labeling in ET. It is of great interest to investigate if there is an isotope effect when the charge-compensating anions, which are also located within the non-conducting layer in the superconducting cation-radical salts, are isotopically labeled. The existence of an isotope effect when the anions are labeled would be indicative of electron-pairing with the mediation of vibrational frequencies associated with the anions. In this paper, the authors present the results of the first isotope effect study in which isotopic labeling in the anion portion of κ-(ET) 2 Cu(NCS) 2 is carried out. The authors find no isotope effect when the carbon and nitrogen atoms of the thiocyanate groups in the anion are replaced with 13 C and 15 N isotopes

  8. Effects of deuterium on the kinetics of beef heart mitochondrial ATPase

    International Nuclear Information System (INIS)

    Urbauer, J.L.; Dorgan, L.J.; Schuster, S.M.

    1984-01-01

    A study was done examining the steady-state kinetics of F1-catalyzed ATP and ITP hydrolyses in the presence or absence of D2O as a function of temperature. The steady-state kinetic parameters kcat and kcat/Km were obtained. For ATP hydrolysis, kcat/Km was independent of temperature in the presence or absence of D2O, while kcat/Km for ITP hydrolysis increased in both cases. The relative magnitudes of change of kcat and kcat/Km in the presence and absence of D2O over the temperature range studied were much different for the cases of ATP and ITP hydrolysis. A normal isotope effect was observed in plots of kcat H2O/kcat D2O versus temperature for ATP hydrolysis, which increased then leveled off as temperature increased. An inverse isotope effect at low temperatures changed to a normal isotope effect and increased dramatically as temperature increased during ITP hydrolysis. The results are discussed in terms of the nature and location of the rate-limiting steps in the reaction mechanisms

  9. The Effect of Ion Energy and Substrate Temperature on Deuterium Trapping in Tungsten

    Science.gov (United States)

    Roszell, John Patrick Town

    Tungsten is a candidate plasma facing material for next generation magnetic fusion devices such as ITER and there are major operational and safety issues associated with hydrogen (tritium) retention in plasma facing components. An ion gun was used to simulate plasma-material interactions under various conditions in order to study hydrogen retention characteristics of tungsten thus enabling better predictions of hydrogen retention in ITER. Thermal Desorption Spectroscopy (TDS) was used to measure deuterium retention from ion irradiation while modelling of TDS spectra with the Tritium Migration Analysis Program (TMAP) was used to provide information about the trapping mechanisms involved in deuterium retention in tungsten. X-ray Photoelectron Spectroscopy (XPS) and Secondary Ion Mass Spectrometry (SIMS) were used to determine the depth resolved composition of specimens used for irradiation experiments. Carbon and oxygen atoms will be among the most common contaminants within ITER. C and O contamination in polycrystalline tungsten (PCW) specimens even at low levels (˜0.1%) was shown to reduce deuterium retention by preventing diffusion of deuterium into the bulk of the specimen. This diffusion barrier was also responsible for the inhibition of blister formation during irradiations at 500 K. These observations may provide possible mitigation techniques for problems associated with tritium retention and mechanical damage to plasma facing components caused by hydrogen implantation. Deuterium trapping in PCW and single crystal tungsten (SCW) was studied as a function of ion energy and substrate temperature. Deuterium retention was shown to decrease with decreasing ion energy below 100 eV/D+. Irradiation of tungsten specimens with 10 eV/D+ ions was shown to retain up to an order of magnitude less deuterium than irradiation with 500 eV/D+ ions. Furthermore, the retention mechanism for deuterium was shown to be consistent across the entire energy range studied (10-500 e

  10. Medium Effects in Reactions with Rare Isotopes

    International Nuclear Information System (INIS)

    Bertulani, C A; Karakoç, M

    2012-01-01

    We discuss medium effects in knockout reactions with rare isotopes of weakly-bound nuclei at intermediate energies. We show that the poorly known corrections may lead to sizable modifications of knockout cross sections and momentum dsitributions.

  11. Synthesis of deuterium-labeled prochlorperazine.

    Science.gov (United States)

    Hawes, E M; Gurnsey, T S; Shetty, H U; Midha, K K

    1983-06-01

    The propylpiperazine side chain of prochlorperazine was labeled with two, four, or six deuterium atoms by lithium aluminum deuteride reduction of the appropriate amide. The isotopic purity of the products after correcting for chlorine isotopes was greater than 95.7%.

  12. Mixing rules for and effects of other hydrogen isotopes and of isotopic swamping on tritium recovery and loss to biosphere from fusion reactors

    International Nuclear Information System (INIS)

    Pendergrass, J.H.

    1978-01-01

    Efficient recovery of bred and unburnt tritium from fusion reactors, and control of its migration within reactors and of its escape into the biosphere are essential for self-sufficient fuel cycles and for public, plant personnel, and environmental protection. Tritium in fusion reactors will be mixed with unburnt deuterium and protium introduced by (n,p) reactions and diffusion into coolant loops from steam cycles. Rational design for tritium recovery and escape prevention must acknowledge this fact. Consequences of isotopic admixture are explored, mixing rules for projected fusion reactor dilute-solution conditions are developed, and a rule of thumb regarding their effects on tritium recovery methods is formulated

  13. Bibliography on vapour pressure isotope effects

    International Nuclear Information System (INIS)

    Illy, H.; Jancso, G.

    1976-03-01

    The bibliography of research on vapour pressure isotope effects from 1919 to December 1975 is presented in chronological order. Within each year the references are listed alphabetically according to the name of the first author of each work. The bibliography is followed by a Compound Index containing the names o compounds, but the type of isotopic substituation is not shown. The Author Index includes all authors of the papers. (Sz.N.Z.)

  14. Study of isotope effects in the hydrogen transport of an 8% CrWVTa martensitic steel

    International Nuclear Information System (INIS)

    Esteban, G.A.; Sedano, L.A.; Perujo, A.; Douglas, K.

    2001-01-01

    A time-dependent gas-phase isovolumetric desorption technique has been used to assess the isotope effects in the diffusive transport parameters of hydrogen in an 8% CrWVTa reduced activation martensitic steel in the temperature range of 423-892 K and driving pressures from 4 x 10 4 - 1 x 10 5 Pa. The experiments have been run with both protium and deuterium obtaining their respective transport parameters, diffusivity (D), Sieverts' constant (K S ), permeability (Φ), trap site density (η t ) and the trapping activation energy (E t ). Isotope effects on steel are analysed and compared with α-iron. A new way to derive more accurate tritium transport parameters is proposed. (orig.)

  15. Effects of deuterium oxide and galvanic vestibular stimulation on visual cortical cell function

    International Nuclear Information System (INIS)

    Reinis, S.; Landolt, J.P.; Weiss, D.S.; Money, K.E.

    1984-01-01

    The spontaneous and evoked unit activities of complex visual cortical cells were recorded from Brodmann's area 18 in immobilized, unanesthetized cats before, during, and after stimulation of the vestibular system. The vestibular system was stimulated by intravenous injection of deuterium oxide (D2O)--a noted nystagmogenic agent--or by direct galvanic stimulation of the labyrinth. Measures of the receptive-field areas, poststimulus time histograms, directional preferences, and the optimal speed of the light bar stimulating the cell were obtained before and after the application of D2O. Directional preferences were determined in a novel manner, using a method derived from a hierarchical clustering technique. Data were collected and analyzed from a) visual cortical cells in cats with intact labyrinths, b) visual cortical cells in cats following bilateral labrinthectomies, and c) nonvisual cortical cells in cats with intact labyrinths. The other cellular characteristics were also altered by the D2O. Galvanic stimulation of the labyrinth resembles, in its effects, the injection of D2O. In labyrinth-intact cats, the time course of area 18 spontaneous activity dramatically increased 30 min or more after D2O was administered. It peaked 2-3 h later and still had not returned to preinjection levels even 7 h after the D2O administration. In bilaterally labyrinthectomized cats, the spontaneous activity of the visual cells did not change following D2O administration. In nonvisual cells from labyrinth-intact cats, the spontaneous activity demonstrated a slight but significant decrease over time after D2O injection. In pilot studies, the cats were injected with D2O. Within 8-10 min afterward, signs of positional nystagmus commenced; and within 30 min, problems in maintaining balance were noted. This continued for 7-8 h before disappearing. In the labyrinthectomized animals, such effects were not observed

  16. Effects of deuterium oxide and galvanic vestibular stimulation on visual cortical cell function

    Energy Technology Data Exchange (ETDEWEB)

    Reinis, S.; Landolt, J.P.; Weiss, D.S.; Money, K.E.

    1984-03-01

    The spontaneous and evoked unit activities of complex visual cortical cells were recorded from Brodmann's area 18 in immobilized, unanesthetized cats before, during, and after stimulation of the vestibular system. The vestibular system was stimulated by intravenous injection of deuterium oxide (D2O)--a noted nystagmogenic agent--or by direct galvanic stimulation of the labyrinth. Measures of the receptive-field areas, poststimulus time histograms, directional preferences, and the optimal speed of the light bar stimulating the cell were obtained before and after the application of D2O. Directional preferences were determined in a novel manner, using a method derived from a hierarchical clustering technique. Data were collected and analyzed from a) visual cortical cells in cats with intact labyrinths, b) visual cortical cells in cats following bilateral labrinthectomies, and c) nonvisual cortical cells in cats with intact labyrinths. The other cellular characteristics were also altered by the D2O. Galvanic stimulation of the labyrinth resembles, in its effects, the injection of D2O. In labyrinth-intact cats, the time course of area 18 spontaneous activity dramatically increased 30 min or more after D2O was administered. It peaked 2-3 h later and still had not returned to preinjection levels even 7 h after the D2O administration. In bilaterally labyrinthectomized cats, the spontaneous activity of the visual cells did not change following D2O administration. In nonvisual cells from labyrinth-intact cats, the spontaneous activity demonstrated a slight but significant decrease over time after D2O injection. In pilot studies, the cats were injected with D2O. Within 8-10 min afterward, signs of positional nystagmus commenced; and within 30 min, problems in maintaining balance were noted. This continued for 7-8 h before disappearing. In the labyrinthectomized animals, such effects were not observed.

  17. Synthesis of deuterium labelled ibuprofen

    International Nuclear Information System (INIS)

    Cappon, V.J.; Halstead, G.W.; Theis, D.L.

    1986-01-01

    The preparations of [ar- 2 H 4 ]-ibuprofen and [ar, 3,3,3- 2 H 7 ]-ibuprofen are described. The deuterium was incorporated into the aromatic ring of [ar- 2 H 4 ]-ibuprofen which is a metabolically stable position. [ar, 3,3,3- 2 H 7 ]-ibuprofen was synthesized by the same route using [ 2 H 3 ]-CH 3 I instead of CH 3 I for use as a GC/MS internal standard in stable isotope labelled bioavailability studies. (author)

  18. Stable Isotope (delta OXYGEN-18, Delta Deuterium, Delta CARBON-13) Dendroclimatological Studies in the Waterloo Region of Southern Ontario, Canada, Between AD 1610 and 1990.

    Science.gov (United States)

    Buhay, William Mark

    Oxygen (delta^{18} O), hydrogen (delta^2H) and carbon (delta^{13}C) isotopes were measured in wood cellulose from elm, white pine and maple trees that grew in southwestern Ontario, Canada. The measured oxygen and hydrogen isotopic data were used for model-based reconstructions of delta^{18}{O}_{meteoric water}, mean annual temperature (MAT) and relative humidity for a period, AD 1610 to 1880, that precedes instrumental records of climate. The carbon isotope measurements were compared with the Cellulose Model inferred climate data to reveal additional environmental information. Modifications made to the Cellulose Model focused on the dynamics of oxygen and hydrogen isotopic fractionation in plants during evapotranspiration and photosynthetic assimilation. For instance, kinetic fractionation of ^{18}O was found to be predictable from theoretical considerations of leaf energy balance and boundary layer dynamics. Kinetic fractionation during evapotranspiration is sensitive to the nature of the boundary layer, which is controlled by leaf size and morphology. Generally, plants with small segmented leaves have a lower component of turbidity in the leaf boundary layer, which results in higher kinetic fractionation values, than do plants having large simple leaves and more turbulent boundary layers. Kinetic ^2H enrichment in plant leaf water can also be rationalized in terms of leaf size and morphology when an apparent temperature-dependent isotope effect, acting in opposition to evaporative enrichment, is taken into account. Accounting for this temperature -dependent isotope effect helps to: (1) reconcile hydrogen kinetic fractionation inconsistencies for different leaves; (2) explain a temperature effect previously attributed to variable biochemical fractionation during cellulose synthesis, and; (3) verify hydrogen biochemical effects in plants. This improved characterization of the oxygen and hydrogen isotopic effects in plants, using the modified Cellulose Model, helped

  19. Isotope effects in the evaporation of water: a status report of the Craig-Gordon model.

    Science.gov (United States)

    Horita, Juske; Rozanski, Kazimierz; Cohen, Shabtai

    2008-03-01

    The Craig-Gordon model (C-G model) [H. Craig, L.I. Gordon. Deuterium and oxygen 18 variations in the ocean and the marine atmosphere. In Stable Isotopes in Oceanographic Studies and Paleotemperatures, E. Tongiorgi (Ed.), pp. 9-130, Laboratorio di Geologia Nucleare, Pisa (1965).] has been synonymous with the isotope effects associated with the evaporation of water from surface waters, soils, and vegetations, which in turn constitutes a critical component of the global water cycle. On the occasion of the four decades of its successful applications to isotope geochemistry and hydrology, an attempt is made to: (a) examine its physical background within the framework of modern evaporation models, (b) evaluate our current knowledge of the environmental parameters of the C-G model, and (c) comment on a general strategy for the use of these parameters in field applications. Despite its simplistic representation of evaporation processes at the water-air interface, the C-G model appears to be adequate to provide the isotopic composition of the evaporation flux. This is largely due to its nature for representing isotopic compositions (a ratio of two fluxes of different isotopic water molecules) under the same environmental conditions. Among many environmental parameters that are included in the C-G model, accurate description and calculations are still problematic of the kinetic isotope effects that occur in a diffusion-dominated thin layer of air next to the water-air interface. In field applications, it is of importance to accurately evaluate several environmental parameters, particularly the relative humidity and isotopic compositions of the 'free-atmosphere', for a system under investigation over a given time-scale of interest (e.g., hourly to daily to seasonally). With a growing interest in the studies of water cycles of different spatial and temporal scales, including paleoclimate and water resource studies, the importance and utility of the C-G model is also likely to

  20. Isotope effects of sulfur in chemical reactions

    International Nuclear Information System (INIS)

    Mikolajczuk, A.

    1999-01-01

    Sulfur is an important component of organic matter because it forms compounds with many elements. Due to high chemical activity of sulfur, it takes part in biological and geological processes in which isotope effects are occurring. It has been shown during last years research of isotope effects that we have take into account not only mass difference but also many other physical properties of nuclides e.g. even or odd number of neutrons in nuclei, shape and distribution of charge, turn of nuclear spin etc. The factor remains that new theoretical ideas have been formed on the base of data, being obtained in fractionation processes of heavy element isotope, particularly uranium. Now it is being well known that effects unconnected with vibration energy have also caused an effect on fractionation of considerably lighter elements like iron and magnesium. The important question is, if these effects would come to light during the separation of sulfur isotopes. Sulfur have three even isotopes M = (32, 34, 36) and one odd M 33). This problem is still open. (author)

  1. Administration of deuterium depletion water and physiological effect of Japanese subjects

    International Nuclear Information System (INIS)

    Kunihiro, Seki

    2003-01-01

    It is from February, 2002 that Deuterium Depletion Water (DDW) was imported by Japan from Hungary. Since then studies were undertaken on normal and patient Japanese subjects to observe the effect of DDW for a long period of time, and the side effects of its administration. Three types of DDW administration were undertaken and the following results are report. Normal male subject was made to consume DDW-105 ppm one liter per day, every day for one year. The stiffness of the shoulders disappeared in normal subjects men and women. The benign neoplasm disappeared. Lack of sleep sensation disappeared. The old-man skin liver spots disappeared. The male sex function was recovered. The airsickness of jet traveling abroad disappeared. In the second type of experiments a 250 liters bath of DDW-105 ppm was administrated and the normal subject was made to take a bath for 20 minutes in water temperature of 39 deg C every day for seven days in a row. The humidity effect of the skin before and after bathing, the liver spots of the skin, weight, and subjective-symptoms investigation were investigated. Side effects or changes in skin aspects were not observed after the bathing experiment. In the third case the patient was made to consume DDW-105 ppm or 25 ppm, and changes of the tumor marker following the administration were measured. In the subjects SK (Kanagawa 58 years old) who suffered from the extramammary Paget disease, it was observed that the value of the tumor marker TPA (Tissue polypeptide antigen) being 120U/L (normal value: 70U/L) at first fell to 58U/L after six months. In a case of prostatic cancer in a 64 years old HT male subject of Tokyo the tumor marker PSA (prostatic specific antigen) was 6.2 ng/ml (normal value: 4.0 ng/ml) in July, 2002. Two months after drinking DDW-105 ppm, it fell to 4.2 ng/ml. A prostatic cancer was excised and all tumor markers also reached a normal value in February, 2003. Now, subject HT consume of DDW-105 one liter every day. His face

  2. Isotope effects in pericyclic reactions, ch. 2

    International Nuclear Information System (INIS)

    Dolbier, W.R. Jr.

    1975-01-01

    A distinction is made between primary and secondary isotope effects, the primary ones being based on the relative large vibrational frequencies and ensuing large zeroprint energies for C-H vibrations whereas the secondary effects are observed in systems where the vibrational modes of the isotopically labelled site are perturbed during transformation from reactant to product. Both effects are utilised in the elucidation of mechanism in pericyclic processes. The main processes dealt with in this chapter are cycloadditions of all types and sigmatropic rearrangements

  3. Deuterium trapping in tungsten

    Science.gov (United States)

    Poon, Michael

    Tungsten is one of the primary material candidates being investigated for use in the first-wall of a magnetic confinement fusion reactor. An ion accelerator was used to simulate the type of ion interaction that may occur at a plasma-facing material. Thermal desorption spectroscopy (TDS) was the primary tool used to analyze the effects of the irradiation. Secondary ion mass spectroscopy (SIMS) was used to determine the distribution of trapped D in the tungsten specimen. The tritium migration analysis program (TMAP) was used to simulate thermal desorption profiles from the D depth distributions. Fitting of the simulated thermal desorption profiles with the measured TDS results provided values of the D trap energies. Deuterium trapping in single crystal tungsten was studied as a function of the incident ion fluence, ion flux, irradiation temperature, irradiation history, and surface impurity levels during irradiation. The results show that deuterium was trapped at vacancies and voids. Two deuterium atoms could be trapped at a tungsten vacancy, with trapping energies of 1.4 eV and 1.2 eV for the first and second D atoms, respectively. In a tungsten void, D is trapped as atoms adsorbed on the inner walls of the void with a trap energy of 2.1 eV, or as D2 molecules inside the void with a trap energy of 1.2 eV. Deuterium trapping in polycrystalline tungsten was also studied as a function of the incident fluence, irradiation temperature, and irradiation history. Deuterium trapping in polycrystalline tungsten also occurs primarily at vacancies and voids with the same trap energies as in single crystal tungsten; however, the presence of grain boundaries promotes the formation of large surface blisters with high fluence irradiations at 500 K. In general, D trapping is greater in polycrystalline tungsten than in single crystal tungsten. To simulate mixed materials comprising of carbon (C) and tungsten, tungsten specimens were pre-irradiated with carbon ions prior to D

  4. Deuterium trapping in tungsten

    International Nuclear Information System (INIS)

    Poon, M.

    2004-01-01

    Tungsten is one of the primary material candidates being investigated for use in the first-wall of a magnetic confinement fusion reactor. An ion accelerator was used to simulate the type of ion interaction that may occur at a plasma-facing material. Thermal desorption spectroscopy (TDS) was the primary tool used to analyze the effects of the irradiation Secondary ion mass spectroscopy (SIMS) was used to determine the distribution of trapped D in the tungsten specimen. The tritium migration analysis program (TMAP) was used to simulate thermal desorption profiles from the D depth distributions. Fitting of the simulated thermal desorption profiles with the measured TDS results provided values of the D trap energies. . Deuterium trapping in single crystal tungsten was studied as a function of the incident ion fluence, ion flux, irradiation temperature, irradiation history, and surface impurity levels during irradiation The results show that deuterium was trapped at vacancies and voids. Two deuterium atoms could be trapped at a tungsten vacancy, with trapping energies of 1.4 eV and 1.2 eV for the first and second D atoms, respectively. In a tungsten void, D is trapped as atoms adsorbed on the inner walls of the void with a trap energy of 2.1 eV, or as D 2 molecules inside the void with a trap energy of 1.2 eV. . Deuterium trapping in polycrystalline tungsten was also studied as a function of the incident fluence, irradiation temperature, and irradiation history. Deuterium trapping in polycrystalline tungsten also occurs primarily at vacancies and voids with the same trap energies as in single crystal tungsten; however, the presence of grain boundaries promotes the formation of large surface blisters with high fluence irradiations at 500 K. In general, D trapping is greater in polycrystalline tungsten than in single crystal tungsten. To simulate mixed materials comprising of carbon (C) and tungsten, tungsten specimens were pre-irradiated with carbon ions prior to D

  5. Deuterium trapping in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Poon, M

    2004-07-01

    Tungsten is one of the primary material candidates being investigated for use in the first-wall of a magnetic confinement fusion reactor. An ion accelerator was used to simulate the type of ion interaction that may occur at a plasma-facing material. Thermal desorption spectroscopy (TDS) was the primary tool used to analyze the effects of the irradiation Secondary ion mass spectroscopy (SIMS) was used to determine the distribution of trapped D in the tungsten specimen. The tritium migration analysis program (TMAP) was used to simulate thermal desorption profiles from the D depth distributions. Fitting of the simulated thermal desorption profiles with the measured TDS results provided values of the D trap energies. . Deuterium trapping in single crystal tungsten was studied as a function of the incident ion fluence, ion flux, irradiation temperature, irradiation history, and surface impurity levels during irradiation The results show that deuterium was trapped at vacancies and voids. Two deuterium atoms could be trapped at a tungsten vacancy, with trapping energies of 1.4 eV and 1.2 eV for the first and second D atoms, respectively. In a tungsten void, D is trapped as atoms adsorbed on the inner walls of the void with a trap energy of 2.1 eV, or as D{sub 2} molecules inside the void with a trap energy of 1.2 eV. . Deuterium trapping in polycrystalline tungsten was also studied as a function of the incident fluence, irradiation temperature, and irradiation history. Deuterium trapping in polycrystalline tungsten also occurs primarily at vacancies and voids with the same trap energies as in single crystal tungsten; however, the presence of grain boundaries promotes the formation of large surface blisters with high fluence irradiations at 500 K. In general, D trapping is greater in polycrystalline tungsten than in single crystal tungsten. To simulate mixed materials comprising of carbon (C) and tungsten, tungsten specimens were pre-irradiated with carbon ions prior to D

  6. Deuterium depleted water. Romanian achievements and prospects

    International Nuclear Information System (INIS)

    Stefanescu, Ioan; Steflea, Dumitru; Titescu, Gheorghe; Tamaian, Radu

    2002-01-01

    The deuterium depleted water (DDW) is microbiologically pure distilled water with a deuterium content lower than that of natural waters which amounts to 140 - 150 ppm D/(D+H); variations depend on geographical zone and altitude. The procedure of obtaining DDW is based on isotopic separation of natural water by vacuum distillation. Isotope concentration can be chosen within 20 to 120 ppm D/(D+H). The ICSI at Rm. Valcea has patented the procedure and equipment for the production of DDW. According to the document SF-01-2002/INC-DTCI - ICSI Rm. Valcea, the product has a D/(D+H) isotope concentration of 25 ± 5. Studies and research for finding the effects and methods of application in different fields were initiated and developed in collaboration with different institutes in Romania. The following important results obtained so far could be mentioned: - absence of toxicity upon organisms; - activation of vascular reactivity; - enhancement of defence capacity of the organism through non-specific immunity activation; - increase of salmonid reproduction capacity and enhancement of the adaptability of alevins to the environmental conditions; - radioprotective effect to ionizing radiation; - maintaining meat freshness through osmotic shock; - stimulation of growth of aquatic macrophytes; - enhancement of culture plant development in certain ontogenetic stages. Mostly, the results and practical applications of the research were patented and awarded with gold medals at international invention fairs. At present, research-development programmes are undergoing to find active biological features of DDW in fighting cancer, on one hand, and its applicability as food additive of pets or performing animals, on the other hand

  7. Isotope dependent, temperature regulated, energy repartitioning in a low-barrier, short-strong hydrogen bonded cluster

    NARCIS (Netherlands)

    Li, X. H.; Oomens, J.; Eyler, J. R.; Moore, D. T.; Iyengar, S. S.

    2010-01-01

    We investigate and analyze the vibrational properties, including hydrogen/deuterium isotope effects, in a fundamental organic hydrogen bonded system using multiple experimental (infrared multiple photon dissociation and argon-tagged action spectroscopy) and computational techniques. We note a

  8. The Impact of Nonequilibrium and Equilibrium Fractionation on Two Different Deuterium Excess Definitions

    Science.gov (United States)

    Dütsch, Marina; Pfahl, Stephan; Sodemann, Harald

    2017-12-01

    The deuterium excess (d) is a useful measure for nonequilibrium effects of isotopic fractionation and can therefore provide information about the meteorological conditions in evaporation regions or during ice cloud formation. In addition to nonequilibrium fractionation, two other effects can change d during phase transitions. The first is the dependence of the equilibrium fractionation factors on temperature, and the second is the nonlinearity of the δ scale on which d is defined. The second effect can be avoided by using an alternative definition that is based on the logarithmic scale. However, in this case d is not conserved when air parcels mix, which can lead to changes without phase transitions. Here we provide a systematic analysis of the benefits and limitations of both deuterium excess definitions by separately quantifying the impact of the nonequilibrium effect, the temperature effect, the δ-scale effect, and the mixing effect in a simple Rayleigh model simulating the isotopic composition of air parcels during moist adiabatic ascent. The δ-scale effect is important in depleted air parcels, for which it can change the sign of the traditional deuterium excess in the remaining vapor from negative to positive. The alternative definition mainly reflects the nonequilibrium and temperature effect, while the mixing effect is about 2 orders of magnitude smaller. Thus, the alternative deuterium excess definition appears to be a more accurate measure for nonequilibrium effects in situations where moisture is depleted and the δ-scale effect is large, for instance, at high latitudes or altitudes.

  9. Isotope effects in the non enzymic glycation of hemoglobin catalyzed by DPG

    International Nuclear Information System (INIS)

    Gil, Herminia; Uzcategui, Jorge

    1993-01-01

    The paradigmatic reaction of glucose with hemoglobin (Hb A o ) has been studied and is known to occur most rapidly at the N-terminal valine of the β-subunit. An initial, rapid imine formation is succeeded by slower Amadori rearrangement. Non enzymic glycation of Hb A o was studied in vitro in buffer Tris 10 mM in H 2 O and D 2 O, pH 7.3, pD 7.8 at 37 deg C at a fixed concentration of 2,3 diphosphoglycerate (DPG). The reaction exhibits identical rates in protium and deuterium oxides. When D-glucose-2-h is compared with D-glucose-2-d, the kinetic isotope effect for the DPG-dependent rate is 2.1 ± 0.3, while the DPG-independent rate constant shows no isotope effect (1.1 ± 0.1). The absence of a rate in isotopic water solvents shows that proton donation for solvent, lyons or DPG does not limit the rate. The substrate isotope effect of around 2 for the DPG kinetic term indicates that the proton abstraction step of the Amadori rearrangement by DPG is wholly or partially rate-limiting for this reaction. (author)

  10. Isotope effects in the non enzymic glycation of hemoglobin catalyzed by DPG

    Energy Technology Data Exchange (ETDEWEB)

    Gil, Herminia; Uzcategui, Jorge [Universidad de Los Andes, Merida (Venezuela). Dept. de Quimica

    1993-12-31

    The paradigmatic reaction of glucose with hemoglobin (Hb A{sub o}) has been studied and is known to occur most rapidly at the N-terminal valine of the {beta}-subunit. An initial, rapid imine formation is succeeded by slower Amadori rearrangement. Non enzymic glycation of Hb A{sub o} was studied in vitro in buffer Tris 10 mM in H{sub 2} O and D{sub 2} O, pH 7.3, pD 7.8 at 37 deg C at a fixed concentration of 2,3 diphosphoglycerate (DPG). The reaction exhibits identical rates in protium and deuterium oxides. When D-glucose-2-h is compared with D-glucose-2-d, the kinetic isotope effect for the DPG-dependent rate is 2.1 {+-} 0.3, while the DPG-independent rate constant shows no isotope effect (1.1 {+-} 0.1). The absence of a rate in isotopic water solvents shows that proton donation for solvent, lyons or DPG does not limit the rate. The substrate isotope effect of around 2 for the DPG kinetic term indicates that the proton abstraction step of the Amadori rearrangement by DPG is wholly or partially rate-limiting for this reaction. (author) 23 refs., 4 figs.

  11. Cytochrome P-450 dependent ethanol oxidation. Kinetic isotope effects and absence of stereoselectivity

    International Nuclear Information System (INIS)

    Ekstroem, G.; Norsten, C.; Cronholm, T.; Ingelman-Sundberg, M.

    1987-01-01

    Deuterium isotope effects [/sup D/(V/K)] and stereoselectivity of ethanol oxidation in cytochrome P-450 containing systems and in the xanthine-xanthine oxidase system were compared with those of yeast alcohol dehydrogenase. The isotope effects were determined by using both a noncompetitive method, including incubation of unlabeled of [1,1- 2 H 2 ] ethanol at various concentrations, and a competitive method, where 1:1 mixtures of [1- 13 C]- and [ 2 H 6 ] ethanol or [2,2,2- 2 H 3 ]- and [1,1- 2 H 2 ] ethanol were incubated and the acetaldehyde formed was analyzed by gas chromatography/mass spectrometry. The /sup D/(V/K) isotope effects of the cytochrome P-450 dependent ethanol oxidation were about 4 with liver microsomes from imidazole-, phenobarbital- or acetone-treated rabbits or with microsomes from acetone- or ethanol-treated rats. Similar isotope effects were reached with reconstituted membranes containing the rabbit ethanol-inducible cytochrome P-450 (LMeb), whereas control rat microsomes and membranes containing rabbit phenobarbital-inducible P-450 LM 2 oxidized the alcohol with /sup D/(V/K) of about 2.8 and 1.8, respectively. Addition of Fe/sup III/EDTA either to microsomes from phenobarbital-treated rabbits or to membranes containing P-450 LMeb significantly lowered the isotope effect. Incubations of all cytochrome P-450 containing systems of the xanthine-xanthine oxidase systems with (1R)- and (1S)-[1- 2 H] ethanol, revealed, taking the isotope effects into account, that 44-66% of the ethanol oxidized had lost the 1-pro-R hydrogen. The data indicate that cytochrome P-450 dependent ethanol oxidation is not stereospecific and that cleavage of the C 1 -H bond appears to be a rate-determining step in the catalysis by the ethanol-inducible form of P-450. The contribution of hydroxyl radicals in ethanol oxidation by the various enzymic systems is discussed

  12. Hydrogen isotope effect through Pd in hydrogen transport pipe

    International Nuclear Information System (INIS)

    Tamaki, Masayoshi

    1992-01-01

    This investigation concerns hydrogen system with hydrogen transport pipes for transportation, purification, isotope separation and storage of hydrogen and its isotopes. A principle of the hydrogen transport pipe (heat pipe having hydrogen transport function) was proposed. It is comprised of the heat pipe and palladium alloy tubes as inlet, outlet, and the separation membrane of hydrogen. The operation was as follows: (1) gas was introduced into the heat pipe through the membrane in the evaporator; (2) the introduced gas was transported toward the condenser by the vapor flow; (3) the transported gas was swept and compressed to the end of the condenser by the vapor pressure; and (4) the compressed gas was exhausted from the heat pipe through the membrane in the condenser. The characteristics of the hydrogen transport pipe were examined for various working conditions. Basic performance concerning transportation, evacuation and compression was experimentally verified. Isotopic dihydrogen gases (H 2 and D 2 ) were used as feed gas for examining the intrinsic performance of the isotope separation by the hydrogen transport pipe. A simulated experiment for hydrogen isotope separation was carried out using a hydrogen-helium gas mixture. The hydrogen transport pipe has a potential for isotope separation and purification of hydrogen, deuterium and tritium in fusion reactor technology. (author)

  13. INTRAMOLECULAR ISOTOPE EFFECTS IN HYDROCARBON MASS SPECTRA

    Energy Technology Data Exchange (ETDEWEB)

    Stevenson, D. P.; Schachtschneider, J. H.

    1963-07-15

    Approximate calculations based on the quasi-equilibrium rate theory of the origin of mass spectra are shown to lead to an approximately correct magnitude for the intramolecular ( pi /sup -/) isotope effect on C--H bond dissociation probabilities of various deuterohydrocarbons. (auth)

  14. Electromigration of hydrogen and deuterium in vanadium and niobium by a resistance method

    International Nuclear Information System (INIS)

    Peterson, D.T.; Jensen, C.L.

    1978-01-01

    The electric mobility of hydrogen and deuterium has been measured at 30 0 C in niobium (Cb) and vanadium by a resistance method. The electric mobility was found to be 5.7 x 10 -4 cm 2 /V-s for hydrogen and 2.8 x 10 -4 for deuterium in niobium. In vanadium the electric mobilities were 2.3 x 10 -3 and 1.3 x 10 -3 cm 2 /V-s for hydrogen and deuterium, respectively. The effective charges calculated using reported diffusion coefficients are positive and are slightly greater for deuterium than for hydrogen in both vanadium and niobium. The resistivity increase due to the hydrogen isotopes in vanadium and niobium was also measured. Hydrogen was found to contribute 0.65 μ ohm-cm/at. % and deuterium 0.58 μ ohm-cm/at. % to the resistivity of niobium. In vanadium, the solute resistivities were found to be 0.98 μ ohm-cm/at. % and 0.90 μ ohm-cm/at. % for hydrogen and deuterium, respectively

  15. The tracer function of isotope composition and deuterium excess parameter of water bodies on prospecting for geothermal water: taking the prospecting for geothermal water in Sanjianshui, Sichuan for example

    International Nuclear Information System (INIS)

    Yang Bo; Yin Guan

    2003-01-01

    Based on the isotope composition features of water bodies in Sanjiashui area, this paper use the theory of deuterium excess parameter (d) to discuss and cause of formulation, recharge source, removed patch, detained time and dynamics feature on ground water. These discussed problems have far-reaching meaning on evaluating the size of geothermal water, exploited potential of thermal spring and find new thermal spring in neighboring area. We analyze the relation of d and tritium content (T) on different water bodies in Sanjianshui area and draw some conclusions. Firstly, all water bodies in Sanjianshui origin from precipitation. Secondly, precipitation of northwest mountain area that have long removed patch and long detained time is the recharge resource of groundwater in basin. In addition, we demonstrate the possibility of existence of geothermal water in several positions of Sanjianshui area. (authors)

  16. Hydrogen isotopic substitution experiments in nanostructured porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Palacios, W.D. [Facultad de Ciencias Exactas y Naturales y Agrimensura - (UNNE), Avenida Libertad 5500, 3400 Corrientes (Argentina); Koropecki, R.R. [INTEC (CONICET-UNL), Gueemes 3450, 3000 Santa Fe (Argentina)], E-mail: rkoro@intec.ceride.gov.ar; Arce, R.D. [INTEC (CONICET-UNL), Gueemes 3450, 3000 Santa Fe (Argentina); Busso, A. [Facultad de Ciencias Exactas y Naturales y Agrimensura - (UNNE), Avenida Libertad 5500, 3400 Corrientes (Argentina)

    2008-04-30

    Nanostructured porous silicon is usually prepared by electrochemical anodization of monocrystalline silicon using a fluorine-rich electrolyte. As a result of this process, the silicon atoms conserve their original crystalline location, and many of the dangling bonds appearing on the surface of the nanostructure are saturated by hydrogen coming from the electrolyte. This work presents an IR study of the effects produced by partial substitution of water in the electrolytic solution by deuterium oxide. The isotopic effects on the IR spectra are analyzed for the as-prepared samples and for the samples subjected to partial thermal effusion of hydrogen and deuterium. We demonstrate that, although deuterium is chemically indistinguishable from hydrogen, it presents a singular behaviour when used in porous silicon preparation. We found that deuterium preferentially bonds forming Si-DH groups. A possible explanation of the phenomenon is presented, based on the different diffusivities of hydrogen and deuterium.

  17. Hydrogen isotopic substitution experiments in nanostructured porous silicon

    International Nuclear Information System (INIS)

    Palacios, W.D.; Koropecki, R.R.; Arce, R.D.; Busso, A.

    2008-01-01

    Nanostructured porous silicon is usually prepared by electrochemical anodization of monocrystalline silicon using a fluorine-rich electrolyte. As a result of this process, the silicon atoms conserve their original crystalline location, and many of the dangling bonds appearing on the surface of the nanostructure are saturated by hydrogen coming from the electrolyte. This work presents an IR study of the effects produced by partial substitution of water in the electrolytic solution by deuterium oxide. The isotopic effects on the IR spectra are analyzed for the as-prepared samples and for the samples subjected to partial thermal effusion of hydrogen and deuterium. We demonstrate that, although deuterium is chemically indistinguishable from hydrogen, it presents a singular behaviour when used in porous silicon preparation. We found that deuterium preferentially bonds forming Si-DH groups. A possible explanation of the phenomenon is presented, based on the different diffusivities of hydrogen and deuterium

  18. The effect of dipolar interaction on the magnetic isotope effect

    DEFF Research Database (Denmark)

    Mojaza, Matin; Pedersen, Jørgen Boiden; Lukzen, Nikita

    2010-01-01

    A multi-channel kinetic description is used to study the magnetic isotope effect (MIE) in zero magnetic field. The maximal isotope effect is equal to the number of channels, two for the hyperfine interaction but four for the electron spin dipole–dipole interaction of the intermediate radical pair....... Quantum mechanical calculations agree with these conclusion and show that large MIE may be obtained even in the presence of a strong exchange interaction. The observed magnesium isotope effect on the rate of enzymatic synthesis of adenosine triphosphate (ATP) is approximately 3 implying that the dipolar...... interaction is responsible for the effect. Our calculations provide support for the proposed mechanism....

  19. Deuterium ion irradiation induced precipitation in Fe–Cr alloy: Characterization and effects on irradiation behavior

    International Nuclear Information System (INIS)

    Liu, P.P.; Yu, R.; Zhu, Y.M.; Zhao, M.Z.; Bai, J.W.; Wan, F.R.; Zhan, Q.

    2015-01-01

    Highlights: • A new phase precipitated in Fe–Cr alloy after deuterium ion irradiation at 773 K. • B2 structure was proposed for the Cr-rich new phase. • Strain fields around the precipitate have been measured by GPA. • The precipitate decrease growth rate of dislocation loop under electron irradiation. - Abstract: A new phase was found to precipitate in a Fe–Cr model alloy after 58 keV deuterium ion irradiation at 773 K. The nanoscale radiation-induced precipitate was studied systematically using high resolution transmission electron microscopy (HRTEM), image simulation and in-situ ultrahigh voltage transmission electron microscopy (HVEM). B2 structure is proposed for the new Cr-rich phase, which adopts a cube-on-cube orientation relationship with regard to the Fe matrix. Geometric phase analysis (GPA) was employed to measure the strain fields around the precipitate and this was used to explain its characteristic 1-dimensional elongation along the 〈1 0 0〉 Fe direction. The precipitate was stable under subsequent electron irradiation at different temperatures. We suggest that the precipitate with a high interface-to-volume ratio enhances the radiation resistance of the material. The reason for this is the presence of a large number of interfaces between the precipitate and the matrix, which may greatly reduce the concentration of point defects around the dislocation loops. This leads to a significant decrease in the growth rate

  20. Influence of deuterium-depleted water on living organisms

    International Nuclear Information System (INIS)

    Stefanescu, I.; Titescu, Gh.; Croitoru, Cornelia; Saros-Rogobete, Irina

    2000-01-01

    Deuterium-depleted water (DDW) production technique consists in the separation of deuterium from water by means of an continuos distillation process under a pressure value of about 133,3 mbar. Water that is used as basic material has an isotopic content of 144 ppm D/(D+H). DDW results as distillate with an isotopic deuterium content of 15-80 ppm, depending on the level we want to achieve. Beginning with 1996 NIR and DCIT Rm. Valcea, which is a DDW producer, co-operated with Romanian specialised institutes for biological effects' evaluation of DDW. These investigations led to the next conclusions: - DDW caused a tendency towards the increase of the basal tone, accompanied by the intensification of the vasoconstrictor effects of phenylefrine, noradrenaline and angiotensin; the increase of the basal tonus and vascular reactivity produced by the DDW persist after the removal of the vascular endothelium; - Animals treated with DDW showed an increase of the resistance both to sublethal and to lethal gamma radiation doses, suggesting a radioprotective action by the stimulation of non-specific immune defence mechanisms; - DDW stimulate immune defence reactions, represented by the opsonic, bactericidal and phagocyte capacity of the immune system, together with increase in the numbers of polymorphonuclear neutrophils; - Investigations regarding artificial reproduction of fish with DDW fecundated solutions confirmed favourable influence in embryo growth stage and resistance in next growth stages; - It was studied germination, growth and quantitative characters' variability at plants; one can remark the favourable influence of DDW on biological process at plants in various ontogenic stages. Further investigations are needed in order to establish the influence of deuterium-depleted water on living organisms. (authors)

  1. Kinetic isotope effects in the CH4 + H→CH3 + H2 system. Predictions of the LMR six-body potential-energy reaction hypersurface

    International Nuclear Information System (INIS)

    Marriott, T.D.

