WorldWideScience

Sample records for normal isotope effect

  1. Normal coordinate treatment of liquid water and calculation of vapor pressure isotope effects

    International Nuclear Information System (INIS)

    Gellai, B.; Van Hook, W.A.

    1983-01-01

    A vibrational analysis of liquid water is reported, assuming a completely hydrogen-bonded network with continuously varying strengths of the hydrogen bonds. Frequency distribution calculations are made for intramolecular stretching and bending modes and for the intramolecular frequency region. The calculated distributions are compared with the experimental spectroscopic ones. As another test, vapor pressure isotope effects are calculated from the theoretical distributions for some isotopic water molecules. Results are compared with those of other authors obtained from a mixture model. (author)

  2. Normalization of oxygen and hydrogen isotope data

    Science.gov (United States)

    Coplen, T.B.

    1988-01-01

    To resolve confusion due to expression of isotopic data from different laboratories on non-corresponding scales, oxygen isotope analyses of all substances can be expressed relative to VSMOW or VPDB (Vienna Peedee belemnite) on scales normalized such that the ??18O of SLAP is -55.5% relative to VSMOW. H3+ contribution in hydrogen isotope ratio analysis can be easily determined using two gaseous reference samples that differ greatly in deuterium content. ?? 1988.

  3. 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

  4. Ubiquitous isotopic anomalies in Ti from normal Allende inclusions

    International Nuclear Information System (INIS)

    Niemeyer, S.; Lugmair, G.W.

    1981-01-01

    A newly developed technique for high-precision isotopic analyses of titanium was applied to terrestrial rocks and course- and fine-grained Allende inclusions. Repeated analyses of three terrestrial rocks gave excellent agreement (usually less than 2 x 10 -4 deviations) with a Ti metal standard. All seven Allende inclusions studied here were previously determined to contain isotopically normal Nd and/or Sm, indicating that none belongs to a small group of peculiar inclusions, dubbed as FUN inclusions. (orig./ME)

  5. 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.

  6. 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

  7. 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)

  8. 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)

  9. Normal processes of phonon-phonon scattering and thermal conductivity of germanium crystals with isotopic disorder

    CERN Document Server

    Kuleev, I G

    2001-01-01

    The effect of normal processes of the phonon-phonon scattering on the thermal conductivity of the germanium crystals with various isotopic disorder degrees is considered. The phonon pulse redistribution in the normal scattering processes both inside each oscillatory branch (the Simons mechanism) and between various phonon oscillatory branches (the Herring mechanism) is accounted for. The contributions of the longitudinal and cross-sectional phonons drift motion into the thermal conductivity are analyzed. It is shown that the pulse redistribution in the Herring relaxation mechanism leads to essential suppression of the longitudinal phonons drift motion in the isotopically pure germanium crystals. The calculations results of thermal conductivity for the Herring relaxation mechanism agree well with experimental data on the germanium crystals with various isotopic disorder degrees

  10. 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

  11. 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

  12. Normal and Inverse Diffusive Isotope Fractionation of Deuterated Toluene and Benzene in Aqueous Systems

    DEFF Research Database (Denmark)

    Rolle, Massimo; Jin, Biao

    2017-01-01

    Diffusive isotope fractionation of organic contaminants in aqueous solution is difficult to quantify, and only a few experimental data sets are available for compounds of environmental interest. In this study, we investigate diffusive fractionation of perdeuterated and nondeuterated benzene...... and toluene. Multitracer experiments were carried out in 1-D gel dissection tubes and in a quasi-2-D flow-through porous medium. The experiments allowed us to simultaneously and directly compare the diffusive and dispersive behavior of benzene and toluene. We observed an unexpected, opposite behavior...... of the two monoaromatic hydrocarbons. Toluene showed a normal diffusive isotope effect (DC7D8/DC7H8 = 0.96) with enrichment of the nondeuterated isotopologue in the direction of the diffusive and transverse dispersive fluxes. Conversely, the measured trends for benzene indicate inverse diffusive...

  13. 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)

  14. 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...

  15. Normal and Inverse Diffusive Isotope Fractionation of Deuterated Toluene and Benzene in Aqueous Systems

    DEFF Research Database (Denmark)

    Rolle, Massimo; Jin, Biao

    2017-01-01

    and toluene. Multitracer experiments were carried out in 1-D gel dissection tubes and in a quasi-2-D flow-through porous medium. The experiments allowed us to simultaneously and directly compare the diffusive and dispersive behavior of benzene and toluene. We observed an unexpected, opposite behavior...... of the two monoaromatic hydrocarbons. Toluene showed a normal diffusive isotope effect (DC7D8/DC7H8 = 0.96) with enrichment of the nondeuterated isotopologue in the direction of the diffusive and transverse dispersive fluxes. Conversely, the measured trends for benzene indicate inverse diffusive...

  16. Normalization Methods and Selection Strategies for Reference Materials in Stable Isotope Analyes. Review

    Energy Technology Data Exchange (ETDEWEB)

    Skrzypek, G. [West Australian Biogeochemistry Centre, John de Laeter Centre of Mass Spectrometry, School of Plant Biology, University of Western Australia, Crawley (Australia); Sadler, R. [School of Agricultural and Resource Economics, University of Western Australia, Crawley (Australia); Paul, D. [Department of Civil Engineering (Geosciences), Indian Institute of Technology Kanpur, Kanpur (India); Forizs, I. [Institute for Geochemical Research, Hungarian Academy of Sciences, Budapest (Hungary)

    2013-07-15

    Stable isotope ratio mass spectrometers are highly precise, but not accurate instruments. Therefore, results have to be normalized to one of the isotope scales (e.g., VSMOW, VPDB) based on well calibrated reference materials. The selection of reference materials, numbers of replicates, {delta}-values of these reference materials and normalization technique have been identified as crucial in determining the uncertainty associated with the final results. The most common normalization techniques and reference materials have been tested using both Monte Carlo simulations and laboratory experiments to investigate aspects of error propagation during the normalization of isotope data. The range of observed differences justifies the need to employ the same sets of standards worldwide for each element and each stable isotope analytical technique. (author)

  17. Normalization Methods and Selection Strategies for Reference Materials in Stable Isotope Analyses - Review

    International Nuclear Information System (INIS)

    Skrzypek, G.; Sadler, R.; Paul, D.; Forizs, I.

    2011-01-01

    A stable isotope analyst has to make a number of important decisions regarding how to best determine the 'true' stable isotope composition of analysed samples in reference to an international scale. It has to be decided which reference materials should be used, the number of reference materials and how many repetitions of each standard is most appropriate for a desired level of precision, and what normalization procedure should be selected. In this paper we summarise what is known about propagation of uncertainties associated with normalization procedures and propagation of uncertainties associated with reference materials used as anchors for the determination of 'true' values for δ''1''3C and δ''1''8O. Normalization methods Several normalization methods transforming the 'raw' value obtained from mass spectrometers to one of the internationally recognized scales has been developed. However, as summarised by Paul et al. different normalization transforms alone may lead to inconsistencies between laboratories. The most common normalization procedures are: single-point anchoring (versus working gas and certified reference standard), modified single-point normalization, linear shift between the measured and the true isotopic composition of two certified reference standards, two-point and multipoint linear normalization methods. The accuracy of these various normalization methods has been compared by using analytical laboratory data by Paul et al., with the single-point and normalization versus tank calibrations resulting in the largest normalization errors, and that also exceed the analytical uncertainty recommended for δ 13 C. The normalization error depends greatly on the relative differences between the stable isotope composition of the reference material and the sample. On the other hand, the normalization methods using two or more certified reference standards produces a smaller normalization error, if the reference materials are bracketing the whole range of

  18. 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

  19. 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.

  20. Study of chromium speciation in normal and diabetic rats by activable enriched stable isotope technique

    International Nuclear Information System (INIS)

    Feng, W.Y.; Qian, Q.F.; Ding, W.J.; Chai, Z.F.

    2000-01-01

    Chromium speciation was investigated in the liver cytosol, serum and urine of normal and diabetic rats after a single intravenous injection of enriched stable isotope 50 Cr tracer solution. Sephadex G-25 gel chromatography combined with instrumental neutron activation analysis was used to isolate and characterize protein-bound chromium in the above materials. The results indicate that Cr is mainly combined with a high-molecular-weight protein either in liver cytosol or serum. A low-molecular-weight, Cr-containing compound (LMWCr) was found in all the observed liver, serum and urine samples of both normal and diabetic rats. Chromium is excreted chiefly as LMWCr in urine. (author)

  1. 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.)

  2. Normalization of stable isotope data for carbonate minerals: implementation of IUPAC guideline

    Science.gov (United States)

    Kim, Sang-Tae; Coplen, Tyler B.; Horita, Juske

    2015-01-01

    Carbonate minerals provide a rich source of geochemical information because their δ13C and δ18O values provide information about surface and subsurface Earth processes. However, a significant problem is that the same δ18O value is not reported for the identical carbonate sample when analyzed in different isotope laboratories in spite of the fact that the International Union of Pure and Applied Chemistry (IUPAC) has provided reporting guidelines for two decades. This issue arises because (1) the δ18O measurements are performed on CO2 evolved by reaction of carbonates with phosphoric acid, (2) the acid-liberated CO2 is isotopically fractionated (enriched in 18O) because it contains only two-thirds of the oxygen from the solid carbonate, (3) this oxygen isotopic fractionation factor is a function of mineralogy, temperature, concentration of the phosphoric acid, and δ18O value of water in the phosphoric acid, (4) researchers may use any one of an assortment of oxygen isotopic fractionation factors that have been published for various minerals at various reaction temperatures, and (5) it sometimes is not clear how one should calculate δ18OVPDB values on a scale normalized such that the δ18O value of SLAP reference water is −55.5 ‰ relative to VSMOW reference water.

  3. Uncertainty evaluation in normalization of isotope delta measurement results against international reference materials.

    Science.gov (United States)

    Meija, Juris; Chartrand, Michelle M G

    2018-01-01

    Isotope delta measurements are normalized against international reference standards. Although multi-point normalization is becoming a standard practice, the existing uncertainty evaluation practices are either undocumented or are incomplete. For multi-point normalization, we present errors-in-variables regression models for explicit accounting of the measurement uncertainty of the international standards along with the uncertainty that is attributed to their assigned values. This manuscript presents framework to account for the uncertainty that arises due to a small number of replicate measurements and discusses multi-laboratory data reduction while accounting for inevitable correlations between the laboratories due to the use of identical reference materials for calibration. Both frequentist and Bayesian methods of uncertainty analysis are discussed.

  4. 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)

  5. Normality test for determining the correction factor of isotopic composition in PWR spent fuel

    International Nuclear Information System (INIS)

    Lee, Y. H.; Shin, H. S.; Noh, S. K.; Seo, K. S.

    2001-01-01

    Normality test has been carried out for the ratios of the measured-to-calculated isotopic compositions in PWR spent fuel, using Shapiro-Wilk W, Lilliefors D, Cramer-von Mises and Anderson-Darling. All 38 istopices have been evaluated by means of the 1.5xIQR rule and then outliers have been discarded. As result, it seems that only 20 nuclides are satisfied with the normality at significance level 5 %. 18 Nuclides(samples) including U-235 have higher significance probability(p-value) than 25 % in W-test and p-values obtained by other three tests exceed the upper limit. Besides, in 6 nuclides including Pu-239, it seems that the p-values are between 5 % and 25 % in W test. From these results, in order to predict the isotopic compositions in the conservative point of view, it is decided that the correction factors for the nuclides are determined at the 95/95 probability and confidence level by using tolerance limit-methods with the assumption that only 18 nuclides are satisfied with thr normality

  6. 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

  7. 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

  8. 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)

  9. 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

  10. 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....

  11. 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...

  12. Theoretical studies on the alpha α decay half-lives of hyper and normal isotopes of Po

    Science.gov (United States)

    Santhosh, K. P.; Nithya, C.

    2018-03-01

    The α decay half-lives of hyper and normal isotopes of Po nuclei are studied in the present work. The inclusion of Λ - N interaction changes the half-life for α decay. The theoretical predictions on the α decay half-lives of normal Po isotopes are compared with experimental results and are seen to be matching well with each other. The neutron shell closure at N = 126 is found to be the same for both normal and hypernuclei. The Geiger-Nuttal (G-N) law for α decay is unaltered in the case of hypernuclei. The hypernuclei will decay into normal nuclei by mesonic or non-mesonic decay modes. Since the half-lives of normal Po nuclei are well within the experimental limits, our theoretical results suggest experimental verification of the α emission from hyper Po nuclei in a cascade process.

  13. Intramolecular kinetic isotope effect in gas-phase proton-transfer reactions

    International Nuclear Information System (INIS)

    Wellman, K.M.; Victoriano, M.E.; Isolani, P.C.; Riveros, J.M.

    1979-01-01

    The k/sub H//k/sub D/ isotope effects were determined by ICR for the reaction of substituted toluenes with several alkoxides. The results showed a definite trend for k/sub H//k/sub D/ starting as a normal isotope effect for appreciably exothermic reaction (> 3 kcal mol -1 ) and proceeding smoothly toward an inverse isotope effect as the reaction approached thermoneutrality or becomes endothermic. These observations were explained by a reaction which involved a double minima potential with a central energy barrier

  14. 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)

  15. 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)

  16. Effects of pions on normal tissues

    International Nuclear Information System (INIS)

    Tokita, N.

    1981-01-01

    Verification of the uniform biological effectiveness of pion beams of various dimensions produced at LAMPF has been made using cultured mammalian cells and mouse jejunum. Normal tissue radiobiology studies at LAMPF are reviewed with regard to biological beam characterization for the therapy program and the current status of acute and late effect studies on rodents

  17. 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.

  18. Chemical and isotopic investigation of warm springs associated with normal faults in Utah

    Science.gov (United States)

    Cole, David R.

    1983-04-01

    Thermal springs associated with normal faults in Utah have been analyzed for major cations and anions, and oxygen and hydrogen isotopes. Springs with measured temperatures averaging greater than 40°C are characterized by Na + K- and SO 4 + Cl-rich waters containing 10 3 to 10 4 mg/l of dissolved solids. Lower temperature springs, averaging less than 40°C, are more enriched in Ca + Mg relative to Na + K. Chemical variations monitored through time in selected thermal springs are probably produced by mixing with non-thermal waters. During the summer months at times of maximum flow, selected hot springs exhibit their highest temperatures and maximum enrichments in most chemical constituents. Cation ratios and silica concentrations remain relatively constant through time for selected Utah thermal springs assuring the applicability of the geothermometer calculations regardless of the time of year. Geothermometer calculations utilizing either the quartz (no steam loss), chalcedony or Mg-corrected Na/K/Ca methods indicate that most thermal springs in Utah associated with normal faults have subsurface temperatures in the range of 25 to less than 120°C. This temperature range suggests fluid circulation is restricted to depths less than about three kilometers assuming an average thermal gradient of about 40°C/km. Thermodynamic calculations suggest that most thermal springs are oversaturated with respect to calcite, quartz, pyrophyllite, (Fe, Mg)-montmorillonite, microcline and hematite, and undersaturated with respect to anhydrite, gypsum, fluorite and anorthite. Chalcedony and cristobalite appear to be the only phases consistently at or near saturation in most waters. Theoretical evaluation of mixing on mineral saturation trends indicates that anhydrite and calcite become increasingly more undersaturated as cold, dilute groundwater mixes with a hot (150°C), NaCl-rich fluid. The evolution of these thermal waters issuing from faults appears to be one involving the

  19. Meteoric water in normal fault systems: Oxygen and hydrogen isotopic measurements on authigenic phases in brittle fault rocks

    Science.gov (United States)

    Haines, S. H.; Anderson, R.; Mulch, A.; Solum, J. G.; Valley, J. W.; van der Pluijm, B. A.

    2009-12-01

    The nature of fluid circulation systems in normal fault systems is fundamental to understanding the nature of fluid movement within the upper crust, and has important implications for the on-going controversy about the strength of faults. Authigenic phases in clay gouges and fault breccias record the isotopic signature of the fluids they formed in equilibrium with, and can be used to understand the ‘plumbing system’ of brittle fault environments. We obtained paired oxygen and hydrogen isotopic measurements on authigenic illite and/or smectite in clay gouge from normal faults in two geologic environments, 1.) low-angle normal faults (Ruby Mountains detachment, NV; Badwater Turtleback, CA; Panamint range-front detachment; CA; Amargosa detachment; CA; Waterman Hills detachment, CA), and 2.) An intracratonic high-angle normal fault (Moab Fault, UT). All authigenic phases in these clay gouges are moderately light isotopically with respect to oxygen (illite δ18O -2.0 - + 11.5 ‰ SMOW, smectite δ18O +3.6 and 17.9 ‰) and very light isotopically with respect to hydrogen (illite δD -148 to -98 ‰ SMOW, smectite δD -147 to -92 ‰). Fluid compositions calculated from the authigenic clays at temperatures of 50 - 130 ○C (as indicated by clay mineralogy) indicate that both illite and smectite in normal fault clay gouge formed in the presence of near-pristine to moderately-evolved meteoric fluids and that igneous or metamorphic fluids are not involved in clay gouge formation in these normal fault settings. We also obtained paired oxygen and hydrogen isotopic measurements on chlorites derived from footwall chlorite breccias in 4 low-angle normal fault detachment systems (Badwater and Mormon Point Turtlebacks, CA, the Chemehuevi detachment, CA, and the Buckskin-Rawhide detachment, AZ). All chlorites are isotopically light to moderately light with respect to oxygen (δ18O +0.29 to +8.1 ‰ SMOW) and very light with respect to hydrogen (δD -97 to -113 ‰) and indicate

  20. Normal variations in the isotopic composition of metabolically relevant transition metals in human blood

    Science.gov (United States)

    Van Heghe, L.; Cloquet, C.; Vanhaecke, F.

    2012-04-01

    Cu, Fe and Zn are transition metals with great catalytic, structural and regulating importance in the human body. Hence, an aberrant metabolism of these elements can have serious implications on the health of a person. It is assumed that, due to differences in isotope fractionation, the isotopic composition of these elements in whole blood of patients can be different from that in blood of healthy subjects. Therefore, isotopic analysis of the element affected by the disease can be a promising approach for early diagnosis. A method for isotopic analysis of Cu, Fe and Zn in human whole blood was developed. The simultaneous chromatographic isolation of these elements and the conditions for isotope ratio measurement via multi-collector ICP - mass spectrometry (MC-ICP-MS) were optimized. So far, only whole blood of supposedly healthy volunteers (reference population) was analyzed. Results for Fe confirmed the known differences in isotopic composition between male and female blood. It is also shown that other parameters can have influence as well, e.g., the isotopic composition of Zn seems to be governed by the diet.

  1. Dual-isotope single-photon emission computed tomography for dopamine and serotonin transporters in normal and parkinsonian monkey brains

    International Nuclear Information System (INIS)

    Li, I-H.; Huang, W.-S.; Yeh, C.-B.; Liao, M.-H.; Chen, C.-C.; Shen, L.-H.; Liu, J.-C.; Ma, K.-H.

    2009-01-01

    Introduction: Parkinson's disease (PD) affects both dopaminergic and serotonergic systems. In this study, we simultaneously evaluated dopamine and serotonin transporters in primates using dual-isotope single-photon emission computed tomography (SPECT) imaging and compared the results with traditional single-isotope imaging. Methods: Four healthy and one 6-OHDA-induced PD monkeys were used for this study. SPECT was performed over 4 h after individual or simultaneous injection of [ 99m Tc]TRODAT-1 (a dopamine transporter imaging agent) and [ 123 I]ADAM (a serotonin transporter imaging agent). Results: The results showed that the image quality and uptake ratios in different brain regions were comparable between single- and dual-isotope studies. The striatal [ 99m Tc]TRODAT-1 uptake in the PD monkey was markedly lower than that in normal monkeys. The uptake of [ 123 I]ADAM in the midbrain of the PD monkey was comparable to that in the normal monkeys, but there were decreased uptakes in the thalamus and striatum of the PD monkey. Conclusions: Our results suggest that dual-isotope SPECT using [ 99m Tc]TRODAT-1 and [ 123 I]ADAM can simultaneously evaluate changes in dopaminergic and serotonergic systems in a PD model.

  2. Dual-isotope single-photon emission computed tomography for dopamine and serotonin transporters in normal and parkinsonian monkey brains

    Energy Technology Data Exchange (ETDEWEB)

    Li, I-H. [Graduate Institute of Medical Sciences, National Defense Medical Center, Taipei 114, Taiwan (China); Huang, W.-S. [Department of Nuclear Medicine, Tri-Service General Hospital, Taipei, 114, Taiwan (China); Yeh, C.-B. [Department of Psychiatry, Tri-Service General Hospital, Taipei, 114, Taiwan (China); Liao, M.-H.; Chen, C.-C.; Shen, L.-H. [Division of Isotope Application, Institute of Nuclear Energy Research, Taoyaun, 325 Taiwan (China); Liu, J.-C. [Department of Biology and Anatomy, National Defense Medical Center, Taipei 114, Taiwan (China); Ma, K.-H. [Department of Biology and Anatomy, National Defense Medical Center, Taipei 114, Taiwan (China)], E-mail: kuohsing91@yahoo.com.tw

    2009-08-15

    Introduction: Parkinson's disease (PD) affects both dopaminergic and serotonergic systems. In this study, we simultaneously evaluated dopamine and serotonin transporters in primates using dual-isotope single-photon emission computed tomography (SPECT) imaging and compared the results with traditional single-isotope imaging. Methods: Four healthy and one 6-OHDA-induced PD monkeys were used for this study. SPECT was performed over 4 h after individual or simultaneous injection of [{sup 99m}Tc]TRODAT-1 (a dopamine transporter imaging agent) and [{sup 123}I]ADAM (a serotonin transporter imaging agent). Results: The results showed that the image quality and uptake ratios in different brain regions were comparable between single- and dual-isotope studies. The striatal [{sup 99m}Tc]TRODAT-1 uptake in the PD monkey was markedly lower than that in normal monkeys. The uptake of [{sup 123}I]ADAM in the midbrain of the PD monkey was comparable to that in the normal monkeys, but there were decreased uptakes in the thalamus and striatum of the PD monkey. Conclusions: Our results suggest that dual-isotope SPECT using [{sup 99m}Tc]TRODAT-1 and [{sup 123}I]ADAM can simultaneously evaluate changes in dopaminergic and serotonergic systems in a PD model.

  3. Limits on the expression of enzyme-mediated solvent isotope effects

    International Nuclear Information System (INIS)

    Northrop, D.B.

    1981-01-01

    Steady-state analysis of primary solvent isotope effects on enzyme-catalyzed reactions, mediated by solvent-shielded di- or triprotic groups on the enzyme, yields equations describing the upper limit of intramolecular isotopic discrimation. For diprotic groups [P/sub H]/[P/sub D/] = 3k/sub H//k/sub D/ + 3), and for triprotic groups [P/sub H/]/[P/sub D/] = [7(k/sub H//k/sub D/ 2 = 10k/sub H/k/sub D/ + 1]/[(k/sub H//k/sub D/) 2 + 10k/sub H//k/sub D/ + 7]. Given a normal intrinsic isotope effect of k/sub H//k/sub D/ = 7, maximal isotopic discrimation in 50:50 H 2 O:D 2 O is therefore 2.2 and 3.3, respectively, versus 1.0 for a monoprotic group. Intermediate values of isotope discrimination may be interpreted with respect to distinguishing enzyme-mediated catalytic mechanisms from those of direct transfer between solvent and substrate, and to identifying mediating groups, by comparisons of isotopic discrimination at high and low concentrations of substrates and by reference to intrinsic and intermolecular isotope effects

  4. 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

  5. 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)

  6. 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

  7. Normal composite face effects in developmental prosopagnosia.

    Science.gov (United States)

    Biotti, Federica; Wu, Esther; Yang, Hua; Jiahui, Guo; Duchaine, Bradley; Cook, Richard

    2017-10-01

    Upright face perception is thought to involve holistic processing, whereby local features are integrated into a unified whole. Consistent with this view, the top half of one face appears to fuse perceptually with the bottom half of another, when aligned spatially and presented upright. This 'composite face effect' reveals a tendency to integrate information from disparate regions when faces are presented canonically. In recent years, the relationship between susceptibility to the composite effect and face recognition ability has received extensive attention both in participants with normal face recognition and participants with developmental prosopagnosia. Previous results suggest that individuals with developmental prosopagnosia may show reduced susceptibility to the effect suggestive of diminished holistic face processing. Here we describe two studies that examine whether developmental prosopagnosia is associated with reduced composite face effects. Despite using independent samples of developmental prosopagnosics and different composite procedures, we find no evidence for reduced composite face effects. The experiments yielded similar results; highly significant composite effects in both prosopagnosic groups that were similar in magnitude to the effects found in participants with normal face processing. The composite face effects exhibited by both samples and the controls were greatly diminished when stimulus arrangements were inverted. Our finding that the whole-face binding process indexed by the composite effect is intact in developmental prosopagnosia indicates that other factors are responsible for developmental prosopagnosia. These results are also inconsistent with suggestions that susceptibility to the composite face effect and face recognition ability are tightly linked. While the holistic process revealed by the composite face effect may be necessary for typical face perception, it is not sufficient; individual differences in face recognition ability

  8. Analysis of simulataneous I-123-IPT/Tc-99m-HMPAO dual isotope brain SPECT in Parkinson's disease and normal volunteers using SPM

    International Nuclear Information System (INIS)

    Chung, Y. A.; Juh, R. H.; Kim, S. H.; Park, Y. H.; Lee, S. Y.; Sohn, H. S.; Chung, S. K.

    2002-01-01

    The basal ganglia are usually poorly delineated in Parkinson's diseases on IPT images. We have studied simultaneous dual isotope brain SPECTs using I-123-IPT and Tc-99m-HMPAO, in order to overcome this limitation of IPT imaging. 17 patients (M: 7, F: 10) with Parkinson's disease (Idiopathic parkison's disease: 12, Multiple system atrophy: 5) and 4 normal volunteers (N) underwent the dual isotope brain SPECT following simultaneously injection of 370 MBq Tc-99m-HMPAO (energy window: 130-146 keV) and 111 MBq I-123-IPT (energy window: 152-168 keV). We first obtained parameters of spatial normalization during spatial normalization of Tc-99m-HMPAO brain SPECT using SPECT template. Using these parameters, we could spatially normalized I-123-IPT brain PSECT to standard space, because these images were obtained simultaneously. The difference between each groups(N vs IPD, N vs MSA, IPD vs MSA) were compared with t-test (p<0.01). We demonstrated decreased perfusion in the head and body caudate and globus pallidus on MSA compared with IPD. No significant hypo- and hyperperfusion area was observed in the other analysis. The method proposed in this study can effectively evaluate the dopamine function, and is easily applicable to conventional gamma camera system with any dual energy window acquisition modes

  9. 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.

  10. 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

  11. 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

  12. 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

  13. 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.

  14. Evaporation and abstraction determined from stable isotopes during normal flow on the Gariep River, South Africa

    Science.gov (United States)

    Diamond, Roger E.; Jack, Sam

    2018-04-01

    Changes in the stable isotope composition of water can, with the aid of climatic parameters, be used to calculate the quantity of evaporation from a water body. Previous workers have mostly focused on small, research catchments, with abundant data, but of limited scope. This study aimed to expand such work to a regional or sub-continental scale. The first full length isotope survey of the Gariep River quantifies evaporation on the river and the man-made reservoirs for the first time, and proposes a technique to calculate abstraction from the river. The theoretically determined final isotope composition for an evaporating water body in the given climate lies on the empirically determined local evaporation line, validating the assumptions and inputs to the Craig-Gordon evaporation model that was used. Evaporation from the Gariep River amounts to around 20% of flow, or 40 m3/s, of which about half is due to evaporation from the surface of the Gariep and Vanderkloof Reservoirs, showing the wastefulness of large surface water impoundments. This compares well with previous estimates based on evapotranspiration calculations, and equates to around 1300 GL/a of water, or about the annual water consumption of Johannesburg and Pretoria, where over 10 million people reside. Using similar evaporation calculations and applying existing transpiration estimates to a gauged length of river, the remaining quantity can be attributed to abstraction, amounting to 175 L/s/km in the lower middle reaches of the river. Given that high water demand and climate change are global problems, and with the challenges of maintaining water monitoring networks, stable isotopes are shown to be applicable over regional to national scales for modelling hydrological flows. Stable isotopes provide a complementary method to conventional flow gauging for understanding hydrology and management of large water resources, particularly in arid areas subject to significant evaporation.

  15. 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.

  16. 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

  17. Trinucleon asymptotic normalization constants including Coulomb effects

    International Nuclear Information System (INIS)

    Friar, J.L.; Gibson, B.F.; Lehman, D.R.; Payne, G.L.

    1982-01-01

    Exact theoretical expressions for calculating the trinucleon S- and D-wave asymptotic normalization constants, with and without Coulomb effects, are presented. Coordinate-space Faddeev-type equations are used to generate the trinucleon wave functions, and integral relations for the asymptotic norms are derived within this framework. The definition of the asymptotic norms in the presence of the Coulomb interaction is emphasized. Numerical calculations are carried out for the s-wave NN interaction models of Malfliet and Tjon and the tensor force model of Reid. Comparison with previously published results is made. The first estimate of Coulomb effects for the D-wave asymptotic norm is given. All theoretical values are carefully compared with experiment and suggestions are made for improving the experimental situation. We find that Coulomb effects increase the 3 He S-wave asymptotic norm by less than 1% relative to that of 3 H, that Coulomb effects decrease the 3 He D-wave asymptotic norm by approximately 8% relative to that of 3 H, and that the distorted-wave Born approximation D-state parameter, D 2 , is only 1% smaller in magnitude for 3 He than for 3 H due to compensating Coulomb effects

  18. 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)

  19. 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.)

  20. 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

  1. 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.

  2. Carbon-13 kinetic isotope effects in the decarbonylations of lactic acid containing 13C at the natural abundance level

    International Nuclear Information System (INIS)

    Zielinski, M.; Czarnota, G.; Papiernik-Zielinska, H.

    1992-01-01

    The 13 C kinetic isotope fractionation in the decarbonylation of lactic acid of natural isotopic composition by sulfuric acid has been studied in the temperature range of 20-80 deg C. The 13 C (1) isotope separation in the decarbonylation of lactic acid by concentrated sulfuric acid depends strongly on the temperature above 40 deg C. Below this temperature the 13 C isotope effect in the decarbonylation of lactic acid by concentrated sulfuric acid is normal similarly as has been found in the decarbonylation of lactic [1- 14 C] acid. The experimental values of k (12C) /k (13C) ratios of isotopic rate constants for 12 C and 13 C are close to, but slightly higher than theoretical 13 C-kinetic isotope effects calculated (neglecting tunneling) under the asumption that the C (1) -OH bond is broken in the rate-controlling step of the dehydration reaction. Dilution of concentrated sulfuric acid with water up to 1.4 molar (H 2 O)/(H 2 SO 4 ) ratio caused the increase of the 13 C isotope fractionation from 1.0273 found in concentrated sulfuric acid at 80.5 deg C to 1.0536±0.0008 (at 80.6 deg C). A discussion of the abnormally high temperature dependence of 14 C and 13 C isotope fractionation in this reaction and the discussion of the problem of relative 14 C/ 13 C kinetic isotope effects is given. (author) 18 refs.; 2 tabs

  3. 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

  4. 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.)

  5. 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)

  6. 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.

  7. 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

  8. Application of in situ current normalized PIGE method for determination of total boron and its isotopic composition

    International Nuclear Information System (INIS)

    Chhillar, Sumit; Acharya, R.; Sodaye, S.; Pujari, P.K.

    2014-01-01

    A particle induced gamma-ray emission (PIGE) method using proton beam has been standardized for determination of isotopic composition of natural boron and enriched boron samples. Target pellets of boron standard and samples were prepared in cellulose matrix. The prompt gamma rays of 429 keV, 718 keV and 2125 keV were measured from 10 B(p,αγ) 7 Be, 10 B(p, p'γ) 10 B and 11 B(p, p'γ) 11 B nuclear reactions, respectively. For normalizing the beam current variations in situ current normalization method was used. Validation of method was carried out using synthetic samples of boron carbide, borax, borazine and lithium metaborate in cellulose matrix. (author)

  9. 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

  10. 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.)