    1976-01-01

    Scope of Study: The purpose of this study was two-fold. First, it served to test, in part, the usefulness of the LMR six-body potential-energy surface (LMR-PES) for transition-state theory predictions of the kinetic isotope effects for both the forward and reverse reactions of CH 4 + H reversible CH 3 + H 2 . In this regard the agreement between experimental and theoretical isotope effects, assuming the former to be accurate, provides information about the accuracy of the curvature of the potential energy surface for motion both parallel and perpendicular to the reaction coordinate. Second, these isotope effects were used to assess the validity of a number of qualitative and semi-quantitative interpretations of kinetic isotope effects developed in physical organic chemistry with regard to this reaction system. The force constants and geometries obtained numerically from the LMR-PES were found to produce reasonable harmonic approximations to the reactant normal mode frequencies. Neglecting tunneling, the LMR-PES reasonably reproduces the experimental k/sub H//k/sub D/ values for the reactions CH 4 + H(D), CH 3 + HD(DH) and CD 2 + HD(DH). Since previous theoretical treatments of primary deuterium kinetic isotope effects have neglected the bending normal mode frequencies, a semi-quantitative study of the effect of neglecting bending frequencies on the VP, EXC, and ZPE elements as well as the transition-state theory kinetic isotope effects was performed. The Swain-Schaad relationship between primary deuterium and tritium kinetic isotope effects was shown to hold to a reasonable degree of accuracy for the LMR-PES reaction system. A relationship between 13-carbon and 14-carbon kinetic isotope effects similar to the Swain-Schaad relationship was derived

  2. Ab Initio Calculations of Deuterium Isotope Effects on Chemical Shifts of Salt-Bridged Lysines

    DEFF Research Database (Denmark)

    Ullah, Saif; Ishimoto, Takayoshi; Williamson, Mike P.

    2011-01-01

    (D), in ammonium and amines decrease as a counterion or water molecule moves closer to the nitrogen. 1Δ15N(D) and 2Δ1H(D) of the NH3+ groups of lysine residues in the B1 domain of protein G have been calculated using truncated side chains and also determined experimentally by NMR. Comparisons show...

  3. The use of deuterium in medicine

    International Nuclear Information System (INIS)

    Roth, E.; Sutton, J.; Marsac, J.

    1981-03-01

    Whenever a corporal function experiences a disturbance reflected either by changes in metabolic activity or modifications of the importance of pools of certain molecules the possibility exists of making use of isotopes in diagnosis. This paper discusses the use of deuterium to measure total body water and extravascular water in the lungs, and gives examples of clinical applications

  4. Photodisintegration of deuterium

    International Nuclear Information System (INIS)

    Hara, K.Y.; Utsunomiya, H.; Goko, S.

    2004-01-01

    Photodisintegration cross sections were measured for deuterium with Laser Compton scattering γ beams at E γ = 2.3 - 4.6 MeV. The present data made it possible to experimentally evaluate R(E) = N a συ for the p(n, γ)D reaction with 6% uncertainty in the energy region to big bang nucleosynthesis (BBN). The result confirms the past theoretical evaluation and the recent calculation based on the effective field theory. The reaction rate for the p(n, γ)D reaction is presented for the BBN in the precision era. (author)

  5. Isotope effect on confinement in DT plasmas

    International Nuclear Information System (INIS)

    Fukuyama, A.; Itoh, K.; Itoh, S.; Yagi, M.; Azumi, M.

    1994-03-01

    Isotope effect on the energy confinement time is discussed for the DT plasma. The transport theory which is based on the ballooning mode turbulence is applied. When the DT plasma is produced under the condition of β p >1, the energy confinement time of DT plasma (50% mixture) is expected to be about 1.2 times better than the D plasma with the same operation condition. (author)

  6. The Effect of Isotopic Substitution on Quantum Proton Transfer Across Short Water Bridges in Biological Systems

    Science.gov (United States)

    Blazejewski, Jacob; Schultz, Chase; Mazzuca, James

    2015-03-01

    Many biological systems utilize water chains to transfer charge over long distances by means of an excess proton. This study examines how quantum effects impact these reactions in a small model system. The model consists of a water molecule situated between an imidazole donor and acceptor group, which simulate a fixed amino acid backbone. A one dimensional energy profile is evaluated using density functional theory at the 6-31G*/B3LYP level, which generates a barrier with a width of 0.6 Å and a height of 20.7 kcal/mol. Quantum transmission probability is evaluated by solving the time dependent Schrödinger equation on a grid. Isotopic effects are examined by performing calculations with both hydrogen and deuterium. The ratio of hydrogen over the deuterium shows a 130-fold increase in transmission probability at low temperatures. This indicates a substantial quantum tunneling effect. The study of higher dimensional systems as well as increasing the number of water molecules in the chain will be necessary to fully describe the proton transfer process. Alma College Provost's Office.

  7. A study of the EMC effect using neutrino and antineutrino interactions in neon and deuterium

    International Nuclear Information System (INIS)

    Guy, J.; Cooper-Sarkar, A.M.; Venus, W.; Apeldoorn, G. van; Jongejans, B.; Tenner, A.; Eijndhoven, N. van; Berggren, M.; Hulth, P.O.; Simopoulou, E.; Vayaki, A.; Bobisut, F.; Sconza, A.; Brisson, V.; Petiau, P.; Vallee, C.; Capiluppi, P.; Giacomelli, G.; Mandrioli, G.; Rossi, A.M.; Cirio, R.; Marzari-Chiesa, A.; Romero, A.; Clayton, E.F.; Miller, D.B.; Mobayyen, M.M.; Coghen, T.; Frodesen, A.G.; Gerbier, G.; Kasper, P.; Neveu, M.; Klein, H.; Morrison, D.R.O.; Parker, M.A.; Faccini-Turluer, M.L.; Vignaud, D.

    1987-01-01

    Nearly 40000 neutrino and antineutrino interactions in BEBC are compared to measure the differences between neon and deuterium in the quark and antiquark distributions and in the nucleon structure functions. The ratio of Ne to D cross sections indicates some decrease between x ≅ 0.2 and x ≅ 0.6. The y distributions show there is no significant increase in the neon sea, but prefer a small decrease. Taken altogether the x and y distributions and the measured total cross-sections indicate some change in the shape of the valence distributions. No significant dependence on A is observed for either the shape of the sea or the ratio of longitudinal to transverse cross-sections. (orig.)

  8. A study of the EMC effect using neutrino and antineutrino interactions in neon and deuterium

    Science.gov (United States)

    Guy, J.; Saitta, B.; van Apeldoorn, G.; Allport, P.; Angelini, C.; Armenise, N.; Baldini, A.; Berggren, M.; Bertrand, D.; Bobisut, F.; Brisson, V.; Bullock, F.; Calicchio, M.; Capiluppi, P.; Cirio, R.; Clayton, E. F.; Coghen, T.; Cooper-Sarkar, A. M.; Erriquez, O.; Faccini-Turluer, M. L.; Fitch, P.; Frodesen, A. G.; Gerbier, G.; Giacomelli, G.; Hulth, P. O.; Jones, G. T.; Jongejans, B.; Kasper, P.; Klein, H.; Mandrioli, G.; Marage, P.; Marzari-Chiesa, A.; Middleton, R. P.; Miller, D. B.; Morrison, D. R. O.; Mobayyen, M. M.; O'Neale, S. W.; Neveu, M.; Parker, M. A.; Petiau, P.; Romero, A.; Rossi, A. M.; Sacton, J.; Sansum, A.; Sconza, A.; Simopoulou, E.; Schmitz, N.; Tenner, A.; Vallee, C.; van Eijndhoven, N.; Varvell, K.; Vayaki, A.; Venus, W.; Vignaud, D.; Wachsmuth, H.; Wittek, W.

    1987-09-01

    Nearly 40000 neutrino and antineutrino interactions in BEBC are compared to measure the differences between neon and deuterium in the quark and antiquark distributions and in the nucleon structure functions. The ratio of Ne to D cross sections indicates some decrease between x˜0.2 and x˜0.6. The y distributions show there is no significant increase in the neon sea, but prefer a small decrease. Taken altogether, the x and y distributions and the measured total cross-sections indicate some change in the shape of the valence distributions. No significant dependence on A is observed for either the shape of the sea or the ratio of longitudinal to transverse cross-sections.

  9. Heat load and deuterium plasma effects on SPS and WSP tungsten

    Directory of Open Access Journals (Sweden)

    Vilémová Monika

    2015-06-01

    Full Text Available Tungsten is a prime choice for armor material in future nuclear fusion devices. For the realization of fusion, it is necessary to address issues related to the plasma–armor interactions. In this work, several types of tungsten material were studied, i.e. tungsten prepared by spark plasma sintering (SPS and by water stabilized plasma spraying (WSP technique. An intended surface porosity was created in the samples to model hydrogen/helium bubbles. The samples were subjected to a laser heat loading and a radiation loading of deuterium plasma to simulate edge plasma conditions of a nuclear fusion device (power density of 108 W/cm2 and 107 W/cm2, respectively, in the pulse intervals up to 200 ns. Thermally induced changes in the morphology and the damage to the studied surfaces are described. Possible consequences for the fusion device operation are pointed out.

  10. Hydrogen isotope effect on muonic x-ray spectra of (CH2)/sub x/ and H2O

    International Nuclear Information System (INIS)

    Mausner, L.F.; Knight, J.D.; Orth, C.J.; Schillaci, M.E.; Naumann, R.A.

    1977-01-01

    We have measured the muonic x-ray intensity patterns of C in (CH 2 )/sub x/ and (CD 2 )/sub x/ and of O in H 2 O and D 2 O. In both cases the relative intensities of the higher Lyman series members are significantly lower in the deuterium compounds, indicating that the initial angular momentum distribution of the muons captured on C and O is weighted to higher l states compared to the normal hydrogen compounds. This isotope effect has not been predicted by any model of negative-meson capture

  11. Isotope effects on chemical shifts in tautomeric systems with double proton transfer. Citronin

    International Nuclear Information System (INIS)

    Hansen, P.E.; Langgard, M.; Bolvig, S.

    1998-01-01

    Primary and secondary deuterium isotope effects on 1 H and 13 C chemical shifts are measured in citrinin, a tautomeric compound with an unusual doubly intramolecularly hydrogen bonded structure. The isotope effects are to a large extent dominated by equilibrium contributions and deuteration leads to more of the deuterated enol forms rather than the deuterated acid form. 1 H 13 C and 17 O nuclear shieldings are calculated using density functional ab initio methods. A very good correlation between calculated nuclear shieldings and experimental 1 H and 13 C chemical shifts is obtained. The tautomeric equilibrium can be analyzed based on the isotope effects on B-6 and C-8 carbons and shows an increase in the o-quinone form on lowering the temperature. Furthermore, upon deuteration the largest equilibrium shift is found for deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration is increasing at lower temperature. (author)

  12. Introduction to Body Composition Assessment Using the Deuterium Dilution Technique with Analysis of Urine Samples by Isotope Ratio Mass Spectrometry (French Edition)

    International Nuclear Information System (INIS)

    2013-01-01

    The IAEA has fostered the more widespread use of a stable isotope technique to assess body composition in different population groups to address priority areas in public health nutrition in Member States. It has done this by supporting national and regional nutrition projects through its technical cooperation programme and coordinated research projects over many years. This publication was developed by an international group of experts to provide practical hands-on guidance in the use of this technique in settings where analysis of stable isotope ratios in biological samples is to be made by isotope ratio mass spectrometry. The publication is targeted at new users of this technique, for example nutritionists, analytical chemists and other professionals. More detailed information on the theoretical background and the practical applications of state of the art methodologies to monitor changes in body composition can be found in IAEA Human Health Series No. 3, Assessment of Body Composition and Total Energy Expenditure in Humans by Stable Isotope Techniques

  13. Introduction to Body Composition Assessment Using the Deuterium Dilution Technique with Analysis of Urine Samples by Isotope Ratio Mass Spectrometry (Spanish Edition)

    International Nuclear Information System (INIS)

    2013-01-01

    The IAEA has fostered the more widespread use of a stable isotope technique to assess body composition in different population groups to address priority areas in public health nutrition in Member States. It has done this by supporting national and regional nutrition projects through its technical cooperation programme and coordinated research projects over many years. This publication was developed by an international group of experts to provide practical hands-on guidance in the use of this technique in settings where analysis of stable isotope ratios in biological samples is to be made by isotope ratio mass spectrometry. The publication is targeted at new users of this technique, for example nutritionists, analytical chemists and other professionals. More detailed information on the theoretical background and the practical applications of state of the art methodologies to monitor changes in body composition can be found in IAEA Human Health Series No. 3, Assessment of Body Composition and Total Energy Expenditure in Humans by Stable Isotope Techniques

  14. Defect annealing and thermal desorption of deuterium in low dose HFIR neutron-irradiated tungsten

    International Nuclear Information System (INIS)

    Shimada, Masashi; Hara, Masanori; Otsuka, Teppei; Oya, Yasuhisa; Hatano, Yuji

    2015-01-01

    Three tungsten samples irradiated at High Flux Isotope Reactor at Oak Ridge National Laboratory were exposed to deuterium plasma (ion fluence of 1 × 10 26 m −2 ) at three different temperatures (100, 200, and 500 °C) in Tritium Plasma Experiment at Idaho National Laboratory. Subsequently, thermal desorption spectroscopy was performed with a ramp rate of 10 °C min −1 up to 900 °C, and the samples were annealed at 900 °C for 0.5 h. These procedures were repeated three times to uncover defect-annealing effects on deuterium retention. The results show that deuterium retention decreases approximately 70% for at 500 °C after each annealing, and radiation damages were not annealed out completely even after the 3rd annealing. TMAP modeling revealed the trap concentration decreases approximately 80% after each annealing at 900 °C for 0.5 h

  15. Defect annealing and thermal desorption of deuterium in low dose HFIR neutron-irradiated tungsten

    Science.gov (United States)

    Shimada, Masashi; Hara, Masanori; Otsuka, Teppei; Oya, Yasuhisa; Hatano, Yuji

    2015-08-01

    Three tungsten samples irradiated at High Flux Isotope Reactor at Oak Ridge National Laboratory were exposed to deuterium plasma (ion fluence of 1 × 1026 m-2) at three different temperatures (100, 200, and 500 °C) in Tritium Plasma Experiment at Idaho National Laboratory. Subsequently, thermal desorption spectroscopy was performed with a ramp rate of 10 °C min-1 up to 900 °C, and the samples were annealed at 900 °C for 0.5 h. These procedures were repeated three times to uncover defect-annealing effects on deuterium retention. The results show that deuterium retention decreases approximately 70% for at 500 °C after each annealing, and radiation damages were not annealed out completely even after the 3rd annealing. TMAP modeling revealed the trap concentration decreases approximately 80% after each annealing at 900 °C for 0.5 h.

  16. Defect annealing and thermal desorption of deuterium in low dose HFIR neutron-irradiated tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, Masashi, E-mail: Masashi.Shimada@inl.gov [Fusion Safety Program, Idaho National Laboratory, Idaho Falls, ID (United States); Hara, Masanori [Hydrogen Isotope Research Center, University of Toyama, Toyama (Japan); Otsuka, Teppei [Kyushu University, Interdisciplinary Graduate School of Engineering Science, Higashi-ku, Fukuoka (Japan); Oya, Yasuhisa [Radioscience Research Laboratory, Faculty of Science, Shizuoka University, Shizuoka (Japan); Hatano, Yuji [Hydrogen Isotope Research Center, University of Toyama, Toyama (Japan)

    2015-08-15

    Three tungsten samples irradiated at High Flux Isotope Reactor at Oak Ridge National Laboratory were exposed to deuterium plasma (ion fluence of 1 × 10{sup 26} m{sup −2}) at three different temperatures (100, 200, and 500 °C) in Tritium Plasma Experiment at Idaho National Laboratory. Subsequently, thermal desorption spectroscopy was performed with a ramp rate of 10 °C min{sup −1} up to 900 °C, and the samples were annealed at 900 °C for 0.5 h. These procedures were repeated three times to uncover defect-annealing effects on deuterium retention. The results show that deuterium retention decreases approximately 70% for at 500 °C after each annealing, and radiation damages were not annealed out completely even after the 3rd annealing. TMAP modeling revealed the trap concentration decreases approximately 80% after each annealing at 900 °C for 0.5 h.

  17. Computational and Empirical Trans-hydrogen Bond Deuterium Isotope Shifts Suggest that N1-N3 A:U Hydrogen Bonds of RNA are Shorter than those of A:T Hydrogen Bonds of DNA

    International Nuclear Information System (INIS)

    Kim, Yong-Ick; Manalo, Marlon N.; Perez, Lisa M.; LiWang, Andy

    2006-01-01

    Density functional theory calculations of isolated Watson-Crick A:U and A:T base pairs predict that adenine 13 C2 trans-hydrogen bond deuterium isotope shifts due to isotopic substitution at the pyrimidine H3, 2h Δ 13 C2, are sensitive to the hydrogen-bond distance between the N1 of adenine and the N3 of uracil or thymine, which supports the notion that 2h Δ 13 C2 is sensitive to hydrogen-bond strength. Calculated 2h Δ 13 C2 values at a given N1-N3 distance are the same for isolated A:U and A:T base pairs. Replacing uridine residues in RNA with 5-methyl uridine and substituting deoxythymidines in DNA with deoxyuridines do not statistically shift empirical 2h Δ 13 C2 values. Thus, we show experimentally and computationally that the C7 methyl group of thymine has no measurable affect on 2h Δ 13 C2 values. Furthermore, 2h Δ 13 C2 values of modified and unmodified RNA are more negative than those of modified and unmodified DNA, which supports our hypothesis that RNA hydrogen bonds are stronger than those of DNA. It is also shown here that 2h Δ 13 C2 is context dependent and that this dependence is similar for RNA and DNA

  18. Spin exchange in polarized deuterium

    International Nuclear Information System (INIS)

    Przewoski, B. von; Meyer, H.O.; Balewski, J.; Doskow, J.; Ibald, R.; Pollock, R.E.; Rinckel, T.; Wellinghausen, A.; Whitaker, T.J.; Daehnick, W.W.; Haeberli, W.; Schwartz, B.; Wise, T.; Lorentz, B.; Rathmann, F.; Pancella, P.V.; Saha, Swapan K.; Thoerngren-Engblom, P.

    2003-01-01

    We have measured the vector and tensor polarization of an atomic deuterium target as a function of the target density. The polarized deuterium was produced in an atomic beam source and injected into a storage cell. For this experiment, the atomic beam source was operated without rf transitions, in order to avoid complications from the unknown efficiency of these transitions. In this mode, the atomic beam is vector and tensor polarized and both polarizations can be measured simultaneously. We used a 1.2-cm-diam and 27-cm-long storage cell, which yielded an average target density between 3 and 9x10 11 at/cm 3 . We find that the tensor polarization decreases with increasing target density while the vector polarization remains constant. The data are in quantitative agreement with the calculated effect of spin exchange between deuterium atoms at low field

  19. Temperature-dependent transitions between normal and inverse isotope effects pertaining to the interaction of H-H and C-H bonds with transition metal centers.

    Science.gov (United States)

    Parkin, Gerard

    2009-02-17

    Deuterium kinetic isotope effects (KIEs) serve as versatile tools to infer details about reaction mechanisms and the nature of transition states, while equilibrium isotope effects (EIEs) associated with the site preferences of hydrogen and deuterium enable researchers to study aspects of molecular structure. Researchers typically interpret primary deuterium isotope effects based on two simple guidelines: (i) the KIE for an elementary reaction is normal (k(H)/k(D) > 1) and (ii) the EIE is dictated by deuterium preferring to be located in the site corresponding to the highest frequency oscillator. In this Account, we evaluate the applicability of these rules to the interactions of H-H and C-H bonds with a transition metal center. Significantly, experimental and computational studies question the predictability of primary EIEs in these systems based on the notion that deuterium prefers to occupy the highest frequency oscillator. In particular, the EIEs for (i) formation of sigma-complexes by coordination of H-H and C-H bonds and (ii) oxidative addition of dihydrogen exhibit unusual temperature dependencies, such that the same system may demonstrate both normal (i.e., K(H)/K(D) > 1) and inverse (i.e., K(H)/K(D) ZPE (where SYM is the symmetry factor, MMI is the mass-moment of inertia term, EXC is the excitation term, and ZPE is the zero-point energy term), and the distinctive temperature profile results from the inverse ZPE (enthalpy) and normal [SYM x MMI x EXC] (entropy) components opposing each other and having different temperature dependencies. At low temperatures, the ZPE component dominates and the EIE is inverse, while at high temperatures, the [SYM x MMI x EXC] component dominates and the EIE is normal. The inverse nature of the ZPE term is a consequence of the rotational and translational degrees of freedom of RH (R = H, CH(3)) becoming low-energy isotopically sensitive vibrations in the product, while the normal nature of the [SYM x MMI x EXC] component

  20. Non - Adiabaticity and Novel Isotope Effect in the Doped Cuprates

    International Nuclear Information System (INIS)

    Kresin, V.; WOLF, S. A.

    1995-01-01

    This paper reports a novel isotope effect which is due to a strong non-adiabaticity that manifests itself in the dependence of the carrier concentration on the isotopic mass. The critical temperature in turn depends on the carrier concentration giving rise to a unique and non-phononic isotope shift. (author)

  1. Chemical and isotopic composition of precipitations in Syria

    International Nuclear Information System (INIS)

    Abou Zakhem, B.; Hafez, R.

    2008-01-01

    13 meteoric stations were selected in syria for cumulative monthly rainfall sampling during two hydrological cycles; 1991-1992 and 1992-1993. The chemical and isotopic compositions of monthly precipitation were studied. The winter and spring rainfall isotopic characteristics were determined, in addition to the syrian or local meteoric line (SMWL) was estimated with a slope of 6.63 and that of both syria and Jordan of 6.73. The effect of climatic factors as temperature and relative air humidity on oxygen-18, deuterium and d-excess were studied and it was found that the relationship between temperature and oxygen-18 and deuterium is a positive linear correlation; however, it is a negative correlation with d-excess. The mean seasonal variation amplitude was determined by 6%, and the amount effect on isotopic content of precipitation was studied. The geographic factors and its affect on isotopic contents of precipitation such as altitude were considered, furthermore, the isotopic gradient with altitude was determined for both oxygen-18 and deuterium (-0.14% and - 0.84%/100 m elevation respectively). The spatial variability of oxygen-18, deuterium, tritium and d-excess indicted the effect of mountain chains and gaps between mountains on the isotopic content of precipitation, the continental effect on tritium build-up by about 33% per 100 Km from the coast. The increase of d-excess values towards the south west proves the eastern mediterranean climate type over this region. (author)

  2. A Reexamination of Deuterium Fractionation on Mars

    Science.gov (United States)

    Pathare, A.; Paige, D. A.

    1997-07-01

    The ratio of deuterium to hydrogen in the Martian atmosphere is enhanced by a factor of 5 with respect to the terrestrial value, probably due to fractionation associated with thermal Jeans escape from the top of the atmosphere. Theoretical analyses of the relative efficiency of H and D escape have suggested that the deuterium enrichment implies Mars has outgassed the vast majority of its H2O and that the Martian atmosphere is presently not exchanging water with a juvenile reservoir. However, measurements of high and variable D/H values within hydrous minerals in SNC meteorites strongly suggest that mixing between the atmosphere and juvenile water has taken place. Furthermore, the lack of any observed enrichment of atmospheric (18) O with respect to (16) O, in spite of fractionating nonthermal escape mechanisms, indicates buffering by some juvenile source of oxygen, most probably in the form of a surface or subsurface reservoir of water. We propose that this apparent paradox in the interpretation of isotopic hydrogen and oxygen fractionation --or lack thereof-- can be resolved by re-examining the standard model of deuterium fractionation efficiency on Mars. Specifically, we demonstrate the importance of using upper atmospheric temperatures more representative of the range experienced by the Martian exosphere over the course of the solar cycle. Preliminary calculations involving changes in effusion velocity and diffusive separation as a function of exospheric temperature indicate that incorporating these more representative lower exospheric temperatures will reduce the relative efficiency of D escape, in which case the observed enrichment of deuterium can indeed result from exchange with a juvenile source of water. We are in the process of confirming these computations with a one-dimensional upper atmospheric photochemical model that considers the effects of changing solar activity and exospheric temperature on ionospheric composition. If our initial calculations are

  3. Isotope exchange reactions on ceramic breeder materials and their effect on tritium inventory

    Energy Technology Data Exchange (ETDEWEB)

    Nishikawa, M; Baba, A [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering; Kawamura, Y; Nishi, M

    1998-03-01

    Though lithium ceramic materials such as Li{sub 2}O, LiAlO{sub 2}, Li{sub 2}ZrO{sub 3}, Li{sub 2}TiO{sub 3} and Li{sub 4}SiO{sub 4} are considered as breeding materials in the blanket of a D-T fusion reactor, the release behavior of the bred tritium in these solid breeder materials has not been fully understood. The isotope exchange reaction rate between hydrogen isotopes in the purge gas and tritium on the surface of breeding materials have not been quantified yet, although helium gas with hydrogen or deuterium is planned to be used as the blanket purge gas in the recent blanket designs. The mass transfer coefficient representing the isotope exchange reaction between H{sub 2} and D{sub 2}O or that between D{sub 2} and H{sub 2}O in the ceramic breeding materials bed is experimentally obtained in this study. Effects of isotope exchange reactions on the tritium inventory in the bleeding blanket is discussed based on data obtained in this study where effects of diffusion of tritium in the grain, absorption of water in the bulk of grain, and adsorption of water on the surface of grain, together with two types of isotope exchange reactions are considered. The way to estimate the tritium inventory in a Li{sub 2}ZrO{sub 3} blanket used in this study shows a good agreement with data obtained in such in-situ experiments as MOZART, EXOTIC-5, 6 and TRINE experiments. (author)

  4. Competition H(D) kinetic isotope effects in the autoxidation of hydrocarbons.

    Science.gov (United States)

    Muchalski, Hubert; Levonyak, Alexander J; Xu, Libin; Ingold, Keith U; Porter, Ned A

    2015-01-14

    Hydrogen atom transfer is central to many important radical chain sequences. We report here a method for determination of both the primary and secondary isotope effects for symmetrical substrates by the use of NMR. Intramolecular competition reactions were carried out on substrates having an increasing number of deuterium atoms at symmetry-related sites. Products that arise from peroxyl radical abstraction at each position of the various substrates reflect the competition rates for H(D) abstraction. The primary KIE for autoxidation of tetralin was determined to be 15.9 ± 1.4, a value that exceeds the maximum predicted by differences in H(D) zero-point energies (∼7) and strongly suggests that H atom abstraction by the peroxyl radical occurs with substantial quantum mechanical tunneling.

  5. Deuterium high pressure target

    International Nuclear Information System (INIS)

    Perevozchikov, V.V.; Yukhimchuk, A.A.; Vinogradov, Yu.I.

    2001-01-01

    The design of the deuterium high-pressure target is presented. The target having volume of 76 cm 3 serves to provide the experimental research of muon catalyzed fusion reactions in ultra-pure deuterium in the temperature range 80-800 K under pressures of up to 150 MPa. The operation of the main systems of the target is described: generation and purification of deuterium gas, refrigeration, heating, evacuation, automated control system and data collection system

  6. Synthesis of deuterium-labelled viloxazine. [Antidepressant

    Energy Technology Data Exchange (ETDEWEB)

    Mamada, Kumiko; Furuta, Takashi; Kasuya, Yasuji

    1988-06-01

    The synthesis of deuterium-labelled viloxazine with high isotopic purity is described. The synthetic procedures employ alkylation of 2-(benzyloxy)phenol with (/sup 2/H/sub 5/)ethyl iodide for the introduction of deuterium. Catalytic removal of the benzyl group of the deuterated product followed by reaction with epichlorohydrin afforded 1,2-epoxy-3-(2'-pentadeuteroethoxy-phenoxy)propane. Addition of 2-aminoethyl hydrogen sulphate to the epoxide and subsequent ring formation into a morpholine derivative produced the desired (/sup 2/H/sub 5/)viloxazine.

  7. Isotope and multiband effects in layered superconductors.

    Science.gov (United States)

    Bussmann-Holder, Annette; Keller, Hugo

    2012-06-13

    In this review we consider three classes of superconductors, namely cuprate superconductors, MgB(2) and the new Fe based superconductors. All of these three systems are layered materials and multiband compounds. Their pairing mechanisms are under discussion with the exception of MgB(2), which is widely accepted to be a 'conventional' electron-phonon interaction mediated superconductor, but extending the Bardeen-Cooper-Schrieffer (BCS) theory to account for multiband effects. Cuprates and Fe based superconductors have higher superconducting transition temperatures and more complex structures. Superconductivity is doping dependent in these material classes unlike in MgB(2) which, as a pure compound, has the highest values of T(c) and a rapid suppression of superconductivity with doping takes place. In all three material classes isotope effects have been observed, including exotic ones in the cuprates, and controversial ones in the Fe based materials. Before the area of high-temperature superconductivity, isotope effects on T(c) were the signature for phonon mediated superconductivity-even when deviations from the BCS value to smaller values were observed. Since the discovery of high T(c) materials this is no longer evident since competing mechanisms might exist and other mediating pairing interactions are discussed which are of purely electronic origin. In this work we will compare the three different material classes and especially discuss the experimentally observed isotope effects of all three systems and present a rather general analysis of them. Furthermore, we will concentrate on multiband signatures which are not generally accepted in cuprates even though they are manifest in various experiments, the evidence for those in MgB(2), and indications for them in the Fe based compounds. Mostly we will consider experimental data, but when possible also discuss theoretical models which are suited to explain the data.

  8. Effects of helium and deuterium irradiation on SPS sintered W–Ta composites at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Mateus, R., E-mail: rmateus@ipfn.ist.utl.pt [Associação Euratom/IST, Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Dias, M. [ITN, Instituto Tecnológico e Nuclear, Estrada Nacional 10, 2686-953 Sacavém (Portugal); Lopes, J. [ITN, Instituto Tecnológico e Nuclear, Estrada Nacional 10, 2686-953 Sacavém (Portugal); ISEL, Instituto Superior de Engenharia de Lisboa, Rua Conselheiro Emídio Navarro, 1, 1959-007 Lisboa (Portugal); Rocha, J.; Catarino, N.; Franco, N. [ITN, Instituto Tecnológico e Nuclear, Estrada Nacional 10, 2686-953 Sacavém (Portugal); Livramento, V. [Associação Euratom/IST, Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); LNEG, Laboratório Nacional de Energia e Geologia, Estrada do Paço do Lumiar, 1649-038 Lisboa (Portugal); and others

    2013-11-15

    Energetic He{sup +} and D{sup +} ions were implanted into different W–Ta composites in order to investigate their stability under helium and deuterium irradiation. The results were compared with morphological and chemical modifications arising from exposure of pure W and Ta. Special attention was given to tantalum hydride (Ta{sub 2}H) formation due to its implications for tritium inventory. Three W–Ta composites with 10 and 20 at.% Ta were prepared from elemental W powder and Ta fibre or powder through low-energy ball milling in argon atmosphere. Spark plasma sintering (SPS) was used as the consolidation process in the temperature range from 1473 to 1873 K. The results obtained from pure elemental samples and composites are similar. However, Ta{sub 2}H is easily formed in pure Ta by using a pre-implantation stage of He{sup +}, whereas in W–Ta composites the same reaction is clearly reduced, and it can be inhibited by controlling the sintering temperature.

  9. Deuterium depleted water effect on seawater spectral energy and marine phytoplankton

    International Nuclear Information System (INIS)

    Mirza, Maria; Zaharia, Mihaela; Cristescu, T.M.; Titescu, Gh.

    2002-01-01

    Solar radiation is the primary source of new energy in most aquatic ecosystems and it is the sun variability in amount and spectral distribution that drives many of the changes in material flux on different time and space scales. The dependency of ecosystem dynamics on sunlight is largely attributable to the simple fact that plants require solar radiation to carry out photosynthesis. The resulting primary production (the rate of the plant growth and reproduction) is an index of aquatic processes, including food web dynamics and biogeochemical cycling of compounds that affect everything from aquatic chemistry to regional and global weather patterns. Light dependent processes in plants (photo-synthesis, photoinhibition, phototaxis and photoprotection) and in aquatic environment, animal vision and microbial mediation of the photo-dissociation of chemical have evolved over millennia and most of them are regulated or at least influenced by the spectral composition of the light field The paper deals with the investigation of relations between water spectral energy modified by deuterium depleted water (DDW) and the microphyte alga Tetraselmis suecica or the total marine micro-phytoplankton growth. (authors)

  10. Impurity effects of hydrogen isotope retention on boronized wall in LHD

    International Nuclear Information System (INIS)

    Oya, Yasuhisa; Okuno, Kenji; Ashikawa, Naoko; Nishimura, Kiyohiko; Sagara, Akio

    2010-11-01

    The impurity effect on hydrogen isotopes retention in the boron film deposited in LHD was evaluated by means of XPS and TDS. It was found that the impurity concentrations in boron film were increased after H-H main plasma exposure in LHD. The ratio of hydrogen retention trapped by impurity to total hydrogen retention during H-H main plasma exposure was reached to 70%, although that of deuterium retention by impurity in D 2 + implanted LHD-boron film was about 35%. In addition, the dynamic chemical sputtering of hydrogen isotopes with impurity as the form of water and / or hydrocarbons was occurred by energetic hydrogen isotopes irradiation. It was expected that the enhancement of impurity concentration during plasma exposure in LHD would induce the dynamic formation of volatile molecules and their re-emission to plasma. These facts would prevent stable plasma operation in LHD, concluding that the dynamic impurity behavior in boron film during plasma exposure is one of key issues for the steady-state plasma operation in LHD. (author)

  11. Fine target of deuterium

    International Nuclear Information System (INIS)

    Diaz Diaz, J.; Granados Gonzalez, C. E.; Gutierrez Bernal, R.

    1959-01-01

    A fine target of deuterium on a tantalum plate by the absorption method is obtained. In order to obtain the de gasification temperature an induction generator of high frequency is used and the deuterium pass is regulated by means of a palladium valve. Two vacuum measures are available, one to measure the high vacuum in the de gasification process of the tantalum plate and the other, for low vacuum, to measure the deuterium inlet in the installation and the deuterium pressure change in the installation after the absorption in the tantalum plate. A target of 48 μ gr/cm 2 thick is obtained. (Author) 1 refs

  12. Effective Application of Bicelles for Conformational Analysis of G Protein-Coupled Receptors by Hydrogen/Deuterium Exchange Mass Spectrometry

    Science.gov (United States)

    Duc, Nguyen Minh; Du, Yang; Thorsen, Thor S.; Lee, Su Youn; Zhang, Cheng; Kato, Hideaki; Kobilka, Brian K.; Chung, Ka Young

    2015-05-01

    G protein-coupled receptors (GPCRs) have important roles in physiology and pathology, and 40% of drugs currently on the market target GPCRs for the treatment of various diseases. Because of their therapeutic importance, the structural mechanism of GPCR signaling is of great interest in the field of drug discovery. Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is a useful tool for analyzing ligand binding sites, the protein-protein interaction interface, and conformational changes of proteins. However, its application to GPCRs has been limited for various reasons, including the hydrophobic nature of GPCRs and the use of detergents in their preparation. In the present study, we tested the application of bicelles as a means of solubilizing GPCRs for HDX-MS studies. GPCRs (e.g., β2-adrenergic receptor [β2AR], μ-opioid receptor, and protease-activated receptor 1) solubilized in bicelles produced better sequence coverage (greater than 90%) than GPCRs solubilized in n-dodecyl-β-D-maltopyranoside (DDM), suggesting that bicelles are a more effective method of solubilization for HDX-MS studies. The HDX-MS profile of β2AR in bicelles showed that transmembrane domains (TMs) undergo lower deuterium uptake than intracellular or extracellular regions, which is consistent with the fact that the TMs are highly ordered and embedded in bicelles. The overall HDX-MS profiles of β2AR solubilized in bicelles and in DDM were similar except for intracellular loop 3. Interestingly, we detected EX1 kinetics, an important phenomenon in protein dynamics, at the C-terminus of TM6 in β2AR. In conclusion, we suggest the application of bicelles as a useful method for solubilizing GPCRs for conformational analysis by HDX-MS.

  13. Intra-event isotope and raindrop size data of tropical rain reveal effects concealed by event averaged data

    Science.gov (United States)

    Managave, S. R.; Jani, R. A.; Narayana Rao, T.; Sunilkumar, K.; Satheeshkumar, S.; Ramesh, R.

    2016-08-01

    Evaporation of rain is known to contribute water vapor, a potent greenhouse gas, to the atmosphere. Stable oxygen and hydrogen isotopic compositions (δ18O and, δD, respectively) of precipitation, usually measured/presented as values integrated over rain events or monthly mean values, are important tools for detecting evaporation effects. The slope ~8 of the linear relationship between such time-averaged values of δD and δ18O (called the meteoric water line) is widely accepted as a proof of condensation under isotopic equilibrium and absence of evaporation of rain during atmospheric fall. Here, through a simultaneous investigation of the isotopic and drop size distributions of seventeen rain events sampled on an intra-event scale at Gadanki (13.5°N, 79.2°E), southern India, we demonstrate that the evaporation effects, not evident in the time-averaged data, are significantly manifested in the sub-samples of individual rain events. We detect this through (1) slopes significantly less than 8 for the δD-δ18O relation on intra-event scale and (2) significant positive correlations between deuterium excess ( d-excess = δD - 8*δ18O; lower values in rain indicate evaporation) and the mass-weighted mean diameter of the raindrops ( D m ). An estimated ~44 % of rain is influenced by evaporation. This study also reveals a signature of isotopic equilibration of rain with the cloud base vapor, the processes important for modeling isotopic composition of precipitation. d-excess values of rain are modified by the post-condensation processes and the present approach offers a way to identify the d-excess values least affected by such processes. Isotope-enabled global circulation models could be improved by incorporating intra-event isotopic data and raindrop size dependent isotopic effects.

  14. Reprint of: Effects of cold deformation, electron irradiation and extrusion on deuterium desorption behavior in Zr-1%Nb alloy

    Science.gov (United States)

    Morozov, O.; Mats, O.; Mats, V.; Zhurba, V.; Khaimovich, P.

    2018-01-01

    The present article introduces the data of analysis of ranges of ion-implanted deuterium desorption from Zr-1% Nb alloy. The samples studied underwent plastic deformation, low temperature extrusion and electron irradiation. Plastic rolling of the samples at temperature ∼300 K resulted in plastic deformation with the degree of ε = 3.9 and the formation of nanostructural state with the average grain size of d = 61 nm. The high degree of defectiveness is shown in thermodesorption spectrum as an additional area of the deuterium desorption in the temperature ranges 650-850 K. The further processing of the sample (that had undergone plastic deformation by plastic rolling) with electron irradiation resulted in the reduction of the average grain size (58 nm) and an increase in borders concentration. As a result the amount of deuterium desorpted increased in the temperature ranges 650-900 K. In case of Zr-1% Nb samples deformed by extrusion the extension of desorption area is observed towards the temperature reduction down to 420 K. The formation of the phase state of deuterium solid solution in zirconium was not observed. The structural state behavior is a control factor in the process of deuterium thermodesorption spectrum structure formation with a fixed implanted deuterium dose (hydrogen diagnostics). It appears as additional temperature ranges of deuterium desorption depending on the type, character and defect content.

  15. Kinetics, isotope effects, and mechanism for the hydrogenation of carbon monoxide on supported nickel catalysts

    International Nuclear Information System (INIS)

    Mori, T.; Masuda, H.; Imai, H.; Miyamoto, A.; Baba, S.; Murakami, Y.

    1982-01-01

    Kinetics and hydrogen-deuterium isotope effects in the methanation of adsorbed CO molecules on a Ni/SiO 2 catalyst were precisely measured by using pulse surface reaction rate analysis (PSRA). When a CO pulse was injected into flowing hydrogen, it was immediately adsorbed on the catalyst and gradually hydrogenated to CH 4 and H 2 O. The amounts of CH 4 and H 2 O produced by the hydrogenation of the adsorbed CO were determined up to various times, and it was found that CH 4 and H 2 O were produced at the same rate. When O 2 instead of CO was injected, H 2 O was immediately produced. From these results, the rate-determining step of the reaction was found to be C-O bond dissociation of an adsorbed CO molecule or a partially hydrogenated CO species. By PSRA, the rate constant for the C-O bond dissocition process per adsorbed CO molecule (k/sub H/) was determined at various temperatures, and the Arrhenius parameters of the rate constant were obtained. The rate constant in flowing deuterium (k/sub D/) was also determined. it was found that k/sub D/ is considerably larger than k/sub H/, indicating an inverse isotope effect. The average value of k/sub H//k/sub D/ was 0.75. From these results, it was concluded that adsorbed CO is not directly dissociated to surface carbon and oxygen atoms but it is partially hydrogenated before C-O bond dissociation under the conditions of the PSRA experiment. 8 figures

  16. Deuterium and oxygen-18 abundance in birds: Implications for DLW energetics studies

    International Nuclear Information System (INIS)

    Tatner, P.

    1990-01-01

    The doubly labeled water (DLW) technique for measuring energy expenditure may employ one ( 18 O) or two ( 18 O and deuterium) stable isotopes as tracers. These occur naturally in the environment, so when they are used as tracers it is necessary to subtract the background levels. Few studies report data on background concentrations. This work provides such data for a range of avian species. Overall, there was a strong positive correlation (r = 0.63) between the 18 O and deuterium concentrations in birds' body water. Variation in the deuterium concentration was less extensive than in the 18 O concentration (1:2.7 parts/million). In the European robin, there was a linked, seasonal variation in 18 O and deuterium abundance producing high summer and low winter values. Throughout the year, a high individual variability was greater in 18 O than in deuterium. A difference between the European robin and the dipper suggests that habitat may also influence background abundance. Investigation of the effect of variation in background abundance on measures of energy expenditure for small passerines (20 g) revealed that employing estimates, instead of direct measurements, had a minor influence over an experimental period of 1 day but could potentially introduce errors as large as 54% over a 2-day period

  17. High resolution deuterium NMR studies of bacterial metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Aguayo, J.B.; Gamcsik, M.P.; Dick, J.D.

    1988-12-25

    High resolution deuterium NMR spectra were obtained from suspensions of five bacterial strains: Escherichia coli, Clostridium perfringens, Klebsiella pneumoniae, Proteus mirabilis, and Staphylococcus aureus. Deuterium-labeled D-glucose at C-1, C-2, and C-6 was used to monitor dynamically anaerobic metabolism. The flux of glucose through the various bacterial metabolic pathways could be determined by following the disappearance of glucose and the appearance of the major end products in the 2H NMR spectrum. The presence of both labeled and unlabeled metabolites could be detected using 1H NMR spectroscopy since the proton resonances in the labeled species are shifted upfield due to an isotopic chemical shift effect. The 1H-1H scalar coupling observed in both the 2H and 1H NMR spectra was used to assign definitively the resonances of labeled species. An increase in the intensity of natural abundance deuterium signal of water can be used to monitor pathways in which a deuteron is lost from the labeled metabolite. The steps in which label loss can occur are outlined, and the influence these processes have on the ability of 2H NMR spectroscopy to monitor metabolism are assessed.

  18. High resolution deuterium NMR studies of bacterial metabolism

    International Nuclear Information System (INIS)

    Aguayo, J.B.; Gamcsik, M.P.; Dick, J.D.

    1988-01-01

    High resolution deuterium NMR spectra were obtained from suspensions of five bacterial strains: Escherichia coli, Clostridium perfringens, Klebsiella pneumoniae, Proteus mirabilis, and Staphylococcus aureus. Deuterium-labeled D-glucose at C-1, C-2, and C-6 was used to monitor dynamically anaerobic metabolism. The flux of glucose through the various bacterial metabolic pathways could be determined by following the disappearance of glucose and the appearance of the major end products in the 2H NMR spectrum. The presence of both labeled and unlabeled metabolites could be detected using 1H NMR spectroscopy since the proton resonances in the labeled species are shifted upfield due to an isotopic chemical shift effect. The 1H-1H scalar coupling observed in both the 2H and 1H NMR spectra was used to assign definitively the resonances of labeled species. An increase in the intensity of natural abundance deuterium signal of water can be used to monitor pathways in which a deuteron is lost from the labeled metabolite. The steps in which label loss can occur are outlined, and the influence these processes have on the ability of 2H NMR spectroscopy to monitor metabolism are assessed

  19. Quasi-isentropic compressibility of a strongly nonideal deuterium plasma at pressures of up to 5500 GPa: Nonideality and degeneracy effects

    Energy Technology Data Exchange (ETDEWEB)

    Mochalov, M. A., E-mail: postmaster@ifv.vniief.ru; Il’kaev, R. I. [Russian Federal Nuclear Center All-Russia Research Institute for Nuclear Physics (Russian Federation); Fortov, V. E. [Russian Academy of Sciences, Joint Institute for High Temperatures (Russian Federation); Mikhailov, A. L.; Blikov, A. O.; Ogorodnikov, V. A. [Russian Federal Nuclear Center All-Russia Research Institute for Nuclear Physics (Russian Federation); Gryaznov, V. K. [Russian Academy of Sciences, Institute for Problems of Chemical Physics (Russian Federation); Iosilevskii, I. L. [Russian Academy of Sciences, Joint Institute for High Temperatures (Russian Federation)

    2017-03-15

    We report on the experimental results on the quasi-isentropic compressibility of a strongly nonideal deuterium plasma that have been obtained on setups of cylindrical and spherical geometries in the pressure range of up to P ≈ 5500 GPa. We describe the characteristics of experimental setups, as well as the methods for the diagnostics and interpretation of the experimental results. The trajectory of metal shells that compress the deuterium plasma was detected using powerful pulsed X-ray sources with a maximal electron energy of up to 60 MeV. The values of the plasma density, which varied from ρ ≈ 0.8 g/cm{sup 3} to ρ ≈ 6 g/cm{sup 3}, which corresponds to pressure P ≈ 5500 GPa (55 Mbar), were determined from the measured value of the shell radius at the instant that it was stopped. The pressure of the compressed plasma was determined using gasdynamic calculations taking into account the actual characteristics of the experimental setups. We have obtained a strongly compressed deuterium plasma in which electron degeneracy effects under the conditions of strong interparticle interaction are significant. The experimental results have been compared with the theoretical models of a strongly nonideal partly degenerate plasma. We have obtained experimental confirmation of the plasma phase transition in the pressure range near 150 GPa (1.5 Mbar), which is in keeping with the conclusion concerning anomaly in the compressibility of the deuterium plasma drawn in [1].

  20. Deuterium trapping in carbon fiber composites under high fluence

    International Nuclear Information System (INIS)

    Airapetov, A.A.; Begrambekov, L.B.; Kuzmin, A.A.; Shigin, P.A.; Zakharov, A.M.

    2010-01-01

    The paper is devoted to investigation of deuterium trapping in CFC, dance graphite MPG-8 and pyrolytic graphite (PG) under plasma ion- and electron irradiation. Number of specific features of deuterium trapping and retention under plasma ion and electron irradiation is presented and discussed. In particular it is shown that 1) deuterium trapping takes place even when energy of impinging ions approaches zero; 2) deuterium is trapped under irradiation by plasma electrons; 3) under irradiation at equal fluences deuterium trapping is higher, when ion flux is smaller. High energy ion penetrating the surfaces are trapped in the traps created at the expense of their kinetic energy. The process may be named 'kinetic trapping'. Under low energy (smaller than 200 eV) electron and/or ion irradiation the energy of inelastic interaction on the surface provides creation of active centers, which initiate dissociation of deuterium sorbed on the surface, penetration of deuterium atoms into graphite and their trapping in specific low energy traps. The term 'potential trapping' is proposed for this type of trapping. Under high energy irradiation such atoms can fill the traps formed through kinetic mechanism. Origination of moveable deuterium atoms from the layer of surface sorption seems to be time dependent process and it is a reason of increase of trapping along with irradiation time. New features of deuterium trapping and retention in graphite evaluated in this study offer new opportunities for analysis and correct estimation of hydrogen isotope trapping and retention in tokamaks having graphite tiles. (authors)

  1. Process for the production of hydrogen/deuterium-containing gas

    International Nuclear Information System (INIS)

    Nitschke, E.; Desai, A.; Ilgner, H.

    1978-01-01

    A process for the production of hydrogen/deuterium-containing gas is described in which the enriched condensate obtained from the production of a hydrogen/deuterium-containing gas mixture is collected and subjected to a direct exchange of isotopes with the feedsteam admitted to the process. Such condensate can be brought into direct exchange of isotopes with the gas water vapor mixture within the process, viz. ahead of the CO conversion section. The exchange of isotopes may be performed according to the counter-current principle. If it is intended to maintain in the hydrogen/deuterium-containing gas a certain definite content of water vapor whose phase condition is superior to the condition achieved when using normal cooling water, this gas, at least 0.6 kg/m 3 of gas, is subjected to an exchange of isotopes with the water fed additionally into the process

  2. High-precision measurement of strong-interaction effects in pionic deuterium

    Energy Technology Data Exchange (ETDEWEB)

    Strauch, Thomas

    2009-06-30

    The hadronic ground state shift {epsilon}{sub 1s} and width {gamma}{sub 1s} in pionic deuterium were measured with high precision at the pion factory of the Paul Scherrer Institut (PSI), Switzerland (PSI-Experiment R-06.03). In this experiment the {pi}D(3p-1s) X-ray transition of about 3 keV was measured using a high-resolution Bragg crystal spectrometer equipped with a large-area position sensitive CCD detector. The characteristic X-radiation stems from a de-excitation cascade of the pionic atom. In order to produce an intense X-ray source, the cyclotron trap was used to stop pions in a cryogenic D{sub 2} target after winding up the pion beam in a magnetic field. The hadronic shift {epsilon}{sub 1s} is obtained from the measured transition energy by comparison to the pure electromagnetic value, where the determination of the broadening {gamma}{sub 1s} requires the precise knowledge of the spectrometer response, obtained from measurements of narrow X-ray transitions from highly ionised atoms, produced in an electron cyclotron resonance ion trap. As the formation rate is assumed to be density dependent, the {pi}D(3p-1s) X-ray energy was measured at three different D{sub 2} pressures. Another cascade process (Coulomb de-excitation) transforms the energy release of de-excitation steps into kinetic energy of the collision partners leading to a Doppler broadening of subsequent X-ray transitions. The hadronic broadening {gamma}{sub 1s} is only obtained after deconvolution of the spectrometer response function and the contributions from Doppler broadening. No energy dependence of the {pi}D(3p-1s) was found, and it is concluded that radiative de-excitation from molecular states is negligible within the experimental accuracy. Hence, the result for the shift reads {epsilon}{sub 1s} = (-2.325{+-}0.031) eV, corresponding to an accuracy of 1.3% and represents the average of the three measured densities. The uncertainty is dominated by the accuracy of the gallium K{alpha}{sub 2

  3. High-precision measurement of strong-interaction effects in pionic deuterium

    International Nuclear Information System (INIS)

    Strauch, Thomas

    2009-01-01

    The hadronic ground state shift ε 1s and width Γ 1s in pionic deuterium were measured with high precision at the pion factory of the Paul Scherrer Institut (PSI), Switzerland (PSI-Experiment R-06.03). In this experiment the πD(3p-1s) X-ray transition of about 3 keV was measured using a high-resolution Bragg crystal spectrometer equipped with a large-area position sensitive CCD detector. The characteristic X-radiation stems from a de-excitation cascade of the pionic atom. In order to produce an intense X-ray source, the cyclotron trap was used to stop pions in a cryogenic D 2 target after winding up the pion beam in a magnetic field. The hadronic shift ε 1s is obtained from the measured transition energy by comparison to the pure electromagnetic value, where the determination of the broadening Γ 1s requires the precise knowledge of the spectrometer response, obtained from measurements of narrow X-ray transitions from highly ionised atoms, produced in an electron cyclotron resonance ion trap. As the formation rate is assumed to be density dependent, the πD(3p-1s) X-ray energy was measured at three different D 2 pressures. Another cascade process (Coulomb de-excitation) transforms the energy release of de-excitation steps into kinetic energy of the collision partners leading to a Doppler broadening of subsequent X-ray transitions. The hadronic broadening Γ 1s is only obtained after deconvolution of the spectrometer response function and the contributions from Doppler broadening. No energy dependence of the πD(3p-1s) was found, and it is concluded that radiative de-excitation from molecular states is negligible within the experimental accuracy. Hence, the result for the shift reads ε 1s = (-2.325±0.031) eV, corresponding to an accuracy of 1.3% and represents the average of the three measured densities. The uncertainty is dominated by the accuracy of the gallium Kα 2 transition used for the energy calibration. From the analysis of the Doppler broadening no

  4. Primary and secondary kinetic isotope effects in the acid-catalyzed dehydration of 1,1'-diadamantylmethylcarbinol in aqueous acetic acid

    International Nuclear Information System (INIS)

    Lomas, J.S.

    1981-01-01

    The sulfuric acid catalyzed dehydration of 1,1'-diadamantyl-methylcarbinol in anhydrous acetic acid proceeds exclusively to 1,1'-bis(1-adamantyl)ethylene. The secondary deuterium isotope effect of 1.32 found for this reaction shows that carbonium ion formation from the protonated alcohol is rate determining. In the presence of water, however, capture of the carbonium ion competes with deprotonation, introducing a primary isotope effect. Consequently, the overall KIE rises, reaching 3.18 for 80% aqueous acetic acid. Analysis of the KIE for 80 to 100% aqueous acetic acid is consistent with a simple classical mechanism involving reversible formation of the intermediate carbonium ion. The primary isotope effect upon deprotonation is at the most 2.98, indicative of an asymmetric transition state close to the carbonium ion

  5. Mechanistic deductions from kinetic isotope effects and pH studies of pyridoxal phosphate dependent carbon-carbon lyases: Erwinia herbicola and Citrobacter freundii tyrosine phenol-lyase

    International Nuclear Information System (INIS)

    Kiick, D.M.; Phillips, R.S.

    1988-01-01

    The pH dependence of the kinetic parameters and primary deuterium isotope effects have been determined for tyrosine phenol-lyase from both Erwinia herbicola and Citrobacter freundii. The primary deuterium isotope effects indicate that proton abstraction from the 2-position of the substrate is partially rate-limiting for both enzymes. The C. freundii enzyme primary deuterium isotope effects [DV = 3.5 and D(V/Ktyr) = 2.5] are pH independent, indicating that tyrosine is not sticky (i.e., does not dissociate slower than it reacts to give products). Since Vmax for both tyrosine and the alternate substrate S-methyl-L-cysteine is also pH independent, substrate binds only to the correctly protonated form of the enzyme. For the E. herbicola enzyme, both Vmax and V/K for tyrosine or S-methyl-L-cysteine are pH dependent, as well as both DV and D(V/Ktyr). Thus, while both the protonated and unprotonated enzyme can bind substrate, and may be interconverted directly, only the unprotonated Michaelis complex is catalytically competent. At pH 9.5, DV = 2.5 and D(V/Ktyr) = 1.5. However, at pH 6.4 the isotope effect on both parameters is equal to 4.1. From these data, the forward commitment factor (cf = 5.2) and catalytic ratio (cvf = 1.1) for tyrosine and S-methyl-L-cysteine (cf = 2.2, cvf = 24) are calculated. Also, the Michaelis complex partition ratio (cf/cvf) for substrate and products is calculated to be 4.7 for tyrosine and 0.1 for S-methyl-L-cysteine

  6. Isotope effect studies of chicken liver NADP malic enzyme: role of the metal ion and viscosity dependence

    International Nuclear Information System (INIS)

    Grissom, C.B.; Cleland, W.W.

    1988-01-01

    The role of the metal ion in the oxidative decarboxylation of malate by chicken liver NADP malic enzyme and details of the reaction mechanism have been investigated by 13 C isotope effects. With saturating NADP and the indicated metal ion at a total concentration 10-fold higher than its K/sub m/, the following primary 13 C kinetic isotope effects at C 4 of malate [ 13 (VK/sub mal/)] were observed at pH 8.0: Mg 2+ , 1.0336; Mn 2+ , 1.0365; Cd 2+ , 1.0366; Zn 2+ , 1.0337; Co 2+ , 1.0283; Ni 2+ , 1.025. Knowing the partitioning of the intermediate oxalacetate between decarboxylation to pyuvate and reduction to malate allows calculation of the intrinsic carbon isotope effect for decarboxylation to pyuvate and reduction to malate allows calculation of the intrinsic carbon isotope effect for decarboxylation. For Mg 2+ as activator, this was 1.049 with NADP and 1.046 with 3-acetylpyridine adenine dinucleotide phosphate, although the intrinsic primary deuterium isotope effects on dehydrogenation were 5.6 and 4.2, and the partition ratios of the oxalacetate intermediate for decarboxylation as opposed to hydride transfer were 0.11 and 3.96. It was not possible to calculate reasonable intrinsic carbon isotope effects with the other metal ions by use of the partitioning ratio of oxalacetate because of decarboxylation by another mechanism. The variation of 13 (VK/sub mal/) with pH was used to dissect the total forward and external components. When the authors attempted to use the variation of 13 (VK/sub mal/) with solution viscosity to determine the internal and external commitments, incorrect values were obtained because of a specific effect of the viscosogen in decreasing the K/sub m/ for malate, so that VK/sub mal/ actually increased with viscosity instead of decreasing, as theory predicts

  7. Effect of coexistent hydrogen isotopes on tracer diffusion of tritium in alpha phase of group-V metal-hydrogen systems

    International Nuclear Information System (INIS)

    Sakamoto, Kan; Hashizume, Kenichi; Sugisaki, Masayasu

    2009-01-01

    Tracer diffusion coefficients of tritium in the alpha phase of group-V metal-hydrogen systems, α-MH(D)xTy (M=V and Ta; x>>y), were measured in order to clarify the effects of coexistent hydrogen isotopes on the tritium diffusion behavior. The hydrogen concentration dependence of such behavior and the effects of the coexistent hydrogen isotopes (protium and deuterium) were determined. The results obtained in the present (for V and Ta) and previous (for Nb) studies revealed that tritium diffusion was definitely dependent on hydrogen concentration but was not so sensitive to the kind of coexistent hydrogen isotopes. By summarizing those data, it was found that the hydrogen concentration dependence of the tracer diffusion coefficient of tritium in the alpha phase of group-V metals could be roughly expressed by a single empirical curve. (author)

  8. A model of the isotope effect of the oxide superconductor

    International Nuclear Information System (INIS)

    Zhang Liyuan.

    1989-03-01

    In this paper, a possible mechanism of producing negative correlation energy centers is proposed. Combining this electronic attractive potential with phonon mediated attractive potential between carriers the isotope effect exponent of La-Sr-Cu-O system is quantitatively explained. Generally, the isotope effect exponent is smaller than 1/2 in this mechanism. (author). 20 refs, 1 fig

  9. Solvent isotope effects on tautomerization equilibria of papain and model thiolamines

    International Nuclear Information System (INIS)

    Creighton, D.J.; Schamp, D.J.

    1980-01-01

    The state of ionization of the active site sulfhydryl group of papain at the pH-optimum of activity (pH approximately 6.5) remains a controversial issue. An alternative approach to the problem is reported here which utilizes the difference between the isotopic fractionation factor of the S-H bond (phi approximately equal to 0.4) and the N-H bond (phi = 0.97). In principle, the tautomerization equilibrium should be subject to an inverse solvent deuterium isotope effect in which the non-ionised form is more stable relative to the ionised form in D 2 O compared to H 2 O (K(H 2 O)/K(D 2 O) = phisub(SH)/phisub(MH) approximately equal to 0.4). This priniciple has been successfully tested on the tautomerization equilibria of cysteine and β-mercaptoethylamine from spectrophotometric titrations. To the extent that these simple thiolamines model the spectral properties of the tautomeric species envisioned in the active site of papain, the tautomerization equilibrium constant for papain is estimated (K(H 2 O) approximately equal to 2) from a comparison of the effect of solvent D 2 O on the mercaptide ion spectra of the thiolamines and the mercaptide ion-like difference absorption spectrum of papain. (Auth.)

  10. Synthesis of deuterium and tritium labelled tyrosine

    International Nuclear Information System (INIS)

    Kanska, M.; Drabarek, S.

    1980-01-01

    A new method of synthesis of tyrosine labelled with deuterium and tritium in the aromatic ring has been developed. Deuterated and tritiated tyrosine was obtained by isotope exchange between tyrosine and deuterated or tritiated water at elevated temperature in hydrochloric acid medium using K 2 PtCl 4 as a catalyst. For synthesis of tritiated tyrosine 1 Ci HTO was used; the specific activity of the product was 5 mCi/mMol. (author)

  11. Novel support effects on the mechanism of propene-deuterium: Addition and exchange reactions over dispersed ZrO2

    International Nuclear Information System (INIS)

    Naito, Shuichi; Tanimoto, Mitsutoshi

    1995-01-01

    The effect on the rate and mechanisms of propene-deuterium reactions of dispersing ZrO 2 on various supports such as silica, alumina, and titanium dioxide has been studied by microwave spectroscopic analysis of monodeuteropropene as well as by kinetic investigation. By dispersal of ZrO 2 on these supports, the rate of the C 3 H 6 -D 2 reactions is increased considerbly compared to that over unsupported ZrO 2 , with the decrease of activation energy. Hydrogen exchange in propene proceeds simultaneously with addition via the associative mechanism through n-propyl and s-propyl intermediates. Through XPS analysis of ZrO 2 /SiO 2 , it was found that a monolayer of ZrO 2 is formed over the silica support. The monolayer catalyst exhibits catalytic behavior quite different from that of unsupported ZrO 2 . On the other hand, alumina surfaces modified by ZrO 2 layers may be the main active sites in the case of ZrO 2 /Al 2 O 3 . The marked enhancement of the reaction rate in the lower loading region of ZrO 2 /TiO 2 may be explained by the strong interaction of atomically dispersed zirconium ions with active centers on TiO 2 . 28 refs., 10 figs., 1 tab

  12. Elimination of the effects of interferents on the quantitative determination of deuterium oxide in biological samples by infrared photometry

    International Nuclear Information System (INIS)

    Arnold, R.N.; Hentges, E.J.; Trenkle, A.

    1986-01-01

    Modifications to a procedure utilising sample purification by lyophilisation and automated infrared analysis were necessary to measure accurately the deuterium oxide content of various tissues and gastrointestinal tract contents of ruminants. Volatile fatty acids produced in the digestive tract of ruminants interfered with the measurement of deuterium oxide by infrared analysis. The volatile fatty acids were removed from samples by making the pH of the samples basic prior to lyophilisation. Contaminants in water extracted from tissues by lyophilisation of samples allowed the removal of the contaminants. The precision (Ssub(x-circumflex)) attained with this procedure was 3-6 mg l -1 for the range of deuterium oxide concentrations between 120 and 800 mg l -1 . (author)

  13. Radiation damage and deuterium trapping in deuterium-ion-irradiated Fe–9Cr alloy

    Energy Technology Data Exchange (ETDEWEB)

    Iwakir, Hirotomo, E-mail: iwakiri@edu.u-ryukyu.ac.jp [Faculty and Graduate School of Education, University of the Ryukyus, Nishihara, Okinawa 903-0213 (Japan); Tani, Munechika [Interdisciplinary Graduate School of Engineering Sciences, Kyusyu University, Kasuga, Fukuoka 816-8580 (Japan); Watanabe, Yoshiyuki [Japan Atomic Energy Agency, Rokkasho, Aomori 039-3212 (Japan); Yoshida, Naoaki [Research Institute for Applied Mechanics, Kyushu University, Kasuga, Fukuoka 816-8580 (Japan)

    2014-01-15

    Thermal desorption of deuterium (D{sub 2}) from deuterium-ion (D{sub 2}{sup +})-irradiated Fe–9Cr was correlated with the microstructural evolution of the alloy during irradiation with 8-keV D{sub 2}{sup +} ions following annealing to determine the retention and desorption behavior of the implanted deuterium and to identify effective traps for them, particularly at high temperature. After irradiation at 573 K, a new desorption stage formed between 650 and 1100 K at higher fluences, and cavities were observed using transmission electron microscopy. The total amount of trapped deuterium following irradiation with a fluence of 3.0 × 10{sup 22} ions/m{sup 2} was 6.8 × 10{sup 17} D{sub 2}/m{sup 2}, or approximately 0.007%. These results indicate that the deuterium atoms recombined to form D{sub 2} molecules at the surfaces of the cavities.

  14. Isotope effects on the optical spectra of semiconductors

    Science.gov (United States)

    Cardona, Manuel; Thewalt, M. L. W.

    2005-10-01

    Since the end of the cold war, macroscopic amounts of separated stable isotopes of most elements have been available “off the shelf” at affordable prices. Using these materials, single crystals of many semiconductors have been grown and the dependence of their physical properties on isotopic composition has been investigated. The most conspicuous effects observed have to do with the dependence of phonon frequencies and linewidths on isotopic composition. These affect the electronic properties of solids through the mechanism of electron-phonon interaction, in particular, in the corresponding optical excitation spectra and energy gaps. This review contains a brief introduction to the history, availability, and characterization of stable isotopes, including their many applications in science and technology. It is followed by a concise discussion of the effects of isotopic composition on the vibrational spectra, including the influence of average isotopic masses and isotopic disorder on the phonons. The final sections deal with the effects of electron-phonon interaction on energy gaps, the concomitant effects on the luminescence spectra of free and bound excitons, with particular emphasis on silicon, and the effects of isotopic composition of the host material on the optical transitions between the bound states of hydrogenic impurities.

  15. Pre-steady state transients in the Drosophila alcohol dehydrogenase catalyzed reaction: isotope effects and stereospecificity

    International Nuclear Information System (INIS)

    Place, A.R.; Eccleston, J.F.

    1987-01-01

    The alcohol dehydrogenase (ADH) isolated from Drosophila is unique among alcohol metabolizing enzymes by not requiring metals for catalysis, by showing 4-pro-S (B-sided) hydride transfer stereospecificity, and by possessing a greater catalytic turnover rate for secondary alcohols than for primary alcohols. They have extended their studies on the kinetic mechanism for this enzyme by examining the pre-steady state transients of ternary complex interconversion using stopped-flow fluorescence methods. When enzyme and a 30-fold molar excess of NADH is mixed with excess acetadehyde, methyl ethyl ketone (MEK), or cyclohexanone a rapid (> 100 s -1 ) transient is observe before the steady-state. The rates are insensitive to isotope substitution. With the substrate MEK, the rate and amplitude suggests a single turnover of the enzyme. Similar pre-steady state transients are observed when enzyme and a 50-fold molar excess of NAD + is mixed with ethanol, 2-propanol, and cyclohexanol. The rates show a hyperbolic concentration dependence and a deuterium isotope effect. With d 6 -deuteroethanol the transient no longer occurs in the pre-steady state. When the optical isomers of secondary alcohols are used as substrates, transients are observed only in the R-(-) isomers for all chain lengths. With 2-S(+)-heptanol and 2-S(+)-octanol no transients occur

  16. Separation of rate processes for isotopic exchange between hydrogen and liquid water in packed columns 10

    International Nuclear Information System (INIS)

    Butler, J.P.; Hartog, J. den; Goodale, J.W.; Rolston, J.H.

    1977-01-01

    Wetproofed platinum catalysts in packed columns promote isotopic exchange between counter-current streams of hydrogen saturated with water vapour and liquid water. The net rate of deuterium transfer from isotopically enriched hydrogen has been measured and separated into two rate processes involving the transfer of deuterium from hydrogen to water vapour and from water vapour to liquid. These are compared with independent measurements of the two rate processes to test the two-step successive exchange model for trickle bed reactors. The separated transfer rates are independent of bed height and characterize the deuterium concentrations of each stream along the length of the bed. The dependences of the transfer rates upon hydrogen and liquid flow, hydrogen pressure, platinum loading and the effect of dilution of the hydrophobic catalyst with inert hydrophilic packing are reported. The results indicate a third process may be important in the transfer of deuterium between hydrogen and liquid water. (author)

  17. Great isotope effects in compounding of sodium isotopes by macrocyclic polyether

    International Nuclear Information System (INIS)

    Knoechel, A.; Wilken, R.D.

    1978-01-01

    Isotope effects appear in the compounding of the two sodium isotopes 24 Na + and 22 Na + with macrocyclic polyethers, whose value was determined for the 13 best known polyethers. A radiometric process was used for determining the different half life periods of the nuclides used. To separate the compound and non-compound types, these were distributed between water and chloroform. The isotope ratio in the chloroform phase was compared with the output isotope ratio and the separation facfor determined from this. When using crown ethers, there was enrichment of 24 Na + by a significant amount (large crown ether) up to 3.1 +- 0.4% for 18 crown 6. The remarkably high results can be correlated by Biegeleisen's theory with other chemical conditions. There is a report on the first results of transferring these conditions to the H + /T + system. (orig.) [de

  18. Calcium hydroxide isotope effect in calcium isotope enrichment by ion exchange

    International Nuclear Information System (INIS)

    Jepson, B.E.; Shockey, G.C.

    1984-01-01

    The enrichment of calcium isotopes has been observed in ion-exchange chromatography with an aqueous phase of calcium hydroxide and a solid phase of sulfonic acid resin. The band front was exceedingly sharp as a result of the acid-base reaction occuring at the front of the band. Single-stage separation coefficients were found to be epsilon( 44 Ca/ 40 Ca) = 11 x 10 -4 and epsilon( 48 Ca/ 40 Ca) = 18 x 10 -4 . The maximum column separation factors achieved were 1.05 for calcium-44 and 1.09 for calcium-48 with the heavy isotopes enriching in the fluid phase. The calcium isotope effect between fully hydrated aqueous calcium ions and undissociated aqueous calcium hydroxide was estimated. For the calcium-44/40 isotope pair the separation coefficient was 13 x 10 -4 . 20 references, 2 figures

  19. Energy Levels of Hydrogen and Deuterium

    Science.gov (United States)

    SRD 142 NIST Energy Levels of Hydrogen and Deuterium (Web, free access)   This database provides theoretical values of energy levels of hydrogen and deuterium for principle quantum numbers n = 1 to 200 and all allowed orbital angular momenta l and total angular momenta j. The values are based on current knowledge of the revelant theoretical contributions including relativistic, quantum electrodynamic, recoil, and nuclear size effects.

  20. Isotope effect in the Knight shift of potassium

    International Nuclear Information System (INIS)

    Sahm, W.; Schwenk, A.

    1975-01-01

    The Knight shifts of the potassium isotopes 39 K and 41 K were determined with high accuracy: Ksup((39)) = 0.274 35(10)% and Ksup((41)) = 0.274 93(12)%. The relative isotope effect ΔK/K = -0.210 (20)% is in agreement with the hyperfine structure anomaly 39 Δ 41 . (orig.) [de

  1. Kinetic isotope effect studies on milk xanthine oxidase and on chicken liver xanthine dehydrogenase

    International Nuclear Information System (INIS)

    D'Ardenne, S.C.; Edmondson, D.E.

    1990-01-01

    The effect of isotopic substitution of the 8-H of xanthine (with 2 H and 3 H) on the rate of oxidation by bovine xanthine oxidase and by chicken xanthine dehydrogenase has been measured. V/K isotope effects were determined from competition experiments. No difference in H/T (V/K) values was observed between xanthine oxidase and xanthine dehydrogenase. Xanthine dehydrogenase exhibited a larger T/D (V/K) value than that observed for xanthine oxidase. Observed H/T (V/K) values for either enzyme are less than those H/T (V/K) values calculated with D/T (V/K) data. These discrepancies are suggested to arise from the presence of a rate-limiting step(s) prior to the irreversible C-H bond cleavage step in the mechanistic pathways of both enzymes. These kinetic complexities preclude examination of whether tunneling contributes to the reaction coordinate for the H-transfer step in each enzyme. No observable exchange of tritium with solvent is observed during the anaerobic incubation of [8- 3 H]xanthine with either enzyme, which suggests the reverse commitment to catalysis (C r ) is essentially zero. With the assumption of adherence to reduced mass relationships, the intrinsic deuterium isotope effect ( D k) for xanthine oxidation is calculated. By the use of these values and steady-state kinetic data, the minimal rate for the hydrogen-transfer step is calculated to be ∼75-fold faster than k cat for xanthine oxidase and ∼10-fold faster than k cat for xanthine dehydrogenase. Values calculated for each enzyme were found to be identical within experimental uncertainty

  2. Diffusion of hydrogen, deuterium, and tritium in niobium

    International Nuclear Information System (INIS)

    Matusiewicz, G.R.

    1981-01-01

    The diffusion of hydrogen in niobium was investigated over the temperature range 148 to 500 degrees Kelvin, using measurements of the elastic after effect caused by long range diffusion (the Gorsky Effect). Relaxation curves for pure annealed niobium were generally not of the single exponential form expected from the Gorsky Effect theory, but were described well by a sum of two exponential curves with different amplitudes and relaxation times. The effects of oxygen and nitrogen interstitials on the diffusion were studied and were not in agreement with conventional trapping models. Deuterium and tritium diffusion in niobium were also studied, and a non-classical isotope effect was observed. Hydrogen diffusion coefficients in several Nb-Ta alloys were measured, and the diffusivity in all these alloys exhibited a non-Arrhenius temperature dependence. Experimental results were compared to several models for diffusion and trapping. A model is presented which can account for the form of the relaxation curves observed in pure, annealed niobium

  3. Recent experimental results on solutions of deuterium in lithium

    International Nuclear Information System (INIS)

    Ihle, H.R.; Wu, C.H.

    1976-01-01

    The existence of a number of stable molecules containing lithium and hydrogen isotopes in the saturated vapor over dilute solutions of hydrogen isotopes in lithium causes an unexpectedly high density of hydrogen isotopes in the vapor at high temperature. An evaluation of the partial pressures of the gas species Li, Li 2 , LiD, Li 2 D, LiD 2 and D 2 over solutions of deuterium in lithium measured in the temperature range 770 to 970 0 K, and extrapolation to higher temperatures, leads to the conclusion that the ratio of the atom fraction of deuterium in the gas to its atom fraction in the liquid exceeds unity above approximately 1240 0 K; this ratio is independent of the deuterium atom fraction in the liquid at low concentrations. Therefore the thermodynamic supposition that hydrogen isotopes can be separated from lithium by fractional distillation even at extremely low concentration exists. A direct verification of this phenomenon was made by Rayleigh distillation of Li-D solutions in the temperature range 970 to 1600 0 K. These measurements yield also the ratio of the deuterium atom fraction in the gas to that in the liquid and are in good agreement with the data obtained by extrapolation of partial pressures. The enrichment and depletion of deuterium in dependence on the number of theoretical plates of a distillation column at total reflux is calculated using the results

  4. Symmetry effects in neutron scattering from isotopically enriched Se isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Lachkar, J.; Haouat, G.; McEllistrem, M. T.; Patin, Y.; Sigaud, J.; Cocu, F.

    1975-06-01

    Differential cross sections for neutron elastic and inelastic scattering from {sup 76}Se, {sup 78}Se, {sup 80}Se and {sup 82}Se, have been measured at 8-MeV incident neutron energy and from {sup 76}Se and {sup 82}Se at 6- and 10-MeV incident energies. The differences observed in the elastic scattering cross sections are interpretable as the effects of isospin term in the scattering potentials. A full analysis of the elastic scattering data are presented.

  5. Chemical and isotopic composition of precipitations in Syria

    International Nuclear Information System (INIS)

    Abou Zakhem, B.; Hafez, R.

    2007-05-01

    The objective of this study is to determine isotopic characteristics of precipitation, the climatic and geographical conditions affecting isotopic composition in order to obtain the input function of groundwater to evaluate the water resources.13 meteoric stations were selected in Syria for cumulative monthly rainfall sampling during two hydrological cycles; 1991-1992 and 1992-1993. The chemical and isotopic compositions of monthly precipitation were studied. The winter and spring rainfall isotopic characteristics were determined, in addition to the Syrian meteoric line (SMWL) was estimated with a slope of 6.62 and that of both Syria and Jordan of 6.73. The effect of climatic factors as temperature and relative air humidity on oxygen-18, deuterium and d-excess were studied and it was found that the relationship between temperature and oxygen-18 and deuterium is a positive linear correlation; however, it is a negative correlation with d-excess. The mean seasonal variation amplitude of 18 O was about 6%, and the amount effect on isotopic content of precipitation was studied. The geographic factors and its affect on isotopic contents of precipitation such as altitude were considered, furthermore, the isotopic gradient with altitude was determined for both oxygen-18 and deuterium (-0.14 % and -0.84% /100m respectively). The spatial distribution of oxygen-18, deuterium, tritium and d-excess indicted the effect of mountain chains and gaps between mountains on the isotopic content, the continental effect on tritium build-up by about 33% per 100 Km from the coast. The increase of d-excess values towards the south west proves the eastern Mediterranean climate type over this region.(author)

  6. Effect of deuterium on the circadian period and metabolism in wild-type and tau mutant Syrian hamsters

    NARCIS (Netherlands)

    Oklejewicz, M; Hut, RA; Daan, S

    2000-01-01

    Homozygous tau mutant Syrian hamsters (tau-/-) have a free-running circadian period (tau) around 20 h and a proportionally higher metabolic rate compared with wild-type hamsters (tau+/+) with a period of circa 24 h. In this study, we applied deuterium oxide (D2O) to hamsters to test whether

  7. Uranium isotopic effect studies on cation and anion exchange resins

    International Nuclear Information System (INIS)

    Sarpal, S.K.; Gupta, A.R.

    1975-01-01

    Uranium isotope effects in exchange reactions involving hexavalent and tetravalent uranium, on ion exchange resins, have been re-examined. The earlier work on uranium isotope effects in electron exchange reactions involving hexavalent and tetravalent uranium, has been critically reviewed. New experimental data on these systems in hydrochloric acid medium, has been obtained, using break-through technique on anion-exchange columns. The isotope effects in these break-through experiments have been reinterpreted in a way which is consistent with the anion exchange behaviour of the various uranium species in these systems. (author)

  8. Theory of the isotope effect in superconducting compounds

    International Nuclear Information System (INIS)

    Culetto, F.J.; Rainer, D.

    1978-05-01

    We present a theoretical analysis of the isotope effect on the superconducting transition temperature. Our method is to calculate via formal perturbation theory the response of the transition temperature to small changes of the masses of the various constituents of the compound. We discuss the relation between the isotope effect and various more fundamental parameters in strong coupling superconductors. As illustrative examples, we consider the systems Pd-H(D) alloys and the binary Chevrel phase superconductor Mo 6 Se 8 , and show that analysis of the isotope effect can yield useful information concerning interaction mechanisms in these compounds. (orig.)

  9. Biosynthetic effects on the stable carbon isotopic compositions of agal lipids: Implications for deciphering the carbon isotopic biomarker record

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Schouten, S.; Klein Breteler, W.C.M.; Blokker, P.; Schogt, N.; Rijpstra, W.I.C.; Grice, K.; Baas, M.

    1998-01-01

    Thirteen species of algae covering an extensive range of classes were cultured and stable carbon isotopic compositions of their lipids were analysed in order to assess carbon isotopic fractionation effects during their biosynthesis. The fatty acids were found to have similar stable carbon isotopic

  10. Calculations of kinetic isotope effects in the Hofmann eliminations of substituted (2-phenylethyl)trimethylammonium ions

    International Nuclear Information System (INIS)

    Lewis, D.E.; Sims, L.B.; Yamataka, H.; McKenna, J.

    1980-01-01

    Theoretical calculations of kinetic isotope effects (KIE) for the Hofmann elimination of the (2-phenylethyl)trimethylammonium ion (I,Z = H) have been carried out for an extensive series of transition-state models encompassing the Elcb-like region of the E2 mechanistic spectrum. The reaction coordinate employed corresponded to the irreversible fragmentation of the base-H'-C/sub β/-C/sub α/-N system, with proton transfer being the dominant contributor. Structural parameters (bond distances and angles) were related to the independent bond orders n/sub α-N/ and n/sub β-H'/ by empirical and semiempirical relationships. The most probable transition-state structure for the reaction was determined by interpolation of the experimental values for the β-D 2 and 15 N KIE into plots of the trends of the calculated KIE. The nonsolvated models obtained in this manner gave only poor agreement between calculated and experimental secondary deuterium (α-D 2 ) and leaving group deuterium [N(CD 3 )/sub x/(CH 3 )/sub 3-x/, x = 1 to 3) KIE; explicit consideration of differential solvation of the reactant and transition state afforded the most chemically reasonable resolution of these discrepancies. Using solvated models, transition-state structures were also determined for the Hofmann elimination of parasubstituted derivatives of I (Z = OCH 3 , Cl, CF 3 ). These transition states are related by a shift parallel to the central E2 diagogonal of an O'Ferrall-Jencks reaction diagram, as predicted by Thorton, indicating that, in the absence of other factors (differing solvent or base, etc.), the extent to which negative charge is accumulated at Cβ in the transition state is solely a factor of the leaving group. Both independent bond orders (n/sub α-N/ and n/sub β-H'/) exhibit a linear dependence on the sigma value of the substituent, allowing for the first time prediction of transition states

  11. Calculation of doublet capture rate for muon capture in deuterium within chiral effective field theory

    Czech Academy of Sciences Publication Activity Database

    Adam, Jiří; Tater, Miloš; Truhlík, Emil; Epelbaum, E.; Machleidt, R.; Ricci, P.

    2012-01-01

    Roč. 709, 1-2 (2012), s. 93-100 ISSN 0370-2693 R&D Projects: GA MŠk LC06002; GA ČR GAP203/11/0701 Institutional support: RVO:61389005 Keywords : negative muon capture * deuteron * effective field theory * meson exchange currents Subject RIV: BE - Theoretical Physics Impact factor: 4.569, year: 2012

  12. Isotope effect in gamma-radiolysis of absorbed ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Lyapina, T G; Kotov, A G [Nauchno-Issledovatel' skij Fiziko-Khimicheskij Inst., Moscow (USSR)

    1975-07-01

    The radiolysis of NH/sub 3/ of various isotopic compounds adsorbed on silica gel or zeolite at 77degK was studied. Experimental data were treated using the kinetic equation dR/dt=GI-kIR where R=radical concentration, G=radical yield, k=radical termination constant and I=radiation dose rate. Both the values of G and R for NH/sub 3/ adsorbed on silica gel are affected by the isotopic effect of /sup 15/N, but not on zeolite. The isotopic effect is explained by the influence of protonated acidity of the silica gel surface.

  13. Isotopic effects in mechanistic studies of biotransformations of fluorine derivatives of L-alanine catalysed by L-alanine dehydrogenase

    International Nuclear Information System (INIS)

    Szymańska-Majchrzak, Jolanta; Pałka, Katarzyna; Kańska, Marianna

    2017-01-01

    Synthesis of 3-fluoro-[2- 2 H]-L-alanine (3-F-[ 2 H]-L-Ala) in reductive amination of 3-fluoropyruvic acid catalysed by L-alanine dehydrogenase (AlaDH) was described. Fluorine derivative was used to study oxidative deamination catalysed by AlaDH applied kinetic (for 3-F-L-Ala in H 2 O - KIE’s on V max : 1.1; on V max /K M : 1.2; for 3-F-L-Ala in 2 H 2 O – on V max : 1.4; on V max /K M : 2.1) and solvent isotope effect methods (for 3-F-L-Ala - SIE’s on V max : 1.0; on V max /K M : 0.87; for 3-F-[2- 2 H]-L-Ala – on V max : 1.4; on V max /K M : 1.5). Studies explain some details of reaction mechanism. - Highlights: • Synthesis of 3-fluoro-[2- 2 H]-L-alanine was performed. • The reactions were catalysed using the enzyme L-alanine dehydrogenase. • Performed reactions involved fluorinated analogues of L-alanine. • Solvent isotope effects of deuterium were determined. • Kinetic isotope effects were determined for obtained 3-fluoro-L-alanine. • The mechanism of reaction catalysed by L-alanine dehydrogenase was proposed.