  11. 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.

  12. 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)

  13. Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism

    Science.gov (United States)

    Zhao, Zhiqiang; Zhang, Zhaojun; Liu, Shu; Zhang, Dong H.

    2017-02-01

    Reactions occurring at a carbon atom through the Walden inversion mechanism are one of the most important and useful classes of reactions in chemistry. Here we report an accurate theoretical study of the simplest reaction of that type: the H+CH4 substitution reaction and its isotope analogues. It is found that the reaction threshold versus collision energy is considerably higher than the barrier height. The reaction exhibits a strong normal secondary isotope effect on the cross-sections measured above the reaction threshold, and a small but reverse secondary kinetic isotope effect at room temperature. Detailed analysis reveals that the reaction proceeds along a path with a higher barrier height instead of the minimum-energy path because the umbrella angle of the non-reacting methyl group cannot change synchronously with the other reaction coordinates during the reaction due to insufficient energy transfer from the translational motion to the umbrella mode.

  14. 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.

  15. 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.

  16. 13C/14C dual isotope breath test measurement of gastric emptying in normal subjects and patients

    International Nuclear Information System (INIS)

    Chew, G.; Bartholomeusz, F.D.L.; Bellon, M.; Chatterton, B.E.

    2000-01-01

    Full text: A more flexible alternative to dual isotope scintigraphy for gastric emptying involves measuring breath C0 2 after administration of absorbable tracers. Method: six patients were given 100g hamburger labelled with 25 MBq 99 Tc m sulphur colloid and 74 KBq 14 C octanoic acid, and 150 ml 10% glucose drink labelled with 8 MBq 67 Ga citrate and ISO mg 13 C acetate and seven normals with 14 C and 13 C labels only. Breath was collected at baseline and then regularly for four hours. The 14 CO 2 and 13 CO 2 activity was measured with liquid scintillation counting and mass spectroscopy. The times to maximum 14 CO 2 , and 13 CO 2 , T max, were determined. Results: Comparison was made between 14 CO 2 T max with scintigraphic retention of 99 Tc m at 100 minutes (SR100m) and 13 CO 2 T max with the scintigraphic half-clearance time of 67 Ga (scint T1/2). In conclusion 14 CO 2 T max and 13 CO 2 T max correlate significantly with SR100m and scint T1/2 respectively. The normal threshold is between 165 and 180 minutes for 14 Co 2 T max; probably > 40 minutes for 13 CO 2 T max but overlap exists between normal and abnormal results in this small preliminary study. Recruitment is to continue to better define normal ranges. Copyright (2000) The Australian and New Zealand Society of Nuclear Medicine Inc

  17. Background levels of heavy metals in surficial sediments of the Gulf of Lions (NW Mediterranean): An approach based on 133Cs normalization and lead isotope measurements

    International Nuclear Information System (INIS)

    Roussiez, Vincent; Ludwig, Wolfgang; Probst, Jean-Luc; Monaco, Andre

    2005-01-01

    This paper presents an attempt to reach natural background levels of heavy metals in surficial sediments of the Gulf of Lions (NW Mediterranean). To correct for the grain-size effect, normalization procedures based on a clay mineral indicator element are commonly used, after a first grain size separation by sieving. In our study, we tested the applicability of this method with respect to commonly used normalizer elements, and found that stable Cs shows the best ability to reflect the fine sediment fraction. Background levels were successfully reached for Co, Cr, Cu, Ni and Pb, compared to various literature references. Nevertheless, in the case of lead, the normalized data depicted a general enrichment in all samples, and the natural levels could only be reached when concentrations were corrected for the atmospheric contribution by analysing lead isotope ratios. Also for Zn, a general enrichment was found in our samples, although less important. - Among several potential normalizers, stable Cs ( 133 Cs) depicted the best ability to correct for the grain-size effect of shelf sediments and was used to estimate regional background levels of heavy metals

  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. 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...

  20. Correlation of the vapor pressure isotope effect with molecular force fields in the liquid state

    International Nuclear Information System (INIS)

    Pollin, J.S.; Ishida, T.

    1976-07-01

    The present work is concerned with the development and application of a new model for condensed phase interactions with which the vapor pressure isotope effect (vpie) may be related to molecular forces and structure. The model considers the condensed phase as being represented by a cluster of regularly arranged molecules consisting of a central molecule and a variable number of molecules in the first coordination shell. The methods of normal coordinate analysis are used to determine the modes of vibration of the condensed phase cluster from which, in turn, the isotopic reduced partition function can be calculated. Using the medium cluster model, the observed vpie for a series of methane isotopes has been successfully reproduced with better agreement with experiment than has been possible using the simple cell model. We conclude, however, that insofar as the medium cluster model provides a reasonable picture of the liquid state, the vpie is not sufficiently sensitive to molecular orientation to permit an experimental determination of intermolecular configuration in the condensed phase through measurement of isotopic pressure ratios. The virtual independence of vapor pressure isotope effects on molecular orientation at large cluster sizes is a demonstration of the general acceptability of the cell model assumptions for vpie calculations

  1. 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.

  2. 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).

  3. 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

  4. 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.

  5. 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).

  6. 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

  7. 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)

  8. 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

  9. 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

  10. 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.)

  11. A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

    Science.gov (United States)

    Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

    2014-12-01

    Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar

  12. 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.

  13. 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.

  14. 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)

  15. Predicating magnetorheological effect of magnetorheological elastomers under normal pressure

    International Nuclear Information System (INIS)

    Dong, X; Qi, M; Ma, N; Ou, J

    2013-01-01

    Magnetorheological elastomers (MREs) present reversible change in shear modulus in an applied magnetic field. For applications and tests of MREs, a normal pressure must be applied on the materials. However, little research paid attention on the effect of the normal pressure on properties of MREs. In this study, a theoretical model is established based on the effective permeability rule and the consideration of the normal pressure. The results indicate that the normal pressure have great influence on magnetic field-induced shear modulus. The shear modulus of MREs increases with increasing normal pressure, such dependence is more significant at high magnetic field levels.

  16. 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)

  17. Adenosine deaminase organic effect in normal and abnormal cerebrospinal fluid

    International Nuclear Information System (INIS)

    Hamad, A.M.; Samarai, M.A.

    2007-01-01

    To study the effect of the organic substances on adenosine deaminase (ADA) activity in normal and abnormal cerebrospinal fluid (CSF). Various concentrations of 2-mercaptopurine, Ame-tycine, Adenosine analogues (Guanine, Thymine) and ATP were tested to see their effect on ADA activity in normal and abnormal CSF. ADA activity in normal and abnormal CSF was remarkably decreased with the increasing of concentrations of substances tested. These effects may have important therapeutic implications. (author)

  18. Late effects on normal tissues: oesophagus

    International Nuclear Information System (INIS)

    Pavy, J.J.; Bosset, J.F.

    1997-01-01

    Radiation-induced late effects of oesophagus are observed after treatment of various cancers. Acute reactions, mainly oesophagitis, are well known and accurately described; late effects share, for most of these, a common consequence: alteration of the main oesophageal function, namely to conduct the food bolus; clinically they are impaired in terms of mobility and stenosis. More rarely, ulcerations and pseudodiverticulae can be observed. Chemotherapy further increases the risk of late effects, especially in case of concomitant chemo-radiotherapy. All numbers and statistical data on oesophagus late effects should be regarded with caution due to recent changes in the therapeutic attitudes (more and more combined chemotherapy-radiotherapy) and some progress in given cancer locations. A common scale like the LENT-SOMA should enable the clinician to better know these late effects on oesophagus which is required to initiate effective prevention measures and adapted treatments. (authors)

  19. 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

  20. 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

  1. 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.

  2. 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.

  3. 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

  4. 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

  5. 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

  6. 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

  7. Spin-filter effect in normal metal/ferromagnetic insulator/normal metal/superconductor structures

    International Nuclear Information System (INIS)

    Li, Hong; Yang, Wei; Yang, Xinjian; Qin, Minghui; Guo, Jianqin

    2007-01-01

    Taking into account the thickness of the ferromagnetic insulator, the spin-filter effect in normal metal/ferromagnetic insulator/normal metal/superconductor (NM/FI/NM/SC) junctions is studied based on the Blonder-Tinkham-Klapwijk (BTK) theory. It is shown that a spin-dependent energy shift during the tunneling process induces splitting of the subgap resonance peaks. The spin polarization due to the spin-filter effect of the FI causes an imbalance of the peaks heights and can enhance the Zeeman splitting of the gap peaks caused by an applied magnetic field. The spin-filter effect has no contribution to the proximity-effect-induced superconductivity in NM interlayer

  8. 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

  9. 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

  10. 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)

  11. 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).

  12. 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

  13. 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

  14. 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

  15. Isotope effect with energy-dependent density of states and impurities

    International Nuclear Information System (INIS)

    Williams, P.J.; Carbotte, J.P.

    1992-01-01

    We have calculated the total isotope coefficient β in a model where there is energy-dependent structure in the electronic density of states. We model the structure with a simple Lorentzian. In our calculation, doping has the effect of shifting the Fermi level and broadening the structure in the density of states. We have treated the dopants both as normal and as magnetic impurities. The asymmetry observed in the experimental data is found in our results. However, the complete range of values observed is difficult to reproduce. We question also whether the shifts in Fermi level required in such models are reasonable

  16. Spin-filtering effect and proximity effect in normal metal/ferromagnetic insulator/normal metal/superconductor junctions

    International Nuclear Information System (INIS)

    Li Hong; Yang Wei; Yang Xinjian; Qin Minghui; Xu Yihong

    2007-01-01

    Taking into account the thickness of the ferromagnetic insulator (FI), the spin-filtering effect and proximity effect in normal metal/ferromagnetic insulator/normal metal/superconductor (NM/FI/NM/SC) junctions are studied based on an extended Blonder-Tinkham-Klapwijk (BTK) theory. It is shown that a spin-dependent energy shift during the tunneling process induces splitting of the sub-energy gap conductance peaks and the spin polarization in the ferromagnetic insulator causes an imbalance of the peak heights. Different from the ferromagnet the spin-filtering effect of the FI cannot cause the reversion of the normalized conductance in NM/FI/NM/SC junctions

  17. 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)

  18. 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)

  19. 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.

  20. 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.)

  1. 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

  2. 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

  3. Effect of nifedipine on gastric emptying in normal subjects

    International Nuclear Information System (INIS)

    Traube, M.; Lange, R.C.; McAllister, R.G.; McCallum, R.W.

    1985-01-01

    Nifedipine (N) inhibits calcium entry into smooth muscle cells and relaxes esophageal smooth muscle. The authors studied N's effect on gastric emptying of liquids and solids. Ten normal subjects underwent radionuclide (In-111-DTPA in water and Tc-99m-sulfur colloid tagged to chicken liver) emptying tests with and without 30 mg N given orally 20 min prior to meal ingestion. Peak plasma N levels were either 30 or 60 min after drug dosing and showed a 3-fold variation (low 145 ng/ml, high 434 ng/ml). Both mean N levels and integral concentration time values were twice as high as those obtained after 30 mg sublingual dosing in normals previously studied in our lab. The authors conclude that plasma N levels which are associated with significant esophageal motility effects do not change gastric emptying in normal subjects. The data also show that N levels are greater after oral than sublingual dosing of 30 mg in normal subjects

  4. 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)

  5. 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.

  6. Superconducting proximity effect in mesoscopic superconductor/normal-metal junctions

    CERN Document Server

    Takayanagi, H; Toyoda, E

    1999-01-01

    The superconducting proximity effect is discussed in mesoscopic superconductor/normal-metal junctions. The newly-developed theory shows long-range phase-coherent effect which explaines early experimental results of giant magnetoresistance oscillations in an Andreev interferometer. The theory also shows that the proximity correction to the conductance (PCC) has a reentrant behavior as a function of energy. The reentrant behavior is systematically studied in a gated superconductor-semiconductor junction. A negative PCC is observed in the case of a weak coupling between the normal metal and the external reservoir. Phase coherent ac effect is also observed when rf is irradiated to the junction.

  7. Clinical and histological effects of blue light on normal skin.

    NARCIS (Netherlands)

    Kleinpenning, M.M.; Smits, T.; Frunt, M.H.A.; Erp, P.E.J. van; Kerkhof, P.C.M. van de; Gerritsen, R.M.

    2010-01-01

    INTRODUCTION: Phototherapy with visible light is gaining interest in dermatological practice. Theoretically, blue light could induce biological effects comparable to ultraviolet A (UVA) radiation. OBJECTIVES: To study the effects of blue light on normal skin in terms of photodamage, skin ageing and

  8. Effect of metoclopramide on normal and delayed gastric emptying in gastroesophageal reflux patients

    Energy Technology Data Exchange (ETDEWEB)

    Fink, S.M.; Lange, R.C.; McCallum, R.W.

    1983-12-01

    Gastric emptying has an important role in the pathophysiology of gastroesophageal reflux disease. The effect of metoclopramide, a gastric prokinetic agent, in gastroesophageal reflux patients with normal as well as delayed emptying was investigated. Twenty-six patients with subjective and objective evidence of gastroesophageal reflux ingested an egg salad sandwich meal labeled with /sub 99m/technetium-DTPA for a baseline study, and then again on a separate day after receiving oral metoclopramide, 10 mg, 30 min prior to the test meal. The mean percent isotope remaining in the stomach after 90 min improved significantly from 70.3 +/- 3.9% (SEM) to 55.2 +/- 4.2% after metoclopramide. Fourteen (54%) had a basal emptying in the normal range of 34-69% retention of isotope at 90 min, (means +/- 2 SD), while it was slow in 12 (46%). For those with delayed basal gastric emptying, the mean retention of 88.9 +/- 2.9% at 90 min was significantly decreased by metoclopramide to 68.6 +/- 6.1%. In those patients with a normal basal gastric emptying and a mean retention of 54.4 +/- 2.3% at 90 min, there was also significant improvement (P less than 0.025) to 43.6 +/- 3.6% after metoclopramide. These data indicate that metoclopramide increased gastric emptying in gastroesophageal reflux patients with normal as well as delayed gastric emptying. Therefore on a patient management level a trial of metoclopramide is warranted in patients with gastroesophageal reflux disease and is not limited by the gastric emptying status of the patient.

  9. Effect of metoclopramide on normal and delayed gastric emptying in gastroesophageal reflux patients

    International Nuclear Information System (INIS)

    Fink, S.M.; Lange, R.C.; McCallum, R.W.

    1983-01-01

    Gastric emptying has an important role in the pathophysiology of gastroesophageal reflux disease. The effect of metoclopramide, a gastric prokinetic agent, in gastroesophageal reflux patients with normal as well as delayed emptying was investigated. Twenty-six patients with subjective and objective evidence of gastroesophageal reflux ingested an egg salad sandwich meal labeled with /sub 99m/technetium-DTPA for a baseline study, and then again on a separate day after receiving oral metoclopramide, 10 mg, 30 min prior to the test meal. The mean percent isotope remaining in the stomach after 90 min improved significantly from 70.3 +/- 3.9% (SEM) to 55.2 +/- 4.2% after metoclopramide. Fourteen (54%) had a basal emptying in the normal range of 34-69% retention of isotope at 90 min, (means +/- 2 SD), while it was slow in 12 (46%). For those with delayed basal gastric emptying, the mean retention of 88.9 +/- 2.9% at 90 min was significantly decreased by metoclopramide to 68.6 +/- 6.1%. In those patients with a normal basal gastric emptying and a mean retention of 54.4 +/- 2.3% at 90 min, there was also significant improvement (P less than 0.025) to 43.6 +/- 3.6% after metoclopramide. These data indicate that metoclopramide increased gastric emptying in gastroesophageal reflux patients with normal as well as delayed gastric emptying. Therefore on a patient management level a trial of metoclopramide is warranted in patients with gastroesophageal reflux disease and is not limited by the gastric emptying status of the patient

  10. Effects of normalization on quantitative traits in association test

    Science.gov (United States)

    2009-01-01

    Background Quantitative trait loci analysis assumes that the trait is normally distributed. In reality, this is often not observed and one strategy is to transform the trait. However, it is not clear how much normality is required and which transformation works best in association studies. Results We performed simulations on four types of common quantitative traits to evaluate the effects of normalization using the logarithm, Box-Cox, and rank-based transformations. The impact of sample size and genetic effects on normalization is also investigated. Our results show that rank-based transformation gives generally the best and consistent performance in identifying the causal polymorphism and ranking it highly in association tests, with a slight increase in false positive rate. Conclusion For small sample size or genetic effects, the improvement in sensitivity for rank transformation outweighs the slight increase in false positive rate. However, for large sample size and genetic effects, normalization may not be necessary since the increase in sensitivity is relatively modest. PMID:20003414

  11. Effects of normalization on quantitative traits in association test

    Directory of Open Access Journals (Sweden)

    Yap Von Bing

    2009-12-01

    Full Text Available Abstract Background Quantitative trait loci analysis assumes that the trait is normally distributed. In reality, this is often not observed and one strategy is to transform the trait. However, it is not clear how much normality is required and which transformation works best in association studies. Results We performed simulations on four types of common quantitative traits to evaluate the effects of normalization using the logarithm, Box-Cox, and rank-based transformations. The impact of sample size and genetic effects on normalization is also investigated. Our results show that rank-based transformation gives generally the best and consistent performance in identifying the causal polymorphism and ranking it highly in association tests, with a slight increase in false positive rate. Conclusion For small sample size or genetic effects, the improvement in sensitivity for rank transformation outweighs the slight increase in false positive rate. However, for large sample size and genetic effects, normalization may not be necessary since the increase in sensitivity is relatively modest.

  12. 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.

  13. 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

  14. Effect analysis of core barrel openings under CEFR normal condition

    International Nuclear Information System (INIS)

    Zhang Yabo; Yang Hongyi

    2008-01-01

    Openings on the bottom of core barrel are important part of the decay heat removal system of China Experimental Fast Reactor (CEFR), which are designed to discharge the decay heat from reactor under accident condition. This paper analyses the effect of the openings design on the normal operation condition using the famouse CFD code CFX. The result indicates that the decay heat can be discharged safely and at the same time the effect of core barrel openings on the normal operation condition is acceptable. (authors)

  15. Oral Topical Doxepin Rinse: Anesthetic Effect in Normal Subjects

    Directory of Open Access Journals (Sweden)

    Joel B Epstein

    2003-01-01

    Full Text Available Oral doxepin rinse has been reported to provide pain relief in patients with oral mucosal lesions due to cancer or cancer therapy. The purpose of this study was to assess the anesthetic effect of doxepin oral rinse in normal subjects to identify the duration of effect and to contrast the anesthetic effect with reported pain relief in patients with oral mucosal lesions. Normal volunteers were provided a solution of doxepin (5 mg/mL for oral rinsing. Oral numbness and adverse effects were recorded for a period of 4 h after rinsing. Doxepin rinse resulted in mucosal anesthesia in all subjects. Sedation/fatigue was reported in four of seven subjects. There were no taste complaints and no nausea reported. The limited duration of numbness/anesthesia in normal subjects compared with prior studies showing pain relief for more than 3 h in patients with mucosal lesions, suggests that the extended duration of pain relief in patients was due to analgesic effects rather than anesthetic effects. The majority of normal subjects reported sedation after use, but this was less common in patients with mucosal lesions.

  16. Proximity effect in normal-superconductor hybrids for quasiparticle traps

    Energy Technology Data Exchange (ETDEWEB)

    Hosseinkhani, Amin [Peter Grunberg Institute (PGI-2), Forschungszentrum Julich, D-52425 Julich (Germany); JARA-Institute for Quantum Information, RWTH Aachen University, D-52056 Aachen (Germany)

    2016-07-01

    Coherent transport of charges in the form of Cooper pairs is the main feature of Josephson junctions which plays a central role in superconducting qubits. However, the presence of quasiparticles in superconducting devices may lead to incoherent charge transfer and limit the coherence time of superconducting qubits. A way around this so-called ''quasiparticle poisoning'' might be using a normal-metal island to trap quasiparticles; this has motivated us to revisit the proximity effect in normal-superconductor hybrids. Using the semiclassical Usadel equations, we study the density of states (DoS) both within and away from the trap. We find that in the superconducting layer the DoS quickly approaches the BCS form; this indicates that normal-metal traps should be effective at localizing quasiparticles.

  17. 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

  18. 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

  19. Proximity effect in normal metal-multiband superconductor hybrid structures

    NARCIS (Netherlands)

    Brinkman, Alexander; Golubov, Alexandre Avraamovitch; Kupriyanov, M. Yu

    2004-01-01

    A theory of the proximity effect in normal metal¿multiband superconductor hybrid structures is formulated within the quasiclassical Green's function formalism. The quasiclassical boundary conditions for multiband hybrid structures are derived in the dirty limit. It is shown that the existence of

  20. Effect of normal processes on thermal conductivity of germanium ...

    Indian Academy of Sciences (India)

    Abstract. The effect of normal scattering processes is considered to redistribute the phonon momentum in (a) the same phonon branch – KK-S model and (b) between differ- ent phonon branches – KK-H model. Simplified thermal conductivity relations are used to estimate the thermal conductivity of germanium, silicon and ...

  1. Age Effects on Cortical Thickness in Cognitively Normal Elderly Individuals

    Directory of Open Access Journals (Sweden)

    Sona Hurtz

    2014-07-01

    Full Text Available Background/Aims: Atrophy in both grey and white matter is found in normal aging. The prefrontal cortex and the frontal lobe white matter are thought to be the most affected regions. Our aim was to examine the effects of normal aging on cortical grey matter using a 3D quantitative cortical mapping method. Methods: We analyzed 1.5-tesla brain magnetic resonance imaging data from 44 cognitively normal elderly subjects using cortical pattern matching and cortical thickness analyses. Linear regression analysis was used to study the effect of age on cortical thickness. 3D map-wide correction for multiple comparisons was conducted with permutation analyses using a threshold of p Results: We found a significant negative association between age and cortical thickness in the right hemisphere (pcorrected = 0.009 and a trend level association in the left hemisphere (pcorrected = 0.081. Age-related changes were greatest in the sensorimotor, bilateral dorsal anterior cingulate and supplementary motor cortices, and the right posterior middle and inferior frontal gyri. Age effects greater in the medial than lateral visual association cortices were also seen bilaterally. Conclusion: Our novel method further validates that normal aging results in diffuse cortical thinning that is most pronounced in the frontal and visual association cortices.

  2. Normal tissue dose-effect models in biological dose optimisation

    International Nuclear Information System (INIS)

    Alber, M.

    2008-01-01

    Sophisticated radiotherapy techniques like intensity modulated radiotherapy with photons and protons rely on numerical dose optimisation. The evaluation of normal tissue dose distributions that deviate significantly from the common clinical routine and also the mathematical expression of desirable properties of a dose distribution is difficult. In essence, a dose evaluation model for normal tissues has to express the tissue specific volume effect. A formalism of local dose effect measures is presented, which can be applied to serial and parallel responding tissues as well as target volumes and physical dose penalties. These models allow a transparent description of the volume effect and an efficient control over the optimum dose distribution. They can be linked to normal tissue complication probability models and the equivalent uniform dose concept. In clinical applications, they provide a means to standardize normal tissue doses in the face of inevitable anatomical differences between patients and a vastly increased freedom to shape the dose, without being overly limiting like sets of dose-volume constraints. (orig.)

  3. 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.

  4. 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.)

  5. 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.

  6. 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...

  7. 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

  8. Effect of nifedipine on gastric emptying in normal subjects

    Energy Technology Data Exchange (ETDEWEB)

    Traube, M.; Lange, R.C.; McAllister, R.G.; McCallum, R.W.

    1985-05-01

    Nifedipine (N) inhibits calcium entry into smooth muscle cells and relaxes esophageal smooth muscle. The authors studied N's effect on gastric emptying of liquids and solids. Ten normal subjects underwent radionuclide (In-111-DTPA in water and Tc-99m-sulfur colloid tagged to chicken liver) emptying tests with and without 30 mg N given orally 20 min prior to meal ingestion. Peak plasma N levels were either 30 or 60 min after drug dosing and showed a 3-fold variation (low 145 ng/ml, high 434 ng/ml). Both mean N levels and integral concentration time values were twice as high as those obtained after 30 mg sublingual dosing in normals previously studied in our lab. The authors conclude that plasma N levels which are associated with significant esophageal motility effects do not change gastric emptying in normal subjects. The data also show that N levels are greater after oral than sublingual dosing of 30 mg in normal subjects.

  9. 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.

  10. 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)

  11. 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

  12. Gas phase 1H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange.

    Science.gov (United States)

    Limbach, Hans-Heinrich; Pery, Tal; Rothermel, Niels; Chaudret, Bruno; Gutmann, Torsten; Buntkowsky, Gerd

    2018-04-25

    The equilibration of H2, HD and D2 between the gas phase and surface hydrides of solid organic-ligand-stabilized Ru metal nanoparticles has been studied by gas phase 1H NMR spectroscopy using closed NMR tubes as batch reactors at room temperature and 800 mbar. When two different nanoparticle systems, Ru/PVP (PVP ≡ polyvinylpyrrolidone) and Ru/HDA (HDA ≡ hexadecylamine) were exposed to D2 gas, only the release of HD from the hydride containing surface could be detected in the initial stages of the reaction, but no H2. In the case of Ru/HDA also the reverse experiment was performed where surface deuterated nanoparticles were exposed to H2. In that case, the conversion of H2 into gaseous HD was detected. In order to analyze the experimental kinetic and spectroscopic data, we explored two different mechanisms taking into account potential kinetic and equilibrium H/D isotope effects. Firstly, we explored the dissociative exchange mechanism consisting of dissociative adsorption of dihydrogen, fast hydride surface diffusion and associative desorption of dihydrogen. It is shown that if D2 is the reaction partner, only H2 will be released in the beginning of the reaction, and HD only in later reaction stages. The second mechanism, dubbed here associative exchange consists of the binding of dihydrogen to Ru surface atoms, followed by a H-transfer to or by H-exchange with an adjacent hydride site, and finally of the associative desorption of dihydrogen. In that case, in the exchange with D2, only HD will be released in the beginning of the reaction. Our experimental results are not compatible with the dissociative exchange but can be explained in terms of the associative exchange. Whereas the former will dominate at low temperatures and pressures, the latter will prevail around room temperature and normal pressures where transition metal nanoparticles are generally used as reaction catalysts.

  13. 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.

  14. 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.

  15. 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...

  16. 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

  17. 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...

  18. 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

  19. Measurement of intestinal progression of a meal and its residues in normal subjects and patients with functional diarrhoea by a dual isotope technique

    Energy Technology Data Exchange (ETDEWEB)

    Jian, R; Najean, Y; Bernier, J J [Hopital Saint-Lazare, 75 - Paris (France). Service de Medecine; Hopital Saint-Louis, 75 - Paris (France))

    1984-07-01

    A new double isotopic method was used to measure the gastrointestinal progression of a meal in nine healthy subjects and seven patients with functional diarrhoea. 51 Chromium chloride (colonic marker) was ingested eight hours before the beginning of the scintigraphic study so that it was by then located in the colon at that time. A second marker, 99m Technetium sulphur colloid labelled the meal. Scintigraphic images were taken before and after the meal for two hours, detecting simultaneously the two isotopes. In the 51Cr window right colon was localised and intracolonic propulsion was studied; and in the 99m Tc window gastric emptying and colon filling of the meal marker was quantified. A propulsive gastrocolic reflex was evidenced in five of the seven patients with functional diarrhoea but in none of the normal subjects. Unabsorbed residues of the meal are propelled rapidly in the ileocaecal region. Small intestinal transit of the meal marker was twice as rapid in patients with functional diarrhoea as in normal subjects.

  20. Isotope Effects Associated with N2O Production by Fungal and Bacterial Nitric Oxide Reductases: Implications for Enzyme Mechanisms

    Science.gov (United States)

    Hegg, E. L.; Yang, H.; Gandhi, H.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.

    2014-12-01

    Nitrous oxide (N2O) is both a powerful greenhouse gas and a key participant in ozone destruction. Microbial activity accounts for over 70% of the N2O produced annually, and the atmospheric concentration of N2O continues to rise. Because the fungal and bacterial denitrification pathways are major contributors to microbial N2O production, understanding the mechanism by which NO is reduced to N2O will contribute to both N2O source tracing and quantification. Our strategy utilizes stable isotopes to probe the enzymatic mechanism of microbial N2O production. Although the use of stable isotopes to study enzyme mechanisms is not new, our approach is distinct in that we employ both measurements of isotopic preferences of purified enzyme and DFT calculations, thereby providing a synergistic combination of experimental and computational approaches. We analyzed δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom) of N2O produced by purified fungal cytochrome P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum as well as bacterial cytochrome c dependent nitric oxide reductase (cNOR) from Paracoccus denitrificans. P450nor exhibits an inverse kinetic isotope effect for Nβ (KIE = 0.9651) but a normal isotope effect for both Nα (KIE = 1.0127) and the oxygen atom (KIE = 1.0264). These results suggest a mechanism where NO binds to the ferric heme in the P450nor active site and becomes Nβ. Analysis of the NO-binding step indicated a greater difference in zero point energy in the transition state than the ground state, resulting in the inverse KIE observed for Nβ. Following protonation and rearrangement, it is speculated that this complex forms a FeIV-NHOH- species as a key intermediate. Our data are consistent with the second NO (which becomes Nα and O in the N2O product) attacking the FeIV-NHOH- species to generate a FeIII-N2O2H2 complex that enzymatically (as opposed to abiotically) breaks down to release N2O. Conversely, our preliminary data

  1. Effects of Consolidation Stress State on Normally Consolidated Clay

    DEFF Research Database (Denmark)

    Lade, Poul V.

    2000-01-01

    The effect of consolidation stress state on the stress-strain and strength characteristics has been studied from experiments on undisturbed block samples of a natural, normally consolidated clay known as San Francisco Bay Mud. The results of experiments on K0-consolidated, hollow cylinder specimens...... and on isotropically consolidated, cubical specimens, both tested in triaxial compression and extension, clearly showed the influence of the undisturbed fabric as well as the effect of the initial consolidation stress states. While the K0-consolidated specimens appeared to retain their original fabric and exhibit...

  2. 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)

  3. Radiosensitization effects of nicotinamide on malignant and normal mouse tissue

    International Nuclear Information System (INIS)

    Jonsson, G.G.; Kjellen, E.; Pero, R.W.; Cameron, R.

    1985-01-01

    Inhibitors of the chromatin-associated enzyme adenosine diphosphate ribosyltransferase have been found to inhibit DNA strand rejoining and to potentiate lethality of DNA-damaging agents both in vivo and in vitro. The authors have in this work examined the radiosensitizing potential of one such inhibitor, nicotinamide, on tumor tissue by using transplanted C3H mouse mammary adenocarcinomas and on normal tissue in a tail-stunting experiment using BALB/cA mice. The data indicate a radiosensitizing effect of nicotinamide on tumor cells as well as on normal tissue. The data indicate a possible role of adenosine diphosphate ribosyltransferase inhibitors as a sensitizing agent in the radiotherapy of malignant tumors

  4. Effect of Image Linearization on Normalized Compression Distance

    Science.gov (United States)

    Mortensen, Jonathan; Wu, Jia Jie; Furst, Jacob; Rogers, John; Raicu, Daniela

    Normalized Information Distance, based on Kolmogorov complexity, is an emerging metric for image similarity. It is approximated by the Normalized Compression Distance (NCD) which generates the relative distance between two strings by using standard compression algorithms to compare linear strings of information. This relative distance quantifies the degree of similarity between the two objects. NCD has been shown to measure similarity effectively on information which is already a string: genomic string comparisons have created accurate phylogeny trees and NCD has also been used to classify music. Currently, to find a similarity measure using NCD for images, the images must first be linearized into a string, and then compared. To understand how linearization of a 2D image affects the similarity measure, we perform four types of linearization on a subset of the Corel image database and compare each for a variety of image transformations. Our experiment shows that different linearization techniques produce statistically significant differences in NCD for identical spatial transformations.

  5. 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.

  6. 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

  7. 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.

  8. 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

  9. Studies on the optogalvanic effect and isotope-selective excitation of ytterbium in a hollow cathode discharge lamp using a pulsed dye laser.