  14. Isotope exchange reaction on solid breeder materials

    International Nuclear Information System (INIS)

    Baba, A.; Nishikawa, M.; Eguchi, T.; Kawagoe, T.

    2000-01-01

    Lithium ceramic materials such as Li 2 O, LiAlO 2 , Li 2 ZrO 3 , Li 2 TiO 3 and Li 4 SiO 4 are considered to be as candidate for the tritium breeding material in a deuterium-tritium (D-T) fusion reactor. In the recent blanket designs, helium gas with hydrogen or deuterium is planned to be used as the blanket purge gas to reduce tritium inventory and promote tritium release from the breeding material. In addition, the rate of isotope exchange reaction between hydrogen isotopes in the purge gas and tritium on the surface of the breeding material is necessary to analyze the tritium release behavior from the breeding materials. However, the rate of isotope exchange reactions between hydrogen isotopes in the purge gas and tritium on the surface of those materials has not been quantified until recently. Recently, the present authors quantified the rate of isotope exchange reaction on Li 2 O and Li 2 ZrO 3 . The overall mass transfer coefficients representing the isotope exchange reaction between H 2 and D 2 O on breeding materials or the same between D 2 and H 2 O are experimentally obtained in this study. Comparison to isotope exchange reaction rates on various breeding materials is also performed in this study. Discussions about the effects of temperature, concentration of hydrogen in the purge gas or flow rate of the purge gas on the conversion of tritiated water to tritium gas are also performed

  15. Stable isotope aided evaluation of Community Nutrition Program: effect of food supplementation schemes on maternal and infant nutritional status

    International Nuclear Information System (INIS)

    Sarr Cisse, Aita; Dossou, Nicole; Ndiaye, Mamadou

    2002-01-01

    The supplementation program of the community nutrition project (PNC) launched by the Senegalese Government in order to protect the most vulnerable groups (children and women) was evaluated. Using a stable isotope (deuterium), we assessed the effect of the PNC on breastmilk output, mother's body composition, and baby's growth at three months of lactation. Breastmilk triglycerides, lactose, protein, and zinc were also determined. Mothers who were supplemented more than 60 days during pregnancy showed a significant increase in fot- free mass as compared to those who were supplemented for less than 30 days (p= .03). Breastmilk output was not influenced by the supplementation, but breastmilk lactose, total protein, and zinc contents increased significantly (p < .01) in the supplemented mothers. Growth of the babies of the supplemented mothers was better than that of those whose mothers were not supplemented. It was concluded that the food supplementation had beneficial effects on both mothers' and babies' nutritional status depending on the onset of the supplementation.

  16. Absence of isotope effect of diffusion in a metallic glass

    International Nuclear Information System (INIS)

    Heesemann, A.; Raetzke, K.; Faupel, F.; Hoffmann, J.; Heinemann, K.

    1995-01-01

    The isotope effect E = d ln(D)/d ln (1/√m) of Co diffusion in structurally relaxed Co 86 Zr 14 and Co 81 Zr 19 glasses has been measured by means of a radiotracer technique. Within experimental accuracy no isotope effect was detected (E < 0.04). This suggests a highly cooperative diffusion mechanism. The connection between diffusion and collective low-frequency relaxations in glasses is discussed. (orig.)

  17. Comparison of the carcinogenic effectiveness in mouse skin of methyl- and ethylnitrosourea, nitrosourethane and nitrosonitro-guanidine and the effect of deuterium labeling

    International Nuclear Information System (INIS)

    Lijinsky, W.

    1982-01-01

    The carcinogenic activities of a number of directly acting methylating and ethylating agents have been compared by mouse skin painting in acetone solution. Nitrosomethylurethane and nitrosoethylurethane failed to induce tumors after greater than 60 weeks treatment. Nitrosomethylurea was somewhat more effective than nitrosoethylurea, as measured by the longer latent period than nitrosoethylurea, as measured Nitrosomethylnitroguanidine, by the same measure, was a weaker carcinogen than nitrosoethylnitroguanidine at both dose levels used (0.02 M and 0.008 M); the latter compound was the most potent skin carcinogen of those examined. There was no significant difference in carcinogenic effectiveness when the alkyl group of the nitrosoureas or the nitronitrosoguanidines contained deuterium instead of hydrogen, which supports the concept that alkylation of cellular macromolecules by the intact alkyl group is responsible for carcinogenesis by these compounds

  18. Atmospheric influence on the deuterium excess signal in polar firn - implications for ice core interpretation

    NARCIS (Netherlands)

    Schlosser, Elisabeth; Oerter, H.; Masson-Delmotte, V.; Reijmer, C.H.

    2008-01-01

    The seasonal deuterium excess signal of fresh snow samples from Neumayer station, coastal Dronning Maud Land, Antarctica, was studied to investigate the relationship between deuterium excess and precipitation origin. An isotope model was combined with a trajectory model to determine the relative

  19. Mass-independent isotope effects in chemical exchange reaction

    International Nuclear Information System (INIS)

    Nishizawa, Kazushige

    2000-01-01

    Isotope effects of some elements in chemical exchange reaction were investigated by use of liquid-liquid extraction, liquid membrane or chromatographic separation. Cyclic polyether was used for every method. All polyethers used in a series of the studies were made clear that they distinguished the isotopes not only by their nuclear masses but also by their nuclear sizes and shapes. Chromium isotopes, for example, were recognized to have enrichment factors being proportional to δ 2 > which is a parameter to show field shift or the nuclear size and shape of the isotope. It follows that the chromium isotopes are separated not by their masses but by their field shift effects. Nuclear spin also played a great role to separate odd mass number isotopes from even mass number isotopes in even atomic number elements. Contribution of the nuclear spin (I=3/2) of 53 Cr to total enrichment factor, ε 53/52 = -0.00028, for 53 Cr to 52 Cr was observed to be, ε spin = -0.0025. (author)

  20. H/D Isotope Effects in Hydrogen Bonded Systems

    Directory of Open Access Journals (Sweden)

    Aleksander Filarowski

    2013-04-01

    Full Text Available An extremely strong H/D isotope effect observed in hydrogen bonded A-H…B systems is connected with a reach diversity of the potential shape for the proton/deuteron motion. It is connected with the anharmonicity of the proton/deuteron vibrations and of the tunneling effect, particularly in cases of short bridges with low barrier for protonic and deuteronic jumping. Six extreme shapes of the proton motion are presented starting from the state without possibility of the proton transfer up to the state with a full ionization. The manifestations of the H/D isotope effect are best reflected in the infra-red absorption spectra. A most characteristic is the run of the relationship between the isotopic ratio nH/nD and position of the absorption band shown by using the example of NHN hydrogen bonds. One can distinguish a critical range of correlation when the isotopic ratio reaches the value of ca. 1 and then increases up to unusual values higher than . The critical range of the isotope effect is also visible in NQR and NMR spectra. In the critical region one observes a stepwise change of the NQR frequency reaching 1.1 MHz. In the case of NMR, the maximal isotope effect is reflected on the curve presenting the dependence of Δd (1H,2H on d (1H. This effect corresponds to the range of maximum on the correlation curve between dH and ΔpKa that is observed in various systems. There is a lack in the literature of quantitative information about the influence of isotopic substitution on the dielectric properties of hydrogen bond except the isotope effect on the ferroelectric phase transition in some hydrogen bonded crystals.

  1. Glutathione reductase: solvent equilibrium and kinetic isotope effects

    International Nuclear Information System (INIS)

    Wong, K.K.; Vanoni, M.A.; Blanchard, J.S.

    1988-01-01

    Glutathione reductase catalyzes the NADPH-dependent reduction of oxidized glutathione (GSSG). The kinetic mechanism is ping-pong, and we have investigated the rate-limiting nature of proton-transfer steps in the reactions catalyzed by the spinach, yeast, and human erythrocyte glutathione reductases using a combination of alternate substrate and solvent kinetic isotope effects. With NADPH or GSSG as the variable substrate, at a fixed, saturating concentration of the other substrate, solvent kinetic isotope effects were observed on V but not V/K. Plots of Vm vs mole fraction of D 2 O (proton inventories) were linear in both cases for the yeast, spinach, and human erythrocyte enzymes. When solvent kinetic isotope effect studies were performed with DTNB instead of GSSG as an alternate substrate, a solvent kinetic isotope effect of 1.0 was observed. Solvent kinetic isotope effect measurements were also performed on the asymmetric disulfides GSSNB and GSSNP by using human erythrocyte glutathione reductase. The Km values for GSSNB and GSSNP were 70 microM and 13 microM, respectively, and V values were 62 and 57% of the one calculated for GSSG, respectively. Both of these substrates yield solvent kinetic isotope effects greater than 1.0 on both V and V/K and linear proton inventories, indicating that a single proton-transfer step is still rate limiting. These data are discussed in relationship to the chemical mechanism of GSSG reduction and the identity of the proton-transfer step whose rate is sensitive to solvent isotopic composition. Finally, the solvent equilibrium isotope effect measured with yeast glutathione reductase is 4.98, which allows us to calculate a fractionation factor for the thiol moiety of GSH of 0.456

  2. Dynamic isotope effect on the product energy partitioning in CH2OH+→CHO++H2

    Science.gov (United States)

    Rhee, Young Min; Kim, Myung Soo

    1998-10-01

    The deuterium isotope effect on the product energy partitioning in the title reaction was investigated both experimentally and theoretically. The measured kinetic energy release (KER) showed a significant dependence on the position of deuteration. A reliable potential energy surface of the reaction was constructed from ab initio results using the recently developed interpolation algorithm. The classical trajectory calculation on this surface well reproduced the experimental finding. Close inspection of the potential energy surface revealed that the isotope effect on KER and the product rotations arose from the alteration of the symmetry of the reaction path near the transition state induced by the mass change upon isotopic substitution. The product vibrations were found to be affected by the change in the coupling constants which also arose from the mass-dependent change in the reaction path. Possibility of the quantum mechanical tunneling was also considered. Tunneling-corrected classical trajectory results were in excellent agreement with the experimental ones, indicating that the reaction proceeds via barrier penetration below the threshold.

  3. Loss of deuterium in faecal solids and by sequestration in reindeer: effect on doubly labelled water studies

    Directory of Open Access Journals (Sweden)

    Geir Gotaas

    2000-03-01

    Full Text Available An underlying assumption when estimating total energy expenditure (TEE using doubly labelled water (DLW is that the injected isotopes (lsO and 2H leave the body only in the form of CO, and H20. However, both isotopes have additional routes of loss. We quantified the loss of 2H (i attached to faecal solids and (ii by sequestration into newly synthesised fat in reindeer (Rangifer tarandus tarandus. Estimates of the errors caused by these processes were applied to data from DLW studies with reindeer in summer and in winter. Given the net rate of faecal dry matter output and lipid synthesis in the present study, ignoring both sources of error caused the TEE of reindeer to be underestimated by approximately 5% in winter and approximately 9% in summer. The separate effect of each source of error was evaluated in summer. If ignored, loss of 2H through sequestration alone caused TEE to be underestimated by approximately 3.7%. Similarly, if ignored, loss of 2H attached to faecal solids alone caused TEE to be underestimated by approximately 5.9%.

  4. Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

    Science.gov (United States)

    Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

    2015-05-27

    The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations.

  5. Bibliography on vapor pressure isotope effects

    International Nuclear Information System (INIS)

    Jancso, G.

    1980-04-01

    The first Bibliography on Vapour Pressure Isotope and covered the literature of the period from 1919 through December 1975. The present Supplement reviews the literature from January 1976 through December 1979. The bibliography is arranged in chronological order; within each year the references are listed alphabetically according to the name of the first author of each work. (author)

  6. Hydrogen/deuterium exchange in mass spectrometry.

    Science.gov (United States)

    Kostyukevich, Yury; Acter, Thamina; Zherebker, Alexander; Ahmed, Arif; Kim, Sunghwan; Nikolaev, Eugene

    2018-03-30

    The isotopic exchange approach is in use since the first observation of such reactions in 1933 by Lewis. This approach allows the investigation of the pathways of chemical and biochemical reactions, determination of structure, composition, and conformation of molecules. Mass spectrometry has now become one of the most important analytical tools for the monitoring of the isotopic exchange reactions. Investigation of conformational dynamics of proteins, quantitative measurements, obtaining chemical, and structural information about individual compounds of the complex natural mixtures are mainly based on the use of isotope exchange in combination with high resolution mass spectrometry. The most important reaction is the Hydrogen/Deuterium exchange, which is mainly performed in the solution. Recently we have developed the approach allowing performing of the Hydrogen/Deuterium reaction on-line directly in the ionization source under atmospheric pressure. Such approach simplifies the sample preparation and can accelerate the exchange reaction so that certain hydrogens that are considered as non-labile will also participate in the exchange. The use of in-ionization source H/D exchange in modern mass spectrometry for structural elucidation of molecules serves as the basic theme in this review. We will focus on the mechanisms of the isotopic exchange reactions and on the application of in-ESI, in-APCI, and in-APPI source Hydrogen/Deuterium exchange for the investigation of petroleum, natural organic matter, oligosaccharides, and proteins including protein-protein complexes. The simple scenario for adaptation of H/D exchange reactions into mass spectrometric method is also highlighted along with a couple of examples collected from previous studies. © 2018 Wiley Periodicals, Inc.

  7. Isotopic effects on phonon anharmonicity in layered van der Waals crystals: Isotopically pure hexagonal boron nitride

    Science.gov (United States)

    Cuscó, Ramon; Artús, Luis; Edgar, James H.; Liu, Song; Cassabois, Guillaume; Gil, Bernard

    2018-04-01

    Hexagonal boron nitride (h -BN) is a layered crystal that is attracting a great deal of attention as a promising material for nanophotonic applications. The strong optical anisotropy of this crystal is key to exploit polaritonic modes for manipulating light-matter interactions in 2D materials. h -BN has also great potential for solid-state neutron detection and neutron imaging devices, given the exceptionally high thermal neutron capture cross section of the boron-10 isotope. A good knowledge of phonons in layered crystals is essential for harnessing long-lived phonon-polariton modes for nanophotonic applications and may prove valuable for developing solid-state 10BN neutron detectors with improved device architectures and higher detection efficiencies. Although phonons in graphene and isoelectronic materials with a similar hexagonal layer structure have been studied, the effect of isotopic substitution on the phonons of such lamellar compounds has not been addressed yet. Here we present a Raman scattering study of the in-plane high-energy Raman active mode on isotopically enriched single-crystal h -BN. Phonon frequency and lifetime are measured in the 80-600-K temperature range for 10B-enriched, 11B-enriched, and natural composition high quality crystals. Their temperature dependence is explained in the light of perturbation theory calculations of the phonon self-energy. The effects of crystal anisotropy, isotopic disorder, and anharmonic phonon-decay channels are investigated in detail. The isotopic-induced changes in the phonon density of states are shown to enhance three-phonon anharmonic decay channels in 10B-enriched crystals, opening the possibility of isotope tuning of the anharmonic phonon decay processes.

  8. Inverse isotope effect in iron-based superconductor

    International Nuclear Information System (INIS)

    Shirage, Parasharam M.; Kihou, Kunihiro; Miyazawa, Kiichi; Lee, Chul-Ho; Kito, Hijiri; Yoshida, Yoshiyuki; Eisaki, Hiroshi; Tanaka, Yasumoto; Iyo, Akira

    2010-01-01

    We have found that (Ba, K)Fe 2 As 2 superconductor (a transition temperature, T c ∼ 38 K) shows an inverse Iron isotope effect (α Fe = -0.18 ± 0.03, where T c ∼ M -αFe and M is the iron isotope mass), i.e. the sample containing the larger iron mass depicts higher T c . Systematic studies using three types of Fe-isotopes ( 54 Fe, natural Fe and 57 Fe) reveal a clear inverse shift on T c by measurements of temperature dependent magnetization and resistivity. The inverse isotope effect that is the first case in high-T c superconductors strongly suggests that superconducting mechanism of the iron-based system is not explained by conventional BCS theory mediated by phonons.

  9. Airborne Observations of Water Vapor Deuterium Excess in the Mid-Latitude Lower Troposphere

    Science.gov (United States)

    Salmon, O. E.; Welp, L.; Shepson, P. B.; Stirm, B. H.

    2017-12-01

    Water vapor is responsible for over half of the natural atmospheric greenhouse effect. As global temperatures increase due to fossil fuel combustion, atmospheric water vapor concentrations are also expected to increase in positive feedback. Additionally, studies have shown that urban areas can influence humidity levels, and the frequency and intensity of precipitation events. It is thus important to understand anthropogenic modification of the hydrological cycle, particularly around urban areas, where over half of the world's population resides. Airborne measurements of water vapor isotopologues containing 2H and 18O were conducted to better understand processes influencing atmospheric moisture levels around urban areas. Airborne measurements were conducted around the Indianapolis and Washington, D.C.-Baltimore areas during afternoon hours in February and March 2016, using a Los Gatos Research Water Vapor Isotope Analyzer installed in Purdue University's experimental aircraft, the Airborne Laboratory for Atmospheric Research. The measurements of 2H and 18O allow for the calculation of deuterium excess (= δ2H - 8*δ18O), which provides information about non-equilibrium processes, such as kinetic effects, air parcel mixing, and transpiration. There are few studies that have reported observations of deuterium excess above the surface level ( 100 m). During the measurement campaign, vertical profiles were frequently conducted from 300 m above the ground to an altitude of approximately 1.5 km, effectively characterizing water vapor isotope profiles spanning the boundary layer and lower free troposphere. Measurements probed the transition from planetary boundary layer air to free troposphere air to provide high resolution deuterium excess information across this interface. Processes such as Rayleigh distillation, atmospheric mixing, and surface fluxes potentially impacting water vapor deuterium excess through the boundary layer and free troposphere with be discussed.

  10. Generalized transition state theory. Quantum effects for collinear reactions of hydrogen molecules and isotopically substituted hydrogen molecules

    International Nuclear Information System (INIS)

    Garrett, B.C.; Truhlar, D.G.

    1979-01-01

    Canonical variational transition state theory, microcanonical variational transition state theory, and Miller's unified statistical theory were used in an attempt to correct two major deficiencies of the conventional transition state theory. These are: (1) the necessity of extra assumptions to include quantum mechanical tunneling effects and (2) the fundamental assumption that trajectories crossing a dividing surface in phase space proceed directly to products. The accuracy of these approximate methods were tested by performing calculations for several collinear reactions of hydrogen, deuterium, chlorine, or iodine, with five isotopes of hydrogen molecules and comparison of these results with those from accurate quantitative calculations of the reaction probabilities as functions of energy and of the thermal rate constants as functions of temperature. 49 references, 28 figures, 17 tables

  11. Neutrino disintegration of deuterium

    International Nuclear Information System (INIS)

    Ying, S.; Haxton, W.; Henley, E.M.

    1989-01-01

    We calculate the rate of both neutral- and charged-current neutrino and antineutrino disintegration of deuterium. These rates are of interest for solar 8 B and hep ( 3 He + p) spectra and supernovae neutrinos, and are relevant for the Sudbury Neutrino Observatory (SNO)

  12. Deuterium in atmospheric cycle

    International Nuclear Information System (INIS)

    Pontikis, M.C.

    Interest of the study concerning the deuterium content variation (HDO) in the atmospheric water. Standards and measurement methods. Molecule HDO cycle in the atmospheric water. Application to the study of hail-generating cumulus-nimbus and of the mantle of snow [fr

  13. Retention and features of deuterium detrapping from radiation-induced damages in steels

    International Nuclear Information System (INIS)

    Tolstolutskaya, G.D.; Ruzhytskiy, V.V.; Karpov, S.A.; Kopanets, I.E.

    2009-01-01

    The accelerators and ion-beam analysis techniques are used for simulation of displacement damage and detailed investigation of distribution profiles of damage and impurity gas atoms (especially helium and hydrogen) in the irradiation of targets for a wide ranges of doses and particle energies. The influence of preimplanted helium and heavy ion-induced damage on deuterium trapping in austenitic and ferritic/martensitic steels was studied. The results obtained for 18Cr10NiTi stainless steel show that ion-implanted deuterium is weakly trapped by defects produced in 5 keV D + displacement cascades. The effective trapping temperature interval is between 300 and 600 K. The characteristics of trapping and the temperature range of hydrogen isotopes retention in traps formed by prior implantation of helium depend on the concentration of implanted helium and on the type of defects developed. The formation of helium bubbles in 18Cr10NiTi steel causes an order of magnitude increase in the content of retained deuterium atoms in the range of temperature 300-600 K and extends the interval of effective trapping temperatures to 1000 K. Energetic heavy-ion irradiation (1.4 MeV Ar + ) has been used for modeling defect cluster formation under displacement cascade conditions to simulate fusion reactor environments. It was found that retention of hydrogen and deuterium strongly increased in this case. It is shown that the presence of a surface-passive film considerably shifts the gas release interval to higher temperatures and reduces the deuterium surface recombination coefficient by several orders of magnitude.

  14. Isotopic research in Antarctica

    International Nuclear Information System (INIS)

    Schuetze, H.

    1983-01-01

    Since 1978 scientists of the Central Institute of Isotope- and Radiation Research of the Academy of Sciences of the GDR have participated in antarctic research. Substantial results have been achieved in research on isotope ratios, on the dynamics of water resources, on concentration of deuterium in lichens, and on age determination of a mummified seal and a penguin colony

  15. Stable isotopes labelled compounds

    International Nuclear Information System (INIS)

    1982-09-01

    The catalogue on stable isotopes labelled compounds offers deuterium, nitrogen-15, and multiply labelled compounds. It includes: (1) conditions of sale and delivery, (2) the application of stable isotopes, (3) technical information, (4) product specifications, and (5) the complete delivery programme

  16. Stable-isotope composition of the water of apple juice

    International Nuclear Information System (INIS)

    Bricout, Jacques; Merlivat, Liliane

    1973-01-01

    By deuterium and oxygen 18 analysis, it was shown that apples' water is enriched in heavier isotopes as compared to rain water. The isotopic composition of the water of reconstituted apple juice is closed to the isotopic content of the rain water used for dilution. Thus, deuterium and oxyden 18 analysis allows a good analytical distinction between natural apple juice and reconstituted juices [fr

  17. Physics of high performance deuterium-tritium plasmas in TFTR

    International Nuclear Information System (INIS)

    McGuire, K.M.; Batha, S.

    1996-11-01

    During the past two years, deuterium-tritium (D-T) plasmas in the Tokamak Fusion Test Reactor (TFTR) have been used to study fusion power production, isotope effects associated with tritium fueling, and alpha-particle physics in several operational regimes. The peak fusion power has been increased to 10.7 MW in the supershot mode through the use of increased plasma current and toroidal magnetic field and extensive lithium wall conditioning. The high-internal-inductance (high-I i ) regime in TFTR has been extended in plasma current and has achieved 8.7 MW of fusion power. Studies of the effects of tritium on confinement have now been carried out in ohmic, NBI- and ICRF- heated L-mode and reversed-shear plasmas. In general, there is an enhancement in confinement time in D-T plasmas which is most pronounced in supershot and high-I i discharges, weaker in L-mode plasmas with NBI and ICRF heating and smaller still in ohmic plasmas. In reversed-shear discharges with sufficient deuterium-NBI heating power, internal transport barriers have been observed to form, leading to enhanced confinement. Large decreases in the ion heat conductivity and particle transport are inferred within the transport barrier. It appears that higher heating power is required to trigger the formation of a transport barrier with D-T NBI and the isotope effect on energy confinement is nearly absent in these enhanced reverse-shear plasmas. Many alpha-particle physics issues have been studied in the various operating regimes including confinement of the alpha particles, their redistribution by sawteeth, and their loss due to MHD instabilities with low toroidal mode numbers. In weak-shear plasmas, alpha-particle destabilization of a toroidal Alfven eigenmode has been observed

  18. Lithium isotope effect accompanying electrochemical intercalation of lithium into graphite

    CERN Document Server

    Yanase, S; Oi, T

    2003-01-01

    Lithium has been electrochemically intercalated from a 1:2 (v/v) mixed solution of ethylene carbonate (EC) and methylethyl carbonate (MEC) containing 1 M LiClO sub 4 into graphite, and the lithium isotope fractionation accompanying the intercalation was observed. The lighter isotope was preferentially fractionated into graphite. The single-stage lithium isotope separation factor ranged from 1.007 to 1.025 at 25 C and depended little on the mole ratio of lithium to carbon of the lithium-graphite intercalation compounds (Li-GIC) formed. The separation factor increased with the relative content of lithium. This dependence seems consistent with the existence of an equilibrium isotope effect between the solvated lithium ion in the EC/MEC electrolyte solution and the lithium in graphite, and with the formation of a solid electrolyte interfaces on graphite at the early stage of intercalation. (orig.)

  19. Process for the separation of deuterium and tritium from water using ammonia and a hydrogen-nitrogen-mixture

    International Nuclear Information System (INIS)

    Mandrin, Ch.

    1986-01-01

    A multistage process for separation of deuterium and tritium from water using ammonia and a hydrogen-nitrogen mixture. In a first stage isotopic exchange takes place between water containing deuterium and tritium, and ammonia depleted in deuterium and tritium. The molar ammonia throughput is chosen to be greater than two third of the molar throughput of water. The advantage of the process consists in the fact that the main product is water almost entirely free from deuterium and tritium. The byproducts are compounds enriched in deuterium and tritium, and nitrogen enriched in N-15

  20. Isotopic quantum correction to liquid methanol at -30 C

    CERN Document Server

    Benmore, C J; Egelstaff, P A; Neuefeind, J

    2002-01-01

    Hydrogen/deuterium (H/D) substitution of molecular liquids in neutron diffraction is a powerful tool for structure determination. However, recent high-energy X-ray studies have found observable differences in the structures of many H and D liquids at the same temperature. In some cases this isotopic quantum effect can be corrected for by measuring the D sample at a slightly different temperature to the H sample. The example of hydroxyl isotopic substitution in liquid methanol at -30 C is presented. The magnitude of the quantum effect is shown to be significant when compared to the size of the first-order isotopic neutron-difference function. (orig.)

  1. Calculations of kinetic isotope effects in the syn-eliminations of (2-phenylethyl)dimethylamine oxides

    International Nuclear Information System (INIS)

    Shafiei-Kermani, H.R.

    1987-01-01

    Transition state theory (TST) calculations of kinetic isotope effects (KIE) for the syn-elimination of (2-phenylethyl)dimethylamine oxides have been carried out for a series of transition state (TS) models encompassing both E1-like and E1cB-like regions of the E2 mechanistic spectrum. A large number of different reaction coordinates were explored for both unsolvated and for coordination of solvent dimethylsulfoxide in the cyclic transition state models. The models of reaction for both solvated and unsolvated models of proton transfer are presented. A simplified method for easier initial screening of reaction coordinate contributions is developed, discussed, and found to produce accurate approximations to the full model KIE values. Both unsolvated and solvated models show E1-like E2 mechanism and the calculated values from both models are in extremely good agreement with experimentally measured KIE. Both models were used to investigate para-substituted derivatives (Z = CL, OCH 3 ) of the parent compound (Z = H). The transition states are related by a shift in structure parallel to the central E2 diagonal of an O'Ferrall-Jencks-Fry reaction diagram, as predicted by Thornton, indicating that in the absence of other factors, the extent to which negative charge is accumulated at C/sub β/ in the transition state is a function primarily of the leaving group. All of the structural parameters such as bond distances and bond angles were related to independent bond orders. Beta-deuterium isotope effects produced by both solvated and nonsolvated models are temperature dependent

  2. Deuterium measurement by emission spectrometry

    International Nuclear Information System (INIS)

    Niemann, E.G.; Heilig, K.; Dumke, I.

    1978-01-01

    The method makes it possible to determine the relative deuterium content of enriched water samples. For this, the relative intensities of the Hα and Dα lines are measured which are emitted by a high-frequency discharge in water vapour. Although the method is not as exact as mass spectrometry, it has the following advantages: - Easy sample preparation (no reduction necessary); - samples of highly different enrichment can be measured one after the other without the danger of memory effects; - much lower apparatus and cost expenditure. The necessary sample size is about the same in both methods. (orig.) [de

  3. Concentration effect on inter-mineral equilibrium isotope fractionation: insights from Mg and Ca isotopic systems

    Science.gov (United States)

    Huang, F.; Wang, W.; Zhou, C.; Kang, J.; Wu, Z.

    2017-12-01

    Many naturally occurring minerals, such as carbonate, garnet, pyroxene, and feldspar, are solid solutions with large variations in chemical compositions. Such variations may affect mineral structures and modify the chemical bonding environment around atoms, which further impacts the equilibrium isotope fractionation factors among minerals. Here we investigated the effects of Mg content on equilibrium Mg and Ca isotope fractionation among carbonates and Ca content on equilibrium Ca isotope fractionation between orthopyroxene (opx) and clinopyroxene (cpx) using first-principles calculations. Our results show that the average Mg-O bond length increases with decreasing Mg/(Mg+Ca) in calcite when it is greater than 1/48[1] and the average Ca-O bond length significantly decreases with decreasing Ca/(Ca+Mg+Fe) in opx when it ranges from 2/16 to 1/48[2]. Equilibrium isotope fractionation is mainly controlled by bond strengths, which could be measured by bond lengths. Thus, 103lnα26Mg/24Mg between dolomite and calcite dramatically increases with decreasing Mg/(Mg+Ca) in calcite [1] and it reaches a constant value when it is lower than 1/48. 103lnα44Ca/40Ca between opx and cpx significantly increases with decreasing Ca content in opx when Ca/(Ca+Mg+Fe) ranges from 2/16 to 1/48 [2]. If Ca/(Ca+Mg+Fe) is below 1/48, 103lnα44Ca/40Ca is not sensitive to Ca content. Based on our results, we conclude that the concentration effect on equilibrium isotope fractionation could be significant within a certain range of chemical composition of minerals, which should be a ubiquitous phenomenon in solid solution systems. [1] Wang, W., Qin, T., Zhou, C., Huang, S., Wu, Z., Huang, F., 2017. GCA 208, 185-197. [2] Feng, C., Qin, T., Huang, S., Wu, Z., Huang, F., 2014. GCA 143, 132-142.

  4. Pollution and Climate Effects on Tree-Ring Nitrogen Isotopes

    Science.gov (United States)

    Savard, M. M.; Bégin, C.; Marion, J.; Smirnoff, A.

    2009-04-01

    Georgian Bay reflect deposition of NOx emissions from cars and coal-power plants, with higher proportions from coal burning in Georgian Bay (Savard et al., 2009b). This interpretation is conceivable because recent monitoring indicates that coal-power plant NOx emissions play an important role in the annual N budget in Ontario, but they are negligible on the Quebec side. CONCLUSION Interpretations of long tree-ring N isotopic series in terms of effects generated by airborne N-species have been previously advocated. Here we further propose that the contrasted isotopic trends obtained for wood samples from two regions reflect different regional anthropogenic N deposition combined with variations of climatic conditions. This research suggests that nitrogen tree-ring series may record both regional climatic conditions and anthropogenic perturbations of the N cycle. REFERENCES Savard, M.M., Bégin,C., Marion, J., Aznar, J.-C., Smirnoff, A., 2009a. Changes of Air Quality in an urban region as inferred from tree-ring width and stable isotopes. Chapter 9 in "Relating Atmospheric Source Apportionment to Vegetation Effects: Establishing Cause Effect Relationships" (A. Legge ed.). Elsevier, Amsterdam; doi: 10.1016/S1474-8177(08)00209x. Savard, M.M., Bégin, C., Smirnoff, A., Marion, J., Rioux-Paquette, E., 2009b. Tree-ring nitrogen isotopes reflect climatic effects and anthropogenic NOx emissions. Env. Sci. Tech (doi: 10.1021/es802437k).

  5. Mass independent isotope effects and their observations in nature

    International Nuclear Information System (INIS)

    Thiemens, M.H.

    2002-01-01

    In 1983, Thiemens and Heidenreich reported the first chemically produced mass independent isotope effect. A significant feature of the fractionation was that it identically produced the isotopic relation observed in the calcium-aluminum inclusions in the Allende meteorite. This δ 17 O=δ 18 O composition had previously been thought to represent a nucleosynthetic component as no chemical process was capable of producing a mass independent isotopic composition. It now appears nearly certain that the meteoritic oxygen isotopic anomalies were produced by chemical, rather than nuclear, processes. Since oxygen is the major element in stony planets this represents a major event in the formation of the solar system. In a recent review (Thiemens, 1999), it has been shown that mass independent isotopic compositions are pervasive in the Earth's atmosphere. Molecules which have been demonstrated to possess mass independent isotopic compositions include: O 2 , O 3 , CO 2 , CO, and N 2 O. In each case, the specific nature of the mass independent isotopic composition has provided details of their atmospheric chemistry that could not have been obtained by any other measurement technique. Most recently, solid materials have been observed to possess mass independent isotopic composition. In this paper, these observations are briefly discussed. These solid reservoirs include: 1) carbonates and sulphates from Mars, 2) terrestrial aerosol sulphate, 3) sulphides and sulphates from the Earth, ranging in time from 3.8 to 2.2 billion years before present, 4) sulphates from the Namibian desert and 5) the Antartic Dry Valleys. The information obtained from these measurements is extraordinarily wide ranging, extending from understanding the history of Martian atmosphereregolith interaction to the evolution of the oxygen in the Earth's earliest atmosphere. As was the case for gas phase species, this information and insight could not have been obtained by any other measurement technique

  6. Transport hysteresis and hydrogen isotope effect on confinement

    Science.gov (United States)

    Itoh, S.-I.; Itoh, K.

    2018-03-01

    A Gedankenexperiment on hydrogen isotope effect is developed, using the transport model with transport hysteresis. The transport model with hysteresis is applied to case where the modulational electron cyclotron heating is imposed near the mid-radius of the toroidal plasmas. The perturbation propagates either outward or inward, being associated with the clockwise (CW) hysteresis or counter-clockwise (CCW) hysteresis, respectively. The hydrogen isotope effects on the CW and CCW hysteresis are investigated. The local component of turbulence-driven transport is assumed to be the gyro-Bohm diffusion. While the effect of hydrogen mass number is screened in the response of CW hysteresis, it is amplified in CCW hysteresis. This result motivates the experimental studies to compare CW and CCW cases in order to obtain further insight into the physics of hydrogen isotope effects.

  7. Isotopes in environmental research

    International Nuclear Information System (INIS)

    Bowen, G.; Rozanski, K.; Vose, P.

    1990-01-01

    Radioactive and stable isotopes have long been considered a very efficient tool for studying physical and biological aspects of how the global ecosystem functions. Their applications in environmental research are numerous, embracing research at all levels. This article looks at only a few of the approaches to environmental problems that involve the use of isotopes. Special attention is given to studies of the Amazon Basin. Environmental isotopes are very efficient tools in water cycle studies. Tritium, a radioactive tracer, is especially useful in studying dynamics of water movement in different compartments of the hydrosphere, both on the local and global scales. Heavy stable isotopes of hydrogen and oxygen (deuterium and oxygen-18) provide information about steady-state characteristics of the water cycle. Isotope methods, some relatively new, have a major role in site-specific studies. Some indicative examples include: Studying turnover of organic matter. Changes in the carbon-13/carbon-12 isotopic ratio of organic matter were used to determine the respective contributions of organic carbon derived from forest and pasture. Studying biological nitrogen fixation. One of the ways nitrogen levels in soil can be maintained for productivity is by biological nitrogen fixation. Studying nitrogen availability and losses. The experimental use of nitrogen-15 is invaluable for defining losses of soil nitrogen to the atmosphere and to groundwater. Studies can similarly be done with stable and radioactive sulphur isotopes. This article indicates some potential uses of isotopes in environmental research. While the major problem of global climate change has not been specifically addressed here, the clearing of the Amazon forest, one focus of the IAEA's environmental programme, may have serious consequences for the global climate. These include substantial reduction of the amount of latent heat transported to the regions outside the tropics and acceleration of the greenhouse

  8. Isotope and mixture effects on neoclassical transport in the pedestal

    Science.gov (United States)

    Pusztai, Istvan; Buller, Stefan; Omotani, John T.; Newton, Sarah L.

    2017-10-01

    The isotope mass scaling of the energy confinement time in tokamak plasmas differs from gyro-Bohm estimates, with implications for the extrapolation from current experiments to D-T reactors. Differences in mass scaling in L-mode and various H-mode regimes suggest that the isotope effect may originate from the pedestal. In the pedestal, sharp gradients render local diffusive estimates invalid, and global effects due to orbit-width scale profile variations have to be taken into account. We calculate neoclassical cross-field fluxes from a radially global drift-kinetic equation using the PERFECT code, to study isotope composition effects in density pedestals. The relative reduction to the peak heat flux due to global effects as a function of the density scale length is found to saturate at an isotope-dependent value that is larger for heavier ions. We also consider D-T and H-D mixtures with a focus on isotope separation. The ability to reproduce the mixture results via single-species simulations with artificial ``DT'' and ``HD'' species has been considered. These computationally convenient single ion simulations give a good estimate of the total ion heat flux in corresponding mixtures. Funding received from the International Career Grant of Vetenskapsradet (VR) (330-2014-6313) with Marie Sklodowska Curie Actions, Cofund, Project INCA 600398, and Framework Grant for Strategic Energy Research of VR (2014-5392).

  9. Synthesis of deuterium labelled cocaine and pseudococaine

    Energy Technology Data Exchange (ETDEWEB)

    Casale, J.F.; Raney, H.T. (State Bureau of Investigation, Raleigh, NC (USA). Drug Chemistry Lab.); Lewin, A.H. (Research Triangle Inst., Research Triangle Park, NC (USA)); Cooper, D.A. (Drug Enforcement Administration, McLean, VA (USA))

    1991-03-01

    Cocaine and pseudococaine were mass-labelled with deuterium at various positions on the tropane ring. The synthetic procedures followed were adaptations of those previously published for the unlabelled compounds. The isotopic purity was greater than 95% for 2-({sup 2}H)-, 4,4-({sup 2}H2)-, and 1,5,6,6,7,7-({sup 2}H6)-cocaine and 3-({sup 2}H)-, 4,4-({sup 2}H2)-, and 1,5,6,6,7,7-({sup 2}H6)-pseudococaine, while that of 3-({sup 2}H)-cocaine exceeded 90%. (author).

  10. Synthesis of deuterium labelled cocaine and pseudococaine

    International Nuclear Information System (INIS)

    Casale, J.F.; Raney, H.T.; Cooper, D.A.

    1991-01-01

    Cocaine and pseudococaine were mass-labelled with deuterium at various positions on the tropane ring. The synthetic procedures followed were adaptations of those previously published for the unlabelled compounds. The isotopic purity was greater than 95% for 2-[ 2 H]-, 4,4-[ 2 H2]-, and 1,5,6,6,7,7-[ 2 H6]-cocaine and 3-[ 2 H]-, 4,4-[ 2 H2]-, and 1,5,6,6,7,7-[ 2 H6]-pseudococaine, while that of 3-[ 2 H]-cocaine exceeded 90%. (author)

  11. Deuterium labeled cannabinoids

    International Nuclear Information System (INIS)

    Driessen, R.A.

    1979-01-01

    Complex reactions involving ring opening, ring closure and rearrangements hamper complete understanding of the fragmentation processes in the mass spectrometric fragmentation patterns of cannabinoids. Specifically labelled compounds are very powerful tools for obtaining more insight into fragmentation mechanisms and ion structures and therefore the synthesis of specifically deuterated cannabinoids was undertaken. For this, it was necessary to investigate the preparation of cannabinoids, appropriately functionalized for specific introduction of deuterium atom labels. The results of mass spectrometry with these labelled cannabinoids are described. (Auth.)

  12. Anharmonic phonons and the isotope effect in superconductivity

    International Nuclear Information System (INIS)

    Crespi, V.H.; Cohen, M.L.; Penn, D.R.

    1991-01-01

    Anharmonic interionic potentials are examined in an Einstein model to study the unusual isotope-effect exponents for the high-T c oxides. The mass dependences of the electron-phonon coupling constant λ and the average phonon frequency √ left-angle ω 2 right-angle are computed from weighted sums over the oscillator levels. The isotope-effect exponent is depressed below 1/2 by either a double-well potential or a potential with positive quadratic and quartic parts. Numerical solutions of Schroedinger's equation for double-well potentials produce λ's in the range 1.5--4 for a material with a vanishing isotope-effect parameter α. However, low phonon frequencies limit T c to roughly 15 K. A negative quartic perturbation to a harmonic well can increase α above 1/2. In the extreme-strong-coupling limit, α is 1/2, regardless of anharmonicity

  13. Predicting big bang deuterium

    Energy Technology Data Exchange (ETDEWEB)

    Hata, N.; Scherrer, R.J.; Steigman, G.; Thomas, D.; Walker, T.P. [Department of Physics, Ohio State University, Columbus, Ohio 43210 (United States)

    1996-02-01

    We present new upper and lower bounds to the primordial abundances of deuterium and {sup 3}He based on observational data from the solar system and the interstellar medium. Independent of any model for the primordial production of the elements we find (at the 95{percent} C.L.): 1.5{times}10{sup {minus}5}{le}(D/H){sub {ital P}}{le}10.0{times}10{sup {minus}5} and ({sup 3}He/H){sub {ital P}}{le}2.6{times}10{sup {minus}5}. When combined with the predictions of standard big bang nucleosynthesis, these constraints lead to a 95{percent} C.L. bound on the primordial abundance deuterium: (D/H){sub best}=(3.5{sup +2.7}{sub {minus}1.8}){times}10{sup {minus}5}. Measurements of deuterium absorption in the spectra of high-redshift QSOs will directly test this prediction. The implications of this prediction for the primordial abundances of {sup 4}He and {sup 7}Li are discussed, as well as those for the universal density of baryons. {copyright} {ital 1996 The American Astronomical Society.}

  14. Partial molar volumes of hydrogen and deuterium in niobium, vanadium, and tantalum

    International Nuclear Information System (INIS)

    Peterson, D.T.; Herro, H.M.

    1983-01-01

    The partial molar volumes of hydrogen and deuterium were measured in vanadium, niobium, and tantalum by a differential pressure technique. One-half of an electrolytically charged sample plat was compressed between hardened steel blocks in a hydraulic press. The activity of hydrogen in the hig pressure region was raised and caused hydrogen to diffuse into the low pressure region. The partia molar volume was calculated from the ratio of the hydrogen concentrations in the high and low pressure regions of the sample. Small isotope effects were found in the partial molar volume. Hydrogen had the larger volume in niobium and tantalum, but the reverse was true in vanadium

  15. Stable isotope analysis

    International Nuclear Information System (INIS)

    Tibari, Elghali; Taous, Fouad; Marah, Hamid

    2014-01-01

    This report presents results related to stable isotopes analysis carried out at the CNESTEN DASTE in Rabat (Morocco), on behalf of Senegal. These analyzes cover 127 samples. These results demonstrate that Oxygen-18 and Deuterium in water analysis were performed by infrared Laser spectroscopy using a LGR / DLT-100 with Autosampler. Also, the results are expressed in δ values (‰) relative to V-SMOW to ± 0.3 ‰ for oxygen-18 and ± 1 ‰ for deuterium.

  16. Synthesis of [methine-3H]DDT and its nitro-analog, and isotope effects in their enzyme-catalyzed dehydrochlorination

    International Nuclear Information System (INIS)

    Kurihara, N.; Ikemoto, Y.; Okutani, S.; Clark, A.G.

    1989-01-01

    [methine- 3 H]1,1-Di-(4-chlorophenyl)-2,2,2-trichloroethane ([methine- 3 H]DDT) and its di-(4-nitrophenyl) analog, both of high purity with a moderately high specific activity were prepared. Chloro-benzene was condensed with [1- 3 H]1-(4-chlorophenyl)-2,2,2-trichloro-ethanol, which has been synthesized by sodium boro[ 3 H]hydride reduction of 4-chlorophenyl trichloromethyl ketone. The purified [ 3 H]DDT had a specific activity of 0.77 Ci/mmol (28.49 GBq/mmol). [methine- 3 H]1,1-Diphenyl-2,2,2-trichloroethane was similarly synthesized and was nitrated to give [methine- 3 H]1,1-di-(4-nitrophenyl)-2,2,2-trichloro-ethane of 1.63 Ci/mmol (60.31 GBq/mmol). Dehydrochlorination with housefly enzyme (glutathione-dependent DDT dehydrochlorinase) showed a remarkable isotope effect. For DDT, the observed tritium isotope effect on V max /K m was 11.51±0.52. For the nitro-analog, the value was 11.3±1.2. We measured deuterium isotope effect on V max /K m for DDT in a competitive mode and obtained the value 4.19±0.34. Based on these values, the magnitude of intrinsic isotope effect values on DDT-dehydrochlorination reaction was discussed. (author)

  17. Stable isotope methods: The effect of gut contents on isotopic ratios of zooplankton

    Science.gov (United States)

    Hill, J. M.; McQuaid, C. D.

    2011-05-01

    In the past decade there has been an increased awareness of the potential for methodological bias resulting from multiple pre-analytical procedures in foodweb interpretations based on stable isotope techniques. In the case of small organisms, this includes the effect of gut contents on whole body signatures. Although gut contents may not reflect actual assimilation, their carbon and nitrogen values will be isotopically lighter than after the same material has been assimilated. The potential skewing of isotopic ratios in whole organism samples is especially important for aquatic environments as many studies involve trophic relationships among small zooplankton. This is particularly important in pelagic waters, where herbivorous zooplankton comprise small taxa. Hence this study investigated the effect of gut contents on the δ13C and δ15N ratios of three size classes of zooplankton (1.0-2.0, 2.0-4.0 and >4.0 mm) collected using bongo net tows in the tropical waters of the south-west Indian Ocean. Animals were collected at night, when they were likely to be feeding, sieved into size classes and separated into genera. We focused on Euphausia spp which dominated zooplankton biomass. Three treatment types were processed: bulk animals, bulk animals without guts and tail muscle from each size class at 10 bongo stations. The δ15N ratios were influenced by zooplankton size class, presumably reflecting ontogenetic changes in diet. ANOVA post hoc results and correlations in δ15N signatures among treatments suggest that gut contents may not affect overall nitrogen signatures of Euphausia spp., but that δ13C signatures may be significantly altered by their presence. Carbon interpretations however, were complicated by potential effects of variation in chitin, lipids and metabolism among tissues and the possibility of opportunistic omnivory. Consequently we advocate gut evacuation before sacrifice in euphausiids if specific tissue dissection is impractical and recommend

  18. Shifts in rotifer life history in response to stable isotope enrichment: testing theories of isotope effects on organismal growth

    Science.gov (United States)

    2017-01-01

    In ecology, stable isotope labelling is commonly used for tracing material transfer in trophic interactions, nutrient budgets and biogeochemical processes. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism growth and metabolism. This assumption is, however, challenged by theoretical considerations and experimental studies on kinetic isotope effects in vivo. Here, I demonstrate profound changes in life histories of the rotifer Brachionus plicatilis fed 15N-enriched algae (0.4–5.0 at%); i.e. at the enrichment levels commonly used in ecological studies. These findings support theoretically predicted effects of heavy isotope enrichment on growth, metabolism and ageing in biological systems and underline the importance of accounting for such effects when using stable isotope labelling in experimental studies. PMID:28405367

  19. Cosmic Deuterium and Social Networking Software

    Science.gov (United States)

    Pasachoff, J. M.; Suer, T.-A.; Lubowich, D. A.; Glaisyer, T.

    2006-08-01

    For the education of newcomers to a scientific field and for the convenience of students and workers in the field, it is helpful to have all the basic scientific papers gathered. For the study of deuterium in the Universe, in 2004-5 we set up http://www.cosmicdeuterium.info with clickable links to all the historic and basic papers in the field and to many of the current papers. Cosmic deuterium is especially important because all deuterium in the Universe was formed in the epoch of nucleosynthesis in the first 1000 seconds after the Big Bang, so study of its relative abundance (D:H~1:100,000) gives us information about those first minutes of the Universe's life. Thus the understanding of cosmic deuterium is one of the pillars of modern cosmology, joining the cosmic expansion, the 3 degree cosmic background radiation, and the ripples in that background radiation. Studies of deuterium are also important for understanding Galactic chemical evolution, astrochemistry, interstellar processes, and planetary formation. Some papers had to be scanned while others are available at the Astrophysical Data System, adswww.harvard.edu, or to publishers' Websites. By 2006, social networking software (http:tinyurl.com/ zx5hk) had advanced with popular sites like facebook.com and MySpace.com; the Astrophysical Data System had even set up MyADS. Social tagging software sites like http://del.icio.us have made it easy to share sets of links to papers already available online. We have set up http://del.icio.us/deuterium to provide links to many of the papers on cosmicdeuterium.info, furthering previous del.icio.us work on /eclipses and /plutocharon. It is easy for the site owner to add links to a del.icio.us site; it takes merely clicking on a button on the browser screen once the site is opened and the desired link is viewed in a browser. Categorizing different topics by keywords allows subsets to be easily displayed. The opportunity to expose knowledge and build an ecosystem of web

  20. Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

    Science.gov (United States)

    Cretnik, Stefan; Bernstein, Anat; Shouakar-Stash, Orfan; Löffler, Frank; Elsner, Martin

    2014-05-20

    Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

  1. Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE Reductive Dehalogenation

    Directory of Open Access Journals (Sweden)

    Stefan Cretnik

    2014-05-01

    Full Text Available Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (biochemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE dehalogenation was investigated. Selective biotransformation reactions (i of tetrachloroethene (PCE to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii of TCE to cis-1,2-dichloroethene (cis-DCE in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were −19.0‰ ± 0.9‰ (PCE and −12.2‰ ± 1.0‰ (TCE (95% confidence intervals. Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (−5.0‰ ± 0.1‰ and TCE (−3.6‰ ± 0.2‰. In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by −16.3‰ ± 1.4‰ (standard error than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of −2.4‰ ± 0.3‰ and the product chloride an isotope effect of −6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals. A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect. These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition. This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I or single electron transfer as reductive dehalogenation mechanisms.

  2. Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition

    International Nuclear Information System (INIS)

    Zielinski, M.; Zielinska, A.; Papiernik-Zielinska, H.; McKenzie, J.A.; Bernasconi, S.; Paul, H.

    1998-01-01

    Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition above and below its melting temperature have been studied and compared with the primary (PKIE) and secondary kinetic isotope effects (SKIE) of 13 C and 18 O, respectively, in the decarboxylation of other heterocyclic acids. The temperature dependence of the secondary oxygen-18 isotope effects is negative in the total 221-255 deg C temperature interval investigated initially. The 13 C KIE measured above melting point of N.A. (temperature interval 235-270 deg C) are located in the range 1.007-1.009. Below melting point of nicotinic acid the 13 C KIE are larger and reveal the negative temperature dependence ( 13 C KIE decreases with decreasing the reaction temperature from 1.013/at 230 deg C to 1.0114/at 221 deg C). A discussion of the above isotopic results is presented. (author)

  3. Deuterium inventory in tungsten after plasma exposure. A microstructural survey

    International Nuclear Information System (INIS)

    Manhard, Armin

    2012-09-01

    Tungsten is a promising material for armouring the plasma-facing wall of future nuclear fusion experiments and power plants. It has a very high melting point, good thermal conductivity and is highly resistant against physical sputtering by energetic particles from the plasma. It also has a very low solubility for hydrogen isotopes. This is important both for safety and also for economic reasons, in particular with regard to the radioactive fusion fuel tritium. Due to this low solubility, the retention of hydrogen isotopes in tungsten materials after exposure to a plasma is dominated by the trapping of hydrogen isotopes at tungsten lattice defects. Therefore, a strong dependence of the hydrogen isotope retention on the microstructure of the tungsten is to be expected. This work describes a survey study of tungsten with different microstructures exposed to deuterium plasmas under a wide range of different plasma exposure conditions. The isotope deuterium was used because its natural abundance is much smaller than that of hydrogen (i.e., 1 H). This allows detecting even very small amounts retained in the tungsten practically without background signal. Furthermore, the use of deuterium allows utilising the nuclear reaction 2 D( 3 He,p) 4 He for depth-resolved quantification of the deuterium inventory up to depths of several microns. In order to standardise the specimens as far as possible, they were all cut from the same initial material from a single manufacturing batch. After a chemo-mechanical polishing procedure, which produces a well-defined surface, the specimens were annealed at either of four different temperatures in order to modify the grain structure and the dislocation density. These were then characterised by scanning electron microscopy and scanning transmission electron microscopy. The specimens were subsequently exposed in a fully characterised deuterium plasma source at different specimen temperatures, ion energies and deuterium fluences. In addition

  4. Total cross section results for deuterium electrodisintegration

    International Nuclear Information System (INIS)

    Skopik, D.M.; Murphy, J.J. II; Shin, Y.M.

    1976-01-01

    Theoretical total cross sections for deuterium electrodisintegration are presented as a function of incident electron energy. The cross section has been calculated using virtual photon theory with Partovi's photodisintegration calculation for E/subx/ > 10 MeV and effective range theory for E/subx/ 2 H(e, n) reaction in Tokamak reactors

  5. Use of isotope effects to characterize intermediates in mechanism-based inactivation of dopamine beta-monooxygenase by beta-chlorophenethylamine

    International Nuclear Information System (INIS)

    Bossard, M.J.; Klinman, J.P.

    1990-01-01

    A mechanism for beta-chlorophenethylamine inhibition of dopamine beta-monooxygenase has been postulated in which bound alpha-aminoacetophenone is generated followed by an intramolecular redox reaction to yield a ketone-derived radical cation as the inhibitory species. Based on the assumption that the ketone radical is the inhibitory intermediate, an analogous system was predicted and verified. In the present study, the role of alpha-aminoacetophenone as the proposed intermediate in the inactivation by beta-chlorophenethylamine was examined in greater detail. From the interdependence of tyramine and alpha-aminoacetophenone concentrations, ketone inactivation is concluded to occur at the substrate site as opposed to potential binding at the reductant-binding site. Using beta-[2-1H]- and beta-[2-2H]chlorophenethylamine, the magnitude of the deuterium isotope effect on inactivation under second-order conditions has been found to be identical to that observed under catalytic turnover, D(kappa inact/Ki) = D(kappa cat/Km) = 6-7. By contrast, the isotope effect on inactivation under conditions of substrate and oxygen saturation, D kappa inact = 2, is 3-fold smaller than that seen on catalytic turnover, D kappa cat = 6. This reduced isotope effect for inactivation is attributed to a normal isotope effect on substrate hydroxylation followed by an inverse isotope effect on the partitioning of the enol of alpha-aminoacetophenone between oxidation to a radical cation versus protonation to regenerate ketone. These findings are unusual in that two isotopically sensitive steps are present in the inactivation pathway whereas only one is observable in turnover

  6. Laser photochemical separation of hydrogen isotopes

    International Nuclear Information System (INIS)

    Fowler, M.C.

    1979-01-01

    A method of separating isotopes of hydrogen utilizing isotopically selective photodissociation of organic acid is disclosed. Specifically acetic or formic acid containing compounds of deuterated nd hydrogenated acid is irradiated by radiation having a wavelength in the infrared spectrum between 9.2 to 10.8 microns to produce deuterium hydroxide and deuterium hydride respectively. Maintaining the acid at an elevated temperature significantly improves the yield of isotope separation

  7. Magic numbers and isotopic effect of ion clusters

    International Nuclear Information System (INIS)

    Wang Guanghou

    1989-04-01

    The magic numbers and isotopic effect as well as stable configurations in relation to the charge state of the clusters are discussed. Ionic (atomic) clusters are small atomic aggregates, a physical state between gas and solid states, and have many interesting properties, some of them are more or less similar to those in nuclei

  8. Isotopes in heterogeneous catalysis

    CERN Document Server

    Hargreaves, Justin SJ

    2006-01-01

    The purpose of this book is to review the current, state-of-the-art application of isotopic methods to the field of heterogeneous catalysis. Isotopic studies are arguably the ultimate technique in in situ methods for heterogeneous catalysis. In this review volume, chapters have been contributed by experts in the field and the coverage includes both the application of specific isotopes - Deuterium, Tritium, Carbon-14, Sulfur-35 and Oxygen-18 - as well as isotopic techniques - determination of surface mobility, steady state transient isotope kinetic analysis, and positron emission profiling.

  9. Use of water stable isotopes in climatology and paleoclimatology illustrated from polar ice cores studies

    International Nuclear Information System (INIS)

    Jouzel, J.; Lorius, C.

    1994-01-01

    The isotopic content of ancient waters (deuterium and oxygen 18) gives a key access to past climatic changes. An essentially linear relationship exists between the isotopic content of a precipitation and the temperature of the site (at least for medium and high latitudes). This link between water isotope atmospheric cycle and climate is presented through various isotopic models and illustrated from the deuterium profile obtained along the Vostok ice core in East Antarctica. This 2 km record which covers a full glacial-interglacial cycle (160000 years) confirms the existence of a link between insolation changes and climate (Milankovitch theory). It shows also that the greenhouse effect has played a role in glacial-interglacial changes in amplifying this orbital forcing. (authors). 10 figs., 23 refs

  10. Transient competitive complexation in biological kinetic isotope fractionation explains nonsteady isotopic effects: Theory and application to denitrification in soils

    Science.gov (United States)

    Maggi, Federico; Riley, William J.

    2009-12-01

    The theoretical formulation of biological kinetic isotope fractionation often assumes first-order or Michaelis-Menten kinetics, the latter solved under the quasi-steady state assumption. Both formulations lead to a constant isotope fractionation factor, therefore they may return incorrect estimations of isotopic effects and misleading interpretations of isotopic signatures when fractionation is not a steady process. We have analyzed the isotopic signature of denitrification in biogeochemical soil systems by Menyailo and Hungate (2006) in which high and variable 15N-N2O enrichment during N2O production and inverse isotope fractionation during N2O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with Michaelis-Menten kinetics. When Michaelis-Menten kinetics were coupled to Monod kinetics to describe biomass and enzyme dynamics, and the quasi-steady state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observed concentrations, and variable and inverse isotope fractionations. These results imply a substantial revision in modeling isotopic effects, suggesting that steady state kinetics such as first-order, Rayleigh, and classic Michaelis-Menten kinetics should be superseded by transient kinetics in conjunction with biomass and enzyme dynamics.

  11. Backbone dynamics of a model membrane protein: measurement of individual amide hydrogen-exchange rates in detergent-solubilized M13 coat protein using 13C NMR hydrogen/deuterium isotope shifts

    International Nuclear Information System (INIS)

    Henry, G.D.; Weiner, J.H.; Sykes, B.D.

    1987-01-01

    Hydrogen-exchange rates have been measured for individual assigned amide protons in M13 coat protein, a 50-residue integral membrane protein, using a 13 C nuclear magnetic resonance (NMR) equilibrium isotope shift technique. The locations of the more rapidly exchanging amides have been determined. In D 2 O solutions, a peptide carbonyl resonance undergoes a small upfield isotope shift (0.08-0.09 ppm) from its position in H 2 O solutions; in 1:1 H 2 O/D 2 O mixtures, the carbonyl line shape is determined by the exchange rate at the adjacent nitrogen atom. M13 coat protein was labeled biosynthetically with 13 C at the peptide carbonyls of alanine, glycine, phenylalanine, proline, and lysine, and the exchange rates of 12 assigned amide protons in the hydrophilic regions were measured as a function of pH by using the isotope shift method. This equilibrium technique is sensitive to the more rapidly exchanging protons which are difficult to measure by classical exchange-out experiments. In proteins, structural factors, notably H bonding, can decrease the exchange rate of an amide proton by many orders of magnitude from that observed in the freely exposed amides of model peptides such as poly(DL-alanine). With corrections for sequence-related inductive effects, the retardation of amide exchange in sodium dodecyl sulfate solubilized coat protein has been calculated with respect to poly(DL-alanine). The most rapidly exchanging protons, which are retarded very little or not at all, are shown to occur at the N- and C-termini of the molecule. A model of the detergent-solubilized coat protein is constructed from these H-exchange data which is consistent with circular dichroism and other NMR results

  12. Isotope effects accompanying evaporation of water from leaky containers.

    Science.gov (United States)

    Rozanski, Kazimierz; Chmura, Lukasz

    2008-03-01

    Laboratory experiments aimed at quantifying isotope effects associated with partial evaporation of water from leaky containers have been performed under three different settings: (i) evaporation into dry atmosphere, performed in a dynamic mode, (ii) evaporation into dry atmosphere, performed in a static mode, and (iii) evaporation into free laboratory atmosphere. The results demonstrate that evaporative enrichment of water stored in leaky containers can be properly described in the framework of the Craig-Gordon evaporation model. The key parameter controlling the degree of isotope enrichment is the remaining fraction of water in the leaking containers. Other factors such as temperature, relative humidity, or extent of kinetic fractionation play only minor roles. Satisfactory agreement between observed and predicted isotope enrichments for both (18)O and (2)H in experiments for the case of evaporation into dry atmosphere could be obtained only when molecular diffusivity ratios of isotope water molecules as suggested recently by Cappa et al. [J. Geophys. Res., 108, 4525-4535, (2003).] were adopted. However, the observed and modelled isotope enrichments for (2)H and (18)O could be reconciled also for the ratios of molecular diffusivities obtained by Merlivat [J. Chem. Phys., 69, 2864-2871 (1978).], if non-negligible transport resistance in the viscous liquid sub-layer adjacent to the evaporating surface is considered. The evaporation experiments revealed that the loss of mass of water stored in leaky containers in the order of 1%, will lead to an increase of the heavy isotope content in this water by ca. 0.35 and 1.1 per thousand, for delta (18)O and delta (2)H, respectively.

  13. Deuterium and phosphorus-31 nuclear magnetic resonance study of the interaction of melittin with dimyristoylphosphatidylcholine bilayers and the effects of contaminating phospholipase A2

    International Nuclear Information System (INIS)

    Dempsey, C.E.; Watts, A.

    1987-01-01

    The interaction of bee venom melittin with dimyristoylphosphatidylcholine (DMPC) selectively deuteriated in the choline head group has been studied by deuterium and phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy. The action of residual phospholipase A 2 in melittin samples resulted in mixtures of DMPC and its hydrolytic products that underwent reversible transitions at temperatures between 30 and 35 0 C from extended bilayers to micellar particles which gave narrow single-line deuterium and phosphorus-31 NMR spectra. Similar transitions were observed in DMPC-myristoyllysophosphatidylcholine (lysoPC)-myristic acid mixtures containing melittin but not in melittin-free mixtures, indicating that melittin is able to stabilize extended bilayers containing DMPC and its hydrolytic products in the liquid-crystalline phase. Melittin, free of phospholipase A 2 activity, and at 3-5 mol % relative to DMPC, induced reversible transitions between extended bilayers and micellar particles on passing through the liquid-crystalline to gel phase transition temperature of the lipid, effects similar to those observed in melittin-acyl chain deuteriated dipalmitoylphosphatidylcholine (DPPC) mixtures. LysoPC at concentrations of 20 mol % or greater relative to DMPC induced transitions between extended bilayers and micellar particles with characteristics similar to those induced by melittin. It is proposed that these melittin- and lysoPC-induced transitions share similar mechanisms. The effects of melittin on the quadrupole splittings and T 1 relaxation times of head-group-deuteriated DMPC in the liquid-crystalline phase share features similar to the effects of metal ions on DPPC head groups, indicating that the conformational properties of the choline head group in PC bilayers may be affected by melittin and by metal ions in a similar manner

  14. Deuterium and phosphorus-31 nuclear magnetic resonance study of the interaction of melittin with dimyristoylphosphatidylcholine bilayers and the effects of contaminating phospholipase A/sub 2/

    Energy Technology Data Exchange (ETDEWEB)

    Dempsey, C.E.; Watts, A.

    1987-09-08

    The interaction of bee venom melittin with dimyristoylphosphatidylcholine (DMPC) selectively deuteriated in the choline head group has been studied by deuterium and phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy. The action of residual phospholipase A/sub 2/ in melittin samples resulted in mixtures of DMPC and its hydrolytic products that underwent reversible transitions at temperatures between 30 and 35/sup 0/C from extended bilayers to micellar particles which gave narrow single-line deuterium and phosphorus-31 NMR spectra. Similar transitions were observed in DMPC-myristoyllysophosphatidylcholine (lysoPC)-myristic acid mixtures containing melittin but not in melittin-free mixtures, indicating that melittin is able to stabilize extended bilayers containing DMPC and its hydrolytic products in the liquid-crystalline phase. Melittin, free of phospholipase A/sub 2/ activity, and at 3-5 mol % relative to DMPC, induced reversible transitions between extended bilayers and micellar particles on passing through the liquid-crystalline to gel phase transition temperature of the lipid, effects similar to those observed in melittin-acyl chain deuteriated dipalmitoylphosphatidylcholine (DPPC) mixtures. LysoPC at concentrations of 20 mol % or greater relative to DMPC induced transitions between extended bilayers and micellar particles with characteristics similar to those induced by melittin. It is proposed that these melittin- and lysoPC-induced transitions share similar mechanisms. The effects of melittin on the quadrupole splittings and T/sub 1/ relaxation times of head-group-deuteriated DMPC in the liquid-crystalline phase share features similar to the effects of metal ions on DPPC head groups, indicating that the conformational properties of the choline head group in PC bilayers may be affected by melittin and by metal ions in a similar manner.

  15. Hydrogen--deuterium exchange in saturated hydrocarbons on α-chromia catalyst

    International Nuclear Information System (INIS)

    Kalman, J.; Guczi, L.

    1977-01-01

    The kinetics of hydrogen--deuterium exchange in methane, ethane, and propane have been studied with unsupported α-chromia as catalyst in the temperature range of 598 to 688 0 K. The apparent activation energies for methane, ethane, and propane are 88, 130, and 84 kJ mol -1 , respectively, similar to those found on chromia gel. The order of reaction with respect to hydrocarbons and deuterium has been determined as also having the kinetic isotope effect. The main initial products are CH 3 D and CD 4 with methane, C 2 H 4 D 2 and C 2 D 6 with ethane, and C 3 H 7 D and C 3 D 8 with propane. A change in product distribution as a function of temperature, conversion, aging, and oxygen--deuterium treatment has been observed. In agreement with the kinetic data and the effect of oxygen, Cr 3+ has been assumed as the active species of the chromia catalyst, whereas Cr 2+ is an inactive site on the surface. There is no direct proof that chromium ion in a valence state higher than 3+ plays an important role in the exchange reaction. It was established that dual Cr 3+ -- Cr 3+ sites are responsible for the formation of ethane-d 2 . After a long deuterium treatment the number of dual sites is decreased, the effect being revealed in the decreased rate of exchange and the small amount of ethane-d 2 . On the contrary, the formation of methane-d 4 is interpreted by the formation of Cr = C bonds by analogy with homogeneous complexes. In the case of propane, the exchange reaction can be adequately interpreted by a π-allyl mechanism

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

    Science.gov (United States)

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

    2011-05-15

    Lipid hydroperoxides undergo homolytic decomposition into the bifunctional 4-hydroxy-2( E )-nonenal and 4-oxo-2( E )-nonenal (ONE). These bifunctional electrophiles are highly reactive and can readily modify intracellular molecules including glutathione (GSH), deoxyribonucleic acid (DNA) and proteins. Lipid hydroperoxide-derived bifunctional electrophiles are thought to contribute to the pathogenesis of a number of diseases. ONE is an α , β -unsaturated aldehyde that can react in multiple ways and with glutathione, proteins and DNA. Heavy isotope-labeled analogs of ONE are not readily available for conducting mechanistic studies or for use as internal standards in mass spectrometry (MS)-based assays. An efficient onestep cost-effective method has been developed for the preparation of C-9 deuterium-labeled ONE. In addition, a method for specific deuterium labeling of ONE at C-2, C-3 or both C-2 and C-3 has been developed. This latter method involved the selective reduction of an intermediate alkyne either by lithium aluminum hydride or lithium aluminum deuteride and quenching with water or deuterium oxide. The availability of these heavy isotope analogs will be useful as internal standards for quantitative studies employing MS and for conducting mechanistic studies of complex interactions between ONE and DNA bases as well as between ONE and proximal amino acid residues in peptides and proteins.

  17. Modification of the isotope effect due to pair breaking

    International Nuclear Information System (INIS)

    Carbotte, J.P.; Greeson, M.; Perez-Gonzalez, A.

    1991-01-01

    We have calculated the effect of pair breaking on the isotope-effect coefficient (β) of a superconductor. We find that, as the pair-breaking scattering rate is increased, β also increases in absolute value. Values of β much larger than the canonical value of 1/2 can easily be achieved even in models where the electron-phonon interaction contributes only a very small amount to the value of the intrinsic critical temperature

  18. Deuterium in New Zealand rivers and streams

    International Nuclear Information System (INIS)

    Stewart, M.K.; Cox, M.A.; James, M.R.; Lyon, G.

    1983-07-01

    Over 750 deuterium measurements on rivers and streams in New Zealand are reported. Monthly samples were collected for periods of several years from a number of representative rivers. These show irregular storm-to-storm as well as seasonal deuterium variations. The seasonal variations range from as low as 1 per mille for lake-fed rivers to 8-10 per mille for rivers with large spring snow-melt contributions. Variations in mean annual ΔD values are believed to reflect changes in climatic variables; the present data will be used to compare with future changes. The bulk of the data are single samples; these show a geographic variation related to the altitude, latitude and climatic character of the catchments, with the highest deuterium contents (ΔD = -20 per mille) occurring in the far north, and lowest contents (-80 per mille) in the inland Otago region. Regression equations derived for the ΔD dependence on altitude (h) and latitude (l), are ΔD = -0.0169 h - 30.2 and westerly influence. Eastern climatic zones have lower deuterium contents because of rainout effects on the axial ranges. Contours of constant

  19. Nanoindentation study of the combined effects of crystallography, heat treatment and exposure to high-flux deuterium plasma in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Zayachuk, Y., E-mail: yevhen.zayachuk@materials.ox.ac.uk [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Culham Centre for Fusion Energy, Culham Science Centre, Abingdon OX14 3DB (United Kingdom); Armstrong, D.E.J. [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Bystrov, K. [FOM Institute DIFFER- Dutch Institute for Fundamental Energy Research, Trilateral Euregio Cluster, De Zaale 20, 3612 AJ Eindhoven (Netherlands); Van Boxel, S. [Culham Centre for Fusion Energy, Culham Science Centre, Abingdon OX14 3DB (United Kingdom); Morgan, T. [FOM Institute DIFFER- Dutch Institute for Fundamental Energy Research, Trilateral Euregio Cluster, De Zaale 20, 3612 AJ Eindhoven (Netherlands); Roberts, S.G. [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Culham Centre for Fusion Energy, Culham Science Centre, Abingdon OX14 3DB (United Kingdom)

    2017-04-01

    tungsten samples were heat-treated to achieve partial recrystallization and exposed to high ion flux deuterium plasma at different temperatures and fluences. Continuous stiffness nanoindentation measurements of near-surface hardness were performed in the grains of specific annealing states and of specific crystallographic orientation, determined by electron backscatter diffraction (EBSD); indentation pile-up was investigated using surface profilometry. Bulk hardness of unexposed tungsten does not strongly depend on grain orientation, but depends on the annealing state of the grain, with values between ∼4.3 GPa for recrystallized grains and ∼5.5 for non-recrystallized ones. Grains with <111> surface normal orientation feature the least pile-up, while grains with <001> orientation the most; pile-up also depends on the annealing state, being generally lower in recrystallized grains. Plasma exposure leads to the increase of hardness, most significantly near the surface. The width of plasma-affected zone increases with the increase of exposure temperature and fluence, as well in recrystallized grains, correlating with the increase of diffusion depth. Plasma exposure does not lead to the emergence of orientation-dependence of hardness. Both indentation pile-up and near-surface indentation pop-ins are generally suppressed by plasma exposure.

  20. The deuterium/hydrogen distribution in chondritic organic matter attests to early ionizing irradiation

    Science.gov (United States)

    Laurent, Boris; Roskosz, Mathieu; Remusat, Laurent; Robert, François; Leroux, Hugues; Vezin, Hervé; Depecker, Christophe; Nuns, Nicolas; Lefebvre, Jean-Marc

    2015-10-01

    Primitive carbonaceous chondrites contain a large array of organic compounds dominated by insoluble organic matter (IOM). A striking feature of this IOM is the systematic enrichment in deuterium compared with the solar hydrogen reservoir. This enrichment has been taken as a sign of low-temperature ion-molecule or gas-grain reactions. However, the extent to which Solar System processes, especially ionizing radiation, can affect D/H ratios is largely unknown. Here, we report the effects of electron irradiation on the hydrogen isotopic composition of organic precursors containing different functional groups. From an initial terrestrial composition, overall D-enrichments and differential intramolecular fractionations comparable with those measured in the Orgueil meteorite were induced. Therefore, ionizing radiation can quantitatively explain the deuteration of organics in some carbonaceous chondrites. For these meteorites, the precursors of the IOM may have had the same isotopic composition as the main water reservoirs of the inner Solar System.

  1. Isotope effects in photo dissociation of ozone with visible light

    Science.gov (United States)

    Früchtl, Marion; Janssen, Christof; Röckmann, Thomas

    2014-05-01

    Ozone (O3) plays a key role for many chemical oxidation processes in the Earth's atmosphere. In these chemical reactions, ozone can transfer oxygen to other trace gases. This is particularly interesting, since O3 has a very peculiar isotope composition. Following the mass dependent fractionation equation δ17O = 0.52 * δ18O, most fractionation processes depend directly on mass. However, O3 shows an offset to the mass dependent fractionation line. Processes, which show such anomalies, are termed mass independent fractionations (MIF). A very well studied example for a chemical reaction that leads to mass independent fractionation is the O3 formation reaction. To what degree O3 destruction reactions need to be considered in order to understand the isotope composition of atmospheric O3 is still not fully understood and an open question within scientific community. We set up new experiments to investigate the isotope effect resulting from photo dissociation of O3 in the Chappuis band (R1). Initial O3 is produced by an electric discharge. After photolysis O3 is collected in a cold trap at the triple point temperature of nitrogen (63K). O3 is then converted to O2 in order to measure the oxygen isotopes of O3 using isotope ratio mass spectrometry. To isolate O3 photo dissociation (R1) from O3 decomposition (R2) and secondary O3 formation (R3), we use varying amounts of carbon monoxide (CO) as O atom quencher (R4). In this way we suppress the O + O3 reaction (R3) and determine the isotope fractionation in R1 and R2 separately. We present first results on the isotope effects in O3 photo dissociation with visible light in the presence of different bath gases. Results are interpreted based on chemical kinetics modeling. (R1) O3 + hυ → O (3P) + O2 (R2) O3 + O (3P) → 2 O2 (R3) O + O2 + M → O3 + M (R4) O (3P) + CO + M → CO2 + M

  2. Marginal-Fermi-liquid theory and the isotope effect

    International Nuclear Information System (INIS)

    Nicol, E.J.; Carbotte, J.P.

    1991-01-01

    In the marginal-Fermi-liquid model, the coupling between two electrons is via charge (attractive) and spin (repulsive) fluctuations, and so it does not exhibit an isotope effect. To include this effect, an additional phonon contribution must be introduced. Using the case of YBa 2 Cu 3 O 7 , for illustrative purposes, with a total isotope effect coefficient of β tot congruent 0.05 at a T c of 90 K, we find that the implied electron-phonon mass renormalization is very small for coupling to high-energy phonons but increases rapidly with decreasing phonon frequency or an increasing amount of spin fluctuations. Finally, we examine how β increases with decreasing T c when charge fluctuations are reduced or spin fluctuations augmented

  3. Isotope effects of trapped electron modes in the presence of impurities in tokamak plasmas

    Science.gov (United States)

    Shen, Yong; Dong, J. Q.; Sun, A. P.; Qu, H. P.; Lu, G. M.; He, Z. X.; He, H. D.; Wang, L. F.

    2016-04-01

    The trapped electron modes (TEMs) are numerically investigated in toroidal magnetized hydrogen, deuterium and tritium plasmas, taking into account the effects of impurity ions such as carbon, oxygen, helium, tungsten and others with positive and negative density gradients with the rigorous integral eigenmode equation. The effects of impurity ions on TEMs are investigated in detail. It is shown that impurity ions have substantially-destabilizing (stabilizing) effects on TEMs in isotope plasmas for {{L}ez}\\equiv {{L}ne}/{{L}nz}>0 (TEM turbulences in hydrogenic isotope plasmas with and without impurities are performed. The relations between the maximum growth rate of the TEMs with respect to the poloidal wave number and the ion mass number are given in the presence of the impurity ions. The results demonstrate that the maximum growth rates scale as {γ\\max}\\propto Mi-0.5 in pure hydrogenic plasmas. The scale depends on the sign of its density gradient and charge number when there is a second species of (impurity) ions. When impurity ions have density profiles peaking inwardly (i.e. {{L}ez}\\equiv {{L}ne}/{{L}nz}>0 ), the scaling also depends on ITG parameter {ηi} . The maximum growth rates scale as {γ\\max}\\propto M\\text{eff}-0.5 for the case without ITG ({ηi}=0 ) or the ITG parameter is positive ({ηi}>0 ) but the impurity ion charge number is low (Z≤slant 5.0 ). However, when {ηi}>0 and the impurity ion charge number is moderate (Z=6.0-8.0 ), the scaling law is found as {γ\\max}\\propto M\\text{eff}-1.0 . Here, Z is impurity ion charge number, and the effective mass number, {{M}\\text{eff}}=≤ft(1-{{f}z}\\right){{M}i}+{{f}z}{{M}z} , with {{M}i} and {{M}Z} being the mass numbers of the hydrogenic and impurity ions, respectively, and {{f}z}=Z{{n}0z}/{{n}0e} being the charge concentration of impurity ions. In addition, with regard to the case of {{L}ez}<0 , the maximum growth rate scaling is {γ\\max}\\propto Mi-0.5 . The possible relations of the results

  4. Investigation of irradiation effects on highly integrated leading-edge electronic components of diagnostics and control systems for LHD deuterium operation

    Science.gov (United States)

    Ogawa, K.; Nishitani, T.; Isobe, M.; Murata, I.; Hatano, Y.; Matsuyama, S.; Nakanishi, H.; Mukai, K.; Sato, M.; Yokota, M.; Kobuchi, T.; Nishimura, T.; Osakabe, M.

    2017-08-01

    High-temperature and high-density plasmas are achieved by means of real-time control, fast diagnostic, and high-power heating systems. Those systems are precisely controlled via highly integrated electronic components, but can be seriously affected by radiation damage. Therefore, the effects of irradiation on currently used electronic components should be investigated for the control and measurement of Large Helical Device (LHD) deuterium plasmas. For the precise estimation of the radiation field in the LHD torus hall, the MCNP6 code is used with the cross-section library ENDF B-VI. The geometry is modeled on the computer-aided design. The dose on silicon, which is a major ingredient of electronic components, over nine years of LHD deuterium operation shows that the gamma-ray contribution is dominant. Neutron irradiation tests were performed in the OKTAVIAN at Osaka University and the Fast Neutron Laboratory at Tohoku University. Gamma-ray irradiation tests were performed at the Nagoya University Cobalt-60 irradiation facility. We found that there are ethernet connection failures of programmable logic controller (PLC) modules due to neutron irradiation with a neutron flux of 3  ×  106 cm-2 s-1. This neutron flux is equivalent to that expected at basement level in the LHD torus hall without a neutron shield. Most modules of the PLC are broken around a gamma-ray dose of 100 Gy. This is comparable with the dose in the LHD torus hall over nine years. If we consider the dose only, these components may survive more than nine years. For the safety of the LHD operation, the electronic components in the torus hall have been rearranged.

  5. Some methods for labelling organic compounds by deuterium

    International Nuclear Information System (INIS)

    Moustapha, C.

    1988-01-01

    The rapid growth of knowledge in the fields of biochemistry, physiology, and molecular biology reflects to a considerable degree the utilization of stable isotopes (specially deuterium) in the study of chemical reactions and fragmentation mechanisms in mass spectrometry, as well as in the pharmacological and biological studies. Organic compounds maybe labelled by deuterium through classic organic reactions by using special deuterated solvents and reagents. This article discusses some reactions, with examples on how to prepare labelled compounds with high isotopic purety. These reactions are: exchange reactions in acid and alkaline media (the exchange in the chromatographic column in liquid and gas phases, the exchange in homogenous medium), reduction reactions of functional groups as well as saturation of the double bounds by deuterium using hydrogenation catalystes, electrochemical reactions using KOLBE, and photochemical reactions. This article also deals with spectroscopic properties of deuterium and the methods which are used to identify its compounds such as infrared, nuclear magnetic resonance, and mass spectroscopy. 37 refs., 2 figs

  6. Spin polarized deuterium

    International Nuclear Information System (INIS)

    Glyde, H.R.; Hernadi, S.I.

    1986-01-01

    Several ground state properties of (electron) spin-polarized deuterium (D) such as the energy, single quasiparticle energies and lifetimes, Landau parameters and sound velocities are evaluated. The calculations begin with the Kolos-Wolneiwicz potential and use the Galitskii-FeynmanHartree-Fock (GFHF) approximation. The deuteron nucleas has spin I = 1, and spin states I/sub z/ = 1,0,-1. We explore D 1 , D 2 and D 3 in which, respectively, one spin state only is populated, two states are equally populated, and three states are equally populated. We find the GFHF describes D 1 well, but D 2 and D 3 less well. The Landau parameters, F/sub L/, are small compared to liquid 3 He and very small for doubly polarized D 1 (i.e. the F/sub L/ decrease with nuclear polarization)

  7. Burn performance of deuterium-tritium, deuterium-deuterium, and catalyzed deuterium ICF targets

    International Nuclear Information System (INIS)

    Harris, D.B.; Blue, T.E.

    1983-01-01

    The University of Illinois hydrodynamic burn code, AFBURN, has been used to model the performance of homogeneous D-T, D 2 , and catalyzed deuterium ICF targets. Yields and gains are compared for power-producing targets. AFBURN is a one-dimensional, two-temperature, single-fluid hydrodynamic code with non-local fusion product energy deposition. The initial conditions for AFBURN are uniformly compressed targets with central hot spots. AFBURN predicts that maximum D 2 target gains are obtained for target rhoR and spark rhoR about seven times larger than the target and spark rhoR for maximum D-T target gains, that the maximum D 2 target gain is approximately one third of the maximum D-T target gain, and that the corresponding yields are approximately equal. By recycling tritium and 3 He from previous targets, D 2 target performance can be improved by about 10%. (author)

  8. Experiments regarding organism behaviour under deuterium-depleted water influence

    International Nuclear Information System (INIS)

    Stefanescu, I.; Steflea, D.; Titescu, Gh.