    Science.gov (United States)

    Kumar, Pankaj; Kumar, Jitendra; Prakash, Om; Saini, Vinod K; Dixit, Sudhir K; Nakhe, Shankar V

    2013-09-01

    This paper presents studies on the pulsed optogalvanic effect and isotope-selective excitation of Yb 555.648 nm (0 cm(-1) → 17 992.007 cm(-1)) and 581.067 nm (17 992.007 cm(-1) → 35 196.98 cm(-1)) transitions, in a Yb/Ne hollow cathode lamp. The Yb atoms were excited by narrow linewidth (500-1000 MHz) Rh110 and Rh6G dye based pulsed lasers. Optogalvanic signal inversion for ground state transition at 555.648 nm was observed beyond a hollow cathode discharge current of 8.5 mA, in contrast to normal optogalvanic signal at 581.067 nm up to maximum current of 14 mA. The isotope-selective excitation studies of Yb were carried out by recording Doppler limited optogalvanic signals as a function of dye laser wavelength. For the 581.067 nm transition, three even isotopes, (172)Yb, (174)Yb, and (176)Yb, and one odd isotope, (171)Yb, were clearly resolved. These data were compared with selective isotope excitation by 10 MHz linewidth continuous-wave dye laser. For 555.648 nm transition, isotopes were not clearly resolved, although isotope peaks of low modulation were observed.

  10. Anomalous isotope effects in the U(IV)-U(VI) exchange system

    International Nuclear Information System (INIS)

    Fujii, Yasuhiko; Nomura, Masao; Okamoto, Makoto; Onitsuka, Hatsuki; Nakanishi, Takashi.

    1992-01-01

    In previous papers, the enrichment of 236 U in the U(IV) - U(VI) chemical exchange system was found to be significantly smaller than the value estimated by the normal mass dependence enrichment of 235 U. Further experiments have been carried out in the present work to confirm the strange phenomenon of the isotopic anomaly in uranium enrichment. The results have indicated that the separation coefficient of 236 U is the same value as one previously reported. To confirm the anomaly of uranium isotope separation, α-ray spectrometry was implemented to check the enrichment behavior of 234 U. Although no theoretical explanation is given for the isotopic anomaly, this is favorable phenomenon for the re-enrichment of recycled uranium which contains isotopes 232 U and 236 U. (author)

  11. 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.)

  12. 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

  13. 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.

  14. 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.

  15. 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...

  16. 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)

  17. 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.

  18. Cardiovascular, endocrine and renal effects of urodilatin in normal humans

    DEFF Research Database (Denmark)

    Bestle, M.H.; Olsen, N.V.; Christensen, P.

    1999-01-01

    remained below 0.1%. The results indicate that even moderately natriuretic doses of urodilatin exert protracted effects on systemic hemodynamic, endocrine, and renal functions, including decreases in cardiac output and renal blood flow, without changes in arterial pressure or glomerular filtration rate......Effects of urodilatin (5, 10, 20, and 40 ng. kg-1. min-1) infused over 2 h on separate study days were studied in eight normal subjects with use of a randomized, double-blind protocol. All doses decreased renal plasma flow (hippurate clearance, 13-37%) and increased fractional Li+ clearance (7......-22%) and urinary Na+ excretion (by 30, 76, 136, and 99% at 5, 10, 20, and 40 ng. kg-1. min-1, respectively). Glomerular filtration rate did not increase significantly with any dose. The two lowest doses decreased cardiac output (7 and 16%) and stroke volume (10 and 20%) without changing mean arterial blood...

  19. Effects of normal aging and Alzheimer's disease on emotional memory.

    Science.gov (United States)

    Kensinger, Elizabeth A; Brierley, Barbara; Medford, Nick; Growdon, John H; Corkin, Suzanne

    2002-06-01

    Recall is typically better for emotional than for neutral stimuli. This enhancement is believed to rely on limbic regions. Memory is also better for neutral stimuli embedded in an emotional context. The neural substrate supporting this effect has not been thoroughly investigated but may include frontal lobe, as well as limbic circuits. Alzheimer's disease (AD) results in atrophy of limbic structures, whereas normal aging relatively spares limbic regions but affects prefrontal areas. The authors hypothesized that AD would reduce all enhancement effects, whereas aging would disproportionately affect enhancement based on emotional context. The results confirmed the authors' hypotheses: Young and older adults, but not AD patients, showed better memory for emotional versus neutral pictures and words. Older adults and AD patients showed no benefit from emotional context, whereas young adults remembered more items embedded in an emotional versus neutral context.

  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

  1. Transient competitive complexation in biological kinetic isotope fractionation explains non-steady isotopic effects: Theory and application to denitrification in soils

    Energy Technology Data Exchange (ETDEWEB)

    Maggi, F.M.; Riley, W.J.

    2009-06-01

    The theoretical formulation of biological kinetic reactions in isotopic applications often assume first-order or Michaelis-Menten-Monod kinetics under the quasi-steady-state assumption to simplify the system kinetics. However, isotopic e ects have the same order of magnitude as the potential error introduced by these simpli cations. Both formulations lead to a constant fractionation factor which may yield incorrect estimations of the isotopic effect and a misleading interpretation of the isotopic signature of a reaction. We have analyzed the isotopic signature of denitri cation in biogeochemical soil systems by Menyailo and Hungate [2006], where high {sup 15}N{sub 2}O enrichment during N{sub 2}O production and inverse isotope fractionation during N{sub 2}O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with the quasi-steady-state Michaelis-Menten-Monod kinetics. When the quasi-steady-state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observations and aided in interpretation of experimental isotopic signatures. These results may imply a substantial revision in using the Rayleigh equation for interpretation of isotopic signatures and in modeling biological kinetic isotope fractionation with first-order kinetics or quasi-steady-state Michaelis-Menten-Monod kinetics.

  2. Isotope effects in mass-spectrometry; Les effets isotopiques en spectrometrie de masse

    Energy Technology Data Exchange (ETDEWEB)

    Leicknam, J P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires. Departement de physico-chimie, service des isotopes stables, section de spectrometrie de masse

    1967-05-01

    In the first part, a review is made of the work concerning the influence of isotopic substitution on the stabilities of ionised molecules and the bond-breaking probabilities; metastable transitions are also affected by this substitution. A model based on the Franck-Condon principle accounts for the experimentally observed isotopic effects for diatomic molecules; to a certain extent it is possible to generalise the calculation for the case of isotopic molecules of carbon dioxide gas. For deuterated polyatomic molecules there exist a {pi} effect making it possible to compare the relative stabilities of the X-H and X-D bonds, and a {gamma} effect which characterizes the different behaviours of the X-H bond in a normal molecule and in its partially deuterated homologue. Usually there is a very marked {pi} effect (e.g. the C-D bonds are more difficult to break than the homologous C-H bonds) and a {gamma} effect, the partial deuteration of a molecule leading in general to an increase in the probability of breakage of a given bond. An interpretation of {pi} and {gamma} effects based on Rosenstock near-equilibrium theory accounts for the observed phenomena, qualitatively at least, in the case of propane and acetylene. In the second part are gathered together results concerning isotopic effects produced during the formation of rearranged ions. The existence of cyclic transition ions has made it possible for Mc Lafferty to explain the existence of these ions in the mass spectrum; isotopic substitution leads to a modification of the rearrangement mechanism, the bonding forces being no longer the same. (author) [French] Dans une premiere partie, on rassemble les travaux concernant l'influence de la substitution isotopique sur les stabilites des molecules ionisees et les probabilites de rupture des liaisons; les transitions metastables sont egalement modifiees par cette substitution. Un modele base sur le principe de Franck-Condon rend compte des effets isotopiques

  3. Effect Of Substrates On The Fractionation Of Hydrogen Isotopes During Lipid-Biosynthesis By Haloarcula marismortui

    Science.gov (United States)

    Dirghangi, S. S.; Pagani, M.

    2010-12-01

    Lipids form an important class of proxies for paleoclimatological research, and hydrogen isotope ratios of lipids are being increasingly used for understanding changes in the hydrological system. Proper understanding of hydrogen isotope fractionation during lipid biosynthesis is therefore important and attention has been directed toward understanding the magnitude of hydrogen isotope fractionation that occurs during lipid biosynthesis in various organisms. Hydrogen isotope ratios of lipids depend on the hydrogen isotopic composition of the ambient water, hydrogen isotopic composition of NADPH used during biosynthesis, growth conditions, pathways of lipid biosynthesis, and substrates in the case of heterotrophic organisms. Recently it has been observed that NADPH contributes a significant part of the hydrogen in fatty acids synthesized by bacteria during heterotrophic growth (Zhang et al, 2009). As NADPH is formed by reduction of NADP+ during metabolism of substrates, different metabolic pathways form NADPH with different D/H ratios, which in turn results in variation in D/H ratios of lipids (Zhang et al, 2009). Therefore, substrates play a significant role in hydrogen isotopic compositions of lipids. For this study, we are investigating the effects of substrates on hydrogen isotope fractionation during biosynthesis of isoprenoidal lipids by heterotrophically growing halophilic archaea. Haloarcula marismortui is a halophilic archaea which synthesizes Archaeol (a diether lipid) and other isoprenoidal lipids. We have grown Haloarcula marismortui in pure cultures on three different substrates and are in the process of evaluating isotopic variability of Archaeol and other lipids associated with substrate and the D/H composition of ambient water. Our results will be helpful for a better understanding of hydrogen isotope fractionations during lipid synthesis by archaea. Also, halophilic archaea are the only source of archaeol in hypersaline environments. Therefore, our

  4. LET effects on normal and radiosensitive cell lines

    International Nuclear Information System (INIS)

    Geard, C.R.; Travisano, M.

    1986-01-01

    Charged particles in the track segment mode were produced by the RARAF Van de Graaff accelerator and used to irradiate two CHO cell lines, a radiosensitive hypermutable line EM9 and its normal parent AA8. Asynchronous cells were irradiated attached to 6 micrometer thick Mylar with protons, deuterons and helium-3 particles at LETs ranging from 10 to 150 keV per micrometer. A 50 kVp x-ray tube integrated into the track segment facility provided a low LET comparison. Following irradiation cells were monitored for clonogenicity, and in a separate series of experiments frequencies of sister chromatid exchanges. Up to 9 experiments were carried out at each LET, with a total of 8 radiations of different LETs being compared. The optimally effective LET for cell survival was between 80 and 120 keV per micrometer, with the 150 keV per micrometer particles indicating energy wastage. The differential between the normal and radiosensitive cell lines was maintained at all LETs

  5. 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

  6. Carbon isotope effects in carbohydrates and amino acids of photosynthesizing organisms

    Energy Technology Data Exchange (ETDEWEB)

    Ivlev, A.A.; Kaloshin, A.G.; Koroleva, M.Ya. (Ministerstvo Geologii SSR, Moscow)

    1982-02-10

    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/sub 2/ and C/sub 3/ fragments arising in decarboxylation of pyruvate, as well as isotope differences of biogenic acceptor and environmental CO/sub 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.

  7. Effect of the magnetic isotope of magnesium, 25Mg, on post-radiation recovery of Saccharomyces cerevisiae

    International Nuclear Information System (INIS)

    Grodzinskij, D.M.; Evstyukhina, T.A.; Kol'tover, V.K.; Korolev, V.G.; Kutlakhmedov, Yu.A.; Grodzinskij, D.M.; Evstyukhina, T.A.; Kol'tover, V.K.; Korolev, V.G.; Kutlakhmedov, Yu.A.; Grodzinskij, D.M.; Evstyukhina, T.A.; Kol'tover, V.K.; Korolev, V.G.; Kutlakhmedov, Yu.A.

    2011-01-01

    Among three stable magnesium isotopes, 24 Mg, 25 Mg, and 26 Mg with natural abundance 79, 10, and 11%, only 25 Mg has the nuclear spin (I=5/2) and, therefore, the nuclear magnetic moment. Two other isotopes are spinless (I=0) and, hence, have no magnetic moment. We have revealed that magnetic isotope 25 Mg, by comparison to nonmagnetic isotope 24 Mg, essentially stimulates the recovery process in the yeast cells, Saccharomyces cerevisiae, after UV irradiation. Thus, we have first documented the magnetic isotope effect in radiation biology. This finding opens up the way to the development of novel radio-protectors based on the stable magnetic isotopes.

  8. Calcium-aluminum-rich inclusions with fractionation and unidentified nuclear effects (FUN CAIs): II. Heterogeneities of magnesium isotopes and 26Al in the early Solar System inferred from in situ high-precision magnesium-isotope measurements

    Science.gov (United States)

    Park, Changkun; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.; Davis, Andrew M.; Bizzarro, Martin

    2017-03-01

    Calcium-aluminum-rich inclusions with isotopic mass fractionation effects and unidentified nuclear isotopic anomalies (FUN CAIs) have been studied for more than 40 years, but their origins remain enigmatic. Here we report in situ high precision measurements of aluminum-magnesium isotope systematics of FUN CAIs by secondary ion mass spectrometry (SIMS). Individual minerals were analyzed in six FUN CAIs from the oxidized CV3 carbonaceous chondrites Axtell (compact Type A CAI Axtell 2271) and Allende (Type B CAIs C1 and EK1-4-1, and forsterite-bearing Type B CAIs BG82DH8, CG-14, and TE). Most of these CAIs show evidence for excess 26Mg due to the decay of 26Al. The inferred initial 26Al/27Al ratios [(26Al/27Al)0] and the initial magnesium isotopic compositions (δ26Mg0) calculated using an exponential law with an exponent β of 0.5128 are (3.1 ± 1.6) × 10-6 and 0.60 ± 0.10‰ (Axtell 2271), (3.7 ± 1.5) × 10-6 and -0.20 ± 0.05‰ (BG82DH8), (2.2 ± 1.1) × 10-6 and -0.18 ± 0.05‰ (C1), (2.3 ± 2.4) × 10-5 and -2.23 ± 0.37‰ (EK1-4-1), (1.5 ± 1.1) × 10-5 and -0.42 ± 0.08‰ (CG-14), and (5.3 ± 0.9) × 10-5 and -0.05 ± 0.08‰ (TE) with 2σ uncertainties. We infer that FUN CAIs recorded heterogeneities of magnesium isotopes and 26Al in the CAI-forming region(s). Comparison of 26Al-26Mg systematics, stable isotope (oxygen, magnesium, calcium, and titanium) and trace element studies of FUN and non-FUN igneous CAIs indicates that there is a continuum among these CAI types. Based on these observations and evaporation experiments on CAI-like melts, we propose a generic scenario for the origin of igneous (FUN and non-FUN) CAIs: (i) condensation of isotopically normal solids in an 16O-rich gas of approximately solar composition; (ii) formation of CAI precursors by aggregation of these solids together with variable abundances of isotopically anomalous grains-possible carriers of unidentified nuclear (UN) effects; and (iii) melt evaporation of these precursors

  9. Studies of isotopic effects in the excited electronic states of molecular systems

    International Nuclear Information System (INIS)

    1982-01-01

    Rare gas halogen (RGH) lasers serve as convenient tools for a range of photophysical processes which exhibit isotope effects. This document summarizes progress in the production of molecular systems in their electronic excited states with the aid of RGH lasers, and the various isotopic effects one can study under these conditions. We conclude that the basic physical mechanisms involved in the isotopically sensitive characteristics of excited molecular electronic states are sufficiently selective to be useful in both the detection and separation of many atomic materials

  10. 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

  11. Secondary partitioning isotope effects on solvolytic ion pair intermediates

    International Nuclear Information System (INIS)

    Abbey, K.J.

    1976-01-01

    The thermal decomposition of N-benzhydryl N-nitrosobenzamide (BNB) has been shown to produce an ion pair which either forms ester or reacts with the solvent. In ethanol, the fraction of ester produced, R, was much smaller than R values obtained from solvolysis or from the diphenyldiazomethane (DDM)-benzoic acid reaction, which was suggested to yield the same ion pair as solvolysis. This difference led to the conclusion that the ionic species for the nitrosamide decomposition is a nitrogen-separated ion pair. This study was initiated on the assumption that BNB led to solvolytic ion pairs, but that both the intimate and solvent-separated ion pairs were produced directly from the nitrosamide. The use of α-tritiated BNB for the study of partitioning isotope effects (PIE's) in this system led to activity ratios much lower than expected from other reported work. Results of studies of ''special'' salt effect were not consistent for all situations, but the results do suggest that the assumption that BNB leads to solvolytic ion pairs is probably valid. The investigation of the more stable p-methoxybenzhydryl benzoate system proved to be highly productive. The ester fraction produced, R, responded dramatically to the addition of common-ion as well as ''special'' salts. The functional relationship of R on salt concentration could be explained in terms of Winstein's solvolytic scheme where the intimate ion pair, the solvent-separated ion pair, and the dissociated ion were important. Tritium-labelled compounds were used for PIE studies on 3 different compounds, and three different methods of reaction are proposed

  12. Heavy-atom isotope effects on binding of reactants to lactate dehydrogenase and pyruvate kinase

    International Nuclear Information System (INIS)

    Gawlita, E.

    1993-04-01

    18 O and 13 C kinetic isotope effects have been measured on the reaction of pyruvate kinase with phospho-enol-pyruvate and ADP using a remote label technique. The magnitude of both investigated isotope effects showed a dependence on the concentration of ADP. However, while the carbon effect was simply 'washed out' to unity at high ATP concentration, the oxygen effect becomes inverse and reached 0.9928 at the highest used concentration of ADP. Such a result testifies that the assumption of the negligible effect of isotopic substitution on enzyme-substrate associations remains correct only for carbon effects. An equilibrium 18 O isotope effect on association of oxalate with lactate dehydrogenase in the presence of NADHP has been evaluated by both experimental and theoretical means. Experimental methods, which involved equilibrium dialysis and gas chromatographic/mass spectrometric measurement of isotopic ration, yielded an inverse value of 0.9840. Semiempirical methods involved vibrational analysis of oxalate in two different environments. The comparison of calculated values with the experimentally determined isotope effect indicated that the AM 1 Hamiltonian proved superior to its PM 3 counterpart in this modelling. 160 refs, 8 figs, 18 tabs

  13. 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)

  14. Isotope effects in the equilibrium and non-equilibrium vaporization of tritiated water and ice

    International Nuclear Information System (INIS)

    Baumgaertner, F.; Kim, M.-A.

    1990-01-01

    The vaporization isotope effect of the HTO/H 2 O system has been measured at various temperatures and pressures under equilibrium as well as non-equilibrium conditions. The isotope effect values measured in equilibrium sublimation or distillation are in good agreement with the theoretical values based on the harmonic oscillator model. In non-equilibrium vaporization at low temperatures ( 0 C), the isotope effect decreases rapidly with decreasing system pressure and becomes negligible when the system pressure is lowered more than one tenth of the equilibrium vapor pressure. At higher temperatures, the isotope effect decreases very slowly with decreasing system pressure. Discussion is extended for the application of the present results to the study of biological enrichment of tritium. (author)

  15. 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

  16. Isotope effects associated with the anaerobic oxidation of sulfide by the purple photosynthetic bacterium, Chromatium vinosum

    International Nuclear Information System (INIS)

    Fry, B.; Gest, H.; Hayes, J.M.

    1984-01-01

    Small inverse isotope effects of 1-3 per thousand were consistently observed for the oxidation of sulfide to elemental sulfur during anaerobic photometabolism by Chromatium vinosum. The inverse fractionation can be accounted for by an equilibrium isotope effect between H 2 S and HS - , and may indicate that C. vinosum (and other photosynthetic bacteria) utilizes H 2 S rather than HS - as the substrate during sulfide oxidation. (Auth.)

  17. Effects of Radiofrequency Induced local Hyperthermia on Normal Canine Liver

    International Nuclear Information System (INIS)

    Suh, Chang Ok; Loh, John J. K.; Seong, Jin Sil

    1991-01-01

    In order to assess the effects of radiofrequency-induced local hyperthermia on the normal liver, histopathologic findings and biochemical changes after localized hyperthermia in canine liver were studied. Hyperthermia was externally administered using the Thermotron RF-8 (Yamamoto Vinyter Co., Japan; Capacitive type heating machine) with parallel opposed electrodes. Thirteen dogs were used and allocated into one control group (N=3) and two treatment groups according to the treatment temperature. Group I (N=5) was heated with 42.5±0.5.deg.C for 30 minutes, and Group(N=5) was heated with 45±0.5.deg.C for 15-30 minutes. Samples of liver tissue were obtained through a needle biopsy immediately after hyperthermia and 7, 14 and 28 days after treatment and examined for SGOT, SGPT and alkaline phosphatase. Although SGOT and SGPT were elevated after hyperthermia in both groups (three of five in each group), there was no liver cell necrosis or hyperthermia related mortality in Group I. A hydropic swelling of hepatocytes was prominent histologic finding. Hyperthermia with 45.deg.C for 30 minutes was fatal and showed extensive liver cell necrosis. In conclusion, liver damage day heat of 42.5±0.5.deg.C for 30 minutes is reversible, and liver damage by heat of 45±0.5.deg.C for 30 minutes can be fatal or irreversible. However, these results cannot be applied directly to human trial. Therefore, in order to apply hyperthermic treatment on human liver tumor safely, close observation of temperature with proper thermometry is mandatory. Hyperthermic treatment should be confined to the tumor area while sparing a normal liver as much as possible

  18. Isotope anomalies in oxygen isotope exchange equilibrium systems

    International Nuclear Information System (INIS)

    Kotaka, M.

    1997-01-01

    The purpose of the present work is to elucidate the isotope anomalies in oxygen isotope exchange equilibrium systems, according to the calculations of the equilibrium constants for oxygen isotopic exchange reactions, and the calculations of the oxygen isotope separation factors between two phases. The equilibrium constants (K65, K67, K68 and K69) of 16 O- 15 O, 16 O 17 O, 16 O- 18 O, and 16 O- 19 O exchange reactions between diatomic oxides were calculated in a wide temperature range on the basis of quantum statistical mechanics. Many equilibrium constants showed the anomalous mass effects, and then had the crossover temperatures and the mass independent fractionation (MIF) temperatures which held K67 = K65, K67 = K68, or K67 = K69, etc. For example, the equilibrium constants for the reactions between OH and the other diatomic oxides (MO) showed the anomalous mass effects, when M was Li, Na, Mg, K, Fe, Al, Ge, Zr, Pt, etc. The 16 O 15 O, 16 O 17 O, 16 O- 18 O, and 16 O- 19 O oxygen isotope separation factors (S65, S67, S68 and S69) between two phases were calculated, when OH and CO were in the first phase, and SiO was in the second phase. Although the oxygen isotopic exchange equilibria in the two phases had no MIF and crossover temperatures, the separation factors showed the anomalous mass effects and had the temperatures. According to what is called the normal mass effects for the equilibrium constant of isotopic exchange reaction, the value of InK68/InK67 is 1.885. Therefore, the value of InS68/InS67 should be 1.885 too. The value calculated, however, widely changed. It can be concluded from the results obtained in the present work that some oxygen isotopic exchange equilibria cause the anomalous mass effects, the anomalous oxygen isotope separation factors, and then isotope anomalies

  19. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yunde [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Laboratory of Basin Hydrology and Wetland Eco-restoration, China University of Geosciences, Wuhan 430074 (China); Zhou, Aiguo, E-mail: aiguozhou@cug.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Gan, Yiqun; Li, Xiaoqian [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China)

    2016-05-05

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO{sub 3}{sup −}, or SO{sub 4}{sup 2−}. • Cl{sup −} significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  20. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    International Nuclear Information System (INIS)

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Li, Xiaoqian

    2016-01-01

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO_3"−, or SO_4"2"−. • Cl"− significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  1. Simultaneous 13C/14C dual isotope breath test measurement of gastric emptying of solid and liquid in normal subjects and patients: comparison with scintigraphy

    International Nuclear Information System (INIS)

    Chew, C. G.; Bartholomeusz, F.D.L.; Bellon, M.; Chatterton, B. E.

    2003-01-01

    To develop a simple method for simultaneous solid and liquid gastric emptying assessment using a dual isotope labelled breath test. 13 patients were given 100 g ground beef labelled with 25 MBq 99m Tc sulphur colloid and 74 KBq 14 C octanoic acid, and 150 ml 10% glucose drink labelled with 8 MBq 67 Ga citrate and 150 mg 13 C acetate. 10 normal volunteers were given the same test meals but labelled with 14 C and 13 C only. Breath was collected at baseline and regularly for 4 hours. The 14 CO 2 and 13 CO 2 activity was measured with liquid scintillation counting and mass spectroscopy. The times to maximum 14 CO 2 and 13 CO 2 , were determined. Comparison was made between times to maximum 14 CO 2 with scintigraphic retention of 99m Tc at 100 minutes and times to maximum 13 CO 2 with the scintigraphic half-clearance time of 67 Ga. For the solid meal, the times to maximum 14 CO 2 were: 60-120 minutes in the 8 patients with normal gastric emptying of 99m Tc; 75-145 minutes for the 10 healthy volunteers; 75-180 minutes for the remaining 5 patients with abnormal gastric emptying of 99m Tc. There was a weak but significant correlation (r = 0.56, p 14 CO 2 and gastric retention of 99m Tc at 100 minutes. For the liquid meal, times to maximum 13 CO 2 were: 20-35 minutes for the 4 with normal gastric emptying of 67 Ga; 15-40 minutes for the 10 healthy volunteers; 20-75 minutes for the remaining 9 patients with abnormal gastric emptying of 67 Ga. There was a strong and significant correlation (r = 0.88, p 13 CO 2 and gastric half-clearance time of 67 Ga. Breath tests utilising test meals labelled with *C isotopes are valid alternatives to scintigraphic studies using 99m Tc and 67 Ga for the simultaneous assessment of gastric emptying of solids and liquids. (author)

  2. Effect of normalization on the neutron spectrum adjustment procedure

    International Nuclear Information System (INIS)

    Zsolnay, E.M.; Zijp, W.L.; Nolthenius, H.J.

    1983-10-01

    Various computer programs currently applied for neutron spectrum adjustment based on multifoil activation data, use different ways to determine the normalization factor to be applied to an unnormalized input spectrum. The influence is shown of the various definitions of the normalization factor on the adjusted results for the case of the ORR and YAYOI spectra considered in the international REAL-80 exercise. The actual expression for defining the normalization factor is more important than previously assumed. The theory of the generalized least squares principle provides an optimal definition for the normalization factor

  3. Effect of dioxin on normal and leukemic human hematopoietic cells

    Energy Technology Data Exchange (ETDEWEB)

    Lambertenghi-Deliliers, G.; Soligo, D. [Univ. degli Studi, Milan (Italy). Dipt. die Ematologia, Ospedale Maggiore Policlinico IRCCS; Fracchiolla, N.S. [Ospedale Maggiore Policlinico IRCCS, Milan (Italy). Dipt. di Ematologia; Servida, F. [Fondazione Matarelli, Milan (Italy); Bertazzi, P.A. [Istituti Clinici di Perfezionamento, Milan (Italy). Dipt. di Medicina del Lavoro

    2004-09-15

    2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) arises from chlorination of phenolic substrates or from partial combustion of organic materials in the presence of chlorine sources. TCDD has a large number of biological effects such as long-lasting skin disease, cardiovascular disease, diabete and cancer. TCDD is the prototypical agonist of the aryl hydrocarbon receptor (AhR), a member of the erb-A family that also includes the receptors for steroids, thyroid hormones, peroxisome proliferators and retinoids. When bound to dioxin, the AhR can bind to DNA and alter the expression of some genes including cytokines and growth factors. In this study, we analyzed the effect of escalating doses of TCDD on human CD34{sup +} progenitor cells from the leukapheresis of normal donors stimulated with G-CSF as well as the human myeloid leukemic cell lines HL60 (promyelocytic leukemia) and K562 (chronic myelogenous leukemia). The possible specific modulation of gene expression induced by the TCDD exposure was then tested by means of microarray analyses.

  4. Effect of donepezil hydrochloride on normal-tension glaucoma

    International Nuclear Information System (INIS)

    Yoshida, Yukiko; Sugiyama, Tetsuya; Ikeda, Tsunehiko; Utsunomiya, Keita; Ogura, Yasuharu; Narabayashi, Isamu

    2007-01-01

    Peroral donepezil hydrochloride is claimed to be effective for Alzheimer disease, by elevating concentration of acetylcholine in the brain resulting in improved recognition and intracerebral circulation. It has been reported that some cases of normal-tension glaucoma (NTG) show cerebral circulation similar to patients of Alzheimer disease. The purpose of this study was to evaluate the effect of donepezil hydrochloride on NTG. This study was made on 10 eyes of 5 NTG patients who showed cerebral circulation similar to Alzheimer disease by 123 I-iofetamine (IMP) single photon emission computed tomography (SPECT). The series comprised 3 males and 2 females. Their age ranged from 64 to 79 years, average 69 years. They were given donepezil hydrochloride at the daily dosis of 5 mg for 6 months. Circulation in the optic nervehead was measured by laser speckle flowmetry. Circulation in the brain and optic nervehead significantly increased after 6 months of treatment. MD value by Humphrey tonometer improved in 5 eyes (50%). There was no change in intraocular pressure. Peroral donepezil hydrochloride may improve optic neuropathy in NTG through its neuroprotective action. (author)

  5. Acute and late effects of multimodal therapy on normal tissues

    International Nuclear Information System (INIS)

    Phillips, T.L.; Fu, K.K.

    1977-01-01

    The increasing use of combined radiation, chemotherapy, and surgery has led to an increased incidence of acute and late complications. The complications are, in general, similar to those seen with each modality alone, but occur with increased incidence. Enhanced effects of combined radiation and surgery are modest in number and consist primarily of problems with wound healing and fibrosis, as well as late gastrointestinal damage. Combinations of radiotherapy and chemotherapy have shown a greater degree of enhanced acute and late reactions. Drugs, such as actinomycin-D and Adriamycin, are particularly dangerous if the marked enhancement of radiation effects caused by the drugs in almost all organs is not appreciated and the radiation dose not adjusted accordingly. Proper selection of drugs can lead to enhanced local control by radiotherapy and/or surgery, as well as eradication of microscopic distant metastases, without increased normal tissue injury. Late induction of malignancy can occur with either radiation or chemotherapy alone and, in some cases, this appears to be enhanced when they are combined

  6. Isotope effects in interstellar molecules by chemical hyperfine interaction

    International Nuclear Information System (INIS)

    Haberkorn, R.; Michel-Beyerle, M.E.

    1977-01-01

    If free radicals recombine on grain surfaces, not only the different masses of isotopes but also their differing nuclear spin moments (e.g. 12 C/ 13 C, 14 N/ 15 N, 17 O/ 18 O) may imply variations in the recombination probability due to hyperfine interaction. This mechanism has not been accounted for so far. (orig.) [de

  7. Solvent isotope effect on the fluorescence of azoalkanes

    International Nuclear Information System (INIS)

    Mirbach, M.J.; Mirbach, M.F.; Cherry, W.R.; Turro, N.J.; Engel, P.

    1977-01-01

    A study of fluorescence quantum yields and fluorescence lifetimes of two cyclic azoalkanes reveal a striking dependence of phisub(F) and tausub(F) on solvent and on isotopic substitution (OH → OD). A mechanism involving specific deactivation of the fluorescent state from a hydrogen bonded complex is proposed to rationalize the data. (orig./HK) [de

  8. Radioactive isotope and isomer separation with using light induced drift effect

    International Nuclear Information System (INIS)

    Hradecny, C.; Slovak, J.; Tethal, T.; Ermolaev, I.M.; Shalagin, A.M.

    1991-01-01

    The isotope separation with using light induced drift (LID) is discussed. The basic theoretical characteristics of the method are deduced: separation simultaneously with an arbitrary high enrichment and without significant losses; separation productivity up to 100 μg/h. These characteristics are sufficient and very convenient for separation of expensive radioactive isotopes and isomers which are applied in medicine and science. The first experimental separation of the radioactive isotopes ( 22,24 Na) by using the LID effect is reported. 13 refs.; 5 figs

  9. The Effect of Intertia, Visocus Damping, Temperature and Normal ...

    Indian Academy of Sciences (India)

    29

    system. However, the present study has shown the appearance of chaos for specific values of normal stress before it disappears again as the normal stress varies further. It is also ... μ and v* are reference frictional shear stress and shear velocity corresponding to the AC laws ...... thesis Harvard University. Zhiren, N. and ...

  10. [Effectiveness of an early discharge program after normal childbirth].

    Science.gov (United States)

    Teulón González, M; Martínez Pillado, M; Cuadrado Martín, M M; Rivero Martín, M J; Cerezuela Requena, J F

    To implement a program of early hospital discharge after an uncomplicated birth, in order to improve the effectiveness, as well as ensuring clinical safety and patient acceptability. Descriptive study of the effectiveness of an early discharge program after uncomplicated delivery between February 2012 and September 2013. The populations are post-partum women and newborns admitted to the University Hospital of Fuenlabrada, with a duration of less than 24h after uncomplicated delivery that met the defined inclusion criteria. Satisfaction was assessed using a Likert scale. The effectiveness of the program was monitored by safety indicators, productivity, adaptation, and continuity of care. A total of 20% of cases capable of early discharge from Fuenlabrada University Hospital completed the program. Almost all (94%) were normal deliveries. The 188 cases included were from 911 patients with uncomplicated childbirth, accounting for 6.5% of the 2,857 total births. The mean stay of patients included showed a decrease of 50% (2.4 to 1.2 days). All patients received continuity of care after hospital discharge. The review consultation was reprogrammed for 4.8% of cases, with 2% of patients re-admitted within 96h. with no serious problems. Four newborns (2%) required attention in the emergency department (mother or newborn) before 96h. The assessment of patient satisfaction achieved a score of 4.5 out of 5. The program achieved a decrease in the average stay by 50%, favouring the autonomy of midwives. This acceptance level is in line with similar interventions. The deployment of the program may be useful for other changes in care processes. Copyright © 2016 SECA. Publicado por Elsevier España, S.L.U. All rights reserved.

  11. Temperature and Pressure Depences on the Isotopic Fractionation Effect in the Thermal Decomposition of Ozone

    Directory of Open Access Journals (Sweden)

    Su-Ju Kim

    1997-12-01

    Full Text Available To understand the mass-independent isotopic fractionation effects, thermal decomposition of ozone was performed. Initial oxygen gas was converted to ozone completely. Then, the ozone was decomposed to oxygen at various temperatures(30~150C. Isotopic compositions of product oxygen and residual ozone were measured using a stable isotope mass spectrometer. The experimental results were compared with the studies which were peformed at the similar conditions. From the raw experimental data, the functions of the instantaneous fractionation factors were calculated by the least square fit. The results clearly showed the temperature dependence. They also showed the pressure dependence and the surface effect. This study may play an important role in the study of ozone decomposition mechanism. It can be applied to explain the mass-independent isotopic pattern found in stratospheric ozone and in meteorites.

  12. Stable isotope studies

    International Nuclear Information System (INIS)

    Ishida, T.

    1992-01-01

    The research has been in four general areas: (1) correlation of isotope effects with molecular forces and molecular structures, (2) correlation of zero-point energy and its isotope effects with molecular structure and molecular forces, (3) vapor pressure isotope effects, and (4) fractionation of stable isotopes. 73 refs, 38 figs, 29 tabs

  13. Mechanistic investigations of the hydrolysis of amides, oxoesters and thioesters via kinetic isotope effects and positional isotope exchange.

    Science.gov (United States)

    Robins, Lori I; Fogle, Emily J; Marlier, John F

    2015-11-01

    The hydrolysis of amides, oxoesters and thioesters is an important reaction in both organic chemistry and biochemistry. Kinetic isotope effects (KIEs) are one of the most important physical organic methods for determining the most likely transition state structure and rate-determining step of these reaction mechanisms. This method induces a very small change in reaction rates, which, in turn, results in a minimum disturbance of the natural mechanism. KIE studies were carried out on both the non-enzymatic and the enzyme-catalyzed reactions in an effort to compare both types of mechanisms. In these studies the amides and esters of formic acid were chosen because this molecular structure allowed development of methodology to determine heavy-atom solvent (nucleophile) KIEs. This type of isotope effect is difficult to measure, but is rich in mechanistic information. Results of these investigations point to transition states with varying degrees of tetrahedral character that fit a classical stepwise mechanism. This article is part of a special issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Isotopic incorporation and the effects of fasting and dietary lipid content on isotopic discrimination in large carnivorous mammals

    Science.gov (United States)

    Rode, Karyn D.; Stricker, Craig A.; Erlenbach, Joy; Robbins, Charles T.; Cherry, Seth; Newsome, Seth D.; Cutting, Amy; Jensen, Shannon; Stenhouse, Gordon; Brooks, Matt; Hash, Amy; Nicassio, Nicole

    2016-01-01

    There has been considerable emphasis on understanding isotopic discrimination for diet estimation in omnivores. However, discrimination may differ for carnivores, particularly species that consume lipid-rich diets. Here, we examined the potential implications of several factors when using stable isotopes to estimate the diets of bears, which can consume lipid-rich diets and, alternatively, fast for weeks to months. We conducted feeding trials with captive brown bears (Ursus arctos) and polar bears (Ursus maritimus). As dietary lipid content increased to ∼90%, we observed increasing differences between blood plasma and diets that had not been lipid extracted (∆13Ctissue-bulk diet) and slightly decreasing differences between plasma δ13C and lipid-extracted diet. Plasma Δ15Ntissue-bulk diet increased with increasing protein content for the four polar bears in this study and data for other mammals from previous studies that were fed purely carnivorous diets. Four adult and four yearling brown bears that fasted 120 d had plasma δ15N values that changed by <±2‰. Fasting bears exhibited no trend in plasma δ13C. Isotopic incorporation in red blood cells and whole blood was ≥6 mo in subadult and adult bears, which is considerably longer than previously measured in younger and smaller black bears (Ursus americanus). Our results suggest that short-term fasting in carnivores has minimal effects on δ13C and δ15N discrimination between predators and their prey but that dietary lipid content is an important factor directly affecting δ13C discrimination and indirectly affecting δ15N discrimination via the inverse relationship with dietary protein content.

  15. Environmental effects of normal and off-normal releases of tritium from CTR systems

    International Nuclear Information System (INIS)

    McKone, T.E.

    1978-08-01

    Near term fusion technology will utilize the deuterium-tritium reaction. To quantify the magnitude of the hazard presented by major tritium release mechanisms, a method is presented for determining doses to the public from releases of tritium as tritiated water vapor or tritiated lithium compounds. Inclusion of this method in a computer model is described. This model uses the Gaussian dispersion method to predict distribution of tritium species in the downwind environment. Movement of tritium into biological systems is determined by treating these systems as a series of interacting water compartments. Dispersion and uptake calculations are applied to two sample sites in order to predict health effects. These effects are compared to the long range effect of introducing tritium into the world water system

  16. Fast neutron biological effects on normal and tumor chromatin

    International Nuclear Information System (INIS)

    Constantinescu, B.; Bugoi, Roxana; Paunica, Tatiana; Radu, Liliana

    1997-01-01

    the relative absorbencies (E/E 0 ) obtained for the thermal transitions of chromatin samples versus fast neutron dose, lower values at higher neutron dose, were observed, indicating a damaged chromatin DNA. The treatment with gyrostan accelerates the damage process, but adding thyroxine and D3 vitamin the negative effect is partially recovered. Some conclusions on the role of gyrostan and of thyroxine and D3 vitamin are presented. To study the influence of metal ions on DNA strand breakage induced by fast neutrons, chromatin irradiations with 100, 200 and 300 Gy were performed separately and in presence of CsCl, CuCl 2 and AlCl 3 in a 5 x 10 -2 M concentration. Fluorescence lifetime values for chromatin-ethidium bromide complexes were determined using a Fluorimeter Edinburgh Anal. Instr. FL-900 CD. Greater values denote a damaged chromatin DNA. The presence of metal cations strongly decreases the time of life values, acting as a trap for the water radiolysis products. Our results suggest a combination of fast neutron irradiation with anticancer drug gyrostan for tumor destruction enhancement and the use of metal ions with hormonal thyroxine and D3 vitamin for a normal cells better protection during neutron therapy.(authors)

  17. Effectiveness of different pre-treatments in recovering pre-burial isotopic ratios of charred plants.

    Science.gov (United States)

    Brinkkemper, O; Braadbaart, F; van Os, B; van Hoesel, A; van Brussel, A A N; Fernandes, R

    2018-02-15

    Isotopic analysis of archaeological charred plant remains offers useful archaeological information. However, adequate sample pre-treatment protocols may be necessary to provide a contamination-free isotopic signal while limiting sample loss and achieving a high throughput. Under these constraints, research was undertaken to compare the performance of different pre-treatment protocols. Charred archaeological plant material was selected for isotopic analysis (δ 13 C and δ 15 N values) by isotope ratio mass spectrometry from a variety of plant species, time periods and soil conditions. Preservation conditions and the effectiveness of cleaning protocols were assessed through Fourier transform infrared spectroscopy and X-ray fluorescence (XRF) spectrometry. An acid-base-acid protocol, successfully employed in radiocarbon dating, was used to define a contamination-free isotopic reference. Acid-base-acid isotopic measurements were compared with those obtained from untreated material and an acid-only protocol. The isotopic signals of untreated material and the acid-only protocol typically did not differ more than 1‰ from those of the acid-base-acid reference. There were no significant isotopic offsets between acid-base-acid and acid-only or untreated samples. Sample losses in the acid-base-acid protocol were on average 50 ± 17% (maximum = 98.4%). Elemental XRF measurements showed promising results in the detection of more contaminated samples albeit with a high rate of false positives. For the large range of preservation conditions described in the study, untreated charred plant samples, water cleaned of sediments, provide reliable stable isotope ratios of carbon and nitrogen. The use of pre-treatments may be necessary under different preservation conditions or more conservative measurement uncertainties should be reported. Copyright © 2017 John Wiley & Sons, Ltd.

  18. Use of Isotopic Data to Determine Influence of Seasonal Effects in Rivers

    Energy Technology Data Exchange (ETDEWEB)

    Michel, R. L. [US Geological Survey, Menlo Park, CA (United States); Aggarwal, P. K.; Araguas Araguas, L.; Newman, B.; Kurttas, T. [International Atomic Energy Agency, Vienna (Austria)

    2013-07-15

    In 2002 the International atomic energy agency and its Member states initiated a programme for the collection and measurement of isotopes (stable isotopes of water and tritium) in river waters. The purpose of this programme is to establish a long term database (GNIR) similar to the global database currently available for precipitation. These isotopic data provide a baseline for studying parameters in hydrologic basins that can be used to monitor any changes in the basin response due to shifts in future climatic or land use factors. Below, selected {sup 18}O and tritium data sets where measurements from several years of routine sampling are available are analysed. A ratio of the average monthly isotopic concentration divided by the average yearly concentration is used to normalize data and makes it possible to compare data from different sites. In general, high flow periods are strongly influenced by younger water whereas baseflow is primarily composed of water of greater age (probably decadal). Using this approach and flow rates, it should be possible to estimate the isotopic concentrations of baseflow. This data set will make it possible to track changes in baseflow concentrations occurring due to future changes in climate or land use. (author)

  19. The effective management of medical isotope production in research reactors

    International Nuclear Information System (INIS)

    Drummond, D.T.

    1993-01-01

    During the 50-yr history of the use of radioisotopes for medical applications, research reactors have played a pivotal role in the production of many if not most of the key products. The marriage between research reactors and production operations is subject to significant challenges on two fronts. The medical applications of the radioisotope products impose some unique constraints and requirements on the production process. In addition, the mandates and priorities of a research reactor are not always congruent with the demands of a production environment. This paper briefly reviews the historical development of medical isotope production, identifies the unique challenges facing this endeavor, and discusses the management of the relationship between the isotope producer and the research reactor operator. Finally, the key elements of a successful relationship are identified

  20. Investigating the effects of abyssal peridotite alteration on Si, Mg and Zn isotopes

    Science.gov (United States)

    Savage, P. S.; Wimpenny, J.; Harvey, J.; Yin, Q.; Moynier, F.

    2013-12-01

    Around 1/3 of Earth's divergent ridge system is now classified as "slow" spreading [1], exposing ultramafic rocks (abyssal peridotites) at the seafloor. Such material is often highly altered by serpentinisation and steatisation (talc formation). It is crucial to understand such processes in order to access the original composition of the mantle, and to quantify any impact on ocean composition. Here we examine the effect of both serpentinisation and steatisation on Si, Mg and Zn isotopes. Hydrothermal alteration and seafloor weathering are both sources of oceanic Si [2] and weathering of abyssal peridotites is a source of oceanic Mg [3]; hence isotopic fractionation as a result of seafloor alteration could affect oceanic Si and Mg isotope composition. Zinc isotopes can provide complimentary information; the magnitude and direction of fractionation is highly dependent on complexing ligand [4] and can provide compositional information on the fluids driving metasomatism. For this study, two cores from the well-characterised abyssal peridotites recovered on ODP Leg 209 were examined [5]. Hole 1274a peridotites exhibit variable serpentinisation at ~200°C, whereas samples from Hole 1268a have been comprehensively serpentinised and then subsequently steatised to talc facies at ~350°C, by a low Mg/Si, low pH fluid. The Si, Mg and Zn isotope compositions of 1274a samples are extremely homogeneous, identical to that of pristine mantle rocks (BSE) i.e., serpentinisation at this locality was predominantly isochemical [5]. In contrast, samples from 1268a show greater isotopic variability. In all samples, Mg is enriched in the heavier isotopes relative to BSE, consistent with formation of isotopically heavy secondary phases [6]. For Si, serpentinised samples are slightly enriched in the lighter isotopes compared to BSE, again consistent with the behaviour of Si during formation of secondary phases [7]. Within the steatised samples, some exhibit enrichments in the lighter Si

  1. ICP-MS as the method of the determination of gallium, indium and thallium isotope ratios in the studies of isotope effects in the chromatography systems

    International Nuclear Information System (INIS)

    Herdzik, I.

    2006-01-01

    The procedure of the determination of gallium, indium and thallium isotope ratios and its application to the studies of the isotope effects in chromatography systems by the ICP-MS method (inductively coupled plasma-mass spectrometry) are presented. It was shown that it is possible to determine the isotope ratios of gallium ( 69/71 Ga), indium ( 113/115 In) and thallium ( 203/205 Tl) with the relative standard deviation 0.03-0.07%. Such precision appeared to be sufficient to calculate the unit separation factors in the column chromatographic processes. (author) [pl

  2. The effect of inertia, viscous damping, temperature and normal ...

    Indian Academy of Sciences (India)

    Nitish Sinha

    2018-04-16

    Apr 16, 2018 ... physical parameters such as inertia, viscous damping, temperature and normal stress on the chaotic ... However, the present study has shown the appearance of chaos for the specific .... Although chaos is a general man-.

  3. Lithium isotope effect in the extraction systems of polyethers: effect of salt concentration

    International Nuclear Information System (INIS)

    Fang Shengqiang; Fu Lian

    1991-01-01

    Separation factors of lithium isotopes at 20 deg C were determined in the extraction systems of B15C5-CHCl 3 /LiBr-H 2 O. The initial concentration of LiBr was controlled in the extent of more than 2 mol/l. It may be established that the increase of LiBr concentration causes a remarkable increase of the separation factor. The essence of this effect due to the change in salt concentration was discussed in connection with examination of relevant phenomena in literature. It can be concluded that the relationship between α and Cm, the concentration of lithium salt, is dependent on K Q and K P express respectively, lithium isotope exchange equilibrium constants between Li-crownether complex and hydrated lithium ion for lithium concentration less than 1-2 mol/l, and between lithium salt ion pair and hydrated lithium ion for lithium concentration more than 2 mol/l in aqueous phase

  4. Isotope effect in monolayer, localised, immobilised adsorption with special reference to neon adsorption on porous glass at cryogenic temperatures

    International Nuclear Information System (INIS)

    Srisaila, S.; Bajpai, M.B.

    1980-01-01

    Using statistical mechanics, a general formula for the separation factor of two isotopes between gas and adsorbate phases in a monolayer, localised, immobile adsorption on a heterogeneous surface, is derived. Special forms of this are discussed for which the familiar Bigeleisen form is one. Purer, Kalplan and Smith, in their work on neon isotopes separation by gas chromatography through porous glass column at cryogenic temperatures, have reported that the separation factor first increased and then decreased as the temperature was decreased, whereas monotonic increase was the normally expected behaviour. Moiseyev has attempted to explain the anomaly after assuming two types of adsorption sites. The present theory gives the conditions in which monotonic and nonmonotonic variations can occur and after making some assumptions, the experimental curve of Purer et al could be reproduced computationally using one form of the general expression. This theoretical treatment highlights the importance of both potential energy and force constant in isotope effect whereas it is only the potential energy that is much involved in most adsorption studies. (auth.)

  5. Chemical Ligation and Isotope Labeling to Locate Dynamic Effects during Catalysis by Dihydrofolate Reductase.

    Science.gov (United States)

    Luk, Louis Y P; Ruiz-Pernía, J Javier; Adesina, Aduragbemi S; Loveridge, E Joel; Tuñón, Iñaki; Moliner, Vincent; Allemann, Rudolf K

    2015-07-27

    Chemical ligation has been used to alter motions in specific regions of dihydrofolate reductase from E. coli and to investigate the effects of localized motional changes on enzyme catalysis. Two isotopic hybrids were prepared; one with the mobile N-terminal segment containing heavy isotopes ((2) H, (13) C, (15) N) and the remainder of the protein with natural isotopic abundance, and the other one with only the C-terminal segment isotopically labeled. Kinetic investigations indicated that isotopic substitution of the N-terminal segment affected only a physical step of catalysis, whereas the enzyme chemistry was affected by protein motions from the C-terminal segment. QM/MM studies support the idea that dynamic effects on catalysis mostly originate from the C-terminal segment. The use of isotope hybrids provides insights into the microscopic mechanism of dynamic coupling, which is difficult to obtain with other studies, and helps define the dynamic networks of intramolecular interactions central to enzyme catalysis. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  6. The effects of shear and normal stress paths on rock friction

    International Nuclear Information System (INIS)

    Olsson, W.A.

    1990-01-01

    The effect of variable normal stress on the coefficient of friction of smooth artificial surfaces in welded tuff was studied. The shear stress response to changes in normal stress during constant-velocity sliding suggests that friction depends on the history of the normal stress; or, more generally, the path in shear/normal stress space. 6 refs., 5 figs

  7. Radioactive Emissions from Fission-Based Medical Isotope Production and Their Effect on Global Nuclear Explosion Detection

    International Nuclear Information System (INIS)

    Bowyer, T.; Saey, P.

    2015-01-01

    The use of medical isotopes, such as Tc-99m, is widespread with over 30 million procedures being performed every year, but the fission-based production of isotopes used for medical procedures causes emissions into the environment. This paper will show that gaseous radioactive isotopes of xenon, such as Xe-133, are released in high quantities, because they have a high fission cross section and they are difficult to scrub from the processes used to produce the medical isotopes due to their largely unreactive nature. Unfortunately, the reasons that large amounts of radioactive xenon isotopes are emitted from isotope production are the same as those that make these isotopes the most useful isotopes for the detection of underground nuclear explosions. Relatively recently, the nuclear explosion monitoring community has established a provisional monitoring network for the Comprehensive Nuclear-Test-Ban Treaty (CTBT) that includes radioactive xenon monitoring as a major component. This community has discovered that emissions from medical isotope production present a more serious problem to nuclear explosion monitoring than thought when the network was first conceived. To address the growing problem, a group of scientists in both the monitoring and the isotope production communities have come together to attempt to find scientific and pragmatic ways to address the emissions problems, recognizing that medical isotope production should not be adversely affected, while monitoring for nuclear explosions should remain effective as isotope production grows, changes, and spreads globally. (author)

  8. 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

  9. Cl and C isotope analysis to assess the effectiveness of chlorinated ethene degradation by zero-valent iron: Evidence from dual element and product isotope values

    International Nuclear Information System (INIS)

    Audí-Miró, Carme; Cretnik, Stefan; Otero, Neus; Palau, Jordi; Shouakar-Stash, Orfan; Soler, Albert

    2013-01-01

    Highlights: ► TCE and cis-DCE Cl isotope fractionation was investigated for the first time with ZVI. ► A C–Cl bond is broken in the rate-limiting step during ethylene ZVI dechlorination. ► Dual C/Cl isotope plot is a promising tool to discriminate abiotic degradation. ► Product-related carbon isotopic fractionation gives evidence of abiotic degradation. ► Hydrogenolysis and β-dichloroelimination pathways occur simultaneously. - Abstract: This study investigated C and, for the first time, Cl isotope fractionation of trichloroethene (TCE) and cis-dichloroethene (cis-DCE) during reductive dechlorination by cast zero-valent iron (ZVI). Hydrogenolysis and β-dichloroelimination pathways occurred as parallel reactions, with ethene and ethane deriving from the β-dichloroelimination pathway. Carbon isotope fractionation of TCE and cis-DCE was consistent for different batches of Fe studied. Transformation of TCE and cis-DCE showed Cl isotopic enrichment factors (ε Cl ) of −2.6‰ ± 0.1‰ (TCE) and −6.2‰ ± 0.8‰ (cis-DCE), with Apparent Kinetic Isotope Effects (AKIE Cl ) for Cl of 1.008 ± 0.001 (TCE) and 1.013 ± 0.002 (cis-DCE). This indicates that a C–Cl bond breakage is rate-determining in TCE and cis-DCE transformation by ZVI. Two approaches were investigated to evaluate if isotope fractionation analysis can distinguish the effectiveness of transformation by ZVI as opposed to natural biodegradation. (i) Dual isotope plots. This study reports the first dual (C, Cl) element isotope plots for TCE and cis-DCE degradation by ZVI. The pattern for cis-DCE differs markedly from that reported for biodegradation of the same compound by KB-1, a commercially available Dehalococcoides-containing culture. The different trends suggest an expedient approach to distinguish abiotic and biotic transformation, but this needs to be confirmed in future studies. (ii) Product-related isotope fractionation. Carbon isotope ratios of the hydrogenolysis product cis

  10. Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

    Science.gov (United States)

    Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

    2013-05-01

    Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

  11. Transition-state analysis of a Vmax mutant of AMP nucleosidase by the application of heavy-atom kinetic isotope effects

    International Nuclear Information System (INIS)

    Parkin, D.W.; Mentch, F.; Banks, G.A.; Horenstein, B.A.; Schramm, V.L.

    1991-01-01

    The transition state of the V max mutant of AMP nucleosidase from Azotobacter vinelandii has been characterized by heavy-atom kinetic isotope effects in the presence and absence of MgATP, the allosteric activator. The enzyme catalyzes hydrolysis of the N-glycosidic bond of AMP at approximately 2% of the rate of the normal enzyme with only minor changes in the K m for substrate, the activation constant for MgATP, and the K i for formycin 5'-phosphate, a tight-binding competitive inhibitor. Isotope effects were measured as a function of the allosteric activator concentration that increases the turnover number of the enzyme from 0.006 s -1 . The kinetic isotope effects were measured with the substrates [1'- 3 H]AMP, [2'- 2 H]AMP, [9- 15 N]AMP, and [1',9- 14 C, 15 N]AMP. All substrates gave significant kinetic isotope effects in a pattern that establishes that the reaction expresses intrinsic kinetic isotope effects in the presence or absence of MgATP. Transition-state analysis using bond-energy and bond-order vibrational analysis indicated that the transition state for the mutant enzyme has a similar position in the reaction coordinate compared to that for the normal enzyme. The mutant enzyme is less effective in stabilizing the carbocation-like intermediate and in the ability to protonate N7 of adenine to create a better leaving group. This altered transition-state structure was confirmed by an altered substrate specificity for the mutant protein

  12. 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

  13. The stable isotope amount effect: New insights from NEXRAD echo tops, Luquillo Mountains, Puerto Rico

    Science.gov (United States)

    Scholl, Martha A.; Shanley, James B.; Zegarra, Jan Paul; Coplen, Tyler B.

    2009-01-01

    The stable isotope amount effect has often been invoked to explain patterns of isotopic composition of rainfall in the tropics. This paper describes a new approach, correlating the isotopic composition of precipitation with cloud height and atmospheric temperature using NEXRAD radar echo tops, which are a measure of the maximum altitude of rainfall within the clouds. The seasonal differences in echo top altitudes and their corresponding temperatures are correlated with the isotopic composition of rainfall. These results offer another factor to consider in interpretation of the seasonal variation in isotopic composition of tropical rainfall, which has previously been linked to amount or rainout effects and not to temperature effects. Rain and cloud water isotope collectors in the Luquillo Mountains in northeastern Puerto Rico were sampled monthly for three years and precipitation was analyzed for δ18O and δ2H. Precipitation enriched in 18O and 2H occurred during the winter dry season (approximately December–May) and was associated with a weather pattern of trade wind showers and frontal systems. During the summer rainy season (approximately June–November), precipitation was depleted in 18O and 2H and originated in low pressure systems and convection associated with waves embedded in the prevailing easterly airflow. Rain substantially depleted in 18O and 2H compared to the aforementioned weather patterns occurred during large low pressure systems. Weather analysis showed that 29% of rain input to the Luquillo Mountains was trade wind orographic rainfall, and 30% of rainfall could be attributed to easterly waves and low pressure systems. Isotopic signatures associated with these major climate patterns can be used to determine their influence on streamflow and groundwater recharge and to monitor possible effects of climate change on regional water resources.

  14. Dew water effects on leaf water using a stable isotope approach

    Science.gov (United States)

    Kim, K.; Lee, X.

    2009-12-01

    The presence of dew is a common meteorological phenomenon in field conditions and takes into account for significant portion of hydrologic processes in terrestrial ecosystems. The isotope composition of leaf water plays an important role in the isotopic water and carbon fluxes between terrestrial plants and the atmosphere. However, the consequence of dew formation in the plant-atmosphere relations has been ignored in many studies. The objective of this study is to improve our understanding of environmental and biological controls on the leaf water in equilibrium with dew water through laboratory experiments. Five species of plants (soybean, corn, sorghum, wheat, cotton) were grown hydroponically with water of a known isotopic content in a greenhouse. On the day of the experiment, they were first moved to ambient environment in full sunlight for at least 6 hr and then into a dark container inside the lab for up to 48 hr in which water vapor isotope ratios, temperature, and humidity were controlled. This arrangement created a step change in the forcing on the plant isotopic exchange. Leaves were sampled prior to the transfer to the dark container and 6 more times every 4 - 12 hr over the experiment. Humidity inside the container was saturated to mimic dew events in field conditions. Water from the leaf samples was extracted by a vacuum line and was analyzed for both δD and δ18O. The dataset will allow us to evaluate leaf water isotopic theories by exploring the transitions of the isotopic ratio of leaf water in response to the step change. Specifically, we are interested in whether the stomatal opening is an effective pathway for gaseous exchange in total darkness and how the transitional behaviors of the isotopic ratio of leaf water differ between the C3 and C4 photosynthesis pathways.

  15. 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

  16. Significance of normalized residual activity value (Nora) - the new parameter of isotopic renography - for the diagnosis of patients with obstructive uropathy

    International Nuclear Information System (INIS)

    Juszczyk-Gontaszewska, M.; Gontaszewski, W.; Rogowski, F.

    2005-01-01

    The aim of this research was to establish NORA values typical of patients with compensated and uncompensated obstructive uropathy. 147 results of renoscintigraphies carried out after the application of Tc-99m DTPA with furosemide diuretic test were analyzed. The patients were divided into three groups: the group with compensated obstructive uropathy, the group with uncompensated obstructive uropathy, and the controlled group. NORA-1 and NORA-2 values were calculated in each patient, for each kidney separately. It was established that the mean NORA-1 values in the three groups (the controlled group, the compensated uropathy group, and the uncompensated uropathy group) were significantly different, thus enabling differentiation between them. Based on the examination described above, the following conclusions wee drawn: 1. NORA is an effective differentiation index for compensated and uncompensated uropathy. 2. NORA values should be routinely calculated in every case of isotopic diuretic renography. (author)

  17. 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

  18. Absolute isotopic abundances of Ti in meteorites

    International Nuclear Information System (INIS)

    Niederer, F.R.; Papanastassiou, D.A.; Wasserburg, G.J.

    1985-01-01

    The absolute isotope abundance of Ti has been determined in Ca-Al-rich inclusions from the Allende and Leoville meteorites and in samples of whole meteorites. The absolute Ti isotope abundances differ by a significant mass dependent isotope fractionation transformation from the previously reported abundances, which were normalized for fractionation using 46 Ti/ 48 Ti. Therefore, the absolute compositions define distinct nucleosynthetic components from those previously identified or reflect the existence of significant mass dependent isotope fractionation in nature. We provide a general formalism for determining the possible isotope compositions of the exotic Ti from the measured composition, for different values of isotope fractionation in nature and for different mixing ratios of the exotic and normal components. The absolute Ti and Ca isotopic compositions still support the correlation of 50 Ti and 48 Ca effects in the FUN inclusions and imply contributions from neutron-rich equilibrium or quasi-equilibrium nucleosynthesis. The present identification of endemic effects at 46 Ti, for the absolute composition, implies a shortfall of an explosive-oxygen component or reflects significant isotope fractionation. Additional nucleosynthetic components are required by 47 Ti and 49 Ti effects. Components are also defined in which 48 Ti is enhanced. Results are given and discussed. (author)

  19. Kinetic isotope effects in reaction of ferment oxidation of tritium-labelled D-galactosamine

    International Nuclear Information System (INIS)

    Akulov, G.P.; Korsakova, N.A.

    1992-01-01

    Primary, secondary and intramolecular kinetic isotopic effects in reaction of ferment oxidation of D-galactosamine labelled by tritium in position 6, were measured. When comparing values of the effects with previously obtained results for similar reaction D-[6- 3 H]galactose, it was ascertained that the presence of aminogroup in galactopyranosyl mainly affects kinetics of substrate-ferment complex formation stage. The possibility to use kinetic isotope effects for increase in molar activity of D-galactosamine, labelled by tritium in position 6, is shown

  20. 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.

  1. 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)

  2. 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

  3. Some measurements of H/D polarizability isotope effects using differential refractometry

    Energy Technology Data Exchange (ETDEWEB)

    Foster Smith, M; Van Hook, W A [Tennessee Univ., Knoxville (USA). Dept. of Chemistry

    1989-05-01

    Refractive index differences between the H and D isomers of some common molecules in the liquid phase were measured between 404.7 and 690.0 nm. The data are combined with information on molar volume isotope effects to yield values for H/D isotope effects on the static polarizability, the vibrational contribution to the static and frequency dependent parts of the polarizability, and the H/D isotope effect on the second moment of the electronic charge distribution. The present results suffice to demonstrate the practicability of this technique to measure the components of the polarizability listed above. However for accurate resolution of the vibrational and second moment contributions, refractive index data of still greater precision will be required. (orig.).

  4. Some measurements of H/D polarizability isotope effects using differential refractometry

    International Nuclear Information System (INIS)

    Foster Smith, M.; Van Hook, W.A.

    1989-01-01

    Refractive index differences between the H and D isomers of some common molecules in the liquid phase were measured between 404.7 and 690.0 nm. The data are combined with information on molar volume isotope effects to yield values for H/D isotope effects on the static polarizability, the vibrational contribution to the static and frequency dependent parts of the polarizability, and the H/D isotope effect on the second moment of the electronic charge distribution. The present results suffice to demonstrate the practicability of this technique to measure the components of the polarizability listed above. However for accurate resolution of the vibrational and second moment contributions, refractive index data of still greater precision will be required. (orig.)

  5. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream.

    Science.gov (United States)

    Nishizawa, Manabu; Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken

    2016-08-01

    Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ(15)NNO2- and δ(18)ONO2-, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of "Candidatus Nitrosocaldus." The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ(18)O value of nitrite produced from ammonia oxidation varied with the δ(18)O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ(18)ONO2- in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of

  6. A multielement isotopic study of refractory FUN and F CAIs: Mass-dependent and mass-independent isotope effects

    Science.gov (United States)

    Kööp, Levke; Nakashima, Daisuke; Heck, Philipp R.; Kita, Noriko T.; Tenner, Travis J.; Krot, Alexander N.; Nagashima, Kazuhide; Park, Changkun; Davis, Andrew M.