    1999-01-01

    Deuterium-depleted water (DDW) is water that has an deuterium content D/(D+H) lower than 145 ppm. The role of naturally occurring D in living organisms was examined by using DDW instead of natural water. The DDW significantly decreased the growth rate of the L 929 fibroblast cell line and also inhibited the tumour growth. These suggest that the naturally occurring D has a central role in signal transduction involved in cell cycle regulation. Beginning with 1996, Institute of Cryogenics and Isotopic Separation, a DDW producer, co-operated with Romanian specialized institutes for evaluation of biological effects of DDW. These investigation lead to the following conclusions: 1. DDW caused a tendency of increasing the basal tone, accompanied by intensification of vasoconstrictor effects of phenylephrine, noradrenaline and angiotensin; the increase of the basal tone and vascular reactivity produced by DDW persists after removing the vascular in endothelium. 2. DDW stimulates immunodefence reactions, represented by the opsonic, bactericidal and phagocyte capacity of the immune system, together with increase in the number of polymorphonuclear neutrophils. 3. Animals treated with DDW showed an increase of the resistance both to the sublethal and to lethal gamma radiation doses, suggesting a radioprotective action. 4. Investigation regarding artificial reproduction of fish with DDW fecundated solutions confirmed favourable influence both in embryo growth stage and resistance in the following growing stages. 5. It was studied germination, growth and quantitative character variability of two genotypes of Avena Sativa; one can remark the favourable influence of DDW on biological process in plants in various ontogenetic stages. (authors)

  9. Carbon-13 kinetic isotope effects in the decarbonylation of lactic acid of natural isotopic composition in phosphoric acid medium

    International Nuclear Information System (INIS)

    Zielinski, M.; Czarnota, G.; Papiernik-Zielinska, H.; Kasprzyk, G.; Gumolka, L.; Staedter, W.

    1993-01-01

    The 13 C kinetic isotope effect fractionation in the decarbonylation of lactic acid (LA) of natural isotopic composition by concentrated phosphoric acids (PA) and by 85% H 3 PO 4 has been studied in the temperature interval of 60-150 deg C. The values of the 13 C (1) isotope effects in the decarbonylation of lactic acid in 100% H 3 PO 4 , in pyrophosphoric acid and in more concentrated phosphoric acids are intermediate between the values calculated assuming that the C (1)- OH bond is broken in the rate-controlling step of dehydration and those calculated for rupture of the carbon-carbon bond in the transition state. In the temperature interval of 90-130 deg C the experimental 13 C fractionation factors determined in concentrated PA approach quite closely the 13 C fractionation corresponding to C (2)- C (1) bond scission. The 13 C (1) kinetic isotope effects in the decarbonylation of LA in 85% orthophosphoric acid in the temperature range of 110-150 deg C coincide with the 13 C isotope effects calculated assuming that the frequency corresponding to the C (1) -OH vibration is lost in the transition state of decarbonylation. A change of the mechanism of decarbonylation of LA in going from concentrated PA medium to 85% H 3 PO 4 has been suggested. A possible secondary 18 O and a primary 18 O kinetic isotope effect in decarbonylation of lactic acid in phosphoric acids media have been discussed, too. (author) 21 refs.; 3 tabs

  10. Isotope effects in ion-exchange equilibria in aqueous and mixed solvent systems

    International Nuclear Information System (INIS)

    Gupta, A.R.

    1979-01-01

    Isotope effects in ion-exchange equilibria in aqueous and mixed solvents are analyzed in terms of the general features of ion-exchange equilibria and of isotope effects in chemical equilibria. The special role of solvent fractionation effects in ion-exchange equilibria in mixed solvents is pointed out. The various situations arising in isotope fractionation in ion exchange in mixed solvents due to solvent fractionation effects are theoretically discussed. The experimental data on lithium isotope effects in ion-exchange equilibria in mixed solvents are shown to conform to the above situations. The limitations of ion-exchange equilibria in mixed solvents for isotope fractionation are pointed out. 3 tables

  11. 2ΔH(D) and 1ΔN(D) isotope effects on nuclear shielding of ammonium ions in complexes with crown ethers and cryptands

    International Nuclear Information System (INIS)

    Hansen, P.E.; Hansen, Aa.E.; Lycka, A.; Buvari-Barcza, A.

    1993-01-01

    One-bond deuterium isotope effects on nitrogen nuclear shielding, 1 ΔN(D) and two-bond isotope effects at 1 H nuclear shielding, 2 ΔH(D), have been investigated in a series of inclusion complexes. The hosts comprise, SC-24, [2.2.2], [2.2.1], [2.2.1] D, [2.2] DD, K5, 18-crown-6 and 18-crown-6 tetracarboxylic acid. The structure of the host [2.2.1] is discussed based on isotope effects and 1 H chemical shifts, and an interesting exchange reaction is observed between CDCl 3 and ammonium ions in the [2.2.1] complex. The counterion dependence is shown to be zero for ammonium ions fully included in cages such as SC-24 and [2.2.2] and for 18-C-6(COOH) 4 . For cryptands and podands such as [2.2.1] and K5 a weak counterion dependence of 2 ΔH(D) opposite to that found for ammonium ions in water is observed, while 1 ΔN(D) and 15 N chemical shifts depend very strongly on the counterions, as also found for ammonium ions in water solution. The anilinium ion shows effects similar to those observed for the ammonium ion. 1 ΔN(D) isotope effects correlate well with δN and 2 ΔH(D) correlate with δNH. The correlation between 1 ΔN(D) and 2 ΔH(D) is different for ammonium ions in water and ions included in crowns, cryptands or podands. This shows that different mechanisms are operating. The 2 ΔH(D) isotope effects and δNH chemical shifts depend on the distance to the nearest acceptor (oxygen or nitrogen), and they also depend on the type of acceptor. 2 ΔH(D) isotope effects are found to be a good gauge of N ... N or N ... O distances of the inclusion complexes. The 2 ΔH(D) isotope effects vary with temperature, but the dramatic changes in the 1 H NMR spectra of the host are not reflected in the isotope effects. The one-bond couplings, 1 J(N,H), correlate with 2 ΔH(D). The variations are much larger for the cryptands than found in water solutions. (au) (50 refs.)

  12. Process for the production of high purity deuterium

    International Nuclear Information System (INIS)

    Arrathoon, R.

    1977-01-01

    A process for the electrolysis of heavy water which results in the production of high purity deuterium without periodic replenishment of the electrolyte with additional deuterated compounds is defined. Electrolysis is effected through the use of an inexpensive cation-action permselective membrane which is essentially a solid polymer electrolyte and which is capable of automatically separating the evolved deuterium and oxygen gas. This cation-active permselective membrane does not introduce any intrinsic impurities or tritium contamination in the generated deuterium gas, does not require periodic revitalization with deuterated compounds or other chemical compounds, and is characterized by an unusually high electrical efficiency

  13. Aerodynamic effects in isotope separation by gaseous diffusion

    International Nuclear Information System (INIS)

    Bert, L.A.; Prosperetti, A.; Fiocchi, R.

    1978-01-01

    The turbulent flow of an isotopic mixture in a porous-walled pipe is considered in the presence of suction through the wall. A simple model is formulated for the evaluation of aerodynamic effects on the separation efficiency. The predictions of the model are found to compare very favourably with experiment. In the limit of small suction velocities, results obtained by other investigators for diffusion in a turbulent steam are recovered. (author)

  14. Ethanol-metabolizing pathways in deermice. Estimation of flux calculated from isotope effects

    International Nuclear Information System (INIS)

    Alderman, J.; Takagi, T.; Lieber, C.S.

    1987-01-01

    The apparent deuterium isotope effects on Vmax/Km (D(V/K] of ethanol oxidation in two deermouse strains (one having and one lacking hepatic alcohol dehydrogenase (ADH] were used to calculate flux through the ADH, microsomal ethanol-oxidizing system (MEOS), and catalase pathways. In vitro, D(V/K) values were 3.22 for ADH, 1.13 for MEOS, and 1.83 for catalase under physiological conditions of pH, temperature, and ionic strength. In vivo, in deermice lacking ADH (ADH-), D(V/K) was 1.20 +/- 0.09 (mean +/- S.E.) at 7.0 +/- 0.5 mM blood ethanol and 1.08 +/- 0.10 at 57.8 +/- 10.2 mM blood ethanol, consistent with ethanol oxidation principally by MEOS. Pretreatment of ADH- animals with the catalase inhibitor 3-amino-1,2,4-triazole did not significantly change D(V/K). ADH+ deermice exhibited D(V/K) values of 1.87 +/- 0.06 (untreated), 1.71 +/- 0.13 (pretreated with 3-amino-1,2,4-triazole), and 1.24 +/- 0.13 (after the ADH inhibitor, 4-methylpyrazole) at 5-7 mM blood ethanol levels. At elevated blood ethanol concentrations (58.1 +/- 2.4 mM), a D(V/K) of 1.37 +/- 0.21 was measured in the ADH+ strain. For measured D(V/K) values to accurately reflect pathway contributions, initial reaction conditions are essential. These were shown to exist by the following criteria: negligible fractional conversion of substrate to product and no measurable back reaction in deermice having a reversible enzyme (ADH). Thus, calculations from D(V/K) indicate that, even when ADH is present, non-ADH pathways (mostly MEOS) participate significantly in ethanol metabolism at all concentrations tested and play a major role at high levels

  15. Vapour pressure isotope effects in liquid hydrogen chloride

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, J.N.C.; Calado, J.C.G. (Instituto Superior Tecnico, Lisbon (Portugal)); Jancso, Gabor (Hungarian Academy of Sciences, Budapest (Hungary). Central Research Inst. for Physics)

    1992-08-10

    The difference between the vapour pressures of HCl and DCl has been measured over the temperature range 170-203 K by a differential manometric technique in a precision cryostat. In this range the vapour pressure of HCl is higher than that of DCl by 3.2% at 170 K, decreasing to 0.9% at 200 K. The reduced partition function ratios f[sub l]/f[sub g] derived from the vapour pressure data can be described by the equation ln(f[sub l]/f[sub g]) = (3914.57[+-]10)/T[sup 2] - (17.730[+-]0.055)/T. The experimentally observed H-D vapour pressure isotope effect, together with the values on the [sup 35]Cl-[sup 37]Cl isotope effect available in the literature, is interpreted in the light of the statistical theory of isotope effects in condensed systems by using spectroscopic data of the vapour and liquid phases. The results indicate that the rotation in liquid hydrogen chloride is hindered. Temperature-dependent force constants for the hindered translational and rotational motions were invoked in order to obtain better agreement between the model calculation and experiment. (author).

  16. Effect of Interband Interaction on Isotope Effect Coefficient of Mg B2 Superconductors

    International Nuclear Information System (INIS)

    Udomsamuthirun, P.; Kumvongsa, C.; Burakorn, A.; Changkanarth, P.; Maneeratanakul, S.

    2005-10-01

    In this research, the exact formula of Tc s equation and the isotope effect coefficient of two-band s-wave superconductors in weak-coupling limit are derived by considering the influence of interband interaction .In each band ,our model consist of two paring interactions : the electron-phonon interaction and non-electron-phonon interaction . According to the numerical calculation, we find that the isotope effect coefficient of MgB 2 , α=3 . 0 with T c 40 K can be found in the weak coupling regime and interband interaction of electron-phonon show more effect on isotope effect coefficient than interband interaction of non-phonon-electron

  17. Hydrogen-deuterium exchange in imidazole as a tool for studying histidine phosphorylation.

    Science.gov (United States)

    Cebo, Małgorzata; Kielmas, Martyna; Adamczyk, Justyna; Cebrat, Marek; Szewczuk, Zbigniew; Stefanowicz, Piotr

    2014-12-01

    Isotope exchange at the histidine C2 atom of imidazole in D2O solution is well known to occur at a significantly slower rate than the exchange of amide protons. Analysis of the kinetics of this isotope-exchange reaction is proposed herein as a method of detecting histidine phosphorylation. This modification of His-containing peptides is challenging to pinpoint because of its instability under acidic conditions as well as during CID-MS analysis. In this work, we investigated the effect of phosphorylation of the histidine side chain in peptides on deuterium-hydrogen exchange (DHX) in the imidazole. The results demonstrate that phosphorylation dramatically slows the rate of the DHX reaction. This phenomenon can be applied to detect phosphorylation of peptides at the histidine residue (e.g., in enzymatic digests). We also found that the influence of the peptide sequence on the exchange kinetics is relatively small. A CID fragmentation experiment revealed that there was no detectable hydrogen scrambling in peptides deuterated at C2 of the imidazole ring. Therefore, MS/MS can be used to directly identify the locations of deuterium ions incorporated into peptides containing multiple histidine moieties.

  18. Isotopic modeling of the sub-cloud evaporation effect in precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Salamalikis, V., E-mail: vsalamalik@upatras.gr [Laboratory of Atmospheric Physics, Department of Physics, University of Patras, GR 26500 Patras (Greece); Argiriou, A.A. [Laboratory of Atmospheric Physics, Department of Physics, University of Patras, GR 26500 Patras (Greece); Dotsika, E. [Stable Isotope Unit, Institute of Nanoscience and Nanotechnology, National Center of Scientific Research ‘Demokritos’, Ag. Paraskevi Attikis, 15310 Athens (Greece)

    2016-02-15

    In dry and warm environments sub-cloud evaporation influences the falling raindrops modifying their final stable isotopic content. During their descent from the cloud base towards the ground surface, through the unsaturated atmosphere, hydrometeors are subjected to evaporation whereas the kinetic fractionation results to less depleted or enriched isotopic signatures compared to the initial isotopic composition of the raindrops at cloud base. Nowadays the development of Generalized Climate Models (GCMs) that include isotopic content calculation modules are of great interest for the isotopic tracing of the global hydrological cycle. Therefore the accurate description of the underlying processes affecting stable isotopic content can improve the performance of iso-GCMs. The aim of this study is to model the sub-cloud evaporation effect using a) mixing and b) numerical isotope evaporation models. The isotope-mixing evaporation model simulates the isotopic enrichment (difference between the ground and the cloud base isotopic composition of raindrops) in terms of raindrop size, ambient temperature and relative humidity (RH) at ground level. The isotopic enrichment (Δδ) varies linearly with the evaporated raindrops mass fraction of the raindrop resulting to higher values at drier atmospheres and for smaller raindrops. The relationship between Δδ and RH is described by a ‘heat capacity’ model providing high correlation coefficients for both isotopes (R{sup 2} > 80%) indicating that RH is an ideal indicator of the sub-cloud evaporation effect. Vertical distribution of stable isotopes in falling raindrops is also investigated using a numerical isotope-evaporation model. Temperature and humidity dependence of the vertical isotopic variation is clearly described by the numerical isotopic model showing an increase in the isotopic values with increasing temperature and decreasing RH. At an almost saturated atmosphere (RH = 95%) sub-cloud evaporation is negligible and the

  19. Isotopic modeling of the sub-cloud evaporation effect in precipitation

    International Nuclear Information System (INIS)

    Salamalikis, V.; Argiriou, A.A.; Dotsika, E.

    2016-01-01

    In dry and warm environments sub-cloud evaporation influences the falling raindrops modifying their final stable isotopic content. During their descent from the cloud base towards the ground surface, through the unsaturated atmosphere, hydrometeors are subjected to evaporation whereas the kinetic fractionation results to less depleted or enriched isotopic signatures compared to the initial isotopic composition of the raindrops at cloud base. Nowadays the development of Generalized Climate Models (GCMs) that include isotopic content calculation modules are of great interest for the isotopic tracing of the global hydrological cycle. Therefore the accurate description of the underlying processes affecting stable isotopic content can improve the performance of iso-GCMs. The aim of this study is to model the sub-cloud evaporation effect using a) mixing and b) numerical isotope evaporation models. The isotope-mixing evaporation model simulates the isotopic enrichment (difference between the ground and the cloud base isotopic composition of raindrops) in terms of raindrop size, ambient temperature and relative humidity (RH) at ground level. The isotopic enrichment (Δδ) varies linearly with the evaporated raindrops mass fraction of the raindrop resulting to higher values at drier atmospheres and for smaller raindrops. The relationship between Δδ and RH is described by a ‘heat capacity’ model providing high correlation coefficients for both isotopes (R"2 > 80%) indicating that RH is an ideal indicator of the sub-cloud evaporation effect. Vertical distribution of stable isotopes in falling raindrops is also investigated using a numerical isotope-evaporation model. Temperature and humidity dependence of the vertical isotopic variation is clearly described by the numerical isotopic model showing an increase in the isotopic values with increasing temperature and decreasing RH. At an almost saturated atmosphere (RH = 95%) sub-cloud evaporation is negligible and the

  20. Direct depth distribution measurement of deuterium in bulk tungsten exposed to high-flux plasma

    Directory of Open Access Journals (Sweden)

    C. N. Taylor

    2017-05-01

    Full Text Available Understanding tritium retention and permeation in plasma-facing components is critical for fusion safety and fuel cycle control. Glow discharge optical emission spectroscopy (GD-OES is shown to be an effective tool to reveal the depth profile of deuterium in tungsten. Results confirm the detection of deuterium. A ∼46 μm depth profile revealed that the deuterium content decreased precipitously in the first 7 μm, and detectable amounts were observed to depths in excess of 20 μm. The large probing depth of GD-OES (up to 100s of μm enables studies not previously accessible to the more conventional techniques for investigating deuterium retention. Of particular applicability is the use of GD-OES to measure the depth profile for experiments where high deuterium concentration in the bulk material is expected: deuterium retention in neutron irradiated materials, and ultra-high deuterium fluences in burning plasma environment.

  1. Stable isotopic characteristic of Taiwan's precipitation: A case study of western Pacific monsoon region

    Science.gov (United States)

    Peng, Tsung-Ren; Wang, Chung-Ho; Huang, Chi-Chao; Fei, Li-Yuan; Chen, Chen-Tung Arthur; Hwong, Jeen-Lian

    2010-01-01

    The stable oxygen and hydrogen isotopic features of precipitation in Taiwan, an island located at the western Pacific monsoon area, are presented from nearly 3,500 samples collected during the past decade for 20 stations. Results demonstrate that moisture sources from diverse air masses with different isotopic signals are the main parameter in controlling the precipitation's isotope characteristics. The air mass from polar continental (Pc) region contributes the precipitation with high deuterium excess values (up to 23‰) and relatively enriched isotope compositions (e.g., - 3.2‰ for δ 18O) during the winter with prevailing northeasterly monsoon. By contrast, air masses from equatorial maritime (Em) and tropical maritime (Tm) supply the precipitation with low deuterium excess values (as low as about 7‰) and more depleted isotope values (e.g., - 8.9‰ and - 6.0‰ for δ 18O of Tm and Em, respectively) during the summer with prevailing southwesterly monsoon. Thus seasonal differences in terms of δ 18O, δD, and deuterium excess values are primarily influenced by the interactions among various precipitation sources. While these various air masses travel through Taiwan, secondary evaporation effects further modify the isotope characteristics of the inland precipitation, such as raindrop evaporation (reduces the deuterium excess of winter precipitation) and moisture recycling (increases the deuterium excess of summer precipitation). The semi-quantitative estimations in terms of evaluation for changes in the deuterium excess suggest that the raindrop evaporation fractions for winter precipitation range 7% to 15% and the proportions of recycling moisture in summer precipitation are less than 5%. Additionally, the isotopic altitude gradient in terms of δ 18O for summer precipitation is - 0.22‰/100 m, greater than - 0.17‰/100 m of winter precipitation. The greater isotopic gradient in summer can be attributed to a higher temperature vs. altitude gradient

  2. Application of Deuterium and Oxygen-18 to Trace Leachate Movement in Bantar Gebang Sanitary Landfill

    International Nuclear Information System (INIS)

    Pujiindiyati, E.R.

    2011-01-01

    Bantar Gebang landfill was constructed in 1986 with total area of 108 ha and approximately 6000 ton/day solid waste is disposed to this landfill. Mostly, the people living surrounding landfill get afraid of impact of the hazardous chemicals produced by waste disposal to their health. The purpose of this investigation was to study the migration of leachate to Cibitung River water and shallow groundwaters near to the river. It is possible to be done because chemical contents and isotopic characteristics of municipal landfill leachate are unique, relative to aqueous media in the most natural environments. Laser absorption method developed by the LGR (Los Gatos Research) was used to measure absolute abundances of 2 HHO, HH 18 O and HHO in a number of water samples. In-situ measurements were also conducted as an additional parameter besides their isotopes. The δ 2 H of the H 2 O in landfill leachate was significantly enriched, with values of - 22.6 0/00 to + 4.3 0/00. This deuterium enrichment was undoubtedly due to the extensive production of microbial methane within the limited reservoir of the landfill. However, the enriched deuterium value in leachate was not detected in the river which still had depleted values. It was probably caused by the amount of natural water in the river was comparatively large, with respect to limited leachate discarded to the river. The electrical conductivity of the leachate was higher (3200 to 7600 μS) and the decreasing values were still monitored in the river to approximately 12 km after streaming the landfills. The effect of the high electrical conductivity and enriched deuterium of leachate was not clearly indicated in the groundwater samples which still represented the local precipitation recharge, except a monitoring well located in Bantar Gebang landfill area which has an indication of leachate contamination. (author)

  3. Application of Deuterium and Oxygen-18 to Trace Leachate Movement in Bantar Gebang Sanitary Landfill

    Directory of Open Access Journals (Sweden)

    E.R. Pujiindiyati

    2011-08-01

    Full Text Available Bantar Gebang landfill was constructed in 1986 with total area of 108 ha and approximately 6000 ton/day solid waste is disposed to this landfill. Mostly, the people living surrounding landfill get afraid of impact of the hazardous chemicals produced by waste disposal to their health. The purpose of this investigation was to study the migration of leachate to Cibitung River water and shallow groundwaters near to the river. It is possible to be done because chemical contents and isotopic characteristics of municipal landfill leachate are unique, relative to aqueous media in the most natural environments. Laser absorption method developed by the LGR (Los Gatos Research was used to measure absolute abundances of 2HHO, HH18O and HHO in a number of water samples. In-situ measurements were also conducted as an additional parameter besides their isotopes. The δ2H of the H2O in landfill leachate was significantly enriched, with values of - 22.6 ‰ to + 4.3 ‰. This deuterium enrichment was undoubtedly due to the extensive production of microbial methane within the limited reservoir of the landfill. However, the enriched deuterium value in leachate was not detected in the river which still had depleted values. It was probably caused by the amount of natural water in the river was comparatively large, with respect to limited leachate discarded to the river.The electrical conductivity of the leachate was higher (3200 to 7600 S and the decreasing values were still monitored in the river to approximately 12 km after streaming the landfills. The effect of the high electrical conductivity and enriched deuterium of leachate was not clearly indicated in the groundwater samples which still represented the local precipitation recharge, except a monitoring well located in Bantar Gebang landfill area which has an indication of leachate contamination.

  4. Deuterium Depth Profile in Neutron-Irradiated Tungsten Exposed to Plasma

    International Nuclear Information System (INIS)

    Shimada, Masashi; Cao, G.; Hatano, Y.; Oda, T.; Oya, Y.; Hara, M.; Calderoni, P.

    2011-01-01

    The effect of radiation damage has been mainly simulated using high-energy ion bombardment. The ions, however, are limited in range to only a few microns into the surface. Hence, some uncertainty remains about the increase of trapping at radiation damage produced by 14 MeV fusion neutrons, which penetrate much farther into the bulk material. With the Japan-US joint research project: Tritium, Irradiations, and Thermofluids for America and Nippon (TITAN), the tungsten samples (99.99 % pure from A.L.M.T., 6mm in diameter, 0.2mm in thickness) were irradiated to high flux neutrons at 50 C and to 0.025 dpa in the High Flux Isotope Reactor (HFIR) at the Oak Ridge National Laboratory (ORNL). Subsequently, the neutron-irradiated tungsten samples were exposed to a high-flux deuterium plasma (ion flux: 1021-1022 m-2s-1, ion fluence: 1025-1026 m-2) in the Tritium Plasma Experiment (TPE) at the Idaho National Laboratory (INL). First results of deuterium retention in neutron-irradiated tungsten exposed in TPE have been reported previously. This paper presents the latest results in our on-going work of deuterium depth profiling in neutron-irradiated tungsten via nuclear reaction analysis. The experimental data is compared with the result from non neutron-irradiated tungsten, and is analyzed with the Tritium Migration Analysis Program (TMAP) to elucidate the hydrogen isotope behavior such as retention and depth distribution in neutron-irradiated and non neutron-irradiated tungsten.

  5. Measurement and Characterization of Hydrogen-Deuterium Exchange Chemistry Using Relaxation Dispersion NMR Spectroscopy.

    Science.gov (United States)

    Khirich, Gennady; Holliday, Michael J; Lin, Jasper C; Nandy, Aditya

    2018-03-01

    One-dimensional heteronuclear relaxation dispersion NMR spectroscopy at 13 C natural abundance successfully characterized the dynamics of the hydrogen-deuterium exchange reaction occurring at the N ε position in l-arginine by monitoring C δ in varying amounts of D 2 O. A small equilibrium isotope effect was observed and quantified, corresponding to ΔG = -0.14 kcal mol -1 . A bimolecular rate constant of k D = 5.1 × 10 9 s -1 M -1 was determined from the pH*-dependence of k ex (where pH* is the direct electrode reading of pH in 10% D 2 O and k ex is the nuclear spin exchange rate constant), consistent with diffusion-controlled kinetics. The measurement of ΔG serves to bridge the millisecond time scale lifetimes of the detectable positively charged arginine species with the nanosecond time scale lifetime of the nonobservable low-populated neutral arginine intermediate species, thus allowing for characterization of the equilibrium lifetimes of the various arginine species in solution as a function of fractional solvent deuterium content. Despite the system being in fast exchange on the chemical shift time scale, the magnitude of the secondary isotope shift due to the exchange reaction at N ε was accurately measured to be 0.12 ppm directly from curve-fitting D 2 O-dependent dispersion data collected at a single static field strength. These results indicate that relaxation dispersion NMR spectroscopy is a robust and general method for studying base-catalyzed hydrogen-deuterium exchange chemistry at equilibrium.

  6. Synthesis of deuterium-labelled compounds for FOTEK project

    International Nuclear Information System (INIS)

    Joergensen, O.; Egsgaard, H.; Larsen, E.

    1996-01-01

    In the FoTech project there have been utilized labelled compounds of stable isotopes as internal standards. Some of these compounds are commercially available ( 13 C-labelled PCB congeners, 13 C-labelled diethylstilbestrol for determination of anabolic steroids). Others, like D 9 -clenbuterol, D 3 -clenbuterol, D 3 -zeramol and D 3 -dimetridazol have been synthesized. General aspects of deuterium compounds labelling are considered. (EG)

  7. Product study of 1-adamantyl and 1-bicyclo[2.2.2]octyl radicals in hydrocarbon solvents. An unusually large hydrogen isotope effect

    International Nuclear Information System (INIS)

    Engel, P.S.; Chae, W.K.; Baughman, S.A.; Marschke, G.E.; Lewis, E.S.; Timberlake, J.W.; Luedtke, A.E.

    1983-01-01

    1-Adamantyl (ada.) and 1-bicyclo[2.2.2]octyl (bo.) radicals have been generated by photolysis of the corresponding azoalkanes in various hydrocarbon solvents. Both radicals abstract hydrogen readily from saturated hydrocarbons and they add to aromatic rings much faster than tert-butyl. does. Despite its reactivity, ada. is remarkably selective in hydrogen atom abstraction, preferring a benzylic hydrogen 25:1 over a cyclohexane hydrogen. The effect of solvent viscosity indicates that formation of the radical dimers biada and bibo occurs in the solvent cage. The most striking result of this work is a deuterium isotope effect of 25 for hydrogen transfer from cyclohexane to ada. at 65 0 C. Steric compression in the transition state is postulated to cause an unusually large tunnel correction and hence a large k/sub H//k/sub D/. 6 tables

  8. Carbon-13 isotope effects on 199Hg nuclear shielding

    International Nuclear Information System (INIS)

    Sebald, Angelika; Wrackmeyer, Bernd

    1985-01-01

    Secondary 13 C/ 12 C isotope effects on 199 Hg nuclear shielding (Δdeltasup(i)( 199 Hg)) are of interest because of the unusual shift to high frequency which has been observed for a few alkyl mercury compounds. Continuing interest in the NMR parameters of mercury compounds prompted a search for the values Δdeltasup(i)( 199 Hg) in a greater variety of organomercurials. This should help to find out about the range of Δdeltasup(i)( 199 Hg) and to obtain a firmer basis for the discussion of the high-frequency shifts. The data and experimental conditions are given for chemical shifts delta 199 Hg, coupling constants sup(n)J( 199 Hg 13 C) and 13 C/ 12 C isotope shifts Δdeltasup(i)( 199 Hg) of fourteen 199 Hg organomercury compounds. The results are discussed. (author)

  9. On line determination of deuterium in hydrogen water exchange reaction by mass spectrometry. IRP-10

    International Nuclear Information System (INIS)

    Sharma, J.D.; Alphonse, K.P.; Mishra, Sushama; Prabhu, S.A.; Mohan, Sadhana; Tangri, V.K.

    2007-01-01

    The Deuterium (D)/Hydrogen (H) analysis at low Concentration is generally carried out by Mass Spectrometry. Mass Spectrometer is specially designed for the measurement of Mass 2 and 3 ratio. The Deuterium analysis of water and hydrogen in concentration range of a few ppm to about 1% plays an important role in the Heavy Water Production Plants. For the enrichment of the Deuterium concentration in H 2 O by H 2 - H 2 O exchange a catalyst is essential as reaction is relatively slow. Heavy Water Division has developed in house Platinum based catalyst for the isotopic exchange of Hydrogen and Water

  10. Kinetic isotope effects and how to describe them

    Directory of Open Access Journals (Sweden)

    Konstantin Karandashev

    2017-11-01

    Full Text Available We review several methods for computing kinetic isotope effects in chemical reactions including semiclassical and quantum instanton theory. These methods describe both the quantization of vibrational modes as well as tunneling and are applied to the ⋅H + H2 and ⋅H + CH4 reactions. The absolute rate constants computed with the semiclassical instanton method both using on-the-fly electronic structure calculations and fitted potential-energy surfaces are also compared directly with exact quantum dynamics results. The error inherent in the instanton approximation is found to be relatively small and similar in magnitude to that introduced by using fitted surfaces. The kinetic isotope effect computed by the quantum instanton is even more accurate, and although it is computationally more expensive, the efficiency can be improved by path-integral acceleration techniques. We also test a simple approach for designing potential-energy surfaces for the example of proton transfer in malonaldehyde. The tunneling splittings are computed, and although they are found to deviate from experimental results, the ratio of the splitting to that of an isotopically substituted form is in much better agreement. We discuss the strengths and limitations of the potential-energy surface and based on our findings suggest ways in which it can be improved.

  11. THE EFFECT OF SPRUCE BARK POLYPHENOLS EXTRACT IN COMBINATION WITH DEUTERIUM DEPLETED WATER (DDW ON GLYCINE MAX L. AND HELIANTHUS ANNUUS L. DEVELOPMENT

    Directory of Open Access Journals (Sweden)

    Corneliu Tanase

    2010-09-01

    Full Text Available The aim of this study was to evaluate the effect of spruce bark aqueous extract and deuterium depleted water (DDW as bioregulators on the plant growth Glycine max L. and Helianthus annuus. The following specific parameteres were closely monitorised: germination energy and germination capacity, plants vegetative organelles growth and development and photoassimilatory pigments concentrations. The results have shown that DDW presents different effects depending on tested plant species. In the case of soybean, DDW presented stimulatory effects on both germination energy and capacity, radicles elongation, primary leaves growth and development but inhibitory effects on photoassimilatory pigments. Spruce bark extract reduced the germination capacity of soybean seeds, but accelerated the germination process of sunflower seeds and present stimulatory effects on plantlets biomass accumulation. The combination of DDW with Picea abies polyphenolic extract promoted soybean plantlet elongation, especially the rootlets ones and stimulated green biomass accumulation for both soybean and sunflower plantlets. Analyzing the photoassimilatory pigments concentration for sunflower, it can be observed an increasing trend (almost 100% comparing with control when introduce into the growth medium DDW and P. abies polyphenolic extract. DDW and P. abies bark extract have shown an important role in plant growth and development, improving photoassimiliation process.

  12. Use of Fourier transformed infrared spectrophotometer (FTIR) for determination of breastmilk output by the deuterium dilution method among Senegalese women

    International Nuclear Information System (INIS)

    Sarr Cisse, Aita; Diaham, Babou; Dossou, Nicole; Guiro, Amadou Tidiane; Wade, Salimata; Bluck, Leslie

    2002-01-01

    Breastmilk output can be estimated from the mother's total body water and water turnover rates after oral administration of deuterium oxide. Usually the deuterium enrichments are determined using a isotope ratio mass spectrometer, which is expensive and requires a specialist for operation and maintenance. Such equipment is dfficult to set up in developing countries. A less expensive method was developed which uses a Fourier transform infrared spectrophotometer (FTIR) for deuterium enrichment analysis. This study evaluated the constraints of using FTIR to study lactating women in Senegal. The deuterium isotope method was found to be adequate for free living subjects and presented few constraints except for the duration of the saliva sampling (14 days). The method offers the opportunity to determine simultaneously breastmilk output, mother's body composition, and breastfeeding practices. Deuterium sample enrichments measured with FTIR were fast and easy, but for spectrum quality some environmental control is required to optimize the results. (Authors)

  13. Magnetic field and magnetic isotope effects on photochemical reactions

    International Nuclear Information System (INIS)

    Wakasa, Masanobu

    1999-01-01

    By at present exact experiments and the theoretical analysis, it was clear that the magnetic field less than 2 T affected a radical pair reaction and biradical reaction. The radical pair life and the dissipative radical yield showed the magnetic field effects on chemical reactions. The radical pair mechanism and the triplet mechanism were known as the mechanism of magnetic field effects. The radical pair mechanism consists of four mechanisms such as the homogeneous hyperfine interaction (HFC), the delta-g mechanism, the relaxation mechanism and the level cross mechanism. In order to observe the magnetic effects of the radical pair mechanism, two conditions need, namely, the recombination rate of singlet radical pair > the dissipation rate and the spin exchange rate > the dissipation rate. A nanosecond laser photo-decomposition equipment can observe the magnetic field effects. The inversion phenomena of magnetic field effect, isolation of the relaxation mechanism and the delta-g mechanism, the magnetic field effect of heavy metal radical reaction, the magnetic field effect in homogeneous solvent, saturation of delta-g mechanism are explained. The succeeded examples of isotope concentration by the magnetic isotope effect are 17 O, 19 Si, 33 S, 73 Ge and 235 U. (S.Y.)

  14. Synthesis of deuterium-labelled compounds for FOTEK project; Syntese af deuterium-maerkede forbindelser til FOeTEK projektet

    Energy Technology Data Exchange (ETDEWEB)

    Joergensen, O.; Egsgaard, H.; Larsen, E. [Forskningscenter Risoe, Roskilde (Denmark)

    1996-06-01

    In the FoTech project there have been utilized labelled compounds of stable isotopes as internal standards. Some of these compounds are commercially available ({sup 13}C-labelled PCB congeners, {sup 13}C-labelled diethylstilbestrol for determination of anabolic steroids). Others, like D{sub 9}-clenbuterol, D{sub 3}-clenbuterol, D{sub 3}-zeramol and D{sub 3}-dimetridazol have been synthesized. General aspects of deuterium compounds labelling are considered. (EG).

  15. Catalyzed deuterium fueled tokamak reactors

    International Nuclear Information System (INIS)

    Southworth, F.H.

    1977-01-01

    Catalyzed deuterium fuel presents several advantages relative to D-T. These are, freedom from tritium breeding, high charged particle power fraction and lowered neutron energy deposition in the blanket. Higher temperature operation, lower power densities and increased confinement are simultaneously required. However, the present study has developed designs which have capitalized upon the advantages of catalyzed deuterium to overcome the difficulties associated with the fuel while obtaining high efficiency

  16. Salt effects on isotope partitioning and their geochemical implications: An overview

    International Nuclear Information System (INIS)

    Horita, J.; Cole, D.R.; Fortier, S.M.

    1996-01-01

    Essential to the use of stable isotopes as natural tracers and geothermometers is the knowledge of equilibrium isotope partitioning between different phases and species, which is usually a function of temperature only. The one exception known to date is oxygen and hydrogen isotope fractionation between liquid water and other phases (steam, gases, minerals), which changes upon the addition of salts to water, i.e., the isotope salt salt effect. Our knowledge of this effect, the difference between activity and composition (a-X) of isotopic water molecules in salt solutions, is very limited and controversial, especially at elevated temperatures. For the last several years, we have been conducting a detailed, systematic experimental study at Oak Ridge National Laboratory to determine the isotope salt effects from room temperature to elevated temperatures (currently to 500 degree C). From this effort, a simple, coherent picture of the isotope salt effect is emerging, that differs markedly from the complex results reported in the literature. In this communication, we present an overview on the isotope salt effect, obtained chiefly from our study. Observed isotope salt effects in salt solutions are significant even at elevated temperatures. The importance and implications of the isotope salt effect for isotopic studies of brine-dominated systems are also discussed in general terms

  17. Rapid deuterium exchange-in time for probing conformational change

    International Nuclear Information System (INIS)

    Dharmasiri, K.; Smith, D.L.

    1995-01-01

    Isotopic exchange of protein backbone amide hydrogens has been used extensively as a sensitive probe of protein structure. One of the salient features of hydrogen exchange is the vast range of exchange rates in one protein. Isotopic exchange methods have been used to study the structural features including protein folding and unfolding (1), functionally different forms of proteins (2), protein-protein complexation (3), and protein stability parameter. Many backbone amide protons that are surface accessible and are not involved in hydrogen bonding undergo rapid deuterium exchange. In order to study, fast exchanging amide protons, fast exchange-in times are necessary

  18. Isotope enrichment effect of gaseous mixtures in standing sound vibration

    International Nuclear Information System (INIS)

    Knesebeck, R.L.

    1984-01-01

    When standing acoustic waves are excited in a tube containing a mixture of two gases, a partial zonal fractioning of the components arises as consequence of mass transport by diffusion, driven by the thermal and pressure gradients which are associeted with the standing waves. This effect is present in each zone corresponding to a quarter wavelength, with the heavier component becoming enriched at the nodes fo the standing waves and deplected at the crests. The magnitude of the enrichment in one of the components of a binary gas mixture is given by Δω=ap 2 /lambda [b + (1-bω)] 2 . Where ω is the mass concentration of the component in the mixture, a and b are parameters which are related to molecular proprieties of the gases, p is the relative pressure amplitude of the standing wave and lambda is its wavelength. For a natural mixture of uranium hexafluorate, with 0.715% of the uranium isotope 340 an enrichment of about 2 x 10 -6 % in the concentration of this isotope is theorecticaly attainable per stage consisting of a quarter wavelenght, when a standing acoustical wave of relative pressure amplitude of 0,2 and wavelenght of 20 cm is used. Since standing acoustical waves are easely excited in gas columns, an isotope enrichment plant made of a cascade of tubes in which standing waves are excited, is presumably feasible with relatively low investment and operation costs. (Author) [pt

  19. Measurement of the deuterium concentration in water samples using a CW chemical deuterium fluoride laser

    International Nuclear Information System (INIS)

    Trautmann, M.

    1979-10-01

    In this study a new method for the determination of the deuterium content in water samples is described. The absorption of the radiation of a CW deuterium fluoride laser by the isotope HDO in the water vapor of the sample is measured by means of an optoacoustic detector (spectrophone). Thereby advantage is taken of the fact that H 2 O hardly absorbs the laser radiation and that D 2 O only exists in negligible concentrations. The isotope ratio of hydrogen can be calculated from the measured relative concentration of HDO. In the course of this investigation the relative absorption cross sections of HDO for the different laser lines were determined. It was thereby established that there exists a very good coincidence of an HDO absorption line with the 2P2 laser line. Using a very sensitive nonresonant spectrophone the relative concentration of HDO in natural water samples could be determined with an accuracy of about 10%. The experiments also demonstrated that with appropriate improvements made to the apparatus and using a second spectrophone as a reference it should be possible to increase this accuracy to 0,1%. (orig.)

  20. Carbon isotope effects in carbohydrates and amino acids of photosynthesizing organisms

    International Nuclear Information System (INIS)

    Ivlev, A.A.; Kaloshin, A.G.; Koroleva, M.Ya.

    1982-01-01

    The analysis of the carbon isotope distribution in carbohydrates and amino acids of some photosynthesizing organisms revealed the close relationship between distribution and the pathways of biosynthesis of the molecules. This relationship is explained on the basis of the previously proposed mechanism of carbon isotope fractionation in a cell, in which the chief part is played by kinetic isotope effects in the pyruvate decarboxylation reaction progressively increased in the conjugated processes of gluconeogenesis. Isotope differences of C 2 and C 3 fragments arising in decarboxylation of pyruvate, as well as isotope differences of biogenic acceptor and environmental CO 2 appearing in assimilation are the main reasons of the observed intramolecular isotopic heterogeneity of biomolecules. The heterogeneity is preserved in metabolites owing to an incomplete mixing of carbon atoms in biochemical reactions. The probable existence of two pools of carbohydrates in photosynthesizing organisms different in isotopic composition is predicted. Two types of intramolecular isotope distribution in amino acids are shown. (author)

  1. Isotopic effects on non-linearity, molecular radius and intermolecular ...

    Indian Academy of Sciences (India)

    water is used in nuclear reactors and is about to become an important fuel analog for possible control of thermonuclear processes. Various physicochemical proper- .... This results in the fact that in the region of standard thermodynamic temperature, the replacement of hydrogen by deuterium either hardly changes the.

  2. Characterization of a deuterium-deuterium plasma fusion neutron generator

    Science.gov (United States)

    Lang, R. F.; Pienaar, J.; Hogenbirk, E.; Masson, D.; Nolte, R.; Zimbal, A.; Röttger, S.; Benabderrahmane, M. L.; Bruno, G.

    2018-01-01

    We characterize the neutron output of a deuterium-deuterium plasma fusion neutron generator, model 35-DD-W-S, manufactured by NSD/Gradel-Fusion. The measured energy spectrum is found to be dominated by neutron peaks at 2.2 MeV and 2.7 MeV. A detailed GEANT4 simulation accurately reproduces the measured energy spectrum and confirms our understanding of the fusion process in this generator. Additionally, a contribution of 14 . 1 MeV neutrons from deuterium-tritium fusion is found at a level of 3 . 5%, from tritium produced in previous deuterium-deuterium reactions. We have measured both the absolute neutron flux as well as its relative variation on the operational parameters of the generator. We find the flux to be proportional to voltage V 3 . 32 ± 0 . 14 and current I 0 . 97 ± 0 . 01. Further, we have measured the angular dependence of the neutron emission with respect to the polar angle. We conclude that it is well described by isotropic production of neutrons within the cathode field cage.

  3. Permeability of hydrogen isotopes through Pd-Ag membrane

    International Nuclear Information System (INIS)

    Yoshida, Hiroshi

    1981-01-01

    This paper represents the permeabilities, diffusion coefficients and isotope effects for hydrogen and deuterium through Pd-25 wt.% Ag alloy tubes The feed gas H 2 or D 2 flowing into the permeation cell was preheated before it reached to the outer surface of the permeation tube made of palladium-silver alloy. Permeation time lag method could be successfully carried out with the present apparatus to measure both permeability and diffusion coefficient. The square-root pressure dependence for the permeation of hydrogen isotopes was observed. The observed systematic temperature dependence indicates that the approximation of the Arrhenius' relation was effective within this experimental conditions. Some tendency of permeation fluxes in relation to the reciprocal temperature, 1/T, was seen. The permeability ratio was larger than the square root of isotopic mass ratio, and it decreased with temperature rise. On the contrary, the diffusion coefficient ratio was much smaller than the square root of isotopic mass ratio. (Kato, T.)

  4. Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride-Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations.

    Science.gov (United States)

    Derakhshani-Molayousefi, Mortaza; Kashefolgheta, Sadra; Eilers, James E; Lu, Yun

    2016-06-30

    We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride-transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD) than in H-tunneling. To examine the isotopic DAD difference explanation, in this paper, following an activated motion-assisted H-tunneling model that requires a shorter DAD in a heavier isotope transfer process, we computed the 2° KIEs at various H/D positions at different DADs (2.9 Å to 3.5 Å) for the hydride-transfer reactions from 2-propanol to the xanthylium and thioxanthylium ions (Xn(+) and TXn(+)) and their 9-phenyl substituted derivatives (Ph(T)Xn(+)). The calculated 2° KIEs match the experiments and the calculated DAD effect on the 2° KIEs fits the observed 1° isotope effect on the 2° KIEs. These support the motion-assisted H-tunneling model and the isotopically different TRS conformations. Furthermore, it was found that the TRS of the sterically hindered Ph(T)Xn(+) system does not possess a longer DAD than that of the (T)Xn(+) system. This predicts a no larger 1° KIE in the former system than in the latter. The observed 1° KIE order is, however, contrary to the prediction. This implicates the stronger DAD-compression vibrations coupled to the bulky Ph(T)Xn(+) reaction coordinate.

  5. Deuterium exchange between hydrofluorocarbons and amines

    International Nuclear Information System (INIS)

    Hammond, W.B.; Bigeleisen, J.; Tuccio, S.A.

    1983-01-01

    The invention consists of a process for obtaining a compound enriched in deuterium which comprises the known method of exposing a gaseous hydrofluorocarbon to infrared laser radiation of a predetermined frequency to selectively cause a chemical reaction involving hydrofluorocarbon molecules containing deuterium without substantially affecting hydrofluorocarbon molecules not containing deuterium, thereby producing, as reaction products, a compound enriched in deuterium and hydrofluorocarbon depleted in deuterium; combined with a new method, which comprises enriching the deuterium content of the depleted hydrofluorocarbon by contacting the depleted hydrofluorocarbon with an alkali metal amide and an amine having a concentration of deuterium at least that which will yield an increase in deuterium concentration of the hydrofluorocarbon upon equilibration, whereby the amine becomes depleted in deuterium

  6. Differentiating the role of lithium and oxygen in retaining deuterium on lithiated graphite plasma-facing components

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, C. N. [Fusion Safety Program, Idaho National Laboratory, P.O. Box 1625-7113, Idaho Falls, Idaho 83415 (United States); School of Nuclear Engineering, Purdue University, 400 Central Drive, West Lafayette, Indiana 47907 (United States); Allain, J. P. [School of Nuclear Engineering, Purdue University, 400 Central Drive, West Lafayette, Indiana 47907 (United States); Department of Nuclear, Plasma and Radiological Engineering, University of Illinois at Urbana-Champaign, Illinois 61801 (United States); Luitjohan, K. E. [School of Nuclear Engineering, Purdue University, 400 Central Drive, West Lafayette, Indiana 47907 (United States); Krstic, P. S. [Institute for Advanced Computational Science, Stony Brook University, New York 11794 (United States); Department of Physics and Astronomy, University of Tennessee, Knoxville, Tennessee 37996 (United States); TheoretiK, Knoxville, Tennessee 379XX (United States); Dadras, J. [Department of Physics and Astronomy, University of Tennessee, Knoxville, Tennessee 37996 (United States); Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles, California 90095 (United States); Skinner, C. H. [Princeton Plasma Physics Laboratory, Princeton, New Jersey 08543 (United States)

    2014-05-15

    Laboratory experiments have been used to investigate the fundamental interactions responsible for deuterium retention in lithiated graphite. Oxygen was found to be present and play a key role in experiments that simulated NSTX lithium conditioning, where the atomic surface concentration can increase to >40% when deuterium retention chemistry is observed. Quantum-classical molecular dynamic simulations elucidated this oxygen-deuterium effect and showed that oxygen retains significantly more deuterium than lithium in a simulated matrix with 20% lithium, 20% oxygen, and 60% carbon. Simulations further show that deuterium retention is even higher when lithium is removed from the matrix. Experiments artificially increased the oxygen content in graphite to ∼16% and then bombarded with deuterium. X-ray photoelectron spectroscopy showed depletion of the oxygen and no enhanced deuterium retention, thus demonstrating that lithium is essential in retaining the oxygen that thereby retains deuterium.

  7. Reaction rates and electrical resistivities of the hydrogen isotopes with, and their solubilities in, liquid lithium

    International Nuclear Information System (INIS)

    Pulham, R.J.; Adams, P.F.; Hubberstey, P.; Parry, G.; Thunder, A.E.

    1976-01-01

    The rate of reaction, k, of hydrogen and of deuterium with liquid lithium have been determined up to pressures of 20kNm -2 and at temperatures between 230 and 270 0 C. The reaction is first order with an apparent activation energy of 52.8 and 55.2 kJmol -1 for hydrogen and deuterium, respectively. The deuterium isotope effect, k/sub H/k/sub D/, decreases from 2.95 at 230 to 2.83 at 270 0 C. Tritium is predicted to react even more slowly than deuterium. The freezing point of lithium is depressed by 0.082 and 0.075 0 C, respectively, by dissolved hydride and deuteride giving eutectics at 0.016 mol percent H and 0.012 mol percent D in the metal-salt phase diagrams. The depression and eutectic concentration are expected to be less for tritium. The increase in the resistivity of liquid lithium caused by dissolved hydrogen isotopes is linear and relatively large, 5 x 10 -8 Ωm (mol percent H or D) -1 . The solubility of lithium hydride and deuteride was determined from the marked change in resistivity on saturation. The liquidus of the metal-salt phase diagram rises steeply from the eutectic point to meet the two-immiscible liquid region. Tritium is expected to be less soluble than deuterium. The partial molar enthalpies of solution are 44.2 and 55.0 kJmol -1 for hydrogen and deuterium, respectively. These values are used to calculate the solvation enthalpies of the isotope anions in the metal

  8. Monopole Effect on Isotopes in Sn and Pb Regions

    Directory of Open Access Journals (Sweden)

    M. KHITER

    2016-11-01

    Full Text Available Abstract. When going toward in description of neutron-rich nuclei, the monopole field plays a determining role in the properties of the quasiparticle states and their interactions. Detailed theoretical in shell model calculations of the characteristics of the neutron-rich isotopes in 132Sn and 208Pb regions are performed using the monopole hamiltonien effect. Some modification mentioned in literatures of effectives interactions are introduced for evaluated the effective single-particle energies. Their effect show a successful and consistent description of excitation energies spectra of these nuclei.Keywords:Nuclear Structure, Monopole Hamiltonian, Odd-Odd Nuclei,Three body Effects, Similarity, 21.60.Cs; 27.60. +j; 21.30.Fe

  9. Hydrogen/deuterium exchange, a unique and effective method for MS fragmentation behavior elucidation of ginkgolides and its application to systematic research in Ginkgo biloba.

    Science.gov (United States)

    Niu, Xingliang; Luo, Jun; Xu, Deran; Zou, Hongyan; Kong, Lingyi

    2017-02-05

    Ginkgolides, the main active constituents of Ginkgo biloba, possess significant selectively inhibition on platelet-activating factor and pancreatic lipase and attract wide attention in pharmacological research area. In our study, an effective hydrogen/deuterium (H/D) exchange method was developed by exchanging the α-Hs of lactone groups in ginkgolides with Ds, which was very useful for the elucidation of the fragmentation patterns of ginkgolides in Quadrupole Time-of-flight Mass Spectrometry (Q-TOF-MS), especially in accurately distinguishing the type and position of substituent in framework of ginkgolides. Then, a systematic research strategy for qualitative and quantitative analysis of ginkgolides, based on H/D exchange, tandem solid-phase extraction and LC-Q-TOF-MS, was developed, which was successfully applied in each medicinal part of G. biloba, which indicated that ginkgolide B was the most abundant ginkgolide in the seeds of G. biloba (60.6μg/g). This research was the successful application of H/D exchange in natural products, and proved that H/D exchange is a potential method for analysis research of complex TCMs active constituents. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Cosmic Ray Deuterium from 0.2 to 3.0 GeV/nucleon

    DEFF Research Database (Denmark)

    Davis, A.J.; Labrador, A.W.; Mewaldt, R.A.

    1996-01-01

    The abundances of cosmic ray protons and deuterium between 0.2 and 3.0 GeV/nucleon were measured by the IMAX balloon--borne magnet spectrometer during a flight in July, 1992. These isotope measurements extend to significantly higher energies than have previously been achieved. A high--resolution ......The abundances of cosmic ray protons and deuterium between 0.2 and 3.0 GeV/nucleon were measured by the IMAX balloon--borne magnet spectrometer during a flight in July, 1992. These isotope measurements extend to significantly higher energies than have previously been achieved. A high...

  11. Deuterium retention and desorption behavior in an advanced reduced-activation alloy

    Energy Technology Data Exchange (ETDEWEB)

    Noh, S.J., E-mail: sjnoh@dankook.ac.kr [Department of Applied Physics, Dankook University, Yongin-si, Gyeonggi-do 448-701 (Korea, Republic of); Kim, H.S.; Byeon, W.J.; Shin, H.W. [Department of Applied Physics, Dankook University, Yongin-si, Gyeonggi-do 448-701 (Korea, Republic of); Lee, Cheol Eui [Department of Physics, Korea University, Seoul 136-713 (Korea, Republic of); Lee, S.K. [Nuclear Fusion Development Division, Korea Atomic Energy Research Institute, 989-111 Daedeok-daero, Yuseong-gu, Daejeon 305-353 (Korea, Republic of)

    2017-07-15

    We present the first experimental results of the deuterium retention and desorption behavior in an advanced reduced-activation alloy (ARAA) under development in Korea. For the in-situ measurement of desorbed gases from samples immediately after irradiation, a thermal desorption spectroscopy (TDS) system clustered with an inductively coupled plasma ion source has been built. Samples were and were not irradiated with helium ions at energies of 1.4, 3.5, and 5.0 keV and then continuously irradiated with 1.7-keV deuterium ions. TDS measurements were performed in situ immediately after deuterium irradiation and after exposure to air for one week. The amount of desorbed deuterium is the largest for the sample without helium irradiation from the TDS results measured in situ immediately after irradiation. Further, the amount of desorbed deuterium is significantly lowered when the helium energy is increased to 3.5 keV with no significant changes thereafter, indicating that the layer formed by implanted helium at near or deeper than the stopping range for 1.7-keV deuterium ions effectively acts as a barrier against deuterium diffusion into the depth. Because of the strong diffusivity of deuterium into the ambient atmosphere, the amounts of desorbed deuterium are greatly reduced for the samples without helium irradiation and with 1.4-keV helium irradiation after exposure to air for one week. In addition, our deuterium results for the ARAA are also compared with the results for F82H by other authors. - Highlights: •The first result of the deuterium retention and desorption in an ARAA is presented. •The ARAA was irradiated with helium and then continuously irradiated with deuterium. •TDS measurements were performed in situ immediately after deuterium irradiation. •TDS measurements were performed after exposure to air for one week. •The effects of helium irradiation and exposure to air were investigated.

  12. Wildcat: A commercial deuterium-deuterium tokamak reactor

    International Nuclear Information System (INIS)

    Evans, K.; Baker, C.C.; Barry, K.M.

    1983-01-01

    WILDCAT is a conceptual design of a catalyzed deuterium-deuterium tokamak commercial fusion reactor. WILDCAT utilizes the beneficial features of no tritium breeding, while not extrapolating unnecessarily from existing deuterium-tritium (D-T) designs. The reactor is larger and has higher magnetic fields and plasma pressures than typical D-T devices. It is more costly, but eliminates problems associated with tritium breeding and has tritium inventories and throughputs approximately two orders of magnitude less than typical D-T reactors. There are both a steady-state version with Alfven-wave current drive and a pulsed version. Extensive comparison with D-T devices has been made, and cost and safety analyses have been included. All of the major reactor systems have been worked out to a level of detail appropriate to a complete conceptual design

  13. Application of Environmental Isotopes in Hydrological Studies Along the River Nile Valley, Egypt

    Energy Technology Data Exchange (ETDEWEB)

    Nada, A. A. [Site and Environmental Dept. NCNSRC, Atomic Energy Authority, Cairo (Egypt)

    2013-07-15

    This paper reviews some of the contributions of isotope techniques to better understanding hydrological problems in Egypt and the Nile basin. The stable isotope composition of precipitation shows considerable variations both in time and space since it is controlled by climatic factors. Surface waters became enriched in deuterium and oxygen-18 relative to their initial isotopic composition as losses by evaporation occur. The GNIP sampling stations at Entebbe and Addis Ababa, which are located at the source of the Nile River, present relatively depleted isotopic contents. Assuming that the central Africa runoff (White Nile downstream from Sudan) represents 30% of the natural discharge of Egypt, and the remaining 70% is derived from Ethiopia (Blue Nile), we obtain a composite depleted stable isotope composition of the river Nile reaching upper Egypt under natural conditions (before the construction of the Aswan High Dam). Stable isotopes were used to estimate the evaporation rate from Lake Nasser, based on the isotopic content of the lake water. The lake can be divided into two sectors: the first sector, with remarkable vertical gradient in O-18 and deuterium, and a second sector, characterized by a lower vertical isotopic gradient. In order to detect this effect, surface Nile water samples have been collected at Cairo after a heavy storm event covering all Egypt at the beginning of November 1994, characterized by very negative deuterium and oxygen-18 contents. The isotopic content of Nile water samples fluctuated and slightly changed with time. The variation of the bomb tritium response of the Nile has been reconstructed using a model based on the contents in the catchment areas of the Nile. Pre-bomb tritium content in the Nile was about 5 TU, reaching a maximum level during the early sixties of about 500 TU. At present the tritium level content of the Nile is about 6 TU. (author)

  14. Advances in deuterium dioxide concentration measurement

    Energy Technology Data Exchange (ETDEWEB)

    Shon, Woojung [University of Science & Technology, Daejeon (Korea, Republic of); Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Yim, Sung Paal, E-mail: nspyim@kaeri.re.kr [University of Science & Technology, Daejeon (Korea, Republic of); Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Lee, Lim; Park, Hyunmin [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Kim, Kwang Rag; Chung, Hongsuk [University of Science & Technology, Daejeon (Korea, Republic of); Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Lee, Cheo Kyung [Handong Global University, Pohang (Korea, Republic of)

    2016-11-01

    Highlights: • Heavy water (D{sub 2}O) with a high purity level is necessary for nuclear fusion application. • D{sub 2}O purity is analyzed using Fourier Transform infrared (FT-IR) spectroscopy and newly introduced off-axis integrated cavity output spectroscopy (OA-ICOS). • OA-ICOS has advantages in terms of analysis of D{sub 2}O vapor. • OA-ICOS is expected that it can be used for accurate isotopic analyses in the future. - Abstract: The deuterium–tritium (D–T) reaction has been identified as the most efficient reaction for fusion devices. Deuterium can be obtained by heavy water electrolysis. Heavy water (D{sub 2}O) with a high purity level is necessary for nuclear fusion application. A D{sub 2}O isotopic analysis is thus very important. A system for a heavy water analysis was built and a newly designed isotopic analysis experiment was carried out. We tried to analyze the D{sub 2}O purity using Fourier Transform infrared (FT-IR) spectroscopy and newly introduced off-axis integrated cavity output spectroscopy (OA-ICOS). We found that the OA-ICOS based on measurement via laser absorption spectroscopy shows very high sensitivity. We ameliorated the sensitivity by an order of magnitude of more than 10{sup 3}–10{sup 5}. We could make the apparatus smaller by employing very tiny diode laser and fiber optics elements of a DFB (Distributed Feedback) type. Consequently, our device has advantages in terms of maintainability and mobility even in a radioactive environment. This new method could be used for an accurate isotopic analysis in the future.

  15. Biotechnological Patents Applications of the Deuterium Oxide in Human Health.

    Science.gov (United States)

    da S Mariano, Reysla M; Bila, Wendell C; Trindade, Maria Jaciara F; Lamounier, Joel A; Galdino, Alexsandro S

    2017-01-01

    Deuterium oxide is a molecule that has been used for decades in several studies related to human health. Currently, studies on D2O have mobilized a "Race for Patenting" worldwide. Several patents have been registered from biomedical and technological studies of D2O showing the potential of this stable isotope in industry and health care ecosystems. Most of the patents related to the applications of the deuterium oxide in human health have been summarized in this review. The following patents databases were consulted: European Patent Office (Espacenet), the United States Patent and Trademark Office (USPTO), the United States Latin America Patents (LATIPAT), Patent scope -Search International and National Patent Collections (WIPO), Google Patents and Free Patents Online. With this review, the information was collected on recent publications including 22 patents related to deuterium oxide and its applications in different areas. This review showed that deuterium oxide is a promising component in different areas, including biotechnology, chemistry and medicine. In addition, the knowledge of this compound was covered, reinforcing its importance in the field of biotechnology and human health. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  16. Theoretical study of non reactive collisions between alkaline atoms and hydrogen or deuterium molecules. Calculations and analysis of the potential surfaces. Application to the fine structure transitions of the Rubidium

    International Nuclear Information System (INIS)

    Rossi, F.N.

    1986-10-01

    The adiabatic potential lines are first obtained through the use of a pseudo-potential, depending on the electronic orbital moment. A perturbative method is then used to generate the potential surfaces, according to the potential lines. A quantum calculation in the thermal energy domain is realized, for the cross-sections concerning the structure transitions of the Rubidium, induced by the collision with hydrogen or deuterium molecules. This allowed the interpretation of the experimentally observed isotopic effect [fr

  17. Deuterium trapping in liquid lithium irradiated by deuterium plasma

    International Nuclear Information System (INIS)

    Pisarev, A.; Moshkunov, K.; Vizgalov, I.; Gasparyan, Yu.

    2013-01-01

    Liquid lithium was irradiated by deuterium plasma to a low fluence of 10 22 –10 23 D/m 2 , cooled down to room temperature, and then slowly heated. The temperature and release rate were measured during heating. Two plateaus on the temperature–time dependence were observed at 180 °C and 660 °C. The first one corresponds to melting of Li and the second one – either to melting or to decomposition of solid LiD. Features of deuterium release in TDS were interpreted in terms of decomposition of lithium deuterides formed during plasma irradiation

  18. Evaluation of matrix effect in isotope dilution mass spectrometry based on quantitative analysis of chloramphenicol residues in milk powder

    International Nuclear Information System (INIS)

    Li, Xiu Qin; Yang, Zong; Zhang, Qing He; Li, Hong Mei

    2014-01-01

    Graphical abstract: -- Highlights: •We develop a strategy to evaluate matrix effect and its impact on the IDMS results. •Matrix effect and IDMS correction factor from different conditions are evaluated. •Ion suppression effect is observed in LLE and HLB pre-treated sample solutions. •Ion enhancement effect is found in MCX pre-treated sample solution. •IDMS correction factor in HLB and MCX solutions in three instruments is close to 1 -- Abstract: In the present study, we developed a comprehensive strategy to evaluate matrix effect (ME) and its impact on the results of isotope dilution mass spectrometry (IDMS) in analysis of chloramphenicol (CAP) residues in milk powder. Stable isotope-labeled internal standards do not always compensate ME, which brings the variation of the ratio (the peak area of analyte/the peak area of isotope). In our investigation, impact factors of this variation were studied in the extraction solution of milk powder using three mass spectrometers coupled with different ion source designs, and deuterium-labeled chloramphenicol (D5-CAP) was used as the internal standard. ME from mobile phases, sample solvents, pre-treatment methods, sample origins and instruments was evaluated, and its impact on the results of IDMS was assessed using the IDMS correction factor (θ). Our data showed that the impact of ME of mobile phase on the correction factor was significantly greater than that of sample solvent. Significant ion suppression and enhancement effects were observed in different pre-treated sample solutions. The IDMS correction factor in liquid–liquid extraction (LLE) and molecular imprinted polymer (MIP) extract with different instruments was greater or less 1.0, and the IDMS correction factor in hydrophilic lipophilic balance (HLB) and mix-mode cation exchange (MCX) extract with different instruments was all close to 1.0. To the instrument coupled with different ion source design, the impact of ME on IDMS quantitative results was

  19. Isotope effects in gas-phase chemical reactions and photodissociation processes: Overview

    International Nuclear Information System (INIS)

    Kaye, J.A.

    1992-01-01

    The origins of isotope effects in equilibrium and non-equilibrium chemical processes are reviewed. In non-equilibrium processes, attention is given to isotope effects in simple bimolecular reactions, symmetry-related reactions, and photodissociation processes. Recent examples of isotope effects in these areas are reviewed. Some indication of other scientific areas for which measurements and/or calculations of isotope effects are used is also given. Examples presented focus on neutral molecule chemistry and in many cases complement examples considered in greater detail in the other chapters of this volume

  20. Compared studies of natural and artificial deuterium depleted water

    International Nuclear Information System (INIS)

    Butnaru, Gallia; Mihacea, Sorina; Sirbovan, Alina; Butnariu, H.; Titescu, Gh.

    2001-01-01

    The biological influence of the deuterium on animals was studied insensitively in the last years. When animal cell cultures were analyzed it turned out an inhibition of the development, due to the reduced deuterium concentration. In the in vivo experiments a decreasing of the number of tumoral cells was pointed out when performing the depleted water treatment. It is obvious that the presence of deuterium in water is necessary for the development, especially for the tumoral cell proliferation. The aim of this work was to establish influence of the natural and artificial deuterium depleted water on the vegetal organisms development. For this purpose, the developmental stages of Lactuca sativa L. growth were followed. The experimental data were compared with the data obtained with distilled water. The birch, wine sap and some fruit juices are considered 'natural depleted' water sources because their deuterium content is smaller in comparison to natural water (D 2 =150 ppm). The effect of artificial deuterium depleted water (29 ppm D 2 ) was analyzed in comparison to three types of wine saps, which also have a reduced deuterium concentration (125-130 ppm D 2 ). If the deuterium depleted water was used, the germination percent and the root and shoot length were higher compared to control in the first stages. In wine sap it had a negative effect on germination and development. After three days the plants were transferred to soil and their development was followed. The foliage area was larger for all of the experimental variants compared to control. The differences were without significance when deuterium depleted water was tested but they were high and very significant in case of wine sap. The experiment pointed out a stimulative effect of the artificial deuterium depleted water. In case of wine sap the effect was negative when the contact was direct, but the growth was stimulated after the stress cessation. The first ontogenetic stages were represented by direct action

  1. Experiments regarding organism's behaviour under deuterium-depleted water influence

    International Nuclear Information System (INIS)

    Stefanescu, I.; Steflea, D.; Titescu, Gh.

    1999-01-01

    Deuterium-depleted water (DDW) has an isotopic content smaller than 45 ppm D/(D+H). The role of naturally occurring D in living organisms was examined by using DDW instead of natural water. The DDW significantly decreased the growth rate of the L929 fibroblast cell line, and also inhibited the tumour growth. These suggest that the naturally occurring D has a central role in signal transduction involved in cell cycle regulation. Beginning with 1996 the Institute of Cryogenics and Isotope Separation, DDW producer, co-operated with Romanian specialised institutes for biological effect's evaluation of DDW. These investigations led to the following conclusions: - DDW caused a tendency of increasing the basal tone, accompanied by the intensification of the vasoconstrictor effects of phenylefrine, noradrenaline and angiotensin; the increase of the basal tone and vascular reactivity produced by the DDW persists after the removal of the vascular endothelium. - DDW stimulates immune defence reactions, represented by the opsonic, bactericidal and phagocyte capacity of the immune system, together with increase in the numbers of polymorphonuclear neutrophils. - Animals treated with DDW showed an increase of the resistance both to sublethal and to lethal gamma radiation doses, suggesting a radioprotective action. - Investigation regarding artificial reproduction of fish with DDW fecundated solutions confirmed favourable influence both in embryo growth stage and in resistance in the following growth stages. - One has studied germination growth and quantitative character's variability at two genotypes of Avena Sativa; one can remark the favourable influence of DDW on biological process at plants in various ontogenic stages. (authors)

  2. Deuterium retention in liquid lithium

    International Nuclear Information System (INIS)

    Baldwin, M.J.; Doerner, R.P.; Luckhardt, S.C.; Conn, R.W.

    2002-01-01

    Measurements of deuterium retention in samples of lithium exposed in the liquid state to deuterium plasma are reported. Retention was measured as a function of plasma ion dose in the range 6x10 19 -4x10 22 D atoms and exposure temperature between 523 and 673 K using thermal desorption spectrometry. The results are consistent with the full uptake of all deuterium ions incident on the liquid metal surface and are found to be independent of the temperature of the liquid lithium over the range explored. Full uptake, consistent with very low recycling, continues until the sample is volumetrically converted to lithium deuteride. This occurs for exposure temperatures where the gas pressure during exposure was both below and slightly above the corresponding decomposition pressure for LiD in Li. (author)

  3. Process for hydrogen isotope exchange and concentration between liquid water and hydrogen gas and catalyst assembly therefor

    International Nuclear Information System (INIS)

    Stevens, W.H.

    1975-01-01

    A bithermal, catalytic, hydrogen isotope exchange process between liquid water and hydrogen gas to effect concentration of the deuterium isotope of hydrogen is described. Liquid water and hydrogen gas are contacted with one another and with at least one catalytically active metal selected from Group VIII of the Periodic Table; the catalyst body has a water repellent, gas and water vapor permeable, organic polymer or resin coating, preferably a fluorinated olefin polymer or silicone resin coating, so that the isotope exchange takes place by two simultaneously occurring, and closely coupled in space, steps and concentration is effected by operating two interconnected sections containing catalyst at different temperatures. (U.S.)

  4. Stable isotope geochemistry of the Tongonan geothermal system, Leyte, Philippines

    International Nuclear Information System (INIS)

    Hulston, J.R.; Stewart, M.K.

    1982-01-01

    Stable isotope and geochemical data on samples from natural features, shallow wells and deep wells collected over a number of years from the Tongonan area of Leyte have been evaluated. The variations in the isotopic compositions of the thermal waters are used to describe natural processes occurring within the system. The effect of the ''excess enthalpy'' of the deep wells on the isotope data is formulated. Water from the deep Tongonan wells shows an oxygen-18 shift of 5 per mille, which is larger than at Wairakei and Broadlands, probably in part because of the high temperatures at Tongonan. Recent measurements indicate that the deuterium shift is very much smaller than previously thought. Isotopic measurements of methane in the gases suggests differing flows from the Eastern and Central Philippine faults

  5. Origin of excess heat generated during loading Pd-impregnated alumina powder with deuterium and hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Dmitriyeva, O., E-mail: olga.dmitriyeva@colorado.edu [Department of Electrical, Computer, and Energy Engineering, University of Colorado, Boulder, CO 80309-0425 (United States); Coolescence LLC, 2450 Central Ave Ste F, Boulder, CO 80301 (United States); Cantwell, R.; McConnell, M. [Coolescence LLC, 2450 Central Ave Ste F, Boulder, CO 80301 (United States); Moddel, G. [Department of Electrical, Computer, and Energy Engineering, University of Colorado, Boulder, CO 80309-0425 (United States)

    2012-09-10

    Highlights: Black-Right-Pointing-Pointer We studied heat produced by hydrogen and deuterium in Pd-impregnated alumina powder. Black-Right-Pointing-Pointer Samples were fabricated using light and heavy water isotopes and varied the gas used for loading. Black-Right-Pointing-Pointer Incorporation of hydrogen and deuterium influenced the amount of heat released or consumed. Black-Right-Pointing-Pointer Pd nanoparticles appear to catalyze hydrogen/deuterium (H/D) exchange chemical reactions. Black-Right-Pointing-Pointer Anomalous heating can be accounted for by chemical rather than nuclear reactions. - Abstract: We studied heat production in Pd-impregnated alumina powder in the presence of hydrogen and deuterium gases, investigating claims of anomalous heat generated as a result of nuclear fusion, usually referred to as a low energy nuclear reaction (LENR). By selecting the water isotope used to fabricate the material and then varying the gas used for loading, we were able to influence the amount of heat released or consumed. We suggest that Pd in its nanoparticle form catalyzes hydrogen/deuterium (H/D) exchange reactions in the material. This hypothesis is supported by heat measurements, residual gas analysis (RGA) data, and calculations of energy available from H/D exchange reactions. Based on the results we conclude that the origin of the anomalous heat generated during deuterium loading of Pd-enriched alumina powder is chemical rather than nuclear.

  6. Origin of excess heat generated during loading Pd-impregnated alumina powder with deuterium and hydrogen

    International Nuclear Information System (INIS)

    Dmitriyeva, O.; Cantwell, R.; McConnell, M.; Moddel, G.

    2012-01-01

    Highlights: ► We studied heat produced by hydrogen and deuterium in Pd-impregnated alumina powder. ► Samples were fabricated using light and heavy water isotopes and varied the gas used for loading. ► Incorporation of hydrogen and deuterium influenced the amount of heat released or consumed. ► Pd nanoparticles appear to catalyze hydrogen/deuterium (H/D) exchange chemical reactions. ► Anomalous heating can be accounted for by chemical rather than nuclear reactions. - Abstract: We studied heat production in Pd-impregnated alumina powder in the presence of hydrogen and deuterium gases, investigating claims of anomalous heat generated as a result of nuclear fusion, usually referred to as a low energy nuclear reaction (LENR). By selecting the water isotope used to fabricate the material and then varying the gas used for loading, we were able to influence the amount of heat released or consumed. We suggest that Pd in its nanoparticle form catalyzes hydrogen/deuterium (H/D) exchange reactions in the material. This hypothesis is supported by heat measurements, residual gas analysis (RGA) data, and calculations of energy available from H/D exchange reactions. Based on the results we conclude that the origin of the anomalous heat generated during deuterium loading of Pd-enriched alumina powder is chemical rather than nuclear.

  7. Liquid hydrogen and deuterium targets

    International Nuclear Information System (INIS)

    Bougon, M.; Marquet, M.; Prugne, P.

    1961-01-01

    A description is given of 1) Atmospheric pressure target: liquid hydrogen, 400 mm thickness; thermal insulation: styrofoam; the hydrogen vapors are used to improve the target cooling; Mylar windows. 2) Vacuum target: 12 liter content: hydrogen or deuterium; liquid thickness 400 mm; thermal insulation is afforded by a vacuum vessel and a liquid nitrogen shield. Recovery and liquefaction of deuterium vapors are managed in the vacuum vessel which holds the target. The target emptying system is designed for operating in a few minutes. (author) [fr

  8. Deuterium in organic matter

    International Nuclear Information System (INIS)

    Straaten, C.M. van der.

    1981-01-01

    In order to obtain an insight in the processes governing the macroclimate on earth, a knowledge is required of the behaviour of climates in the past. It is well known that D/H ratio of rain varies with temperature determined by latitude as well as by season. Because land plants use this water during the assimilation process, it is expected that the D/H variations are propagated in the organic plant matter. The D/H palaeoclimatic method has therefore been applied to peat to distinguish between the chemical constituents and trace the stable hydrogen fraction in the organic matter. The relation between the hydrogen isotopic composition of precipitation and climatic factors such as the temperature have also been studied. (Auth.)

  9. Charge exchange effect on laser isotope separation of atomic uranium

    International Nuclear Information System (INIS)

    Niki, Hideaki; Izawa, Yasukazu; Otani, Hiroyasu; Yamanaka, Chiyoe

    1982-01-01

    Uranium isotope separating experiment was performed using the two-step photoionization technique with dye laser and nitrogen laser by heating uranium metal with electron beam and producing atomic beam using generated vapour. The experimental results are described after explaining the two-step photoionization by laser, experimental apparatus, the selection of exciting wavelength and others. Enrichment factor depends largely on the spectrum purity of dye laser which is the exciting source. A large enrichment factor of 48.3 times was obtained for spectrum width 0.03A. To put the uranium isotope separation with laser into practice, the increase of uranium atomic density is considered to be necessary for improving the yield. Experimental investigation was first carried out on the charge exchange effect that seems most likely to affect the decrease of enrichment factor, and the charge exchange cross-section was determined. The charge exchange cross-section depends on the relative kinetic energy between ions and atoms. The experimental result showed that the cross-section was about 5 x 10 -13 cm 2 at 1 eV and 10 -13 cm 2 at 90 eV. These values are roughly ten times as great as those calculated in Lawrence Livermore Laboratory, and it is expected that they become the greatest factor for giving the upper limit of uranium atomic density in a process of practical application. (Wakatsuki, Y.)

  10. Introduction to chemistry and applications in nature of mass independent isotope effects special feature.

    Science.gov (United States)

    Thiemens, Mark H

    2013-10-29

    Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented.

  11. The isotope effect on divertor conditions and neutral pumping in horizontal divertor configurations in JET-ILW Ohmic plasmas

    Directory of Open Access Journals (Sweden)

    J. Uljanovs

    2017-08-01

    Full Text Available Understanding the impact of isotope mass and divertor configuration on the divertor conditions and neutral pressures is critical for predicting the performance of the ITER divertor in DT operation. To address this need, ohmically heated hydrogen and deuterium plasma experiments were conducted in JET with the ITER-like wall in varying divertor configurations. In this study, these plasmas are simulated with EDGE2D-EIRENE outfitted with a sub-divertor model, to predict the neutral pressures in the plenum with similar fashion to the experiments. EDGE2D-EIRENE predictions show that the increased isotope mass results in up to a 25% increase in peak electron densities and 15% increase in peak ion saturation current at the outer target in deuterium when compared to hydrogen for all horizontal divertor configurations. Indicating that a change from hydrogen to deuterium as main fuel decreases the neutral mean free path, leading to higher neutral density in the divertor. Consequently, this mechanism also leads to higher neutral pressures in the sub-divertor. The experimental data provided by the hydrogen and deuterium ohmic discharges shows that closer proximity of the outer strike point to the pumping plenum results in a higher neutral pressure in the sub-divertor. The diaphragm capacitance gauge pressure measurements show that a two to three-fold increase in sub-divertor pressure was achieved in the corner and nearby horizontal configurations compared to the far-horizontal configurations, likely due to ballistic transport (with respect to the plasma facing components of the neutrals into the sub-divertor. The corner divertor configuration also indicates that a neutral expansion occurs during detachment, resulting in a sub-divertor neutral density plateau as a function of upstream density at the outer-mid plane.

  12. Hydrogen isotope separation in hydrophobic catalysts between hydrogen and liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Linsen, E-mail: yls2005@mail.ustc.edu.cn [China Academy of Engineering Physics, Mianyang 621900 (China); Luo, Deli [Science and Technology on Surface Physics and Chemistry Laboratory, Jiangyou 621907 (China); Tang, Tao; Yang, Wan; Yang, Yong [China Academy of Engineering Physics, Mianyang 621900 (China)

    2015-11-15

    Hydrogen isotope catalytic exchange between hydrogen and liquid water is a very effective process for deuterium-depleted potable water production and heavy water detritiation. To improve the characteristics of hydrophobic catalysts for this type of reaction, foamed and cellular structures of hydrophobic carbon-supported platinum catalysts were successfully prepared. Separation of deuterium or tritium from liquid water was carried out by liquid-phase catalytic exchange. At a gas–liquid ratio of 1.53 and exchange temperature of 70 °C, the theoretical plate height of the hydrophobic catalyst (HETP = 34.2 cm) was slightly lower than previously reported values. Changing the concentration of the exchange column outlet water yielded nonlinear changes in the height of the packing layer. Configurations of deuterium-depleted potable water and detritiation of heavy water provide references for practical applications.

  13. Thermal x-rays and deuterium production in stellar flares

    International Nuclear Information System (INIS)

    Colgate, S.A.

    1977-01-01

    The x-ray spectrum of flares is shown to be necessarily thermal up to greater than or equal to 200 keV because the self magnetic field of any electron stream required for a thick or thin target source is inconsistently large. The resulting flare model can then be related to stellar luminosity, convection and magnetic fields to result in a maximum possible γ-burst (Mullan, 1976) and continuous x-ray flux. One of the most striking isotopic anomalies observed is the extreme enrichment of Helium (3) in some solar flares and the mysterious depletion of deuterium. It is discussed how deuterium may be produced and emitted in the largest flares associated with γ-bursts but in amounts insufficient to support the tentative conclusion of Colemen and Worden

  14. The isotope altitude effect reflected in groundwater: a case study from Slovenia.

    Science.gov (United States)

    Mezga, Kim; Urbanc, Janko; Cerar, Sonja

    2014-01-01

    This paper presents the stable isotope data of oxygen (δ(18)O) and hydrogen (δ(2)H) in groundwater from 83 sampling locations in Slovenia and their interpretation. The isotopic composition of water was monitored over 3 years (2009-2011), and each location was sampled twice. New findings on the isotopic composition of sampled groundwater are presented, and the data are also compared to past studies regarding the isotopic composition of precipitation, surface water, and groundwater in Slovenia. This study comprises: (1) the general characteristics of the isotopic composition of oxygen and hydrogen in groundwater in Slovenia, (2) the spatial distribution of oxygen isotope composition (δ(18)O) and d-excess in groundwater, (3) the groundwater isotope altitude effect, (4) the correlation between groundwater d-excess and the recharge area altitude of the sampling location, (5) the relation between hydrogen and oxygen isotopes in groundwater in comparison to the global precipitation isotope data, (6) the groundwater isotope effect of distance from the sea, and (7) the estimated relation between the mean temperature of recharge area and δ(18)O in groundwater.

  15. Isotopic shifts in chemical exchange systems. 1. Large isotope effects in the complexation of Na+ isotopes by macrocyclic polyethers

    International Nuclear Information System (INIS)

    Knoechel, A.; Wilken, R.D.

    1981-01-01

    The complexation of 24 Na + and 22 Na + by 18 of the most widely used macrocyclic polyethers (crown ethers and monocyclic and bicyclic aminopolyethers) has been investigated in view of possible equilibrium isotope shifts. Solvated salts and polyether complexes were distributed differently into two phases and isotope ratios determined in both phases. Chloroform/water systems were shown to be particularly suitable to the investigations allowing favorable distribution for Na + and 13 of the 18 polyethers employed. With crown ethers 24 Na + enrichment varied from nonsignficant values (for large crown ethers) up to 3.1 +- 0.4% (18-crown-6). In the case of bicyclic aminopolyethers, ligands with cages of optimum size to accommodate Na + showed 24 Na + enrichment between O (nonsignificant) (2.2/sub B/2./sub B/) and 5.2 +- 1.8% (2.2.1). In contrast, for 2.2.2. and its derivatives, being too large for Na + , 22 Na + enrichment varying from O (nonsignificant) (2.2.2.p) up to 5.4 +- 0.5% (2.2.2.) has been observed. These values are remarkably high. They are explained by different bonding in solvate structure and polyether complex by using the theoretical approach of Bigeleisen

  16. Isotope effect on superconductivity and Raman phonons of Pyrochlore Cd2Re2O7

    Science.gov (United States)

    Razavi, F. S.; Hajialamdari, M.; Reedyk, M.; Kremer, R. K.

    2018-06-01

    Cd2Re2O7 is the only α-Pyrochlore exhibiting superconductivity with a transition temperature (Tc) of ∼ 1 K. In this study, we present the effect of oxygen isotope (18O) as well as combined 18O and cadmium isotope (116Cd) substitution on the superconductivity and Raman scattering spectrum of Cd2Re2O7. The change of Tc and the energy gap Δ(T) are reported using various techniques including point contact spectroscopy. The shift in Raman phonon frequencies upon isotope substitution will be compared with measurement of the isotope effect on the superconducting transition temperature.