    2018-01-01

    Calcium-aluminum-rich inclusions (CAIs) are the oldest dated objects that formed inside the Solar System. Among these are rare, enigmatic objects with large mass-dependent fractionation effects (F CAIs), which sometimes also have large nucleosynthetic anomalies and a low initial abundance of the short-lived radionuclide 26Al (FUN CAIs). We have studied seven refractory hibonite-rich CAIs and one grossite-rich CAI from the Murchison (CM2) meteorite for their oxygen, calcium, and titanium isotopic compositions. The 26Al-26Mg system was also studied in seven of these CAIs. We found mass-dependent heavy isotope enrichment in all measured elements, but never simultaneously in the same CAI. The data are hard to reconcile with a single-stage melt evaporation origin and may require reintroduction or reequilibration for magnesium, oxygen and titanium after evaporation for some of the studied CAIs. The initial 26Al/27Al ratios inferred from model isochrons span a range from <1 × 10-6 to canonical (∼5 × 10-5). The CAIs show a mutual exclusivity relationship between inferred incorporation of live 26Al and the presence of resolvable anomalies in 48Ca and 50Ti. Furthermore, a relationship exists between 26Al incorporation and Δ17O in the hibonite-rich CAIs (i.e., 26Al-free CAIs have resolved variations in Δ17O, while CAIs with resolved 26Mg excesses have Δ17O values close to -23‰). Only the grossite-rich CAI has a relatively enhanced Δ17O value (∼-17‰) in spite of a near-canonical 26Al/27Al. We interpret these data as indicating that fractionated hibonite-rich CAIs formed over an extended time period and sampled multiple stages in the isotopic evolution of the solar nebula, including: (1) an 26Al-poor nebula with large positive and negative anomalies in 48Ca and 50Ti and variable Δ17O; (2) a stage of 26Al-admixture, during which anomalies in 48Ca and 50Ti had been largely diluted and a Δ17O value of ∼-23‰ had been achieved in the CAI formation region; and (3

  7. The effect of normal load on polytetrafluoroethylene tribology.

    Science.gov (United States)

    Barry, Peter R; Chiu, Patrick Y; Perry, Scott S; Sawyer, W Gregory; Phillpot, Simon R; Sinnott, Susan B

    2009-04-08

    The tribological behavior of oriented poly(tetrafluoroethylene) (PTFE) sliding surfaces is examined as a function of sliding direction and applied normal load in classical molecular dynamics (MD) simulations. The forces are calculated with the second-generation reactive empirical bond-order potential for short-range interactions, and with a Lennard-Jones potential for long-range interactions. The range of applied normal loads considered is 5-30 nN. The displacement of interfacial atoms from their initial positions during sliding is found to vary by a factor of seven, depending on the relative orientation of the sliding chains. However, within each sliding configuration the magnitude of the interfacial atomic displacements exhibits little dependence on load over the range considered. The predicted friction coefficients are also found to vary with chain orientation and are in excellent quantitative agreement with experimental measurements.

  8. 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

  9. 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

  10. 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...

  11. 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.)

  12. Effects of trace element concentration on enzyme controlled stable isotope fractionation during aerobic biodegradation of toluene.

    Science.gov (United States)

    Mancini, Silvia A; Hirschorn, Sarah K; Elsner, Martin; Lacrampe-Couloume, Georges; Sleep, Brent E; Edwards, Elizabeth A; Lollar, Barbara Sherwood

    2006-12-15

    The effects of iron concentration on carbon and hydrogen isotopic fractionation during aerobic biodegradation of toluene by Pseudomonas putida mt-2 were investigated using a low iron medium and two different high iron media. Mean carbon enrichment factors (epsilonc) determined using a Rayleigh isotopic model were smaller in culture grown under high iron conditions (epsilonc = -1.7+/-0.1%) compared to low iron conditions (epsilonc = -2.5+/-0.3%). Mean hydrogen enrichment factors (epsilonH) were also significantly smaller for culture grown under high iron conditions (epsilonH = -77 +/-4%) versus low iron conditions (EpsilonH = -159+/-11%). A mechanistic model for enzyme kinetics was used to relate differences in the magnitude of isotopic fractionation for low iron versus high iron cultures to the efficiency of the enzymatic transformation. The increase of carbon and hydrogen enrichment factors at low iron concentrations suggests a slower enzyme-catalyzed substrate conversion step (k2) relative to the enzyme-substrate binding step (k-l) at low iron concentration. While the observed differences were subtle and, hence, do not significantly impact the ability to use stable isotope analysis in the field, these results demonstrated that resolvable differences in carbon and hydrogen isotopic fractionation were related to low and high iron conditions. This novel result highlights the need to further investigate the effects of other trace elements known to be key components of biodegradative enzymes.

  13. Isotopic effects in the neon fixed point: uncertainty of the calibration data correction

    Science.gov (United States)

    Steur, Peter P. M.; Pavese, Franco; Fellmuth, Bernd; Hermier, Yves; Hill, Kenneth D.; Seog Kim, Jin; Lipinski, Leszek; Nagao, Keisuke; Nakano, Tohru; Peruzzi, Andrea; Sparasci, Fernando; Szmyrka-Grzebyk, Anna; Tamura, Osamu; Tew, Weston L.; Valkiers, Staf; van Geel, Jan

    2015-02-01

    The neon triple point is one of the defining fixed points of the International Temperature Scale of 1990 (ITS-90). Although recognizing that natural neon is a mixture of isotopes, the ITS-90 definition only states that the neon should be of ‘natural isotopic composition’, without any further requirements. A preliminary study in 2005 indicated that most of the observed variability in the realized neon triple point temperatures within a range of about 0.5 mK can be attributed to the variability in isotopic composition among different samples of ‘natural’ neon. Based on the results of an International Project (EUROMET Project No. 770), the Consultative Committee for Thermometry decided to improve the realization of the neon fixed point by assigning the ITS-90 temperature value 24.5561 K to neon with the isotopic composition recommended by IUPAC, accompanied by a quadratic equation to take the deviations from the reference composition into account. In this paper, the uncertainties of the equation are discussed and an uncertainty budget is presented. The resulting standard uncertainty due to the isotopic effect (k = 1) after correction of the calibration data is reduced to (4 to 40) μK when using neon of ‘natural’ isotopic composition or to 30 μK when using 20Ne. For comparison, an uncertainty component of 0.15 mK should be included in the uncertainty budget for the neon triple point if the isotopic composition is unknown, i.e. whenever the correction cannot be applied.

  14. Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

    Science.gov (United States)

    Green, Christopher T.; Böhlke, John Karl; Bekins, Barbara A.; Phillips, Steven P.

    2010-01-01

    Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field‐scale (apparent) estimated reaction rates and isotopic fractionations and local‐scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample‐based estimates of “apparent” parameters with “true“ (intrinsic) values. For this aquifer, non‐Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport.

  15. A Distinct Magnetic Isotope Effect Measured in Atmospheric Mercury in Epiphytes

    Science.gov (United States)

    Ghosh, S.; Odom, A. L.

    2007-12-01

    Due to the importance of Mercury as an environmental contaminant, mercury cycling in the atmosphere has been extensively studied. However, there still remain uncertainties in the relative amounts of natural and anthropogenic emissions, atmospheric deposition rates as well as the spatial variation of atmospheric mercury. Part of a study to determine the isotopic composition of mercury deposited from the atmosphere has involved the use of epiphytes as monitors. The greatest advantage of such natural monitors is that a widespread, high-density network is possible at low cost. One of the disadvantages at present is that these monitors likely contain different mercury species (for example both gaseous, elemental mercury trapped by adsorption and Hg (II) by wet deposition). The project began with the understanding that biochemical reactions involving metallothioneins within the epiphytes might have produced an isotopic effect. One such regional network was composed of samples of Tillandsia usenoides (common name: Spanish moss) collected along the eastern Coastal Plain of the U.S. from northern Florida to North Carolina. The isotopic composition of a sample is expressed as permil deviations from a standard. The deviations are defined as δAHg = \\left(\\frac{Rsample}{Rstd}-1 \\right)1000 ‰ , where A represents the atomic mass number. R=\\frac{AHg}{202Hg} were measured for the isotopes 198Hg, 199Hg, 200Hg, 201Hg, 202Hg and 204Hg relative to the mercury standard SRM NIST 3133, by a standard-sample bracketing technique. For all samples, the delta values of the even-N plotted against atomic mass numbers define a linear curve. For the odd-N isotopes, δ199Hg and δ201Hg deviate from this mass-dependent fractionation (MDF) relationship and indicate a mass-independent fractionation (MIF) effect and a negative anomaly, i.e. a depletion in 199Hg and 201Hg relative to the even-N isotopes. These deviations are expressed as Δ199Hg = δ199Hgtotal - δ199HgMDF. A Δ201Hg/Δ199Hg

  16. Isotopic and spin-nuclear effects in solid hydrogens (Review Article)

    Science.gov (United States)

    Freiman, Yuri A.; Crespo, Yanier

    2017-12-01

    The multiple isotopic family of hydrogens (H2, HD, D2, HT, DT, T2) due to large differences in the de Boer quantum parameter and inertia moments displays a diversity of pronounced quantum isotopic solid-state effects. The homonuclear members of this family (H2, D2, T2) due to the permutation symmetry are subjects of the constraints of quantum mechanics which link the possible rotational states of these molecules to their total nuclear spin giving rise to the existence of two spin-nuclear modifications, ortho- and parahydrogens, possessing substantially different properties. Consequently, hydrogen solids present an unique opportunity for studying both isotope and spin-nuclear effects. The rotational spectra of heteronuclear hydrogens (HD, HT, DT) are free from limitations imposed by the permutation symmetry. As a result, the ground state of these species in solid state is virtually degenerate. The most dramatic consequence of this fact is an effect similar to the Pomeranchuk effect in 3He which in the case of the solid heteronuclear hydrogens manifests itself as the reentrant broken symmetry phase transitions. In this review article we discuss thermodynamic and kinetic effects pertaining to different isotopic and spin-nuclear species, as well as problems that still remain to be solved.

  17. Effect of volume loading with water, normal saline, palm wine and ...

    African Journals Online (AJOL)

    A comparative study of the diuretic effect of water, normal saline, palm wine and Lipton tea was carried out on forty (40) randomly selected, apparently normal undergraduate students of Medicine and Pharmacy at the University of Uyo, Nigeria. One and a half (1.5) litres of water, normal saline, palm wine and Lipton tea were ...

  18. Memory Effects Study of Measuring Radioactive Xenon Isotopes With β-γ Coincidence Method

    International Nuclear Information System (INIS)

    Jia Huaimao; Wang Shilian; Wang Jun; Li Qi; Zhao Yungang; Fan Yuanqing; Zhang Xinjun

    2010-01-01

    The β-γ coincidence technique is a kind of the key important method to detect radioactive xenon isotopes for the Comprehensive Nuclear-Test-Ban Treaty (CTBT). This paper describes noble gases memory effects of β-γ coincidence detector. Xenon memory effects were measured and its influence on detector's minimum detectable activity (MDA) was evaluated. The methods of reducing xenon memory effects were studied. In conclusion, aluminium coated plastic scintillator and YAP scintillator can remarkably decrease xenon memory effects. (authors)

  19. Study on the Effect of the Separating Unit Optimization on the Economy of Stable Isotope Separation

    Directory of Open Access Journals (Sweden)

    YANG Kun

    2015-01-01

    Full Text Available An economic criterion called as yearly net profit of single separating unit (YNPSSU was presented to evaluate the influence of structure optimization on the economy. Using YNPSSU as a criterion, economic analysis was carried out for the structure optimization of separating unit in the case of separating SiF4 to obtain the 28Si and 29Si isotope. YNPSSU was calculated and compared with that before optimization. The results showed that YNPSSU was increased by 12.3% by the structure optimization. Therefore, the structure optimization could increase the economy of the stable isotope separation effectively.

  20. Effect of Different Carbon Substrates on Nitrate Stable Isotope Fractionation During Microbial Denitrification

    DEFF Research Database (Denmark)

    Wunderlich, Anja; Meckenstock, Rainer; Einsiedl, Florian

    2012-01-01

    -labeled water and 18O-labeled nitrite were added to the microcosm experiments to study the effect of putative backward reactions of nitrite to nitrate on the stable isotope fractionation. We found no evidence for a reverse reaction. Significant variations of the stable isotope enrichment factor ε were observed......In batch experiments, we studied the isotope fractionation in N and O of dissolved nitrate during dentrification. Denitrifying strains Thauera aromatica and “Aromatoleum aromaticum strain EbN1” were grown under strictly anaerobic conditions with acetate, benzoate, and toluene as carbon sources. 18O...... of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification....

  1. Kinetic isotope effect studies of the S-adenosylmethionine synthetase reaction

    International Nuclear Information System (INIS)

    Markham, G.D.; Parkin, D.W.; Schramm, V.L.

    1986-01-01

    S-adenosylmethionine (AdoMet) synthetase catalyzes a unique substitution reaction at the 5' carbon of MgATP. Kinetic isotope effect (V/K) measurements have been used to investigate the mechanism of AdoMet synthetase from E. coli. Changes in 3 H/ 14 C ratios when AdoMet is formed from a mixture of either ([5'- 14 C]ATP and [5'- 12 C,1'- 3 H]ATP) or ([5'- 3 H]ATP and [5'- 1 H,1'- 14 C]ATP) were examined. The effects of varying the concentrations of the co-substrate methionine and the monovalent cation activator K + were investigated. Substitution of 14 C for 12 C at the 5' position of ATP yields a primary V/K kinetic isotope effect ( 12 C/ 14 C) of 1.128 +/- 0.004 at low K + and methionine concentrations. The observed isotope effect diminishes slightly to 1.107 +/- 0.003 when both K + and methionine are present at saturating concentrations, suggesting that MgATP has only a low commitment to catalysis from at conditions near Vmax. No secondary V/K 3 H isotope effect from [5'- 3 H]ATP was detected ( 1 H/ 3 H) = 0.997 +/- 0.003. The magnitude of the primary 14 C isotope effect and the small secondary 3 H effect demonstrate that AdoMet synthesis occurs with a S/sub N/ 2 transition state which is symmetric with respect to the sulfur nucleophile and the departing tripolyphosphate group

  2. Effect of Calcium Oxide Microstructure on the Diffusion of Isotopes

    CERN Document Server

    Fernandes Ramos, João Pedro; Stora, T

    2012-01-01

    Calcium oxide (CaO) powder targets have been successfully used at CERN-ISOLDE to produce neutron deficient exotic argon and carbon isotopes under proton irradiation at high temperatures (>1000°C). These targets outperform the other related targets for the production of the same beams. However, they presented either slow release rates (yields) from the beginning or a rapid decrease over time. This problem was believed to come from the target microstructure degradation, justifying the material investigation. In order to do so, the synthesis, reactivity in ambient air and sintering kinetics of CaO were studied, through surface area determination by N2 adsorption, X-ray diffraction for crystalline phase identification and crystallite size determination, and scanning and transmission electron microscopy to investigate the microstructure. The synthesis studies revealed that a nanometric material is obtained from the decarbonation of CaCO3 in vacuum at temperatures higher than 550°C, which is very reactive in air....

  3. 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)

  4. Fine print in isotope effects: the glucose anomeric equilibrium and binding of glucose to human brain hexokinase

    International Nuclear Information System (INIS)

    Lewis, B.E; Schramm, V.L.

    2002-01-01

    Binding isotope effects are a sensitive measure of changes in molecular vibrational character that occur during ligand-receptor binding. In this study, we have measured isotope effects on the binding of glucose to human brain hexokinase using the ultrafiltration method, with the following results: 0.991±0.001, 0.908±0.003, 1.010±0.001, 0.974±0.002, 1.022±0.002 for [ 14 C]-glucose mixed with [1- 3 H]-, [2- 3 H]-, [3- 3 H]-, [5- 3 H]-, [6,6- 3 H]-glucose, respectively. Comparing the observed data with isotope effects on the anomeric equilibrium in glucose reported previously proves the existence of binding isotope effects in this system. Preliminary computational results are presented to explain the observed binding isotope effects in terms of hydrogen bond patterns and molecular crowding found in the binary complex of sugar and enzyme. (author)

  5. 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

  6. Studies on the magnetic after-effect of hydrogen isotopes in hexagonal crystals

    International Nuclear Information System (INIS)

    Herbst, G.

    1979-01-01

    The behaviour of hydrogen isotopes in hexagonal gadolinium, in intermetallic compounds of the RECo 5 type (RE = rare earth metal), and in cobalt alloys with small concentrations of alloyed impurity atoms was studied using the magnetic after-effect method in the temperature range between 4.2 K and 300 K. (orig./WBU) [de

  7. 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.

  8. Kinetic isotope effect in the reaction of dehydration of fructose into 5-hydroxymethylfurfural

    International Nuclear Information System (INIS)

    Grin', S.A.; Tsimbaliev, S.R.; Gel'fand, S.Yu.

    1993-01-01

    Kinetic isotopic effect in the reaction of fructose dehydration into 5- hydroxymethylfurfural was determined. The results suggest hydrogen participation in the limiting stage of the process. The assumption that proton addition to 4, 5, 6 -trihydroxy - 2- on - hexal is the limiting stage is made

  9. A new cascade method for studying isotope effect in chemical exchange system without valance change

    International Nuclear Information System (INIS)

    Wen Xiaoning; Luo Wenzong

    1987-01-01

    A new cascade method for studying isotope effect in chemical exchange system without valance change is developed and described. This method is simple to use and consumes less extractant as compared with the commonly used Woodward method. It is also convenient for unstable systems

  10. Kinetic mechanism and isotope effects of Pseudomonas cepacia 3-hydroxybenzoate-t-hydroxylase

    International Nuclear Information System (INIS)

    Wang, L.H.; Yu, Y.; Hamzah, R.Y.; Tu, S.C.

    1986-01-01

    The kinetic mechanism of Pseudomonas cepacia 3-hydroxybenzoate-6-hydroxylase has been delineated. Double reciprocal plots of initial rate versus m-hydroxybenzoate concentration at a constant level of oxygen and several fixed concentrations of NADH yielded a set of converging lines. Similar reciprocal plots of velocity versus NADH concentration at a constant oxygen level and several fixed m-hydroxybenzoate concentrations also showed converging lines. In contrast, double reciprocal plots of initial rate versus NADH concentration at a fixed m-hydroxybenzoate level and several oxygen concentrations showed a series of parallel lines. Parallel lines were also obtained from double reciprocal plots of initial rate versus m-hydroxybenzoate concentration at a fixed NADH level and varying oxygen concentrations. These results suggest a sequential binding of m-hydroxybenzoate and NADH by the hydroxylase. The enzyme-bound FAD is reduced and NAD is released. The reduced enzyme subsequently reacts with oxygen leading to the formation of other products. This hydroxylase exhibited a primary isotope effect of /sup D/V = 3.5 for (4R)-[4- 2 H] NADH but no isotope effect was observed with (4S)-[4- 2 H]NADH. An isotope effect of /sup T/V/K = 5.0 was also observed using (4R)-[4- 3 H]NADH. This tritium isotope effect was apparently independent of m-hydroxybenzoate concentration

  11. Stable isotope enrichment in laboratory ant colonies: effects of colony age, metamorphosis, diet, and fat storage

    Science.gov (United States)

    Ecologists use stable isotopes to infer diets and trophic levels of animals in food webs, yet some assumptions underlying these inferences have not been thoroughly tested. We used laboratory-reared colonies of Solenopsis invicta Buren (Formicidae: Solenopsidini) to test the effects of metamorphosis,...

  12. Calcium isotope effects in ion exchange electromigration and calcium isotope analysis by thermo-ionization mass spectrometry

    International Nuclear Information System (INIS)

    Fujii, Y.; Hoshi, J.; Iwamoto, H.; Okamoto, M.; Kakihana, H.

    1985-01-01

    Calcium ions were made to electromigrate along a cation exchange membrane. The abundance ratios of the calcium isotopes (Ca-40, 42, 43, 44, 48) in the migrated bands were measured by thermo-ionization mass spectrometry. The lighter isotopes were enriched in the front part of the migrated band. The increments in the isotope abundance ratios were found to be proportional to the mass difference of the isotopes. The observed epsilon-values per unit mass difference (epsilon/ΔM) were 1.26 x 10 -4 (at 20 0 C), 1.85 x 10 -4 (at 25 0 C) and 2.4 x 10 -4 (at 40 0 C). The mass spectrometry was improved by using a low temperature for the evaporation of CaI 2 . (orig.)

  13. Mechanistic Insights into Dye-Decolorizing Peroxidase Revealed by Solvent Isotope and Viscosity Effects

    Energy Technology Data Exchange (ETDEWEB)

    Shrestha, Ruben [Department; Huang, Gaochao [Department; Meekins, David A. [Department; Geisbrecht, Brian V. [Department; Li, Ping [Department

    2017-08-18

    Dye-decolorizing peroxidases (DyPs) are a family of H2O2-dependent heme peroxidases that have shown potential applications in lignin degradation and valorization. However, the DyP kinetic mechanism remains underexplored. Using structural biology and solvent isotope (sKIE) and viscosity effects, many mechanistic characteristics have been determined for the B-class ElDyP from Enterobacter lignolyticus. Its structure revealed that a water molecule acts as the sixth axial ligand and two channels at diameters of ~3.0 and 8.0 Å lead to the heme center. A conformational change of ERS* to ERS, which have identical spectral characteristics, was proposed as the final step in DyPs’ bisubstrate Ping-Pong mechanism. This step is also the rate-determining step in ABTS oxidation. The normal KIE of wild-type ElDyP with D2O2 at pD 3.5 suggested that compound 0 deprotonation by the distal aspartate is rate-limiting in the formation of compound I, which is more reactive under acidic pH than under neutral or alkaline pH. The viscosity effects and other biochemical methods implied that the reducing substrate binds with compound I instead of the free enzyme. The significant inverse sKIEs of kcat/KM and kERS* suggested that the aquo release in ElDyP is mechanistically important and may explain the enzyme’s adoption of two-electron reduction for compound I. The distal aspartate is catalytically more important than the distal arginine and plays key roles in determining ElDyP’s optimum acidic pH. The kinetic mechanism of D143H-ElDyP was also briefly studied. The results obtained will pave the way for future protein engineering to improve DyPs’ lignolytic activity.

  14. Ca isotopes in refractory inclusions

    International Nuclear Information System (INIS)

    Niederer, F.R.; Papanastassiou, D.A.

    1984-01-01

    We report measurements of the absolute isotope abundance of Ca in Ca-Al-rich inclusions from the Allende and Leoville meteorites. Improved high precision measurements are reported also for 46 Ca. We find that nonlinear isotope effects in Ca are extremely rare in these inclusions. The absence of nonlinear effects in Ca, except for the effects in FUN inclusions, is in sharp contrast to the endemic effects in Ti. One fine-grained inclusion shows an excess of 46 Ca of (7 +- 1) per mille, which is consistent with addition of only 46 Ca or of an exotic (*) component with 46 Ca* approx. 48 Ca*. FUN inclusion EK-1-4-1 shows a small 46 Ca excess of (3.3 +- 1.0) per mille; this confirms that the exotic Ca components in EK-1-4-1 were even more deficient in 46 Ca relative to 48 Ca than is the case for normal Ca. The Ca in the Ca-Al-rich inclusions shows mass dependent isotope fractionation effects which have a range from -3.8 to +6.7 per mille per mass unit difference. This range is a factor of 20 wider than the range previously established for bulk meteorites and for terrestrial and lunar samples. Ca and Mg isotope fractionation effects in the Ca-Al-rich inclusions are common and attributed to kinetic isotope effects. (author)

  15. Normal mere exposure effect with impaired recognition in Alzheimer's disease.

    Science.gov (United States)

    Willems, Sylvie; Adam, Stéphane; Van der Linden, Martial

    2002-02-01

    We investigated the mere exposure effect and the explicit memory in Alzheimer's disease (AD) patients and elderly control subjects, using unfamiliar faces. During the exposure phase, the subjects estimated the age of briefly flashed faces. The mere exposure effect was examined by presenting pairs of faces (old and new) and asking participants to select the face they liked. The participants were then presented with a forced-choice explicit recognition task. Controls subjects exhibited above-chance preference and recognition scores for old faces. The AD patients also showed the mere exposure effect but no explicit recognition. These results suggest that the processes involved in the mere exposure effect are preserved in AD patients despite their impaired explicit recognition. The results are discussed in terms of Seamon et al.'s (1995) proposal that processes involved in the mere exposure effect are equivalent to those subserving perceptual priming. These processes would depend on extrastriate areas which are relatively preserved in AD patients.

  16. Isotope puzzle in sputtering

    International Nuclear Information System (INIS)

    Zheng Liping

    1998-01-01

    Mechanisms affecting multicomponent material sputtering are complex. Isotope sputtering is the simplest in the multicomponent materials sputtering. Although only mass effect plays a dominant role in the isotope sputtering, there is still an isotope puzzle in sputtering by ion bombardment. The major arguments are as follows: (1) At the zero fluence, is the isotope enrichment ejection-angle-independent or ejection-angle-dependent? (2) Is the isotope angular effect the primary or the secondary sputter effect? (3) How to understand the action of momentum asymmetry in collision cascade on the isotope sputtering?

  17. An unusual isotope effect in a high-transition-temperature superconductor

    International Nuclear Information System (INIS)

    Gweon, G.-H.; Sasagawa, T.; Zhou, S.Y.; Graf, J.; Takagi, H.; Lee, D.-H.; Lanzara, A.

    2004-01-01

    In conventional superconductors, the electron pairing that allows superconductivity is caused by exchange of virtual phonons, which are quanta of lattice vibration. For high-transition-temperature (high-Tc) superconductors, it is far from clear that phonons are involved in the pairing at all. For example, the negligible change in Tc of optimally doped Bi2Sr2CaCu2O8 (Bi2212) upon oxygen isotope substitution (16O to 18O leads to Tc decreasing from 92 to 91 K) has often been taken to mean that phonons play an insignificant role in this material. Here we provide a detailed comparison of the electron dynamics of Bi2212 samples containing different oxygen isotopes, using angle-resolved photoemission spectroscopy. Our data show definite and strong isotope effects. Surprisingly, the effects mainly appear in broad high-energy humps, commonly referred to as ''incoherent peaks''. As a function of temperature and electron momentum, the magnitude of the isotope effect closely correlates with the superconducting gap--that is, the pair binding energy. We suggest that these results can be explained in a dynamic spin-Peierls picture, where the singlet pairing of electrons and the electron-lattice coupling mutually enhance each other

  18. 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)

  19. 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.

  20. the effect of ascorbic acid and propranolol on normal sleep

    African Journals Online (AJOL)

    sleep promoting effects in the wistar rats in doses of propranolol. Conclusion: It is possible ... motor activities as swimming, flying, walking, running, rearing and hopping etc. ..... The Homotypical Cortex - The ssociation Areas. Physiological and ...

  1. Normal mere exposure effect with impaired recognition in Alzheimer's disease

    OpenAIRE

    Willems, Sylvie; Adam, Stéphane; Van der Linden, Martial

    2002-01-01

    We investigated the mere exposure effect and the explicit memory in Alzheimer's disease (AD) patients and elderly control subjects, using unfamiliar faces. During the exposure phase, the subjects estimated the age of briefly flashed faces. The mere exposure effect was examined by presenting pairs of faces (old and new) and asking participants to select the face they liked. The participants were then presented with a forced-choice explicit recognition task. Controls subjects exhibited above-ch...

  2. Mass balance and isotope effects during nitrogen transport through septic tank systems with packed-bed (sand) filters

    Science.gov (United States)

    Hinkle, S.R.; Böhlke, J.K.; Fisher, L.H.

    2008-01-01

    Septic tank systems are an important source of NO3- to many aquifers, yet characterization of N mass balance and isotope systematics following septic tank effluent discharge into unsaturated sediments has received limited attention. In this study, samples of septic tank effluent before and after transport through single-pass packed-bed filters (sand filters) were evaluated to elucidate mass balance and isotope effects associated with septic tank effluent discharge to unsaturated sediments. Chemical and isotopic data from five newly installed pairs and ten established pairs of septic tanks and packed-bed filters serving single homes in Oregon indicate that aqueous solute concentrations are affected by variations in recharge (precipitation, evapotranspiration), NH4+ sorption (primarily in immature systems), nitrification, and gaseous N loss via NH3 volatilization and(or) N2 or N2O release during nitrification/denitrification. Substantial NH4+ sorption capacity was also observed in laboratory columns with synthetic effluent. Septic tank effluent ??15N-NH4+ values were almost constant and averaged + 4.9??? ?? 0.4??? (1 ??). In contrast, ??15N values of NO3- leaving mature packed-bed filters were variable (+ 0.8 to + 14.4???) and averaged + 7.2??? ?? 2.6???. Net N loss in the two networks of packed-bed filters was indicated by average 10-30% decreases in Cl--normalized N concentrations and 2-3??? increases in ??15N, consistent with fractionation accompanying gaseous N losses and corroborating established links between septic tank effluent and NO3- in a local, shallow aquifer. Values of ??18O-NO3- leaving mature packed-bed filters ranged from - 10.2 to - 2.3??? (mean - 6.4??? ?? 1.8???), and were intermediate between a 2/3 H2O-O + 1/3 O2-O conceptualization and a 100% H2O-O conceptualization of ??18O-NO3- generation during nitrification.

  3. The effects of normal paraffins mobilizers on irradiated polypropylene

    International Nuclear Information System (INIS)

    Chen Wenxiu; Gao Ling

    1995-01-01

    The n-paraffins blended with polypropylene (PP) as mobilizer had been investigated. The effectiveness of mobilizer (n-paraffins) on irradiated polypropylene is dependent on the molecular weight of mobilizer and its content on polypropylene. The n-docosame (n-C 22 ) possesses the best effectiveness of radiation tolerance on PP among the mobilizer paraffins: n-decane (n-C 10 ), n-hexadecane (n-C 16 ), n-docosane (n-C 22 ) and n-hexatriacontane (n-C 36 ). The 2% (w/w) content of a given mobilizer is the most effective at reducing the embrittlement of irradiated PP as evidenced by the elongation at break. The physical properties of polypropylene with mobilizers such as density, Young's modulus, the Fraction of free volume and the weight swelling ratio in p-xylene at room temperature were measured. Above phenomena are related with the constructive of blended PP and demonstrated by its physical properties

  4. Excitation functions and isotopic effects in (n, p) reactions for stable nickel isotopes from reaction threshold to 20 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Lalremruata, B. [Department of Physics, University of Pune, Ganeshkhind, Pune-411007, Maharashtra (India)], E-mail: marema@physics.unipune.ernet.in; Ganesan, S. [Reactor Physics Design Division, BARC, Mumbai 58 (India); Bhoraskar, V.N. [Department of Physics, University of Pune, Ganeshkhind, Pune-411007, Maharashtra (India)], E-mail: vnb@physics.unipune.ernet; Dhole, S.D. [Department of Physics, University of Pune, Ganeshkhind, Pune-411007, Maharashtra (India)], E-mail: sanjay@physics.unipune.ernet.in

    2009-05-01

    The excitation function for (n, p) reactions from reaction threshold to 20 MeV on five nickel isotopes viz; {sup 58}Ni, {sup 60}Ni, {sup 61}Ni, {sup 62}Ni and {sup 64}Ni were calculated using Talys-1.0 nuclear model code involving the fixed set of global parameters. A good agreement between the calculated and measured data is obtained with minimum effort on parameter fitting and only one free parameter called 'Shell damping factor'. This is of importance to the validation of nuclear model approaches with increased predictive power. The systematic decrease in (n, p) cross-sections with increasing neutron number in reactions induced by neutrons on isotopes of nickel is explained in terms of the proton separation energy and the pre-equilibrium model. The compound nucleus and pre-equilibrium reaction mechanism as well as the isotopic effects were also studied.

  5. Combined effects of radiotherapy and chemotherapy normal tissue, 1

    International Nuclear Information System (INIS)

    Watanabe, Noriaki

    1983-01-01

    The combined effects of radiation and drugs on the fine vasculature of mouse liver were investigated by microangiography. The fine vasculature of the liver showed dilatations one day after 1000 rad of irradiation to the liver. The fine vasculature of the liver showed marked dilatations and slight extravasations one day after 1000 rad of irradiation to the whole body. The fine vasculature of the liver showed dilatations and partial narrowings after the administration of BLM, 2mg/kg/day ip for 5 days. The combined effects of BLM and radiation was greater than that with radiation alone. The fine vasculature of the liver showed marked dilatations and slight extravasation after the administration of BLM, 2mg/kg/day ip for 5 days and MMC 2mg/kg ip on day 6. This findings is about the same as that after the administration of BLM and 1000 rad of irradiation. The administration of urokinase did not diminish the effects of radiation on the fine vasculature of the liver. The administration of YM-08310 diminished the effects of irradiation on the fine vasculature of the liver. (author)

  6. Isotope effect of optical activity measurements on L-α-alanine

    International Nuclear Information System (INIS)

    Darge, W.; Laczko, I.; Thiemann, W.