  17. Solid deuterium centrifuge pellet injector

    International Nuclear Information System (INIS)

    Foster, C.A.

    1982-01-01

    Pellet injectors are needed to fuel long pulse tokamak plasmas and other magnetic confinement devices. For this purpose, an apparatus has been developed that forms 1.3-mm-diam pellets of frozen deuterium at a rate of 40 pellets per second and accelerates them to a speed of 1 km/s. Pellets are formed by extruding a billet of solidified deuterium through a 1.3-mm-diam nozzle at a speed of 5 cm/s. The extruding deuterium is chopped with a razor knife, forming 1.3-mm right circular cylinders of solid deuterium. The pellets are accelerated by synchronously injecting them into a high speed rotating arbor containing a guide track, which carries them from a point near the center of rotation to the periphery. The pellets leave the wheel after 150 0 of rotation at double the tip speed. The centrifuge is formed in the shape of a centrifugal catenary and is constructed of high strength KEVLAR/epoxy composite. This arbon has been spin-tested to a tip speed of 1 km/s

  18. Deuterium pellet injector gun design

    International Nuclear Information System (INIS)

    Lunsford, R.V.; Wysor, R.B.; Bryan, W.E.; Shipley, W.D.; Combs, S.K.; Foust, C.R.; Milora, S.L.; Fisher, P.W.

    1985-01-01

    The Deuterium Pellet Injector (DPI), an eight-pellet pneumatic injector, is being designed and fabricated for the Tokamak Fusion Test Reactor (TFTR). It will accelerate eight pellets, 4 by 4 mm maximum, to greater than 1500 m/s. It utilizes a unique pellet-forming mechanism, a cooled pellet storage wheel, and improved propellant gas scavenging

  19. Solid deuterium centrifuge pellet injector

    International Nuclear Information System (INIS)

    Foster, C.A.

    1983-01-01

    Pellet injectors are needed to fuel long pulse tokamak plasmas and other magnetic confinement devices. For this purpose, an apparatus has been developed that forms 1.3-mm-diam pellets of frozen deuterium at a rate of 40 pellets per second and accelerates them to a speed of 1 km/s. Pellets are formed by extruding a billet of solidified deuterium through a 1.3-mm-diam nozzle at a speed of 5 cm/s. The extruding deuterium is chopped with a razor knife, forming 1.3-mm right circular cylinders of solid deuterium. The pellets are accelerated by synchronously injecting them into a high speed rotating arbor containing a guide track, which carries them from a point near the center of rotation to the periphery. The pellets leave the wheel after 150 0 of rotation at double the tip speed. The centrifuge is formed in the shape of a centrifugal catenary and is constructed of high strength Kevlar/epoxy composite. This arbor has been spin-tested to a tip speed of 1 km/s

  20. Isotope Effect on the Thermal Conductivity of Graphene

    Directory of Open Access Journals (Sweden)

    Hengji Zhang

    2010-01-01

    Full Text Available The thermal conductivity (TC of isolated graphene with different concentrations of isotope (C13 is studied with equilibrium molecular dynamics method at 300 K. In the limit of pure C12 or C13 graphene, TC of graphene in zigzag and armchair directions are ~630 W/mK and ~1000W/mK, respectively. We find that the TC of graphene can be maximally reduced by ~80%, in both armchair and zigzag directions, when a random distribution of C12 and C13 is assumed at different doping concentrations. Therefore, our simulation results suggest an effective way to tune the TC of graphene without changing its atomic and electronic structure, thus yielding a promising application for nanoelectronics and thermoelectricity of graphene-based nano device.

  1. Deuterium dilution technique for body composition assessment: resolving methodological issues in children with moderate acute malnutrition.

    Science.gov (United States)

    Fabiansen, Christian; Yaméogo, Charles W; Devi, Sarita; Friis, Henrik; Kurpad, Anura; Wells, Jonathan C

    2017-08-01

    Childhood malnutrition is highly prevalent and associated with high mortality risk. In observational and interventional studies among malnourished children, body composition is increasingly recognised as a key outcome. The deuterium dilution technique has generated high-quality data on body composition in studies of infants and young children in several settings, but its feasibility and accuracy in children suffering from moderate acute malnutrition requires further study. Prior to a large nutritional intervention trial among children with moderate acute malnutrition, we conducted pilot work to develop and adapt the deuterium dilution technique. We refined procedures for administration of isotope doses and collection of saliva. Furthermore, we established that equilibration time in local context is 3 h. These findings and the resulting standard operating procedures are important to improve data quality when using the deuterium dilution technique in malnutrition studies in field conditions, and may encourage a wider use of isotope techniques.

  2. Electrochemical H-D isotope effect at metal-perovskite proton conductor interfaces

    DEFF Research Database (Denmark)

    Kek, D.; Bonanos, N.

    1999-01-01

    The H-D isotope effect on the electrode kinetics of a metal-proton conductor interface has been investigated. The current-voltage behaviour depends on the nature of the electrode (Ni, Ag), the atmosphere (H(2), D(2)), the partial pressures of the gases, and the temperature. The isotope effect was...

  3. Effects of trophic level and metamorphosis on discrimination of hydrogen isotopes in a plant-herbivore system

    Science.gov (United States)

    Peters, Jacob M.; Wolf, Nathan; Stricker, Craig A.; Collier, Timothy R.; Martinez del Rio, Carlos

    2012-01-01

    The use of stable isotopes in ecological studies requires that we know the magnitude of discrimination factors between consumer and element sources. The causes of variation in discrimination factors for carbon and nitrogen have been relatively well studied. In contrast, the discrimination factors for hydrogen have rarely been measured. We grew cabbage looper caterpillars (Trichoplusia ni) on cabbage (Brassica oleracea) plants irrigated with four treatments of deuterium-enriched water (δD = -131, -88, -48, and -2‰, respectively), allowing some of them to reach adulthood as moths. Tissue δD values of plants, caterpillars, and moths were linearly correlated with the isotopic composition of irrigation water. However, the slope of these relationships was less than 1, and hence, discrimination factors depended on the δD value of irrigation water. We hypothesize that this dependence is an artifact of growing plants in an environment with a common atmospheric δD value. Both caterpillars and moths were significantly enriched in deuterium relative to plants by ~45‰ and 23‰ respectively, but the moths had lower tissue to plant discrimination factors than did the caterpillars. If the trophic enrichment documented here is universal, δD values must be accounted for in geographic assignment studies. The isotopic value of carbon was transferred more or less faithfully across trophic levels, but δ15N values increased from plants to insects and we observed significant non-trophic 15N enrichment in the metamorphosis from larvae to adult.

  4. Effect of density of state on isotope effect exponent of two-band superconductors

    International Nuclear Information System (INIS)

    Udomsamuthirun, P.; Kumvongsa, C.; Burakorn, A.; Changkanarth, P.; Yoksan, S.

    2005-01-01

    The exact formula of T c 's equation and the isotope effect exponent of two-band s-wave superconductors in weak-coupling limit are derived by considering the influence of two kinds of density of state: constant and van Hove singularity. The paring interaction in each band consisted of two parts: the electron-phonon interaction and non-electron-phonon interaction are included in our model. We find that the interband interaction of electron-phonon show more effect on isotope exponent than the intraband interaction and the isotope effect exponent with constant density of state can fit to experimental data, MgB 2 and high-T c superconductor, better than van Hove singularity density of state

  5. Effects of stereochemistry on the rates of hydrogen--deuterium exchange of protons α to the nitrosamino group

    International Nuclear Information System (INIS)

    Fraser, R.R.; Ng, L.K.

    1976-01-01

    Measurement of the rates of exchange of four benzylic protons of rigid dibenzazepine were made in tert-butyl alcohol-O-d containing potassium tert-butoxide at several concentrations. Each pseudoaxial proton exchanged 100-fold faster than its geminal partner (pseudoequatorial), likely as a result of a stereoelectronic effect. Each syn proton exchanged 1000-fold faster than the anti proton in the same biaryl environment. The lack of any significant effect of added crown either on the rate of exchange of either a syn or an antiproton indicates lack of involvement of the counterion. A suggested explanation for the unusual preference for syn exchange in this work is based on the symmetry properties of the anionic intermediate. This intermediate, like butadiene dianion, has an attractive interaction between the terminal atoms of the four-atom π system in the highest occupied molecular orbital (HOMO). This explanation is similar to that of Epiotis and co-workers, which accounts for the well-established preferential stability of cis over trans dihalo and dialkoxy ethylenes

  6. Competing quantum effects in the free energy profiles and diffusion rates of hydrogen and deuterium molecules through clathrate hydrates.

    Science.gov (United States)

    Cendagorta, Joseph R; Powers, Anna; Hele, Timothy J H; Marsalek, Ondrej; Bačić, Zlatko; Tuckerman, Mark E

    2016-11-30

    Clathrate hydrates hold considerable promise as safe and economical materials for hydrogen storage. Here we present a quantum mechanical study of H 2 and D 2 diffusion through a hexagonal face shared by two large cages of clathrate hydrates over a wide range of temperatures. Path integral molecular dynamics simulations are used to compute the free-energy profiles for the diffusion of H 2 and D 2 as a function of temperature. Ring polymer molecular dynamics rate theory, incorporating both exact quantum statistics and approximate quantum dynamical effects, is utilized in the calculations of the H 2 and D 2 diffusion rates in a broad temperature interval. We find that the shape of the quantum free-energy profiles and their height relative to the classical free energy barriers at a given temperature, as well as the rate of diffusion, are strongly affected by competing quantum effects: above 25 K, zero-point energy (ZPE) perpendicular to the reaction path for diffusion between cavities decreases the quantum rate compared to the classical rate, whereas at lower temperatures tunneling outcompetes the ZPE and as a result the quantum rate is greater than the classical rate.

  7. Deuterium used as artificial tracer in column studies under saturated water flow conditions

    Science.gov (United States)

    Koeniger, P.; Geiges, M.; Leibundgut, Ch.

    2003-04-01

    In contrast to numerous investigations using deuterium as an environmental tracer, hydrological investigations with deuterium-labelled water are rather rare. Currently applications in groundwater studies are restricted due to increasing costs of spiking large water quantities but an application as intelligent tracer might be of advantage especially in combination with other tracers and under distinct environmental conditions. Therefore deuterium was applied as artificial tracer in column experiments that are well proved as a tool to characterise tracer behaviour in recent studies. Deuterium was tested in comparison to the more familiar conservative tracer fluorescein. Varying experimental conditions, e.g. column length (0.5, 1.0, 1.5 m), initial tracer concentration (0.01, 0.02, 0.2 mg) and flow velocity (1.5 to 6.0 m/d) were used to investigate tracer behaviour under saturated water flow conditions. Deuterium was analysed using an H/Device with chrome reduction connected to an isotope ratio mass spectrometer and expressed in relative concentrations [per mill V-SMOW]. Theoretical tracer breakthrough curves were calculated using a one dimensional dispersion model. The results indicate higher mean transport velocities and smaller dispersion for deuterium in all experiments. Due to different molecule properties that also determine the interaction of soil substrate and tracer, deuterium indicates a more conservative transport behaviour. Deuterium is non-toxic, completely soluble, chemically and biologically stable and not subject to light-influenced decay. Furthermore, it shows promise for investigations of water flow in the unsaturated zone, and of interactions of water in soil-plant-atmosphere systems. A further discussion of problems, together with possibilities for applying deuterium as an artificial tracer, will be presented.

  8. Transport of negative hydrogen and deuterium ions in RF-driven ion sources

    International Nuclear Information System (INIS)

    Gutser, R; Wuenderlich, D; Fantz, U

    2010-01-01

    Negative hydrogen ion sources are major components of neutral beam injection systems for plasma heating in future large-scale fusion experiments such as ITER. In order to fulfill the requirements of the ITER neutral beam injection, a high-performance, large-area RF-driven ion source for negative ions is being developed at the MPI fuer Plasmaphysik. Negative hydrogen ions are mainly generated on a converter surface by impinging neutral particles and positive ions under the influence of magnetic fields and the plasma sheath potential. The 3D transport code TrajAn has been applied in order to obtain the total and spatially resolved extraction probabilities for H - and D - ions under identical plasma parameters and the realistic magnetic field topology of the ion source. A comparison of the isotopes shows a lower total extraction probability in the case of deuterium ions, caused by a different transport effect. The transport calculation shows that distortions of the spatial distributions of ion birth and extraction by the magnetic electron suppression field are present for both negative hydrogen and deuterium ions.

  9. Quantification of protein backbone hydrogen-deuterium exchange rates by solid state NMR spectroscopy

    International Nuclear Information System (INIS)

    Lopez del Amo, Juan-Miguel; Fink, Uwe; Reif, Bernd

    2010-01-01

    We present the quantification of backbone amide hydrogen-deuterium exchange rates (HDX) for immobilized proteins. The experiments make use of the deuterium isotope effect on the amide nitrogen chemical shift, as well as on proton dilution by deuteration. We find that backbone amides in the microcrystalline α-spectrin SH3 domain exchange rather slowly with the solvent (with exchange rates negligible within the individual 15 N-T 1 timescales). We observed chemical exchange for 6 residues with HDX exchange rates in the range from 0.2 to 5 s -1 . Backbone amide 15 N longitudinal relaxation times that we determined previously are not significantly affected for most residues, yielding no systematic artifacts upon quantification of backbone dynamics (Chevelkov et al. 2008b). Significant exchange was observed for the backbone amides of R21, S36 and K60, as well as for the sidechain amides of N38, N35 and for W41ε. These residues could not be fit in our previous motional analysis, demonstrating that amide proton chemical exchange needs to be considered in the analysis of protein dynamics in the solid-state, in case D 2 O is employed as a solvent for sample preparation. Due to the intrinsically long 15 N relaxation times in the solid-state, the approach proposed here can expand the range of accessible HDX rates in the intermediate regime that is not accessible so far with exchange quench and MEXICO type experiments.

  10. Ultraviolet radiation-damage absorption peak in solid deuterium-tritium. Revision 1

    International Nuclear Information System (INIS)

    Fearon, E.M.; Tsugawa, R.T.; Souers, P.C.; Poll, J.D.; Hunt, J.L.

    1985-01-01

    An ultraviolet absorption peak has been seen in solid deuterium-tritium and hydrogen-tritium at a sensor temperature of 5 K. The peak occurs at 3.6 eV and is about 1.5 eV wide. It bleaches out when the temperature is raised to about 10 K but reappears upon cooling and is, therefore, radiation induced. At 5 K, the peak forms on a time scale of minutes and appears to represent part-per-million levels of electron-mass defects. The suggested model is that of a trapped electron, where the peak is the ground state-to-the-conduction band transition. A marked isotope effect is seen between D-T and H-T

  11. Melting diagram of hydrogen-deuterium solutions for pressures up to 100 atm

    International Nuclear Information System (INIS)

    Bereznyak, N.G.; Sheinina, A.A.

    1985-01-01

    Curves of the onset of melting of hydrogen-deuterium solutions of three different concentrations versus the vapor pressure up to ∼140 atm are measured. The topology of the melting diagram of H 2 --D 2 solutions at elevated pressures is determined. The isotope separation coefficients between the liquid and solid phases are calculated

  12. Lamb shift in the muonic deuterium atom

    Energy Technology Data Exchange (ETDEWEB)

    Krutov, A. A.; Martynenko, A. P. [Samara State University, Pavlov street 1, 443011, Samara (Russian Federation); Samara State University, Pavlov Street 1, 443011, Samara, Russia and Samara State Aerospace University named after academician S.P. Korolyov, Moskovskoye Shosse 34, 443086, Samara (Russian Federation)

    2011-11-15

    We present an investigation of the Lamb shift (2P{sub 1/2}-2S{sub 1/2}) in the muonic deuterium ({mu}D) atom using the three-dimensional quasipotential method in quantum electrodynamics. The vacuum polarization, nuclear-structure, and recoil effects are calculated with the account of contributions of orders {alpha}{sup 3}, {alpha}{sup 4}, {alpha}{sup 5}, and {alpha}{sup 6}. The results are compared with earlier performed calculations. The obtained numerical value of the Lamb shift at 202.4139 meV can be considered a reliable estimate for comparison with forthcoming experimental data.

  13. Defect trapping of deuterium implanted in aluminium

    International Nuclear Information System (INIS)

    Kido, Y.; Kakeno, M.; Yamada, K.; Hioki, T.; Kawamoto, J.

    1982-01-01

    The behaviour of deuterium implanted in Al was studied by the D( 3 He,p) 4 He and the D(d,p)T nuclear reactions. Changes of the depth profiles of the deuterium after heat treatments indicated that the implanted deuterium was trapped by the defect produced during the deuterium implantation and the release probability of the trapped deuterium increased as the specimen temperature was raised. Assuming a thermal equilibrium locally in the region of high defect concentration, the trapping energy of deuterium in Al was determined to be 0.12eV. Since the release probability for the single crystal was considerably larger than that for the polycrystal specimens, the deuterium was considered to be strongly trapped in the grain boundaries. Distributions of displaced Al atoms and the recovery of the lattice damage by annealing were measured by the channelling technique. (author)

  14. Carbon and hydrogen isotopic effects of stomatal density in Arabidopsis thaliana

    Science.gov (United States)

    Lee, Hyejung; Feakins, Sarah J.; Sternberg, Leonel da S. L.

    2016-04-01

    Stomata are key gateways mediating carbon uptake and water loss from plants. Varied stomatal densities in fossil leaves raise the possibility that isotope effects associated with the openness of exchange may have mediated plant wax biomarker isotopic proxies for paleovegetation and paleoclimate in the geological record. Here we use Arabidopsis thaliana, a widely used model organism, to provide the first controlled tests of stomatal density on carbon and hydrogen isotopic compositions of cuticular waxes. Laboratory grown wildtype and mutants with suppressed and overexpressed stomatal densities allow us to directly test the isotope effects of stomatal densities independent of most other environmental or biological variables. Hydrogen isotope (D/H) measurements of both plant waters and plant wax n-alkanes allow us to directly constrain the isotopic effects of leaf water isotopic enrichment via transpiration and biosynthetic fractionations, which together determine the net fractionation between irrigation water and n-alkane hydrogen isotopic composition. We also measure carbon isotopic fractionations of n-alkanes and bulk leaf tissue associated with different stomatal densities. We find offsets of +15‰ for δD and -3‰ for δ13C for the overexpressed mutant compared to the suppressed mutant. Since the range of stomatal densities expressed is comparable to that found in extant plants and the Cenozoic fossil record, the results allow us to consider the magnitude of isotope effects that may be incurred by these plant adaptive responses. This study highlights the potential of genetic mutants to isolate individual isotope effects and add to our fundamental understanding of how genetics and physiology influence plant biochemicals including plant wax biomarkers.

  15. Silver diffusion and isotope effect in silver rubidium iodide

    International Nuclear Information System (INIS)

    Arzigian, J.S.

    1980-01-01

    The diffusion coefficient of silver in RbAg 4 I 5 was measured in both superionic phases using radiotracer Ag-110m and serial sectioning with a low temperature sectioning apparatus. The activation energies for diffusion in alpha-RbAg 4 I 5 and beta-RbAg 4 I 5 , respectively, are 0.11 +- 0.01 eV and 0.20 +- 0.04 eV. An isotope effect for diffusion was also measured in both superionic phases. Ag-105 and Ag-110m radioisotopes were used with gamma spectroscopy and energy discrimination. The effect is small, with no significant temperature variation, with the value at 333 0 K being 0.12 +- 0.01. The second-order phase transition at 208 0 K has a small effect, if any, on the magnitude of the effect. The data suggest that a highly cooperative transport mechanism is responsible for the unusually high values of both the conductivity and diffusion coefficient. Although it is not possible to deduce the particular mechanism involved, theories inolving ionic polarons, or cooperative motion, such as crowdions or solitons, seem consistent with the observed results

  16. Design study of fuel circulating system using Pd-alloy membrane isotope separation method

    International Nuclear Information System (INIS)

    Naito, T.; Yamada, T.; Yamanaka, T.; Aizawa, T.; Kasahara, T.; Nishikawa, M.; Asami, N.

    1980-01-01

    Design study on the fuel circulating system (FCS) for a tokamak experimental fusion reactor (JXFR) has been carried out to establish the system concept, to plan the development program, and to evaluate the feasibility of diffusion system. The FCS consists of main vacuum system, fuel gas refiners, isotope separators, fuel feeders, and auxiliary systems. In the system design, Pd-alloy membrane permeation method is adopted for fuel refining and isotope separating. All impurities are effectively removed and hydrogen isotopes are sufficiently separated by Pd-alloy membrane. The isotope separation system consists of 1st (47 separators) and 2nd (46 separators) cascades for removing protium and separating deuterium, respectively. In the FCS, while cryogenic distillation method appears to be practicable, Pd-alloy membrane diffusion method is attractive for isotope separation and refining of fuel gas. The choice will have to be based on reliability, economic, and safety analyses

  17. Modeling of the Process of Three-Isotope (H, D, T) Exchange Between Hydrogen Gas and Water Vapour on Pt-SDBC Catalyst over a Wide Range of Deuterium Concentration

    International Nuclear Information System (INIS)

    Fedorchenko, O.A.; Alekseev, I.A.; Tchijov, A.S.; Uborsky, V.V.

    2005-01-01

    The large scale studies of Combined Electrolysis and Catalytic Exchange (CECE) process in Petersburg Nuclear Physics Institute showed a complicated influence of various factors on the process caused by the presence of two simultaneous isotope exchange sub processes: counter-current phase exchange (between liquid water and water vapour) and co-current catalytic exchange (between hydrogen gas and water vapour). A laboratory scale set-up of glass made apparatuses was established in such a way that it allows us to study phase and catalytic exchange apart. A computer model of the set-up has been developed.The catalytic isotope exchange model formulation is presented. A collection of reversible chemical reactions is accompanied by diffusion of the gaseous reactants and reaction products in the pores of catalyst carrier. This has some interesting features that are demonstrated. Thus it was noted that the flow rates ratio (gas to vapour - λ = G/V) as well as the concentrations of reactants exert influence on the process efficiency

  18. Determination of the variation of mercury isotope concentration based on spectral-phase effects

    International Nuclear Information System (INIS)

    Ganeev, A.A.; Man', D.D.; Turkin, Yu.I.

    1988-01-01

    A method of isotopic atomic-absorption analysis, based on spectral-phase effects in which there is no need to use several sources of radiation with pure isotopes of the analyte element, was developed. The method made it possible to simplify the analysis and to determine the variation of the concentration of mercury isotopes from one deposit to another with an accuracy several times higher that of traditional methods of spectral isotopic analysis. The method was tested on mercury 198 and mercury 202. The isotopic analyzer is diagramed and described. The mechanism of spectral-phase effects was determined by the difference in effective photon lifetimes, corresponding to different components of the hyperfine structure of the resonance line of mercury at 254 nm

  19. Isotope hydrology. Raigon aquifer hydrochemistry - Uruguay

    International Nuclear Information System (INIS)

    Plata Bedmar, A.; Dellepere, A.; Roma, M.T; Ramirez, M.; Garat, S.; Padros, D.; Caristo, R.; Lavanca, R.; Aranda, E.; Michelis, G.; Monroi, F.; Luaces, A.

    2001-01-01

    The purpose of this study is the Raigon Acuifer investigation by isotopic techniques as well as the dynamic behavior in the water resources. These techniques are based on the natural water isotope deuterium, oxygen-18, tritium and carbon-14 measurement. The hydrochemistry is used like a complementary tool

  20. Hot muonic deuterium and tritium from cold targets

    International Nuclear Information System (INIS)

    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.; Martoff, C.J.; Petitjean, C.

    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

  1. The sensitizing phenomenon of X-ray film in the experiment of metals loaded with deuterium

    International Nuclear Information System (INIS)

    Chen Suhe; Wang Dalun; Chen Wenjang; Li Yijun; Fu Yibei; Zhang Xinwei

    1993-01-01

    The sensitizing phenomenon of X-ray film was studied, in metals loaded with deuterium, by a cycle method of temperature and pressure (CMTP). The experimental results showed that the sensitization of X-ray film was derived from the chemical reaction and the anomalous effect of metals loaded with deuterium. (author)

  2. The need for accurate deuterium analysis in a heavy water plant and its achievement

    International Nuclear Information System (INIS)

    Singh, R.R.; Pradhan, D.G.

    1979-01-01

    Importance of Mass Spectrometer as an analytical tool for deuterium analysis in heavy water plants is discussed. Some of the important requirements such as memory effect and H 3 + correction are described with reference to the Mass Spectrometer used at HWP (Talcher). For achieving the accuracy required, use of international deuterium standards and error estimation found by intercalibration are discussed. (auth.)

  3. Isotope enrichment by electron spin resonance transitions of the intermediate radical pair

    International Nuclear Information System (INIS)

    Okazaki, M.; Shiga, T.; Sakata, S.; Konaka, R.; Toriyama, K.

    1988-01-01

    Microwave effects on the spin adduct yield were observed in the photoreduction of menadione in micellar solutions with ordinary sodium dodecyl sulfate (SDS), deuterium-labeled SDS, and a mixture of them. A large isotope effect was found in the microwave modulation of the spin adduct yield, which is due to the ESR transitions of the transient radical pair in the reaction. It is demonstrated for the first time that the microwave field can be used to enrich one of the isotopes which coexist in the system

  4. Melatonin labeled with hydrogen isotopes

    International Nuclear Information System (INIS)

    Dmitrevskaya, L.I.; Smushkevich, Yu.I.; Kurkovskaya, L.N.; Ponomarenko, N.K.; Suvorov, N.N.

    1989-01-01

    A study has been made of isotope exchange between melatonin and deuterium (D 2 O) or tritium (HTO) oxide under different conditions. The ease of isotope exchange for the indole ring hydrogens of melatonin in an acidic medium decreases over the series H 4 > H 2 H 6 >> H 7 , enabling the authors to process a route for production of melatonin labeled with hydrogen isotopes at positions 4,6, and 2 of the indole ring. A method has been suggested for producing melatonin labeled with hydrogen isotopes at position 2 by desulfurization of 2-(2,4-dinitro-phenylsulfenyl)melatonin at Ni(Re) (D)

  5. Melatonin labelled by hydrogen isotopes

    International Nuclear Information System (INIS)

    Dmitrevskaya, L.I.; Smushkevich, Yu.I.; Kurkovskaya, L.N.; Ponomarenko, N.K.; Suvorov, N.N.

    1988-01-01

    Isotope exchange of melatonin with deuterium (D 2 O) and tritium (HTO) oxides under different conditions is studied. Simplicity of isotope exchange of hydrogens of the indole ring of melatonin in the acidic medium decreases in series H 4 >H 2 >H 6 >>H 7 , that permits to suggest the way of melatonin preparation labelled by hydrogen isotopes in positions 4,6 and 2 of the indole ring. The way of melatonin preparation labelled by hydrogen isotopes in position 2 according to the reaction of desulfation 2-(2,4-dinitrophenylsulphenyl) melatonin at catalyst Ni(Re)(D) is suggested

  6. Modelling the Spatial Isotope Variability of Precipitation in Syria

    Energy Technology Data Exchange (ETDEWEB)

    Kattan, Z.; Kattaa, B. [Department of Geology, Atomic Energy Commission of Syria (AECS), Damascus (Syrian Arab Republic)

    2013-07-15

    Attempts were made to model the spatial variability of environmental isotope ({sup 18}O, {sup 2}H and {sup 3}H) compositions of precipitation in syria. Rainfall samples periodically collected on a monthly basis from 16 different stations were used for processing and demonstrating the spatial distributions of these isotopes, together with those of deuterium excess (d) values. Mathematically, the modelling process was based on applying simple polynomial models that take into consideration the effects of major geographic factors (Lon.E., Lat.N., and altitude). The modelling results of spatial distribution of stable isotopes ({sup 18}O and {sup 2}H) were generally good, as shown from the high correlation coefficients (R{sup 2} = 0.7-0.8), calculated between the observed and predicted values. In the case of deuterium excess and tritium distributions, the results were most likely approximates (R{sup 2} = 0.5-0.6). Improving the simulation of spatial isotope variability probably requires the incorporation of other local meteorological factors, such as relative air humidity, precipitation amount and vapour pressure, which are supposed to play an important role in such an arid country. (author)

  7. Biological isotopy. Introduction to the isotopic effects and to their applications in biology

    International Nuclear Information System (INIS)

    Tcherkez, G.

    2010-01-01

    Since their discovery in the beginning of the 20. century, the study of stable isotopes has considerably developed. This domain, which remained limited in its applications until the 1990's, has become particularly important thereafter thanks to its practical applications and in particular to its economical impacts. Many techniques used in fraud control, in drugs use control, in selection of high-yield plants etc are based on isotopic abundance measurements. This reference book gives a synthesis of our actual knowledge on the use of stable isotopes and of isotope fractionation in biology. It presents the basic notions of isotopic biochemistry and explains the origin of the isotopic effects. The application principles of these effects to metabolism, to organisms physiology, to environmental biology etc are explained and detailed using examples and exercises. The first chapters present the basic knowledge which defines, from a mathematical point-of-view, the isotopic effects of chemical reactions or of physical processes taking place in biology. The measurements principle of natural isotopes abundance is then synthesised. Finally, all these notions are applied at different scales: enzymes, physiology, metabolism, environment, ecosystems and fraud crackdown. (J.S.)

  8. Isotope effect of impurity diffusion of cadmium in silver

    International Nuclear Information System (INIS)

    Rockosch, H.J.; Herzig, C.

    1984-01-01

    The isotope effect of impurity diffusion of cadmium in silver single crystals was measured with the radioisotopes 115 Cd/ 109 Cd by gamma spectrometry. As a mean value E = 0.37 at T = 1060 K was obtained. The correlation factor f /SUB Cd/ = 0.41 is in disagreement with previous results of other investigators due to their unfavourable experimental approach. The present value of f /SUB Cd/ , however, is consistent with those of In and Sn in Ag. A comparison with the corresponding correlation factors in the copper solvent reveals a distinct influence of lattice perturbations because of the different atomic volumes of the solvents. Since the size effect is neglected in the electrostatic diffusion model, the agreement with this model is only qualitative. The frequency ratios for vacancy jumps were calculated. The free binding enthalpy of the vacancy-impurity complex was estimated to be Δg /SUB Cd/ = -0.064 eV. This value is smaller than those for In and Sn in Ag and complies with the relative diffusivities of these impurities in Ag

  9. Deuterium and big bang nucleosynthesis

    International Nuclear Information System (INIS)

    Burles, S.

    2000-01-01

    Measurements of deuterium absorption in high redshift quasar absorption systems provide a direct inference of the deuterium abundance produced by big bang nucleosynthesis (BBN). With measurements and limits from five independent absorption systems, we place strong constraints on the primordial ratio of deuterium to hydrogen, (D/H) p = 3.4 ± 0.3 x 10 -5 [1,2]. We employ a direct numerical treatment to improve the estimates of critical reaction rates and reduce the uncertainties in BBN predictions of D/H and 7 Li/H by a factor of three[3] over previous efforts[4]. Using our measurements of (D/H) p and new BBN predictions, we find at 95% confidence the baryon density ρ b = (3.6 ± 0.4) x 10 -31 g cm -3 (Ω b h 2 65 = 0.045 ± 0.006 in units of the critical density), and cosmological baryon-photon ratio η = (5.1 ± 0.6) x 10 -10

  10. Regional and temporal variations of deuterium in the precipitation and atmospheric moisture of Central Europe

    International Nuclear Information System (INIS)

    Huebner, H.; Kowski, P.; Hermichen, W.D.; Richter, W.; Schuetze, H.

    1979-01-01

    Regional and temporal variations of deuterium in precipitation and in atmospheric moisture provide the opportunity to balance water cycles as additional but independent information. Variations of deuterium have been measured in precipitation samples from six stations in different zones of the German Democratic Republic since 1972. The aim of the subsequent mathematical processing was to find a functional connection between the deuterium variations and the meteorological parameters causing them. The isotopic content of atmospheric moisture in different air masses and the isotopic content of precipitation are determined by the evaporation conditions of the area of origin and by the number and intensity of evaporation and condensation (precipitation) processes en route from this area of origin to the observation point. Obviously the temperatures at which evaporation and condensation processes take place are of crucial importance. The deuterium values are correlated with the monthly mean temperature. It has been observed, for example, that the equations of regression between precipitation and atmospheric moisture (valid in the case of Leipzig station) differ only with regard to their absolute terms. This follows from the fact that the deuterium is generally enriched by up to 80 per mille in precipitation. Following the well-known fact that many meteorological phenomena show frequencies, an attempt was made to apply the Fourier analysis for the deltaD variations. Relevant harmonic parts were found in all the deltaD series studied, which are repetitious and independent of the station and the observation period. (author)

  11. Effect of interband interaction on isotope effect exponent of MgB2 ...

    Indian Academy of Sciences (India)

    The interband interaction of the electron–phonon interaction shows more effect on the isotope exponent than on the non-phonon interaction. Acknowledgement. The authors would like to thank Thailand Research Fund for financial support and the University of the Thai Chamber of Commerce for partial financial support and.

  12. Thermodynamic properties of solid deuterium in premelting region

    International Nuclear Information System (INIS)

    Udovichenko, B.G.; Esel'son, V.B.; Manzhelij, V.G.

    1984-01-01

    Thermal expansion and isothermal compressibility of solid normal deuterium are measured near the melting line under pressures up to 500 atm. The earlier measurement method is improved to operate in a wider range of working pressures. The effects are discussed which are produced by zero trranslational oscillations in the thermodynamic properties of deuterium. The change in the molar volume in the range from T=0 to the melting temperature is considered as a quantum characteristic of the crystal. The molar volumes of solid deuterium observed at the melting line at moderate P are compared and specified. At P=O and T=0 the molar volume of o-D 2 is found to be V 00 =(20.03+-0.07) cm 3 /mole which follows from the thermodynamic experiment

  13. Vibrational modes of deuterium in KD2PO4

    International Nuclear Information System (INIS)

    Mizoguchi, Kohji; Agui, Akane; Tominaga, Yasunori; Nakai, Yusuke; Ikeda, Susumu.

    1993-01-01

    In order to study the deuteration effect in hydrogen-bonded compounds such as KH 2 PO 4 , hydrogen and deuterium modes in KH 2 PO 4 and K(D x H 1-x ) 2 PO 4 (x = 95 %) were investigated by means of inelastic neutron-scattering measurements over a wide energy range. By comparing Raman spectra of KH 2 PO 4 and KD 2 PO 4 with neutron-scattering spectra, the vibrational modes of deuterium and those of PO 4 tetrahedrons in the energy range of 30 < ε < 150 meV have been investigated. At least two deuterium modes have been found at 87 meV and 106 meV. (author)

  14. Pressure dependent isotopic fractionation in the photolysis of formaldehyde-d2

    DEFF Research Database (Denmark)

    Nilsson, E.J.K.; Schmidt, Johan Albrecht; Johnson, Matthew Stanley

    2014-01-01

    role in the observed pressure dependent photolytic fractionation of deuterium. The model shows that part of the fractionation is a result of competition between the isotopologue dependent rates of unimolecular dissociation and collisional relaxation. We suggest that the remaining fractionation is due......The isotope effects in formaldehyde photolysis are the key link between the δD of methane emissions and the δD of atmospheric in situ hydrogen production. A few recent studies have suggested that a pressure dependence in the isotopic fractionation can partly explain enrichment of deuterium...... with altitude in the atmosphere. The mechanism and the extent of this pressure dependency is, however, not adequately described. In the present work D2CO and H2CO were photolyzed in a static reaction chamber at bath gas pressures of 50, 200, 400, 600 and 1000 mbar; these experiments compliment and extend our...

  15. Isotope effects in lithium hydride and lithium deuteride crystals by molecular dynamics simulations.

    Science.gov (United States)

    Dammak, Hichem; Antoshchenkova, Ekaterina; Hayoun, Marc; Finocchi, Fabio

    2012-10-31

    Molecular dynamics (MD) simulations have been carried out to study isotope effects in lithium hydride and lithium deuteride crystals. Quantum effects on nuclear motion have been included through a quantum thermal bath (QTB). The interatomic forces were described either within the density functional theory (DFT) in the generalized gradient approximation (GGA) or by the phenomenological approach using the shell model. For both models, the isotopic shift in the lattice parameter can be successfully predicted by QTB-MD simulations. The slope of the experimental isotopic shift in pressure is satisfactorily reproduced by QTB-MD within DFT-GGA, in contrast to both density functional perturbation theory and QTB-MD with the shell model. We have analyzed the reasons for these discrepancies through the vibrational densities of states and the isotopic shifts in bulk modulus. The results illustrate the importance of anharmonic contributions to vibrations and to the isotopic pressure shift between LiH and LiD.

  16. Thermal Conductivity of Nanotubes: Effects of Chirality and Isotope Impurity

    OpenAIRE

    Gang, Zhang; Li, Baowen

    2005-01-01

    We study the dependence of thermal conductivity of single walled nanotubes (SWNT) on chirality and isotope impurity by nonequilibrium molecular dynamics method with accurate potentials. It is found that, contrary to electronic conductivity, the thermal conductivity is insensitive to the chirality. The isotope impurity, however, can reduce the thermal conductivity up to 60% and change the temperature dependence behavior. We also study the dependence of thermal conductivity on tube length for t...

  17. Application of environmental isotope tracing technology to geothermal geochemistry

    International Nuclear Information System (INIS)

    Shang Yingnan

    2006-01-01

    This paper reviews the recent application and development of environmental isotope tracing technology to geothermal geochemistry in the following aspects: gas isotopes (He, C) tracing of warm springs; H, O isotope tracing on the origin and cause of geothermal water, environmental isotope dating of geothermal water, and the advantage of excess parameter of deuterium (d) in geothermal research. The author also suggests that isotope method should combine with other geological methods to expand its advantage. (authors)

  18. Isotopic equilibrium constants of the deuterium exchange between HDO and H{sub 2}S, H{sub 2}Se and H{sub 2}Te; Etude des constantes des equilibres isotopiques du deuterium entre l'eau et les hydrures des metalloides de la deuxieme famille

    Energy Technology Data Exchange (ETDEWEB)

    Marx, D [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1959-11-15

    We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH{sub 2} + OHD {r_reversible} SHD + OH{sub 2}; SeH{sub 2} + OHD {r_reversible} SeHD + OH{sub 2}; TeH{sub 2} + OHD {r_reversible} TeHD + OH{sub 2}. In gaseous phase, statistical thermodynamics leads to the expression: K (Z{sub OHD} x Z{sub RH{sub 2}})/(Z{sub OH{sub 2}} x Z{sub RHD}) x e{sup W/T} (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [French] Nous avons determine experimentalement la constante K de chacun des equilibres isotopiques suivants: SH{sub 2} + OHD {r_reversible} SHD + OH{sub 2}; SeH{sub 2} + OHD {r_reversible} SeHD + OH{sub 2}; TeH{sub 2} + OHD {r_reversible} TeHD + OH{sub 2}. En phase gazeuse, la thermodynamique donne l'expression: K = (Z{sub OHD} x Z{sub RH{sub 2}})/(Z{sub OH{sub 2}} x Z{sub RHD}) x e{sup W/T} (R representant un atome de soufre, selenium ou tellure). Les fonctions de partition Z de chacune des molecules ont ete calculees et, grace a nos resultats experimentaux, nous avons determine la constante W. Connaissant W, la constante d'equilibre K a pu etre tabulee en fonction de la temperature. (auteur)

  19. Matrix effects in laser ablation molecular isotopic spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Staci, E-mail: staci.brown@cepast.famu.edu [Department of Physics, Florida A and M University, 2077 E. Paul Dirac Drive, Tallahassee, FL 32310 (United States); Ford, Alan, E-mail: alan.ford@alakaidefense.com [Alakai Defense Systems, 197 Replacement Ave, Suite 102, Fort Leonard Wood, MO 65473 (United States); Akpovo, Charlemagne C., E-mail: charlemagne.akpovo@cepast.famu.edu [Department of Physics, Florida A and M University, 2077 E. Paul Dirac Drive, Tallahassee, FL 32310 (United States); Martinez, Jorge, E-mail: jmartinez@cepast.famu.edu [Department of Physics, Florida A and M University, 2077 E. Paul Dirac Drive, Tallahassee, FL 32310 (United States); Johnson, Lewis, E-mail: lewis@cepast.famu.edu [Department of Physics, Florida A and M University, 2077 E. Paul Dirac Drive, Tallahassee, FL 32310 (United States)

    2014-11-01

    Recently, it has been shown that laser-induced breakdown spectroscopy (LIBS) can be used for the detection of isotopes of elements via isotopic shifts in diatomic species in a technique known as laser ablation molecular isotopic spectrometry (LAMIS). While LAMIS works quite well for isotopic analysis of pure compounds under optimal conditions, it is desirable for it to be applicable for a variety of compounds and matrices. However, the LIBS plasma emission associated with LAMIS depends on several parameters, including the applied electric field of the laser pulse, the physical properties of the material being investigated, and the presence of additional elements other than the element of interest. In this paper, we address some of the pitfalls arising from these dependencies when using LAMIS for the determination of the relative isotopic abundance of boron-containing materials with varying chemical matrices. - Highlights: • LAMIS usually determines isotopic composition of boron compounds within 3 percent. • LaBO{sub 3} and some boron-containing mixtures yield inaccurate LAMIS results. • Higher laser energy reduces variability but does not remedy poor LAMIS outcomes.

  20. Investigation of the feeding effect on the 13C/12C isotope ratio of the hormones in bovine urine using gas chromatography/combustion isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Balizs, Gabor; Jainz, Annett; Horvatovich, Peter

    2005-01-01

    The effect of the feeding on the 13C/12C isotope ratio of four endogenous steroid hormones testosterone (T), epi-testosterone (epi-T), dehydroepiandrosterone (DHEA) and etiocholanolone (ETIO) in bovine urine was investigated. An analytical method to determine the accurate isotope ratio was developed