    1976-01-01

    If an optically active organic substance is labelled in the chirality center with another isotopic species (such as 15 N for 14 N) a pronounced variation of rotatory power is predicted. It was tried to varify this idea experimentally on L-α-alanine and found an isotope effect in ORD (optical rotatory dispersion). The magnitude of the rotation is mainly dependent on the pH of the solvent. The ratio of the optical activity alanine- 14 N/alanine- 15 N is about 1.02. It can be seen that the ratios of the molecular rotations are consistently lower than the corresponding ratios of the specific rotations. This is of course due to the fact that the molecular mass 15 M is larger than 14 M. This means tthat the mass difference is already taken into account so that the ratio of the molecular rotations could be defined as the ''net'' isotope effect in the ORDs of 15 N-substitued alanine. From the fact the ORD is different for the isotope-substitued alanine, one can reasonably assume that the absorption coefficient is also different. This leads to speculations about certain problems in the chemical evolution of the biosphere, such as the origin of optical activity. (T.G.)

  7. Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

    Energy Technology Data Exchange (ETDEWEB)

    Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joël [Laboratoire de Glaciologie et Géophysique de l’Environnement, CNRS, F-38041 Grenoble (France); Univ. Grenoble Alpes, LGGE, F-38041 Grenoble (France); Meusinger, Carl; Johnson, Matthew S. [Copenhagen Center for Atmospheric Research (CCAR), Department of Chemistry, University of Copenhagen, Copenhagen (Denmark); Jost, Rémy [Laboratoire de Interdisciplinaire de Physique (LIPHY) Univ. de Grenoble, Grenoble (France); Bhattacharya, S. K. [Research Center for Environmental Changes, Academia Sinica, Nangang, Taipei 115, Taiwan (China)

    2014-06-28

    Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. [“Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry,” J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ({sup 15}N, {sup 17}O, and {sup 18}O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ{sup 15}N, δ{sup 18}O, and Δ{sup 17}O). From these measurements an average photolytic isotopic fractionation of {sup 15}ε = (−15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of {sup 15}ε = (−47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from −40 to −74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of {sup 14}NO{sub 3}{sup −} and {sup 15}NO{sub 3}{sup −} in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying

  8. Preliminary Failure Modes, Effects and Criticality Analysis (FMECA) of the conceptual Brayton Isotope Power System (BIPS) Flight System

    International Nuclear Information System (INIS)

    Miller, L.G.

    1976-01-01

    A failure modes, effects and criticality analysis (FMECA) was made of the Brayton Isotope Power System Flight System (BIPS-FS) as presently conceived. The components analyzed include: Mini-BRU; Heat Source Assembly (HSA); Mini-Brayton Recuperator (MBR); Space Radiator; Ducts and Bellows, Insulation System; Controls; and Isotope Heat Source (IHS)

  9. Using Beads and Divided Containers to Study Kinetic and Equilibrium Isotope Effects in the Laboratory and in the Classroom

    Science.gov (United States)

    Campbell, Dean J.; Brewer, Emily R.; Martinez, Keri A.; Fitzjarrald, Tamara J.

    2017-01-01

    The purpose of this laboratory experiment is to study fundamental concepts of kinetics and equilibria and the isotope effects associated with both of these concepts. The concepts of isotopes in introductory and general chemistry courses are typically used within the contexts of atomic weights and radioactivity. Kinetic and equilibrium isotope…

  10. 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

  11. Large effect of irradiance on hydrogen isotope fractionation of alkenones in Emiliania huxleyi

    Science.gov (United States)

    van der Meer, Marcel T. J.; Benthien, Albert; French, Katherine L.; Epping, Eric; Zondervan, Ingrid; Reichart, Gert-Jan; Bijma, Jelle; Sinninghe Damsté, Jaap S.; Schouten, Stefan

    2015-07-01

    The hydrogen isotopic (δD) composition of long-chain alkenones produced by certain haptophyte algae has been suggested as a potential proxy for reconstructing paleo sea surface salinity. However, environmental parameters other than salinity may also affect the δD of alkenones. We investigated the impact of the level of irradiance on hydrogen isotopic fractionation of alkenones versus growth water by cultivating two strains of the cosmopolitan haptophyte Emiliania huxleyi at different light intensities. The hydrogen isotope fractionation decreased by approximately 40‰ when irradiance was increased from 15 to 200 μmol photons m-2 s-1 above which it was relatively constant. The response is likely a direct effect of photosystem I and II activity as the relationship of the fractionation factor α versus light intensity can be described by an Eilers-Peeters photosynthesis model. This irradiance effect is in agreement with published δD data of alkenones derived from suspended particulate matter collected from different depths in the photic zone of the Gulf of California and the eastern tropical North Pacific. However, haptophyte algae tend to bloom at relatively high light intensities (>500 μmol photons m-2 s-1) occurring at the sea surface, at which hydrogen isotope fractionation is relatively constant and not affected by changes in light intensity. Alkenones accumulating in the sediment are likely mostly derived from these surface water haptophyte blooms, when the largest amount of biomass is produced. Therefore, the observed irradiance effect is unlikely to affect the applicability of the hydrogen isotopic composition of sedimentary long chain alkenones as a proxy for paleosalinity.

  12. Solvent isotope effects upon the thermodynamics of some transition-metal redox couples in aqueous media

    International Nuclear Information System (INIS)

    Weaver, M.J.; Nettles, S.M.

    1980-01-01

    The effects of substituting D 2 O for H 2 O as solvent upon the formal potentials of a number of transition-metal redox couples containing aquo, ammine, and simple chelating ligands have been investigated with the intention of evaluating the importance of specific solvation factors in the thermodynamics of such couples. The solvent liquid junction formed between H 2 O and D 2 O was shown to have a negligible effect on the measured formal potentials. Substantial solvent isotope effects were observed for a number of these systems, particularly for couples containing aquo ligands. The effects of separately deuterating the ligands and the surrounding solvent were investigated for some ammine couples. Possible origins of the solvent isotope effects are discussed in terms of changes in metal-ligand and ligand-solvent interactions. It is tentatively concluded that the latter influence provides the predominant contribution to the observed effects for aquo couples arising from increases in the extent of hydrogen bonding between the aquo ligands and surrounding solvent when D 2 O replaces H 2 O. The implications of these results in unraveling the solvent isotope effects upon the kinetics of simple redox reactions are also considered

  13. Cardiovascular, endocrine and renal effects of urodilatin in normal humans

    DEFF Research Database (Denmark)

    Bestle, M.H.; Olsen, N.V.; Christensen, P.

    1999-01-01

    remained below 0.1%. The results indicate that even moderately natriuretic doses of urodilatin exert protracted effects on systemic hemodynamic, endocrine, and renal functions, including decreases in cardiac output and renal blood flow, without changes in arterial pressure or glomerular filtration rate...... highest doses. The renin-angiotensin-aldosterone system was inhibited by the three lowest doses but activated by the hypotensive dose of 40 ng. kg-1. min-1. Plasma vasopressin increased by factors of up to 5 during infusion of the three highest doses. Atrial natriuretic peptide immunoreactivity (including...

  14. The Effects of Internal Waves on Acoustic Normal Modes.

    Science.gov (United States)

    1984-12-01

    thatp HTp HTv + CvS(!!)(..)(25 The hydrodynamic equations appropriate to an ocean are Du p b + p(fxuL) + Vp - = V-A + F (2.6a) Do + pv.u 0(2.6b) pT Ln+ V...Payne, "User’s Manual for NEMESIS and PLMODE," Applied Research Laboratories Technical Memorandum No. 80-6 . (ARL-TM-80-6), Applied Research Laboratories...1, 6th edition, Reference Manual , 1979. 56. 3. Turner, Buoyancy Effects in Fluids (Cambridqe University Press, Cambridge, London, 1972) Chap. 8. 57. W

  15. Dissolution rates of unirradiated UO2, UO2 doped with 233U, and spent fuel under normal atmospheric conditions and under reducing conditions using an isotope dilution method

    International Nuclear Information System (INIS)

    Ollila, Kaija; Albinsson, Yngve; Oversby, Virginia; Cowper, Mark

    2003-10-01

    The experimental results given in this report allow us to draw the following conclusions. 1) Tests using unirradiated fuel pellet materials from two different manufacturers gave very different dissolution rates under air atmosphere testing. Tests for fragments of pellets from different pellets made by the same manufacturer gave good agreement. This indicates that details of the manufacturing process have a large effect on the behavior of unirradiated UO 2 in dissolution experiments. Care must be taken in interpreting differences in results obtained in different laboratories because the results may be affected by manufacturing effects. 2) Long-term tests under air atmosphere have begun to show the effects of precipitation. Further testing will be needed before the samples reach steady state. 3) Testing of unirradiated UO 2 in systems containing an iron strip to produce reducing conditions gave [U] less than detection limits ( 235 U added as spike was recovered, indicating that 90% of the spike had precipitated onto the solid sample or the iron strip. 9) Tests of UO 2 pellet materials containing 233 U to provide an alpha decay activity similar to that expected for spent fuel 3000 and 10,000 years after disposal showed that the pellet materials behaved as expected under air atmosphere conditions, showing that the manufacturing method was successful. 10) Early testing of the 233 U-doped materials under reducing conditions showed relatively rapid (30 minute) dissolution of small amounts of U at the start of the puff test procedure. Results of analyses of an acidified fraction of the same solutions after 1 or 2 weeks holding indicate that the solutions were inhomogeneous, indicating the presence of colloidal material or small grains of solid. 11) Samples from the 233 U-doped tests initially indicated dissolution of solid during the first week of testing, with some indication of more rapid dissolution of the material with the higher doping. 12) The second cycle of testing

  16. Dose formation and hematologic effects with prolonged internal exposure of rats by isotope 131I

    International Nuclear Information System (INIS)

    Sova, O.A.; Drozd, Yi.P.

    2013-01-01

    Processes in single dose formation and long-term domestic revenue 131 I in rats was investigated. Original method of estimating absorbed doses in hemacyte for macro-dosemeters indicators was proposed. Dose factors for hemacyte and the dynamics of the blood-forming organs doses for prolonged two cases of prolonged exposure was calculated. Hematologic effects were studied for two variants of entry of the isotope. Peculiarities of doses formation and identified hematological effects are discussed

  17. Isotope effect on the zero point energy shift upon condensation. I. Formulation and application to ethylene, methane, and fluoromethanes

    International Nuclear Information System (INIS)

    Kornblum, Z.C.; Ishida, T.

    1978-01-01

    A method of evaluating the isotope effect (IE) on the zero point energy (ZPE) shift upon condensation due to the London dispersion forces in the liquid has been formulated. It is expressed to the first order, as a product of an isotope-independent liquid factor and a factor of isotopic differences in gas-phase properties. The theory has been tested by calculating the effective atomic charges for carbon and hydrogen in ethylene, according to the CNDO/2 molecular orbital algorithm, and it correctly predicts the magnitude of the IE on the ZPE shift and the first-order sum rules involving the isotopic ethylenes. However, it fails to explain the difference in vapor pressures of isotopic isomers. The theory has also been applied to the D/H and to the 13 C/ 12 C isotope effects in methane and fluoromethanes. The results obtained from the CNDO/2 calculations have been compared with the experimental values of the total infrared absorption intensities and of the IE on the ZPE shift of isotopic methanes. Based on these calculations, the molecular properties that enhance the stronger dispersion forces in the liquid phase between the lighter molecules than between the isotopically heavier molecules, and hence favor a large IE on the ZPE shift, have been deduced

  18. Perceptual differentiation and category effects in normal object recognition

    DEFF Research Database (Denmark)

    Gerlach, Christian; Law, I; Gade, A

    1999-01-01

    The purpose of the present PET study was (i) to investigate the neural correlates of object recognition, i.e. the matching of visual forms to memory, and (ii) to test the hypothesis that this process is more difficult for natural objects than for artefacts. This was done by using object decision...... tasks where subjects decided whether pictures represented real objects or non-objects. The object decision tasks differed in their difficulty (the degree of perceptual differentiation needed to perform them) and in the category of the real objects used (natural objects versus artefacts). A clear effect...... be the neural correlate of matching visual forms to memory, and the amount of activation in these regions may correspond to the degree of perceptual differentiation required for recognition to occur. With respect to behaviour, it took significantly longer to make object decisions on natural objects than...

  19. A novel methodology to investigate isotopic biosignatures

    Science.gov (United States)

    Horner, T. J.; Lee, R. B. Y.; Henderson, G. M.; Rickaby, R. E. M.

    2012-04-01

    An enduring goal of trace metal isotopic studies of Earth History is to find isotopic 'fingerprints' of life or of life's individual physiochemical processes. Generally, such signatures are sought by relating an isotopic effect observed in controlled laboratory conditions or a well-characterized environment to a more complex system or the geological record. However, such an approach is ultimately limited because life exerts numerous isotopic fractionations on any one element so it is hard to dissect the resultant net fractionation into its individual components. Further, different organisms, often with the same apparent cellular function, can express different isotopic fractionation factors. We have used a novel method to investigate the isotopic fractionation associated with a single physiological process-enzyme specific isotopic fractionation. We selected Cd isotopes since only one biological use of Cd is known, CdCA (a Cd/Zn carbonic anhydrase from the coastal diatom T. Weissflogii). Thus, our investigation can also inform the long standing mystery as to why this generally toxic element appears to have a nutrient-like dissolved isotopic and concentration profile in the oceans. We used the pET-15b plasmid to insert the CdCA gene into the E. coli genome. There is no known biochemical function for Cd in E. coli, making it an ideal vector for studying distinct physiological processes within a single organism. The uptake of Cd and associated isotopic fractionation was determined for both normal cells and those expressing CdCA. It was found that whole cells always exhibited a preference for the light isotopes of Cd, regardless of the expression of CdCA; adsorption of Cd to cell surfaces was not seen to cause isotopic fractionation. However, the cleaning procedure employed exerted a strong control on the observed isotopic composition of cells. Using existing protein purification techniques, we measured the Cd isotopic composition of different subcellular fractions of E

  20. 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)

  1. First-principles theory of anharmonicity and the inverse isotope effect in superconducting palladium-hydride compounds.

    Science.gov (United States)

    Errea, Ion; Calandra, Matteo; Mauri, Francesco

    2013-10-25

    Palladium hydrides display the largest isotope effect anomaly known in the literature. Replacement of hydrogen with the heavier isotopes leads to higher superconducting temperatures, a behavior inconsistent with harmonic theory. Solving the self-consistent harmonic approximation by a stochastic approach, we obtain the anharmonic free energy, the thermal expansion, and the superconducting properties fully ab initio. We find that the phonon spectra are strongly renormalized by anharmonicity far beyond the perturbative regime. Superconductivity is phonon mediated, but the harmonic approximation largely overestimates the superconducting critical temperatures. We explain the inverse isotope effect, obtaining a -0.38 value for the isotope coefficient in good agreement with experiments, hydrogen anharmonicity being mainly responsible for the isotope anomaly.

  2. Tungsten isotopic compositions of iron meteorites: Chronological constraints vs. cosmogenic effects

    Science.gov (United States)

    Markowski, A.; Quitté, G.; Halliday, A. N.; Kleine, T.

    2006-02-01

    High-precision W isotopic compositions are presented for 35 iron meteorites from 7 magmatic groups (IC, IIAB, IID, IIIAB, IIIF, IVA, and IVB) and 3 non-magmatic groups (IAB, IIICD, and IIE). Small but resolvable isotopic variations are present both within and between iron meteorite groups. Variations in the 182W/ 184W ratio reflect either time intervals of metal-silicate differentiation, or result from the burnout of W isotopes caused by a prolonged exposure to galactic cosmic rays. Calculated apparent time spans for some groups of magmatic iron meteorites correspond to 8.5 ± 2.1 My (IID), 5.1 ± 2.3 My (IIAB), and 5.3 ± 1.3 My (IVB). These time intervals are significantly longer than those predicated from models of planetesimal accretion. It is shown that cosmogenic effects can account for a large part of the W isotopic variation. No simple relationship exists with exposure ages, compromising any reliable method of correction. After allowance for maximum possible cosmogenic effects, it is found that there is no evidence that any of the magmatic iron meteorites studied here have initial W isotopic compositions that differ from those of Allende CAIs [ ɛ182W = - 3.47 ± 0.20; [T. Kleine, K. Mezger, H. Palme, E. Scherer and C. Münker, Early core formation in asteroids and late accretion of chondrite parent bodies: evidence from 182Hf- 182W in CAIs, metal-rich chondrites and iron meteorites, Geochim. Cosmochim. Acta (in press)]. Cosmogenic corrections cannot yet be made with sufficient accuracy to obtain highly precise ages for iron meteorites. Some of the corrected ages nevertheless require extremely early metal-silicate segregation no later than 1 My after formation of CAIs. Therefore, magmatic iron meteorites appear to provide the best examples yet identified of material derived from the first planetesimals that grew by runaway growth, as modelled in dynamic simulations. Non-magmatic iron meteorites have a more radiogenic W isotopic composition than magmatic

  3. Isotope and fast ions turbulence suppression effects: Consequences for high-β ITER plasmas

    Science.gov (United States)

    Garcia, J.; Görler, T.; Jenko, F.

    2018-05-01

    The impact of isotope effects and fast ions on microturbulence is analyzed by means of non-linear gyrokinetic simulations for an ITER hybrid scenario at high beta obtained from previous integrated modelling simulations with simplified assumptions. Simulations show that ITER might work very close to threshold, and in these conditions, significant turbulence suppression is found from DD to DT plasmas. Electromagnetic effects are shown to play an important role in the onset of this isotope effect. Additionally, even external ExB flow shear, which is expected to be low in ITER, has a stronger impact on DT than on DD. The fast ions generated by fusion reactions can additionally reduce turbulence even more although the impact in ITER seems weaker than in present-day tokamaks.

  4. 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).

  5. Isotopic test of capillary permeability to albumin in diabetic patients: effects of hypertension, microangiopathy, and duration of diabetes

    International Nuclear Information System (INIS)

    Valensi, P.; Attali, J.R.; Behar, A.; Sebaoun, J.

    1987-01-01

    Capillary permeability to albumin (CPA) was studied by performing an isotopic noninvasive test with venous compression on 87 nonselected diabetics with no edema, no cardiac failure, and no peripheral vascular disease. Excessive albumin retention (AR greater than or equal to 8%) ten minutes after removal of the compression was found in 27 patients (31%). The radioactivity disappearance curve was then analyzed using the Fast Fourier Transform (FFT). An abnormal isotopic CPA test was thus found in at least 45 out of the 87 patients. The prevalence of an abnormal test was not different in type 1 and type 2 diabetics. We studied the independent effects of hypertension, presence of specific clinical signs of microangiopathy (retinopathy and/or significant proteinuria), and duration of diabetes. Among diabetics free of specific clinical signs of microangiopathy, the prevalence of an AR greater than or equal to 8% was significantly higher in those with hypertension (11/19) than in those with normal blood pressure (2/28) and in nondiabetic hypertensive patients (0/16). Among normotensive diabetics, the prevalence of an abnormal test was higher, but not significantly, in patients with specific clinical signs of microangiopathy (8/11) than in those free of them (7/18). Seven normotensive diabetics without specific clinical signs of microangiopathy had an abnormal test; five of them had had diabetes for more than five years. The prevalence of diabetes of more than five years duration was significantly higher in patients with an abnormal test (35/45) than in normotensive diabetics free of specific clinical signs of microangiopathy with a normal test (4/11)

  6. The Isotopologue Record of Repeat Vital Effect Offenders: Tracking (Dis)equilibrium Effects in Sea Urchins and Nannofossil Using Clumped Isotopes

    Science.gov (United States)

    John, C. M.; Davies, A.; Drury, A. J.

    2016-12-01

    Vital effects vary between species and affect various isotopic systems in unequal proportion. The magnitude of the response of different isotopic systems might thus be key in understanding biologically-mediated disequilibrium, especially in groups that show a tendency to be "repeat offenders" with regards to vital effects. Here we present carbon, oxygen, and clumped isotope data from echinoderm calcite and nannofossil ooze, both of which exhibit strong vital effects in bulk isotopes. Our study is the first to investigate the clumped isotope (dis)equilibrium of echinoids. Results from two echinoids, three marine gastropods and a bivalve mollusk from modern beach deposits of Bali, Indonesia, highlight a significant offset in clumped isotopes of a regular echinoid test from expected values, interpreted as evidence of a similar "vital effect" as observed in surface corals. This is in contrast to the test of an irregular "sand dollar" echinoid, with clumped isotope values within error of expected sea surface temperature. Furthermore, data on the inter-skeletal variability in the clumped isotopic composition of two regular echinoid species shows that the spines of the echinoids are in equilibrium with seawater with respect to clumped isotopes, but the test is not. For the nannofossil material, no clumped isotope vital effects are observed, consistent with previously published studies but at odds with strong vital effects in carbon and oxygen isotopes, often correlated with cell-size. In addition, we reveal that the <63 micron fraction of deep-sea ooze could constitute useful material for clumped isotope studies. An intriguing result of our study is that vital effects are mostly absent in clumped isotopes, even in phylums known for important isotopic effects. It remains to be explained why some parts of the echinoids show clear vital effects, notably enrichment in clumped isotopes of urchin tests. Mechanisms that could explain this include pH effects during calcification

  7. Forward treatment planning techniques to reduce the normalization effect in Gamma Knife radiosurgery.

    Science.gov (United States)

    Cheng, Hao-Wen; Lo, Wei-Lun; Kuo, Chun-Yuan; Su, Yu-Kai; Tsai, Jo-Ting; Lin, Jia-Wei; Wang, Yu-Jen; Pan, David Hung-Chi

    2017-11-01

    In Gamma Knife forward treatment planning, normalization effect may be observed when multiple shots are used for treating large lesions. This effect can reduce the proportion of coverage of high-value isodose lines within targets. The aim of this study was to evaluate the performance of forward treatment planning techniques using the Leksell Gamma Knife for the normalization effect reduction. We adjusted the shot positions and weightings to optimize the dose distribution and reduce the overlap of high-value isodose lines from each shot, thereby mitigating the normalization effect during treatment planning. The new collimation system, Leksell Gamma Knife Perfexion, which contains eight movable sectors, provides an additional means to reduce the normalization effect by using composite shots. We propose different techniques in forward treatment planning that can reduce the normalization effect. Reducing the normalization effect increases the coverage proportion of higher isodose lines within targets, making the high-dose region within targets more uniform and increasing the mean dose to targets. Because of the increase in the mean dose to the target after reducing the normalization effect, we can set the prescribed marginal dose at a higher isodose level and reduce the maximum dose, thereby lowering the risk of complications. © 2017 Shuang Ho Hospital-Taipei Medical University. Journal of Applied Clinical Medical Physics published by Wiley Periodicals, Inc. on behalf of American Association of Physicists in Medicine.

  8. Experimental investigation of nitrogen isotopic effects associated with ammonia degassing at 0-70 °C

    Science.gov (United States)

    Deng, Yuying; Li, Yingzhou; Li, Long

    2018-04-01

    Ammonia degassing is a common process in natural alkaline waters and in the atmosphere. To quantitatively assess the nitrogen cycle in these systems, the essential parameter of nitrogen isotope fractionation factors associated with ammonia degassing is required, but still not constrained yet. In this study, we carried out laboratory experiments to examine the nitrogen isotope behavior during ammonia degassing in alkaline conditions. The experiments started with ammonium sulfate solution with excess sodium hydroxide. The reaction can be described as: NH4+ + OH- (excess) → NH3·nH2O → NH3 (g)↑. Two sets of experiments, one with ammonia degassing under static conditions and the other with ammonia degassing by bubbling of N2 gas, were carried out at 2, 21, 50, and 70 °C. The results indicate that kinetic isotopic effects are dominated during efficient degassing of ammonia in the bubbling experiments, which yielded kinetic nitrogen isotope fractionation factors αNH3(g)-NH3(aq) of 0.9898 at 2 °C, 0.9918 at 21 °C, 0.9935 at 50 °C and 0.9948 at 70 °C. These values show a good relationship with temperature as 103lnαNH3(g)-NH3(aq) = 14.6 - 6.8 × 1000/T. In contrast, isotopic effects during less efficient degassing of ammonia in the static experiments are more complicated. The results do not match either kinetic isotope fractionation or equilibrium isotope fractionation but sit between these two. The most likely cause is that back dissolution of the degassed ammonia occurred in these experiments and consequently shifted kinetic isotope fractionation toward equilibrium isotope fractionation. Our experimental results highlight complicated isotopic effects may occur in natural environments, and need to be fully considered in the interpretation of field data.

  9. 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.)

  10. Isotope Effects in the Reactions of Chloroform Isotopologues with Cl, OH and OD

    DEFF Research Database (Denmark)

    Nilsson, Elna Johanna Kristina; Johnson, Matthew Stanley; Nielsen, Claus J.

    2009-01-01

    The kinetic isotope effects in the reactions of CHCl3, CDCl3, and 13CHCl3 with Cl, OH, and OD radicals have been determined in relative rate experiments at 298 ( 1 K and atmospheric pressure monitored by long path FTIR spectroscopy. The spectra were analyzed using a nonlinear least-squares spectral.......002, kCHCl3+OD/kCDCl3+OD ) 3.95 ( 0.03, and kCHCl3+OD/k13CHCl3+OD ) 1.032 ( 0.004. Larger isotope effects in the OH reactions than in the Cl reactions are opposite to the trends for CH4 and CH3Cl reported in the literature. The origin of these differences was investigated using electronic structure...

  11. A study on the isotope effects in the reduction of carbon dioxide by zinc

    International Nuclear Information System (INIS)

    Senegacnik, M.

    1957-06-01

    We have determined the isotope effects which occur in the reduction of carbon dioxide by zinc. It has been shown that in the case of irreversible surface reactions, Bernstein's equation which permits the calculation of the fractionation factor is still valid. These experimental factors are in good agreement with those obtained by calculating the partition functions of the adsorbed activated complexes. In the reaction mechanism used, the model of the activated complex corresponds to the dissociation of one of the carbon oxygen bonds CO 2 → CO + O. Perturbations arising from the slight reversibility of the reaction Zn + CO 2 ↔ ZnO + CO on the isotope effects on the carbon and oxygen atoms have also been calculated. (author) [fr

  12. Evidence for H2/D2 isotope effects on Fischer-Tropsch synthesis over supported ruthenium catalysts

    International Nuclear Information System (INIS)

    Kellner, C.S.; Bell, A.T.

    1981-01-01

    The effects of using D 2 rather than H 2 during Fischer-Tropsch synthesis were investigated using alumina- and silica-supported Ru catalysts. For the alumina-supported catalysts, the rate of CD 4 formation was 1.4 to 1.6 times faster than the formation of CH 4 . A noticeable isotope effect was also observed for higher molecular weight products. The magnitude of the isotope effects observed using the silica-supported catalyst was much smaller than that found using the alumina-supported catalysts. The formation of olefins relative to paraffins was found to be higher when H 2 rather than D 2 was used, independent of the catalyst support. The observed isotope effects are explained in terms of a mechanism for CO hydrogenation and are shown to arise from a complex combination of the kinetic and equilibrium isotope effects associated with elementary processes occurring on the catalyst surface

  13. Concerted and stepwise mechanisms in cycloaddition reactions: potential surfaces and isotope effects

    International Nuclear Information System (INIS)

    Houk, K.N.; Yi Li; Storer, Joey; Raimondi, Laura; Beno, Brett

    1994-01-01

    CASSCF/6-31G * calculations have been performed on concerted and stepwise Diels-Alder reactions of butadiene with ethene, the dimerization of butadiene, and the dimerization of cyclobutadiene. The relative energies of concerted and stepwise mechanisms are compared, and the factors influencing these ''energies of concert'' are discussed. The comparison of calculated isotope effects to experimental data provides support for theoretical results. (Author)

  14. pH-Free Measurement of Relative Acidities, Including Isotope Effects.

    Science.gov (United States)

    Perrin, Charles L

    2017-01-01

    A powerful pH-free multicomponent NMR titration method can measure relative acidities, even of closely related compounds, with excellent accuracy. The history of the method is presented, along with details of its implementation and a comparison with earlier NMR titrations using a pH electrode. Many of its areas of applicability are described, especially equilibrium isotope effects. The advantages of the method, some practical considerations, and potential pitfalls are considered. © 2017 Elsevier Inc. All rights reserved.

  15. Kinetic tritium isotopic effects in the position 2 for 5'-hydroxy-L-tryptophane

    International Nuclear Information System (INIS)

    Boroda, E.; Kanska, M.

    2006-01-01

    Tryptophanase converts 5'-hydroxy-L-tryptophane to pyrogronic acid and ammonia, however there are known conditions for the reversed reaction. Mechanism of the processes are not known till now. Kinetic isotopic effect (KIE) permits finding the rate determining stage in the multistage process. In presented communication, 5'-hydroxy-[2- 3 H]-L-tryptophane was synthesized and the KIE in the room temperature determined for different reaction stages

  16. Relative rate study of the kinetic isotope effect in the 13CH3D + Cl reaction

    DEFF Research Database (Denmark)

    Joelsson, Lars Magnus Torvald; Forecast, Roslyn; Schmidt, Johan Albrecht

    2014-01-01

    The 13CH3D/12CH4kinetic isotope effect, α13CH3D, of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. α13CH3D is found to be 1.60 ± 0.04. In addition, a quantum chemistry/transition state theory model with tunneling...

  17. Kinetic Isotope Effects (KIE) and Density Functional Theory (DFT): A Match Made in Heaven?

    DEFF Research Database (Denmark)

    Christensen, Niels Johan; Fristrup, Peter

    2015-01-01

    Determination of experimental kinetic isotope effects (KIE) is one of the most useful tools for the exploration of reaction mechanisms in organometallic chemistry. The approach has been further strengthened during the last decade with advances in modern computational chemistry. This allows for th...... reaction). The approach is highlighted by using recent examples from both stoichiometric and catalytic reactions, homogeneous and heterogeneous catalysis, and enzyme catalysis to illustrate the expected accuracy and utility of this approach....

  18. Environmental effects on the stable carbon and oxygen isotopic ...

    African Journals Online (AJOL)

    USER

    2010-08-16

    Aug 16, 2010 ... which may be influenced by the river run-off due to heavy rainfall. The coral skeleton was ... including cloud cover (Weber and Woodhead, 1972;. Muscatine et al. ..... The effect of colony topography on climate signals in coral ...

  19. Hypoglycemic effect of Mucuna pruriens seed extract on normal and streptozotocin-diabetic rats.

    Science.gov (United States)

    Bhaskar, Anusha; Vidhya, V G; Ramya, M

    2008-12-01

    The hypoglycemic effect of the aqueous extract of the seeds of Mucuna pruriens was investigated in normal, glucose load conditions and streptozotocin (STZ)-induced diabetic rats. In normal rats, the aqueous extract of the seeds of Mucuna pririens (100 and 200 mg/kg body weight) significantly (Ppruriens has an anti-hyperglycemic action and it could be a source of hypoglycemic compounds.

  20. 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)

  1. 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

  2. Solvent and solute isotope effects in the aqueous solution of gases. Progress report, July 1, 1978-October 31, 1979

    International Nuclear Information System (INIS)

    Benson, B.B.; Krause, D. Jr.

    1979-10-01

    After developing a 3 He/ 4 He dual beam collection system for the mass spectrometer, the isotopic fractionation factor was determined for helium dissolved in H 2 O, D 2 O, seawater and ethanol. In all solvents the temperature dependence of the fractionation is different from that for a simple isotope vapor pressure effect. Addition of salt to H 2 O increases the fractionation, and the relative salting-out coefficient changes with temperature. A double isotopic effect occurs - the fractionations in D 2 O and H 2 O differ. In ethanol the fractionation is 25% less than in H 2 O

  3. 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

  4. Communication: Isotopic effects on tunneling motions in the water trimer

    International Nuclear Information System (INIS)

    Videla, Pablo E.; Rossky, Peter J.; Laria, D.

    2016-01-01

    We present results of ring polymer molecular dynamics simulations that shed light on the effects of nuclear quantum fluctuations on tunneling motions in cyclic [H 2 O] 3 and [D 2 O] 3 , at the representative temperature of T = 75 K. In particular, we focus attention on free energies associated with two key isomerization processes: The first one corresponds to flipping transitions of dangling OH bonds, between up and down positions with respect to the O–O–O plane of the cluster; the second involves the interchange between connecting and dangling hydrogen bond character of the H-atoms in a tagged water molecule. Zero point energy and tunneling effects lead to sensible reductions of the free energy barriers. Due to the lighter nature of the H nuclei, these modifications are more marked in [H 2 O] 3 than in [D 2 O] 3 . Estimates of the characteristic time scales describing the flipping transitions are consistent with those predicted based on standard transition-state-approximation arguments

  5. Communication: Isotopic effects on tunneling motions in the water trimer

    Energy Technology Data Exchange (ETDEWEB)

    Videla, Pablo E. [Departamento de Química Inorgánica Analítica y Química-Física e INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428 Buenos Aires (Argentina); Rossky, Peter J. [Department of Chemistry, Rice University, Houston, Texas 77251-1892 (United States); Laria, D., E-mail: dhlaria@cnea.gov.ar [Departamento de Química Inorgánica Analítica y Química-Física e INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428 Buenos Aires (Argentina); Departamento de Física de la Materia Condensada, Comisión Nacional de Energía Atómica, Avenida Libertador 8250, 1429 Buenos Aires (Argentina)

    2016-02-14

    We present results of ring polymer molecular dynamics simulations that shed light on the effects of nuclear quantum fluctuations on tunneling motions in cyclic [H{sub 2}O]{sub 3} and [D{sub 2}O]{sub 3}, at the representative temperature of T = 75 K. In particular, we focus attention on free energies associated with two key isomerization processes: The first one corresponds to flipping transitions of dangling OH bonds, between up and down positions with respect to the O–O–O plane of the cluster; the second involves the interchange between connecting and dangling hydrogen bond character of the H-atoms in a tagged water molecule. Zero point energy and tunneling effects lead to sensible reductions of the free energy barriers. Due to the lighter nature of the H nuclei, these modifications are more marked in [H{sub 2}O]{sub 3} than in [D{sub 2}O]{sub 3}. Estimates of the characteristic time scales describing the flipping transitions are consistent with those predicted based on standard transition-state-approximation arguments.

  6. On the Isotopic Altitude Effect of Precipitation in the Northern Adriatic (Croatia)

    Energy Technology Data Exchange (ETDEWEB)

    Roller-Lutz, Z.; Mance, D.; Hunjak, T., E-mail: Roller@medri.hr [Stable Isotope Laboratory, Medical Faculty, University of Rijeka, Rijeka (Croatia); Lutz, H. O. [Stable Isotope Laboratory, Medical Faculty, University of Rijeka, Rijeka (Croatia); Physics Faculty, Bielefeld University, Bielefeld (Germany)

    2013-07-15

    The upper (northern) Adriatic is very rich in precipitation. This input into the water system and its stable isotope composition is a basic factor, knowledge of which is required for proper use and management of water resources. The geomorphology of the region (e.g., mountains of 1400 m next to the sea) can cause specific local conditions. The isotopic composition of precipitation has been measured in various locations at different altitudes. For {delta}{sup 18}O this 'altitude effect' is found to lie around -0.2 per mille /100 m; its exact value depends on the specific location and the season. The {delta}{sup 2}H values and the d-excess vary correspondingly. (author)

  7. Sensitized charge carrier injection into organic crystals studied by isotope effects in weak magnetic fields

    International Nuclear Information System (INIS)

    Bube, W.; Michel-Beyerle, M.E.; Haberkorn, R.; Steffens, E.

    1977-01-01

    The magnetic field (H approximately 50 Oe) dependence of the rhodamine sensitized triplet exciton density in anthracene crystals is influenced by isotopic substitution. This confirms the hyperfine interaction as mechanism explaining the change of the spin multiplicity in the initially formed singlet state of the radical pair. The isotope effect occurs in the sensitizing dye ( 14 N/ 15 N) rather than at the molecular site of the injected charge within the crystal. This can be understood in terms of the high hopping frequency of the charge carriers as compared to the time constant of the hyperfine induced singlet-triplet transition. Since the dye molecules adsorb in an oriented fashion, the angular dependence of the magnetic field modulation of the triplet exciton density can be interpreted without assuming any additional interactions. (Auth.)

  8. Isotope effect on hydrated electron relaxation dynamics studied with time-resolved liquid jet photoelectron spectroscopy

    Science.gov (United States)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2016-05-01

    The excited state relaxation dynamics of the solvated electron in H2O and D2O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H2O and 102 ± 8 fs in D2O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.

  9. Isotopic spin effect in three-pion Bose-Einstein correlations

    International Nuclear Information System (INIS)

    Suzuki, N.

    1998-01-01

    Bose-Einstein (BE) correlations of identical particles in multiple production processes are extensively studied last years because they give an information on the space-time region of interaction. The basic effect is analogous to Hanbury-Brown - Twiss (HBT) interferometry in optics and suggests statistical production of the particles (mainly π mesons). The possible presence of coherent pionic component (for example, in the case of disoriented chiral condensate formation) modifies the HBT effect. On the other hand, the pions (contrary to photons) are subject to isotopic spin (and electric charge) conservation and so they can not be emitted independently. While the corresponding change of the statistical part is not essential for large multiplicities, the coherent part changes substantially when isotopic spin conservation is taken into account. BE correlations of the pions in the presence of both statistical and coherent components are reconsidered taking into account isotopic spin conservation in the coherent part. That will result in appearance of additional contribution to pionic correlation function. (author)

  10. Quantum Dynamics Study of the Isotopic Effect on Capture Reactions: HD, D2 + CH3

    Science.gov (United States)

    Wang, Dunyou; Kwak, Dochan (Technical Monitor)

    2002-01-01

    Time-dependent wave-packet-propagation calculations are reported for the isotopic reactions, HD + CH3 and D2 + CH3, in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probabilities for different initial rotational-vibrational states are presented in this study. This study shows that excitations of the HD(D2) enhances the reactivities; whereas the excitations of the CH3 umbrella mode have the opposite effects. This is consistent with the reaction of H2 + CH3. The comparison of these three isotopic reactions also shows the isotopic effects in the initial-state-selected reaction probabilities. The cumulative reaction probabilities (CRP) are obtained by summing over initial-state-selected reaction probabilities. The energy-shift approximation to account for the contribution of degrees of freedom missing in the six dimensionality calculation is employed to obtain approximate full-dimensional CRPs. The rate constant comparison shows H2 + CH3 reaction has the biggest reactivity, then HD + CH3, and D2 + CH3 has the smallest.

  11. The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

    Science.gov (United States)

    Freeman, K. H.; Boreham, C. J.; Summons, R. E.; Hayes, J. M.

    1994-01-01

    Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.

  12. Effect of complexing reagents on the ionization constant of boric acid and its relation to isotopic exchange separation factor

    International Nuclear Information System (INIS)

    Sharma, B.K.; Subramanian, R.; Mathur, P.K.

    1991-01-01

    The effect of change in concentration of complexing reagents having two or more hydroxyl groups, viz., ethylene glycol, propylene glycol, dextrose and mannitol on the ionization constant of boric acid has been studied by pH-metric titration method. The effect of increase in ionization constant of boric acid on isotopic exchange separation factor for the separation of isotopes of boron by ion exchange chromatography has been studied by the batch method. (author). 9 refs

  13. Diffusion related isotopic fractionation effects with one-dimensional advective–dispersive transport

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Bruce S. [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada); Lollar, Barbara Sherwood [Earth Sciences Department, University of Toronto, 22 Russell Street, Toronto, ON M5S 3B1 (Canada); Passeport, Elodie [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada); Chemical Engineering and Applied Chemistry Department, University of Toronto, 200 College Street, Toronto, ON M5S 3E5 (Canada); Sleep, Brent E., E-mail: sleep@ecf.utoronto.ca [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada)

    2016-04-15

    Aqueous phase diffusion-related isotope fractionation (DRIF) for carbon isotopes was investigated for common groundwater contaminants in systems in which transport could be considered to be one-dimensional. This paper focuses not only on theoretically observable DRIF effects in these systems but introduces the important concept of constraining “observable” DRIF based on constraints imposed by the scale of measurements in the field, and on standard limits of detection and analytical uncertainty. Specifically, constraints for the detection of DRIF were determined in terms of the diffusive fractionation factor, the initial concentration of contaminants (C{sub 0}), the method detection limit (MDL) for isotopic analysis, the transport time, and the ratio of the longitudinal mechanical dispersion coefficient to effective molecular diffusion coefficient (D{sub mech}/D{sub eff}). The results allow a determination of field conditions under which DRIF may be an important factor in the use of stable carbon isotope measurements for evaluation of contaminant transport and transformation for one-dimensional advective–dispersive transport. This study demonstrates that for diffusion-dominated transport of BTEX, MTBE, and chlorinated ethenes, DRIF effects are only detectable for the smaller molar mass compounds such as vinyl chloride for C{sub 0}/MDL ratios of 50 or higher. Much larger C{sub 0}/MDL ratios, corresponding to higher source concentrations or lower detection limits, are necessary for DRIF to be detectable for the higher molar mass compounds. The distance over which DRIF is observable for VC is small (less than 1 m) for a relatively young diffusive plume (< 100 years), and DRIF will not easily be detected by using the conventional sampling approach with “typical” well spacing (at least several meters). With contaminant transport by advection, mechanical dispersion, and molecular diffusion this study suggests that in field sites where D{sub mech}/D{sub eff} is

  14. Diffusion related isotopic fractionation effects with one-dimensional advective–dispersive transport

    International Nuclear Information System (INIS)

    Xu, Bruce S.; Lollar, Barbara Sherwood; Passeport, Elodie; Sleep, Brent E.

    2016-01-01

    Aqueous phase diffusion-related isotope fractionation (DRIF) for carbon isotopes was investigated for common groundwater contaminants in systems in which transport could be considered to be one-dimensional. This paper focuses not only on theoretically observable DRIF effects in these systems but introduces the important concept of constraining “observable” DRIF based on constraints imposed by the scale of measurements in the field, and on standard limits of detection and analytical uncertainty. Specifically, constraints for the detection of DRIF were determined in terms of the diffusive fractionation factor, the initial concentration of contaminants (C_0), the method detection limit (MDL) for isotopic analysis, the transport time, and the ratio of the longitudinal mechanical dispersion coefficient to effective molecular diffusion coefficient (D_m_e_c_h/D_e_f_f). The results allow a determination of field conditions under which DRIF may be an important factor in the use of stable carbon isotope measurements for evaluation of contaminant transport and transformation for one-dimensional advective–dispersive transport. This study demonstrates that for diffusion-dominated transport of BTEX, MTBE, and chlorinated ethenes, DRIF effects are only detectable for the smaller molar mass compounds such as vinyl chloride for C_0/MDL ratios of 50 or higher. Much larger C_0/MDL ratios, corresponding to higher source concentrations or lower detection limits, are necessary for DRIF to be detectable for the higher molar mass compounds. The distance over which DRIF is observable for VC is small (less than 1 m) for a relatively young diffusive plume (< 100 years), and DRIF will not easily be detected by using the conventional sampling approach with “typical” well spacing (at least several meters). With contaminant transport by advection, mechanical dispersion, and molecular diffusion this study suggests that in field sites where D_m_e_c_h/D_e_f_f is larger than 10, DRIF

  15. Lattice Boltzmann Simulation of Kinetic Isotope Effect During Snow Crystal Formation

    Science.gov (United States)

    Lu, G.; Depaolo, D. J.; Kang, Q.; Zhang, D.

    2007-12-01

    and allows us to scale the numerical calculations to atmospheric conditions. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). However, few natural crystals form under such conditions. At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, and kinetic effects control isotopic fractionation. Fractionation factors for dendritic crystals are similar to those predicted by the spherical diffusion model, but the model also gives estimates of crystal heterogeneity. Dendritic crystals are constrained to be relatively large, with dimension much greater than about 20D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. An approach using a larger scale simulation and the domain decomposition method can provide a vapor flux for a nested smaller scale calculation. The results clarify the controls on crystal growth, and the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation.

  16. Effects of a prolonged standardized diet on normalizing the human metabolome123

    OpenAIRE

    Winnike, Jason H; Busby, Marjorie G; Watkins, Paul B; O'Connell, Thomas M

    2009-01-01

    Background: Although the effects of acute dietary interventions on the human metabolome have been studied, the extent to which the metabolome can be normalized by extended dietary standardization has not yet been examined.

  17. Evaluating cleansing effects on trace elements and stable isotope values in feathers of oiled birds.

    Science.gov (United States)

    Valladares, Sonia; Moreno, Roćio; Jover, Lluis; Sanpera, Carola

    2010-01-01

    Feathers of seabirds are widely used as a nondestructive tissue for pollution monitoring of trace elements, as well as convenient samples for trophic ecology studies by means of stable isotope analysis (SIA). Nevertheless, feathers can be occasionally impregnated with oil from deliberate ship discharges and from massive oil spill accidents. The feather structure makes them effective traps for particles and are subject to external contamination. It is unknown to what extent the oil adhered to feathers can change trace element concentrations or stable isotope signatures. This study has two primary objectives: (1) to assess if there are differences between trace element concentrations and stable isotope signatures of oiled and clean feathers, and (2) to determine if the cleansing of oiled feathers using commonly applied techniques such as sodium hydroxide (NaOH) washes in combination with an organic solvent (hexane) is more effective than using NaOH alone. In order to do this, we analysed trace elements (Se, Hg, Pb, Cu and Zn) and stable isotopes (delta(13)C and delta(15)N) of individual feathers of yellow-legged gulls (Larus michahellis) which were affected by the 2002 Prestige oil spill in Galicia (NW Spain). Two sets of feathers were analysed, one group were oil-free (Control group) and the other had oil adhered to its surface (Oiled group). We expected to find differences between control and oiled feathers when cleaning exclusively with NaOH and no differences when using hexane. Our results did not show significant differences between Control and Oiled groups as a consequence of the cleansing method used. Unexpectedly, the additional cleansing with hexane resulted in decreasing selenium concentrations and increasing zinc and delta(15)N values in all groups of feathers.

  18. Laser assisted aerodynamic isotope separation

    International Nuclear Information System (INIS)

    Berg, H. van den

    1985-01-01

    It is shown that the efficiency of conventional aerodynamic isotope seperation can be improved by two orders of magnitude with the aid of a relatively weak cw infrared laser which is used to induce isotopically selective condensation. Overall isotope enrichment factors in excess of 2 are obtained as compared to about 1.02 in the conventional seperation. Sulphur isotopes in SF 6 as well as Silicon isotopes in SiF 4 and Bromine isotopes in CF 3 Br are seperated on a laboratory scale. Infrared vibrational predissociation by itself and in combination with isotopically selective condensation are also shown to be effective new ways of isotope separation. (orig.) [de

  19. Effect of amino acids on the precipitation kinetics and Ca isotopic composition of gypsum

    Science.gov (United States)

    Harouaka, Khadouja; Kubicki, James D.; Fantle, Matthew S.

    2017-12-01

    Stirred gypsum (CaSO4 · 2H2O) precipitation experiments (initial Ωgypsum = 2.4 ± 0.14, duration ≈ 1.0-1.5 h) were conducted in the presence of the amino acids glycine (190 μM), L-alanine (190 μM), D- and L-arginine (45 μM), and L-tyrosine (200 μM) to investigate the effect of simple organic compounds on both the precipitation kinetics and Ca isotopic composition of gypsum. Relative to abiotic controls, glycine, tyrosine, and alanine inhibited precipitation rates by ∼22%, 27%, and 29%, respectively, while L- and D-arginine accelerated crystal growth by ∼8% and 48%, respectively. With the exception of tyrosine, amino acid induced inhibition resulted in fractionation factors (αs-f) associated with precipitation that were no more than 0.3‰ lower than amino acid-free controls. In contrast, the tyrosine and D- and L-arginine experiments had αs-f values associated with precipitation that were similar to the controls. Our experimental results indicate that Ca isotopic fractionation associated with gypsum precipitation is impacted by growth inhibition in the presence of amino acids. Specifically, we propose that the surface-specific binding of amino acids to gypsum can change the equilibrium fractionation factor of the bulk mineral. We investigate the hypothesis that amino acids can influence the growth of gypsum at specific crystal faces via adsorption and that different faces have distinct fractionation factors (αface-fluid). Accordingly, preferential sorption of amino acids at particular faces changes the relative, face-specific mass fluxes of Ca during growth, which influences the bulk isotopic composition of the mineral. Density functional theory (DFT) calculations suggest that the energetic favorability of glycine sorption onto gypsum crystal faces occurs in the order: (1 1 0) > (0 1 0) > (1 2 0) > (0 1 1), while glycine sorption onto the (-1 1 1) face was found to be energetically unfavorable. Face-specific fractionation factors constrained by

  20. Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

    Science.gov (United States)

    Epov, Vladimir N

    2011-08-07

    A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions. This journal is © the Owner Societies 2011

  1. Measurement of the isotope effect of the diffusion of silver and gold in gold and of silver in silver-gold alloys

    International Nuclear Information System (INIS)

    Wolter, D.

    1974-01-01

    The silver isotopes Ag 105 and Agsup(110m) and the gold isotopes Au 195 and Au 199 were used for isotope effect measurements. The isotope effect of the gold self-diffusion was measured on four monocrystals samples at about 850 0 C, that of silver in gold monocrystals at five different temperatures between 731 0 C and 1050 0 C. Furthermore, the isotope effect for silver at 904 0 C was measured on seven silver-gold alloys of varying silver concentration. The correlation factor was determined from the measurements. (HPOE/LH) [de

  2. Hybrid quantum and classical methods for computing kinetic isotope effects of chemical reactions in solutions and in enzymes.

    Science.gov (United States)

    Gao, Jiali; Major, Dan T; Fan, Yao; Lin, Yen-Lin; Ma, Shuhua; Wong, Kin-Yiu

    2008-01-01

    A method for incorporating quantum mechanics into enzyme kinetics modeling is presented. Three aspects are emphasized: 1) combined quantum mechanical and molecular mechanical methods are used to represent the potential energy surface for modeling bond forming and breaking processes, 2) instantaneous normal mode analyses are used to incorporate quantum vibrational free energies to the classical potential of mean force, and 3) multidimensional tunneling methods are used to estimate quantum effects on the reaction coordinate motion. Centroid path integral simulations are described to make quantum corrections to the classical potential of mean force. In this method, the nuclear quantum vibrational and tunneling contributions are not separable. An integrated centroid path integral-free energy perturbation and umbrella sampling (PI-FEP/UM) method along with a bisection sampling procedure was summarized, which provides an accurate, easily convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. In the ensemble-averaged variational transition state theory with multidimensional tunneling (EA-VTST/MT), these three aspects of quantum mechanical effects can be individually treated, providing useful insights into the mechanism of enzymatic reactions. These methods are illustrated by applications to a model process in the gas phase, the decarboxylation reaction of N-methyl picolinate in water, and the proton abstraction and reprotonation process catalyzed by alanine racemase. These examples show that the incorporation of quantum mechanical effects is essential for enzyme kinetics simulations.

  3. Covariance of oxygen and hydrogen isotopic composition in plant water: Species effects

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, L.W.; DeNiro, M.J. (Univ. of California, Los Angeles (United States))

    1989-12-01

    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species-specific factors on leaf water enrichment of D and {sup 18}O have not been studied for different plants growing together. To learn whether leaf water enrichment patterns and processes for D and {sup 18}O are different for individual species growing under the same environmental conditions the authors tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show high sloped (m in the leaf water equation {delta}D = m {delta}{sup 18}O + b) than in C{sub 3} plants. They determined the relationships between the stable hydrogen ({delta}D) and oxygen ({delta}{sup 18}O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes.

  4. 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)

  5. The effect of natural weathering on the chemical and isotopic composition of biotites

    International Nuclear Information System (INIS)

    Clauer, N.; Bonnot-Courtois, C.

    1982-01-01

    The effect of progressive natural weathering on the isotopic (Rb-Sr, K-Ar, deltaD, delta 18 O) and chemical (REE, H 2 O + ) compositions of biotite has been studied on a suite of migmatitic biotites from the Chad Republic. During the early stages of weathering the Rb-Sr system is strongly affected, the hydrogen and oxygen isotope compositions change markedly, the minerals are depleted in light REE, the water content increases by a factor of two, and the K-Ar system is relatively little disturbed. During intensive weathering the K-Ar system is more strongly disturbed than the Rb-Sr system. Most of the isotopic and chemical modifications take place under nonequilibrium conditions and occur before newly formed kaolinite and/or smectite can be detected. These observations suggest that (a) 'protominerals' may form within the biotite structure during the initial period of weathering, and (b) only when chemical equilibrium is approached in the weathering profile are new minerals able to form. (author)

  6. Oxygen isotope fractionation effects in soil water via interaction with cations (Mg, Ca, K, Na) adsorbed to phyllosilicate clay minerals

    Science.gov (United States)

    Oerter, Erik; Finstad, Kari; Schaefer, Justin; Goldsmith, Gregory R.; Dawson, Todd; Amundson, Ronald

    2014-07-01

    In isotope-enabled hydrology, soil and vadose zone sediments have been generally considered to be isotopically inert with respect to the water they host. This is inconsistent with knowledge that clay particles possessing an electronegative surface charge and resulting cation exchange capacity (CEC) interact with a wide range of solutes which, in the absence of clays, have been shown to exhibit δ18O isotope effects that vary in relation to the ionic strength of the solutions. To investigate the isotope effects caused by high CEC clays in mineral-water systems, we created a series of monominerallic-water mixtures at gravimetric water contents ranging from 5% to 32%, consisting of pure deionized water of known isotopic composition with homoionic (Mg, Ca, Na, K) montmorillonite. Similar mixtures were also created with quartz to determine the isotope effect of non-, or very minimally-, charged mineral surfaces. The δ18O value of the water in these monominerallic soil analogs was then measured by isotope ratio mass spectrometry (IRMS) after direct headspace CO2 equilibration. Mg- and Ca-exchanged homoionic montmorillonite depleted measured δ18O values up to 1.55‰ relative to pure water at 5% water content, declining to 0.49‰ depletion at 30% water content. K-montmorillonite enriched measured δ18O values up to 0.86‰ at 5% water content, declining to 0.11‰ enrichment at 30% water. Na-montmorillonite produces no measureable isotope effect. The isotope effects observed in these experiments may be present in natural, high-clay soils and sediments. These findings have relevance to the interpretation of results of direct CO2-water equilibration approaches to the measurement of the δ18O value of soil water. The adsorbed cation isotope effect may bear consideration in studies of pedogenic carbonate, plant-soil water use and soil-atmosphere interaction. Finally, the observed isotope effects may prove useful as molecular scale probes of the nature of mineral

  7. Covariance of oxygen and hydrogen isotopic compositions in plant water: species effects

    International Nuclear Information System (INIS)

    Cooper, L.W.; DeNiro, M.J.

    1989-01-01

    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species—specific factors on leaf water enrichment of D and 18 O have not been studied for different plants growing together. Accordingly, to learn whether leaf water enrichment patterns and processes for D and 18 O are different for individual species growing under the same environmental conditions we tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show higher slopes (m in the leaf water equation °D = m ° 18 O + b) than in C 3 plants. We determined the relationships between the stable hydrogen (°D) and oxygen (° 18 O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. Slopes (m in the above leaf water equation) ranged from 1.50 to 3.21, compared to °8 for meteoric water, but differences in slope could not be attributed to carboxylation pathway (CAM vs. C 3 ) nor climate (coastal California vs. Sonoran Desert). Higher slopes were correlated with greater overall ranges of leaf water enrichment of D and 18 O. Water in plants with higher slopes also differed most from unaltered meteoric water. Leaf water isotope ratios in plants with lower slopes were better correlated with temperature and humidity. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes

  8. Vinyl ether hydrolysis. VII. Isotope effects on catalysis by aqueous hydrofluoric acid

    International Nuclear Information System (INIS)

    Kresge, A.J.; Chen, H.J.; Chiang, Y.

    1977-01-01

    Comparison of rates of hydrolysis of three vinyl ethers catalyzed by HF in H 2 O and DF in D 2 O at 25 0 C gives primary isotope effects in the range k/sub H//k/sub D/ = 3.3 to 3.5. The unexpectedly small size of these effects may be attributed to strong, ω = 1325 to 1450 cm -1 , hydrogenic bending vibrations in the proton transfer transition states of these reactions along with the lack of compensatory bending vibrations in the diatomic proton donor

  9. Secondary isotope effects and tunneling in elimination reaction of quaternary ammonium salts

    International Nuclear Information System (INIS)

    Lin, S.

    1993-01-01

    In order to gain more experimental evidence of the tunneling effect on the non-transferred isotopically-substituted hydrogen in the rate determining step and to investigate in more detail concerning the variable nature of the E2 transition state, tritium tracer-labeled β- and/or α-phenyl substituted ethyltrimethylammonium ions in the elimination reaction and their 2,2-d 2 analogues were studied. The three different substrates are 2-(p-trifluoromethylphenyl)ethyltrimethylammonium bromide (I), 1-phenylethyltrimethylammonium bromide (II) and 1-phenyl- 2-p-chlorophenylethyltrimethylammonium bromide (III). The reactions were found to proceed via a concerted E2 process. The proton is more than one-half transferred to the base at the transition state, especially for case I and III. There is more C beta -H and less C alpha -N bond rupture at the transition state when an electron-withdrawing group is introduced on the β-phenyl ring, i.e., more carbonion character in the transition state. The secondary tritium isotope effects were measured and they were found larger than the maximum value. (1.17) for rehybridization. It was found that these values were strongly temperature dependent. They increase as the temperature goes down. The Arrenhius pre-exponential factors were below unity and the exponential factor to convert the isotope effect of D/T to H/T were much greater than predicted for zero-point energy effects alone (3.26). Tunneling turns to be the only plausible explanation. By reviewing this evidence, one may conclude that the contribution of tunneling is indeed a common occurrence in proton transfer processes. For elimination of compound I, the tunneling effect is greatest while it is less for the other two, which are about the same, but the nature of their transition states is quite different. The variable nature of the transition states for the three eliminations are discussed in terms of the More O'Ferral-Jencks diagram

  10. Study of the matrix specific mass discrimination effects during inductively coupled plasma mass spectrometry isotope ratio measurements

    International Nuclear Information System (INIS)

    Vassileva, E.; Quetel, Ch.R.

    2004-01-01

    Sample matrix related effects on mass discrimination during inductively coupled plasma mass spectrometry (ICP-MS) isotope ratio measurements have only been rarely reported. However, they can lead to errors larger than the uncertainty claimed on the ratio results when not properly taken into account or corrected for. These matrix specific affects were experienced during an Isotope Dilution Mass Spectrometry (IDMS) campaign we carried out for the certification of the Cd amount content in some food digest samples (7% acidity and salts content around 450μg g -1 ). Dilution was not possible for Cd only present at the low ng g -1 level. Up to 1% difference was observed on Cd isotope ratio results between measurements performed directly or after matrix separation. This was a significant difference considering that less than 1.5% relative combined uncertainty was eventually estimated for these IDMS measurements. Similar results could be obtained either way after the implementation of necessary corrections. The direct measurement approach associated to a correction for mass discrimination effects using the food digest sample itself (and the IUPAC table values as reference for the natural Cd isotopic composition) was preferred as it was the easiest. Consequently, the impact of matrix effects on mass discrimination during isotope ratio measurements with two types of ICP- MS (quadrupole and magnetic sector instruments) was studied for 4 elements (Li, Cu, Cd and Tl). Samples of varying salinity (up to 0.25%) and acidity (up to 7%) characteristics were prepared using isotopic certified reference materials of these elements. The long term and short-term stability, respectively reproducibility and repeatability, of the results, as well as the evolution of the difference to certified ratio values were monitored. As expected the 13 investigated isotopic ratios were all sensitive to variations in salt and acid concentrations. Our experiments also showed that simultaneous variation

  11. Dual temperature effects on oxygen isotopic ratio of shallow-water coral skeleton: Consequences on seasonal and interannual records

    Science.gov (United States)

    Juillet-Leclerc, A.; Reynaud, S.

    2009-04-01

    Oxygen isotopic ratio from coral skeleton is regarded for a long time as promising climate archives at seasonal scale. Although in isotopic disequilibrium relative to seawater, it is supposed to obey to the isotope thermometer. Indeed, coral oxygen isotopic records are strongly temperature dependent, but d18O-temperature calibrations derived from different corals are highly variable. The isotope thermometer assumption does not take into account vital effects due to biogenic origin of the mineral. Corals are animals living in symbiosis with algae (zooxanthellae). Interactions between symbiont photosynthesis and coral skeleton carbonation have been abundantly observed but they remain poorly understood and the effects of photosynthesis on coral growth and skeleton oxygen ratio are ignored. Coral cultured under two light conditions enabled to relate metabolic parameters and oxygen isotopic variability with photosynthetic activity. By examining responses provided by each colony they revealed that photosynthesis significantly affected d18O, by an opposite sense compared with the sole temperature influence. Since temperature and light changes are associated during seasonal variations, this complicates the interpretation of seasonal record. Additionally, this complexity is amplified because photosynthetic activity is also directly impacted by temperature variability. Thus, the annual isotopic amplitude due to the "physical" temperature influence is partly compensated through photosynthesis. Similar opposite effect is also shown by extension rate of the cultured colonies. First, we will examine and quantify consequences of photosynthesis on growth rate and oxygen isotopic signature, from cultured corals. Second, we will consider the consequences of this vital effect on data series, at seasonal and interannual time scales.

  12. The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

    Science.gov (United States)

    von Sperber, C.; Tamburini, F.; Bernasconi, S. M.; Frossard, E.

    2013-12-01

    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi) (1-2). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. The enzymatic hydrolysis leads, via a nucleophilic attack, to the incorporation of one oxygen atom from the water into the newly formed Pi molecule. During the incorporation, an isotopic fractionation occurs, which might be used to identify the origin of Pi in the environment (3-6). While the effect of phosphomonoesterases and phosphodiesterases on the oxygen isotope composition of phosphate has been examined, there are, so far, no studies dealing with the effect of phytases (4-6). Phytases catalyze the hydrolysis of myo-inositol-hexakis-phosphate (IP6), which is an important component of organic P in many ecosystems (7). Enzymatic assays with phytase from wheat germ and Aspergillus niger were prepared under sterile and temperature controlled conditions in order to determine the effect of phytases on the oxygen isotope composition of phosphate, which has been liberated from IP6 via enzymatic hydrolysis. Assays with phytase from wheat germ lead to a turnover of the substrate close to 100%, while assays with phytase from Aspergillus niger lead to a turnover of the substrate close to 80%. In the case of the assays with phytase from wheat germ, our results indicate that one sixth of the total 24 oxygen which are associated to the phosphates in IP6 are exchanged with oxygen from water. From this we conclude that the incorporation of one oxygen atom from water occurs only at four phosphate molecules of IP6, while two phosphate molecules do not experience an incorporation of oxygen. This suggests that during the enzymatic hydrolysis, four P-O bonds and two C-O bonds are broken. Provided that, the isotopic fractionation can be calculated with an isotopic mass balance resulting in -8.4‰ (×3.6 SD). This is a value very similar to those reported

  13. Iso-effect tables and therapeutic ratios for epidermoid cancer and normal tissue stroma

    International Nuclear Information System (INIS)

    Cohen, L.; Creditor, M.

    1983-01-01

    Available literature on radiation injury to normal tissue stroma and ablation of epidermoid carcinoma was surveyed. Computer programs (RAD3 and RAD1) were then used to derive cell kinetic parameters and generate iso-effect tables for the relevant tissues. The two tables provide a set of limiting doses for tolerance of normal connective tissue (16% risk of injury) and for ablation of epidermoid cancer (16% risk of recurrence) covering a wide range of treatment schedules. Calculating the ratios of normal tissue tolerance to tumor control doses for each treatment scheme provides an array of therapeutic ratios, from which appropriate treatment schemes can be selected

  14. Crack growth resistance for anisotropic plasticity with non-normality effects

    DEFF Research Database (Denmark)

    Tvergaard, Viggo; Legarth, Brian Nyvang

    2006-01-01

    For a plastically anisotropic solid a plasticity model using a plastic flow rule with non-normality is applied to predict crack growth. The fracture process is modelled in terms of a traction–separation law specified on the crack plane. A phenomenological elastic–viscoplastic material model...... is applied, using one of two different anisotropic yield criteria to account for the plastic anisotropy, and in each case the effect of the normality flow rule is compared with the effect of non-normality. Conditions of small scale yielding are assumed, with mode I loading conditions far from the crack......-tip, and various directions of the crack plane relative to the principal axes of the anisotropy are considered. It is found that the steady-state fracture toughness is significantly reduced when the non-normality flow rule is used. Furthermore, it is shown that the predictions are quite sensitive to the value...

  15. 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.

  16. Plutonium isotope ratios in polychaete worms

    International Nuclear Information System (INIS)

    Beasley, T.M.; Fowler, S.W.

    1976-01-01

    Reference is made to recent reports that suggest that terrestrial and aquatic organisms may preferentially take up 238 Pu compared with sup(239+240)Pu. It is stated that although kinetic isotope effects are known to occur in biological systems for low mass number elements, such as H, C and N, such effects are generally discounted with higher mass numbers, and differences in the biological 'uptake' of isotopes of high mass number elements, such as those of Pu, are normally attributable to differences in the chemical or physical forms of the isotopes or to different quantities of isotopes available to organisms. This has been applied to explain differential Pu isotope behaviour in animals under controlled laboratory conditions, but it is not certain that it can be applied to explain anomalies of Pu isotope behaviour in organisms contaminated by nuclear test debris or by wastes from nuclear fuel reprocessing plants. Geochemical weathering may also have an effect. Described here are experiments in which it was found that deposit feeding marine worms living in sediments contaminated in different ways with Pu isotopes did not show preferential accumulation of 238 Pu. The worms had been exposed to different chemical and physical forms of the isotopes, including exposure to laboratory-labelled sediment, sediment collected from a former weapons test site, and sediment contaminated by wastes from a nuclear fuel reprocessing plant. The worms were allowed to accumulate Pu for times of 5 to 40 days. Isotope ratios were determined by α-spectrometric techniques. It is considered that the results are important for environmental samples where Pu activity levels are low. (U.K.)

  17. Effect of gamma irradiation on membranes of normal and pathological erythrocytes (beta-thalassemia)

    International Nuclear Information System (INIS)

    Sportelli, L.; Bonincontro, A.; Cametti, C.; Consiglio Nazionale delle Ricerche, Rome

    1987-01-01

    The influence of ionizing radiation on the membrane of human normal erythrocytes has extensively been studied and a variety of effects including changes in the cation fluxes or in non-electrolytes permeability, in membrane fluidity, in peroxidation of unsaturated lipids as well as chemical composition or structural modifications has been observed. However, only few studies deal with the effects of ionizing radiation on pathological red blood cells. In this work, we have investigated by means of electron spin resonance (ESR) spectroscopy the effects of 60 Co γ-radiation on the normal and homozygous β-thalassemic human erythrocyte membranes. (orig.)

  18. 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

  19. Late effects of normal tissues (lent) scoring system: the soma scale

    International Nuclear Information System (INIS)

    Mornex, F.; Pavy, J.J.; Denekamp, J.

    1997-01-01

    Radiation tolerance of normal tissues remains the limiting factor for delivering tumoricidal dose. The late toxicity of normal tissues is the most critical element of an irradiation: somatic, functional and structural alterations occur during the actual treatment itself, but late effects manifest months to years after acute effects heal, and may progress with time. The optimal therapeutic ratio ultimately requires not only complete tumor clearance, but also minimal residual injury to surrounding vital normal tissues. The disparity between the intensity of acute and late effects and the inability to predict the eventual manifestation of late normal tissue injury has made radiation oncologists recognize the importance of careful patient follow-up. There is so far no uniform toxicity scoring system to compare several clinical studies in the absence of a 'common toxicity language'. This justifies the need to establish a precise evaluation system for the analysis of late effects of radiation on normal tissues. The SOMA/LENT scoring system results from an international collaboration. European Organization Treatment of Cancer (EORTC) and Radiation Therapy Oncology Group (RTOG) have created subcommittees with the aim of addressing the question of standardized toxic effects criteria. This effort appeared as a necessity to standardize and improve the data recording, to then describe and evaluate uniform toxicity at regular time intervals. The current proposed scale is not yet validated, and should be used cautiously. (authors)

  20. 13C Kinetic isotopic effect of polymerization on monomers with multiple bond

    International Nuclear Information System (INIS)

    Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

    1988-01-01

    13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

  1. Multidimensional Normalization to Minimize Plate Effects of Suspension Bead Array Data.

    Science.gov (United States)

    Hong, Mun-Gwan; Lee, Woojoo; Nilsson, Peter; Pawitan, Yudi; Schwenk, Jochen M

    2016-10-07

    Enhanced by the growing number of biobanks, biomarker studies can now be performed with reasonable statistical power by using large sets of samples. Antibody-based proteomics by means of suspension bead arrays offers one attractive approach to analyze serum, plasma, or CSF samples for such studies in microtiter plates. To expand measurements beyond single batches, with either 96 or 384 samples per plate, suitable normalization methods are required to minimize the variation between plates. Here we propose two normalization approaches utilizing MA coordinates. The multidimensional MA (multi-MA) and MA-loess both consider all samples of a microtiter plate per suspension bead array assay and thus do not require any external reference samples. We demonstrate the performance of the two MA normalization methods with data obtained from the analysis of 384 samples including both serum and plasma. Samples were randomized across 96-well sample plates, processed, and analyzed in assay plates, respectively. Using principal component analysis (PCA), we could show that plate-wise clusters found in the first two components were eliminated by multi-MA normalization as compared with other normalization methods. Furthermore, we studied the correlation profiles between random pairs of antibodies and found that both MA normalization methods substantially reduced the inflated correlation introduced by plate effects. Normalization approaches using multi-MA and MA-loess minimized batch effects arising from the analysis of several assay plates with antibody suspension bead arrays. In a simulated biomarker study, multi-MA restored associations lost due to plate effects. Our normalization approaches, which are available as R package MDimNormn, could also be useful in studies using other types of high-throughput assay data.

  2. 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.

  3. Oxygen isotope effect on 55Mn nuclear magnetic shielding in permanganate

    International Nuclear Information System (INIS)

    Haase, A.R.; Lutz, O.; Mueller, M.; Nolle, A.

    1976-01-01

    By Fourier transform NMR spectroscopy the 55 Mn resonance lines of the different permanganate species 55 Mn 16 Osub(4-n) 18 Osub(n) - (n=0,1,2,3,4) have been resolved in aqueous solutions of potassium permanganate. An isotope effect on the Larmor frequency of 55 Mn of (0.599 +- 0.015)ppm to lower frequency was found for the substition of an 16 O atom by an 18 O atom in the permanganate ion. An oxygen exchange rate in the permanganate-water system is given. (orig.) [de

  4. 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

  5. Recovery of Normal Body Weight in Adolescents with Anorexia Nervosa: The Nurses’ Perspective on Effective Interventions

    NARCIS (Netherlands)

    Annemarie van Elburg; prof Berno van Meijel; Esther Meerwijk; Laura Beukers; Joyce van Ommen; René Bakker

    2011-01-01

    Little is known about effective nursing interventions for adolescents with anorexia nervosa. The purpose of this study was to discover which aspects of nursing care are most effective, according to nurses, in recovery of normal body weight in adolescents with anorexia nervosa. METHODS: A qualitative

  6. Meissner effect in diffusive normal metal/d-wave superconductor junctions

    NARCIS (Netherlands)

    Yokoyama, Takehito; Tanaka, Yukio; Golubov, Alexandre Avraamovitch; Inoue, Jun-ichiro; Asano, Yasuhiro

    2005-01-01

    The Meissner effect in diffusive normal metal/insulator/d-wave superconductor junctions is studied theoretically in the framework of the Usadel equation under the generalized boundary condition. The effect of midgap Andreev resonant states (MARS) formed at the interface of d-wave superconductor is

  7. Recommended parameters for effect assessment of radioactive airborne effluents under normal condition of nuclear facilities

    International Nuclear Information System (INIS)

    Li Hong; Fang Dong; Sun Chengzhi; Xiao Naihong

    2003-01-01

    A set of models and default parameters are recommended for effect assessment of radioactive airborne effluents under normal condition of nuclear facilities in order to standardize the environmental effect assessment of nuclear facilities, and to simplify the observation and investigation in early phase. The paper introduces the input data and default parameters used in the model

  8. Review of RBE values of 15 MeV neutrons for effects on normal tissues

    NARCIS (Netherlands)

    Broerse, J.J.

    1974-01-01

    Values of the relative biological effectiveness (RBE) of fast neutrons for effect on normal tissue depend not only on the neutron energy and the dose, but also on the type of tissue irradiated. Values of the RBE of 15 MeV neutrons are reviewed for rapidly proliferating rodent tissue, such as mouse

  9. The effect of a micro bubble dispersed gas phase on hydrogen isotope transport in liquid metals under nuclear irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Fradera, J., E-mail: jfradera@ubu.es; Cuesta-López, S., E-mail: scuesta@ubu.es

    2013-12-15

    The present work intend to be a first step towards the understanding and quantification of the hydrogen isotope complex phenomena in liquid metals for nuclear technology. Liquid metals under nuclear irradiation in, e.g., breeding blankets of a nuclear fusion reactor would generate tritium which is to be extracted and recirculated as fuel. At the same time that tritium is bred, helium is also generated and may precipitate in the form of nano bubbles. Other liquid metal systems of a nuclear reactor involve hydrogen isotope absorption processes, e.g., tritium extraction system. Hence, hydrogen isotope absorption into gas bubbles modelling and control may have a capital importance regarding design, operation and safety. Here general models for hydrogen isotopes transport in liquid metal and absorption into gas phase, that do not depend on the mass transfer limiting regime, are exposed and implemented in OpenFOAM® CFD tool for 0D–3D simulations. Results for a 0D case show the impact of a He dispersed phase of nano bubbles on hydrogen isotopes inventory at different temperatures as well as the inventory evolution during a He nucleation event. In addition, 1D and 2D axisymmetric cases are exposed showing the effect of a He dispersed gas phase on hydrogen isotope permeation through a lithium lead eutectic alloy and the effect of vortical structures on hydrogen isotope transport at a backward facing step. Exposed results give a valuable insight on current nuclear technology regarding the importance of controlling hydrogen isotope transport and its interactions with nucleation event through gas absorption processes.

  10. Are your covariates under control? How normalization can re-introduce covariate effects.

    Science.gov (United States)

    Pain, Oliver; Dudbridge, Frank; Ronald, Angelica

    2018-04-30

    Many statistical tests rely on the assumption that the residuals of a model are normally distributed. Rank-based inverse normal transformation (INT) of the dependent variable is one of the most popular approaches to satisfy the normality assumption. When covariates are included in the analysis, a common approach is to first adjust for the covariates and then normalize the residuals. This study investigated the effect of regressing covariates against the dependent variable and then applying rank-based INT to the residuals. The correlation between the dependent variable and covariates at each stage of processing was assessed. An alternative approach was tested in which rank-based INT was applied to the dependent variable before regressing covariates. Analyses based on both simulated and real data examples demonstrated that applying rank-based INT to the dependent variable residuals after regressing out covariates re-introduces a linear correlation between the dependent variable and covariates, increasing type-I errors and reducing power. On the other hand, when rank-based INT was applied prior to controlling for covariate effects, residuals were normally distributed and linearly uncorrelated with covariates. This latter approach is therefore recommended in situations were normality of the dependent variable is required.

  11. The normal function of a speciation gene, Odysseus, and its hybrid sterility effect.

    Science.gov (United States)

    Sun, Sha; Ting, Chau-Ti; Wu, Chung-I

    2004-07-02

    To understand how postmating isolation is connected to the normal process of species divergence and why hybrid male sterility is often the first sign of speciation, we analyzed the Odysseus (OdsH) gene of hybrid male sterility in Drosophila. We carried out expression analysis, transgenic study, and gene knockout. The combined evidence suggests that the sterility phenotype represents a novel manifestation of the gene function rather than the reduction or loss of the normal one. The gene knockout experiment identified the normal function of OdsH as a modest enhancement of sperm production in young males. The implication of a weak effect of OdsH on the normal phenotype but a strong influence on hybrid male sterility is discussed in light of Haldane's rule of postmating isolation.

  12. Disentangling effects of growth and nutritional status on seabird stable isotope ratios

    Science.gov (United States)

    Sears, J.; Hatch, Shyla A.; O'Brien, D. M.

    2009-01-01

    A growing number of studies suggest that an individual's physiology affects its carbon and nitrogen stable isotope signatures, obscuring a signal often assumed to be only a reflection of diet and foraging location. We examined effects of growth and moderate food restriction on red blood cell (RBC) and feather ??15N and ??13C in rhinoceros auklet chicks (Cerorhinca monocerata), a piscivorous seabird. Chicks were reared in captivity and fed either control (75 g/day; n = 7) or ~40% restricted (40 g/day; n = 6) amounts of high quality forage fish. We quantified effects of growth on isotopic fractionation by comparing ??15N and ??13C in control chicks to those of captive, non-growing subadult auklets (n = 11) fed the same diet. To estimate natural levels of isotopic variation, we also collected blood from a random sample of free-living rhinoceros auklet adults and chicks in the Gulf of Alaska (n = 15 for each), as well as adult feather samples (n = 13). In the captive experiment, moderate food restriction caused significant depletion in ??15N of both RBCs and feathers in treatment chicks compared to control chicks. Growth also induced depletion in RBC ??15N, with chicks exhibiting lower ??15N when they were growing the fastest. As growth slowed, ??15N increased, resulting in an overall pattern of enrichment over the course of the nestling period. Combined effects of growth and restriction depleted ??15N in chick RBCs by 0.92???. We propose that increased nitrogen-use efficiency is responsible for 15N depletion in both growing and food-restricted chicks. ??15N values in RBCs of free-ranging auklets fell within a range of only 1.03???, while feather ??15N varied widely. Together, our captive and field results suggest that both growth and moderate food restriction can affect stable isotope ratios in an ecologically meaningful way in RBCs although not feathers due to greater natural variability in this tissue. ?? 2008 Springer-Verlag.

  13. The oxygen isotope effect on the in-plane penetration depth in cuprate superconductors

    International Nuclear Information System (INIS)

    Khasanov, R; Shengelaya, A; Morenzoni, E; Conder, K; Savic, I M; Keller, H

    2004-01-01

    Muon spin rotation (μSR) studies of the oxygen isotope ( 16 O/ 18 O) effect (OIE) on the in-plane magnetic field penetration depth λ ab in cuprate high-temperature superconductors (HTS) are presented. First, the doping dependence of the OIE on the transition temperature T c in various HTS is briefly discussed. It is observed that different cuprate families show similar doping dependences of the OIE on T c . Then, bulk μSR, low-energy μSR, and magnetization studies of the total and site-selective OIE on λ ab are described in some detail. A substantial OIE on λ ab was observed in various cuprate families at all doping levels, suggesting that cuprate HTS are non-adiabatic superconductors. The experiments clearly demonstrate that the total OIE on T c and λ ab arise from the oxygen sites within the superconducting CuO 2 planes, demonstrating that the phonon modes involving the movement of planar oxygen are dominantly coupled to the supercarriers. Finally, it is shown that the OIE on T c and λ ab exhibit a relation that appears to be generic for different families of cuprate HTS. The observation of these unusual isotope effects implies that lattice effects play an essential role in cuprate HTS and have to be considered in any realistic model of high-temperature superconductivity

  14. The oxygen isotope effect on the in-plane penetration depth in cuprate superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Khasanov, R [Physik-Institut der Universitaet Zuerich, CH-8057 Zurich (Switzerland); Shengelaya, A [Physik-Institut der Universitaet Zuerich, CH-8057 Zurich (Switzerland); Morenzoni, E [Laboratory for Muon Spin Spectroscopy, Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Conder, K [Laboratory for Neutron Scattering, ETH Zuerich and PSI Villigen, CH-5232 Villigen PSI (Switzerland); Savic, I M [Faculty of Physics, University of Belgrade, 11001 Belgrade (Serbia and Montenegro); Keller, H [Physik-Institut der Universitaet Zuerich, CH-8057 Zurich (Switzerland)

    2004-10-13

    Muon spin rotation ({mu}SR) studies of the oxygen isotope ({sup 16}O/{sup 18}O) effect (OIE) on the in-plane magnetic field penetration depth {lambda}{sub ab} in cuprate high-temperature superconductors (HTS) are presented. First, the doping dependence of the OIE on the transition temperature T{sub c} in various HTS is briefly discussed. It is observed that different cuprate families show similar doping dependences of the OIE on T{sub c}. Then, bulk {mu}SR, low-energy {mu}SR, and magnetization studies of the total and site-selective OIE on {lambda}{sub ab} are described in some detail. A substantial OIE on {lambda}{sub ab} was observed in various cuprate families at all doping levels, suggesting that cuprate HTS are non-adiabatic superconductors. The experiments clearly demonstrate that the total OIE on T{sub c} and {lambda}{sub ab} arise from the oxygen sites within the superconducting CuO{sub 2} planes, demonstrating that the phonon modes involving the movement of planar oxygen are dominantly coupled to the supercarriers. Finally, it is shown that the OIE on T{sub c} and {lambda}{sub ab} exhibit a relation that appears to be generic for different families of cuprate HTS. The observation of these unusual isotope effects implies that lattice effects play an essential role in cuprate HTS and have to be considered in any realistic model of high-temperature superconductivity.

  15. Calcium isotopic anomalies in the Allende meteorite

    International Nuclear Information System (INIS)

    Lee, T.; Papanastassiou, D.A.; Wasserburg, G.J.

    1978-01-01

    We report isotopic anomalies in Ca which were found in two Ca-Al-rich inclusions of the Allende meteorite. These inclusions previously had been shown to contain special anomalies for Mg and O which were attributed to fractionation and unknown nuclear effects. The Ca data, when corrected for mass fractionation by using 40 Ca/ 44 Ca as a standard, show nonlinear isotopic effects in 48 Ca of +13.5 per mil and in 42 Ca of +1.7 per mil for one sample. The second sample shows a 48 Ca depletion of -2.9 per mil, but all other isotopes are normal. Samples with large excesses in 26 Mg show no Ca anomalies. The effects demonstrate that isotopic anomalies exist for higher-atomic-number refractory elements in solar-system materials and do not appear to be readily explainable by a simple model. The correlation of O, Mg, and Ca results on the same inclusions requires the addition and preservation in the solar system of components from idverse nucleosynthetic sources. Observed anomalous Mg and Ca compositions for coexisting mineral phases are uniform within each inclusion, and require initial isotopic homogeneity within an inclusion but the preservation of wide variations between inclusions. Assuming formation of these inclusions by condensation from a gaseous part of the solar nebula, this implies isotopic heterogeneity on a scale of 10-10 2 km within the nebula

  16. Oxygen isotopes in tree rings record variation in precipitation δ18O and amount effects in the south of Mexico.

    Science.gov (United States)

    Brienen, Roel J W; Hietz, Peter; Wanek, Wolfgang; Gloor, Manuel

    2013-12-01

    [1] Natural archives of oxygen isotopes in precipitation may be used to study changes in the hydrological cycle in the tropics, but their interpretation is not straightforward. We studied to which degree tree rings of Mimosa acantholoba from southern Mexico record variation in isotopic composition of precipitation and which climatic processes influence oxygen isotopes in tree rings ( δ 18 O tr ). Interannual variation in δ 18 O tr was highly synchronized between trees and closely related to isotopic composition of rain measured at San Salvador, 710 km to the southwest. Correlations with δ 13 C, growth, or local climate variables (temperature, cloud cover, vapor pressure deficit (VPD)) were relatively low, indicating weak plant physiological influences. Interannual variation in δ 18 O tr correlated negatively with local rainfall amount and intensity. Correlations with the amount of precipitation extended along a 1000 km long stretch of the Pacific Central American coast, probably as a result of organized storm systems uniformly affecting rainfall in the region and its isotope signal; episodic heavy precipitation events, of which some are related to cyclones, deposit strongly 18 O-depleted rain in the region and seem to have affected the δ 18 O tr signal. Large-scale controls on the isotope signature include variation in sea surface temperatures of tropical north Atlantic and Pacific Ocean. In conclusion, we show that δ 18 O tr of M . acantholoba can be used as a proxy for source water δ 18 O and that interannual variation in δ 18 O prec is caused by a regional amount effect. This contrasts with δ 18 O signatures at continental sites where cumulative rainout processes dominate and thus provide a proxy for precipitation integrated over a much larger scale. Our results confirm that processes influencing climate-isotope relations differ between sites located, e.g., in the western Amazon versus coastal Mexico, and that tree ring isotope records can help in

  17. Laser separation of uranium isotopes

    International Nuclear Information System (INIS)

    Porter, J.T.

    1981-01-01

    Method and apparatus for separating uranium isotopes are claimed. The method comprises the steps of irradiating a uranyl source material at a wavelength selective to a desired isotope and at an effective temperature for isotope spectral line splitting below about 77 deg.K., further irradiating the source material within the fluorescent lifetime of the source material to selectively photochemically reduce the excited isotopic species, and chemically separating the reduced isotope species from the remaining uranyl salt compound

  18. Effect of baking and fermentation on the stable carbon and nitrogen isotope ratios of grain-based food.

    Science.gov (United States)

    Bostic, Joshua N; Palafox, Sherilyn J; Rottmueller, Marina E; Jahren, A Hope

    2015-05-30

    Isotope ratio mass spectrometry (IRMS) is used extensively to reconstruct general attributes of prehistoric and modern diets in both humans and animals. In order to apply these methods to the accurate determination of specific intakes of foods/nutrients of interest, the isotopic signature of individually consumed foods must be constrained. For example, 86% of the calories consumed in the USA are derived from processed and prepared foods, but the relationship between the stable isotope composition of raw ingredients and the resulting products has not been characterized. To examine the effect of common cooking techniques on the stable isotope composition of grain-based food items, we prepared yeast buns and sugar cookies from standardized recipes and measured bulk δ(13) C and δ(15) N values of samples collected throughout a 75 min fermentation process (buns) and before and after baking at 190°C (buns and cookies). Simple isotope mixing models were used to determine if the isotopic signatures of 13 multi-ingredient foods could be estimated from the isotopic signatures of their constituent raw ingredients. No variations in δ(13) C or δ(15) N values were detected between pre- and post-baked yeast buns (pre: -24.78‰/2.61‰, post: -24.75‰/2.74‰), beet-sugar cookies (pre: -24.48‰/3.84‰, post: -24.47‰/3.57‰), and cane-sugar cookies (pre: -19.07‰/2.97‰, post: -19.02‰/3.21‰), or throughout a 75 min fermentation process in yeast buns. Using isotopic mass balance equations, the δ(13) C/δ(15) N values of multi-ingredient foods were estimated from the isotopic composition of constituent raw ingredients to within 0.14 ± 0.13‰/0.24 ± 0.17‰ for gravimetrically measured recipes and 0.40 ± 0.38‰/0.58 ± 0.53‰ for volumetrically measured recipes. Two common food preparation techniques, baking and fermentation, do not substantially affect the carbon or nitrogen isotopic signature of grain-based foods. Mass-balance equations can be used to

  19. Isotopic effect on the quantum tunneling of the magnetization of molecular nanomagnets

    International Nuclear Information System (INIS)

    Sessoli, Roberta; Caneschi, Andrea; Gatteschi, Dante; Sorace, Lorenzo; Cornia, Andrea; Wernsdorfer, Wolfgang

    2001-01-01

    The molecular cluster [Fe 8 (tacn) 6 O 2 (OH) 12 ]Br 8 ·9H 2 O, Fe 8 , characterized by S=10, with biaxial magnetic anisotropy is an ideal system to investigate quantum effects in the dynamics of the magnetization. Resonant quantum tunneling gives rise to stepped hysteresis cycles and below 0.35 K pure quantum tunneling of the magnetization has been observed. The role of hyperfine fields in promoting the tunneling as a source of dynamic broadening of the states involved in the tunnel transition is investigated by preparing and characterizing two isotopically enriched samples using 57 Fe and 2 H. The relaxation rate in the tunneling regime is proportional to the hyperfine field generated by the nuclei. Also, the intrinsic linewidth of the tunneling resonance scales with the hyperfine field as confirmed by calculations of the super (or transfer) and direct hyperfine interactions. Preliminary results on a novel cluster of formula [Fe 4 (OCH 3 ) 6 (dpm) 6 ], Fe 4 , suited for a more dramatic isotope effect on the tunneling rate are also reported

  20. Isotopic effect on the quantum tunneling of the magnetization of molecular nanomagnets

    Energy Technology Data Exchange (ETDEWEB)

    Sessoli, Roberta E-mail: sessoli@chim1.unifi.it; Caneschi, Andrea; Gatteschi, Dante; Sorace, Lorenzo; Cornia, Andrea; Wernsdorfer, Wolfgang

    2001-05-01

    The molecular cluster [Fe{sub 8}(tacn){sub 6}O{sub 2}(OH){sub 12}]Br{sub 8}{center_dot}9H{sub 2}O, Fe{sub 8}, characterized by S=10, with biaxial magnetic anisotropy is an ideal system to investigate quantum effects in the dynamics of the magnetization. Resonant quantum tunneling gives rise to stepped hysteresis cycles and below 0.35 K pure quantum tunneling of the magnetization has been observed. The role of hyperfine fields in promoting the tunneling as a source of dynamic broadening of the states involved in the tunnel transition is investigated by preparing and characterizing two isotopically enriched samples using {sup 57}Fe and {sup 2}H. The relaxation rate in the tunneling regime is proportional to the hyperfine field generated by the nuclei. Also, the intrinsic linewidth of the tunneling resonance scales with the hyperfine field as confirmed by calculations of the super (or transfer) and direct hyperfine interactions. Preliminary results on a novel cluster of formula [Fe{sub 4}(OCH{sub 3}){sub 6}(dpm){sub 6}], Fe{sub 4}, suited for a more dramatic isotope effect on the tunneling rate are also reported.

  1. Trace element and isotopic effects arising from magma migration beneath mid-ocean ridges

    International Nuclear Information System (INIS)

    Kenyon, P.M.

    1990-01-01

    The trace element concentrations and isotopic ratios in the magma erupted on mid-ocean ridges may differ from those in the source material due to physical effects such as porous flow dispersion, exchange of trace elements between the fluid and solid phases during magma migration, and convective mixing in magma chambers. These differences are in addition to those produced by better known processes such as fractional crystallization and partial melting. The effects of the three former processes are described. It is predicted that magma typically reaches the sub-ridge magma chambers with a spatial heterogeneity only slightly reduced from that of the source material, but with a subdued variation in time. Convective mixing then further reduces the spatial heterogeneity. Application of the results for convective mixing to a recent Fourier analysis of 87 Sr/ 86 Sr variations along the Mid-Atlantic Ridge suggests that the falloff in amplitude of variation observed with decreasing wavelength in the Mid-Atlantic Ridge data cannot be explained by convective mixing in magma chambers. Instead, it is postulated that this falloff is due to the mechanics of the production and/or the solid-state convective mixing of chemical and isotopic heterogeneities in the solid mantle. (orig.)

  2. Isotopic study of the effect of Tarbela reservoir on the groundwater system in the downstream areas

    International Nuclear Information System (INIS)

    Sajjad, M.I.; Tasneem, M.A.; Hussain, S.D.; Khan, I.H.; Ali, M.; Latif, Z.

    1994-04-01

    Isotopic studies were carried out on the right side of river Indus, downstream of Tarbela dam to study the effect of Tarbela Reservoir on the groundwater system. The main objectives of the study were to determine the hydraulic connection, if any, between the Tarbela Lake and the groundwater appearing in the ponds near Gadon Amazai, see the effect of Tarbela dam on the groundwater system in the downstream areas, compute the relative contribution of different recharge sources towards groundwater system and to estimate residence time of groundwater in the area. Isotopic data reveals that the ponds near Gadoon Amazai area are being recharged by local rains and there is no contribution of Tarbela lake. The area around Gadoon Amazai, Topi and Kalabat is solely recharged by local rains while the area around Swabi, Zaida and Lahor has mixed recharge with major contribution from local canal system. Tritium data suggests that the residence time of groundwater in the study area varies from a few years to 30 years. Te groundwater in the area has low dissolved salt contents and is, generally, of good quality. (author) 19 figs

  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. Prediction of isotope effects for anticipated intermediate structures in the course of bacterial denitrification

    International Nuclear Information System (INIS)

    Morgenstern, M.A.; Schowen, R.L.

    1989-01-01

    Vibrational-analysis methods have been used to estimate the equilibrium 14 N/ 15 N isotope effects to be expected for conversion of nitrite anion to thirteen possible intermediate-state and product-state structures [HONO, NO + , NO, NO - , FeNO, ON * NO 2 , O * NNO 2 , O 2 NNO 2 , ONO * N, O * NON, ONNO, * NNO, N * NO] in the reduction of nitrite ion to nitrous oxide denitrifying bacteria. The results, taken in combination with previous experimental isotope-effect and tracer studies of the Pseudomonas stutzeri and related systems, are consistent with a suggestion that a second nitrite anion enters the enzyme-catalytic cycle at the stage of a nitrosyl-ion intermediate but re-emerges after entry of the reducing electrons; the product nitrous oxide is then formed by disproportionation of enzymically generated hyponitrous acid. The calculations are consistent with contributions, under different experimental conditions, of several different transition states to limiting the rate of the enzymic reaction. These transition states (and the corresponding experimental conditions) are the transition states for N-O fission in the generation of a mononitrogen electrophilic species from nitrite anion (high reductant, high nitrite concentrations), for attack of nitrite on this electrophile (high reductant, low nitrite concentrations) and for electron transfer to a dinitrogen-trioxide-like species (low reductant concentration). (orig.)

  5. 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.)

  6. Antiproton-nucleus interaction and nuclear E2 resonance effect in molybdenum and neodymium isotopes

    International Nuclear Information System (INIS)

    Kanert, W.

    1986-01-01

    Antiprotonix X-radiation from 92 Mo, 94 Mo, 95 Mo, 98 Mo, 100 Mo and 146 Nd, 148 Nd was measured with Ge detectors at the LEAR (CERN). The nuclear E2 resonance effect (configuration mixing by dynamic electric quadrupole interaction) was for the first time observed in antiprotonic atoms. It effects in 94 Mo, 95 Mo, and 98 Mo a mixing of the atomic levels (7,6) and (5,4). From the resulting weakening of the antiprotonic X-ray line (7→6) in comparison with the nonresonant isotope 92 Mo information on the effects of the strong interaction in the (5,4) level was obtained which is in Mo not directly observable. The absorption widths by strong interactions in the level (6,5) resulted for 92 Mo, 94 Mo, 95 Mo, and 98 Mo to 1.4±0.3 keV, 2.3±0.9 keV, 1.9±0.4 keV, and 2.3±0.7 keV, the energy shifts by strong interactions to 0.46±0.08 keV, 0.64±0.22 keV, 0.74±0.12 keV, and 0.55±0.16 keV. In the nonresonant isotope 92 Mo the absorption width of the level (7,6) to 19.5±1.2 eV. A fit of the effective scattering length to the data for 92 Mo resulted anti a = (0.25+3.05i) fm. In 100 Mo the predicted case of strong coupling could be experimentally established by the nearly complete extinction of the line (8→7) and the broadening of the line (9→8). In 148 Nd the nuclear E2 resonance effect effects a mixing of the levels (9,8) and (8,6) and by this a reduction of the line (9→8) in comparison to 146 Nd. For this isotope information on the effects of the strong interaction could be extracted separately for the fine structure components. (orig.) [de

  7. 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

  8. Effect of sildenafil citrate (Viagra) on coronary flow in normal subjects.

    Science.gov (United States)

    Ishikura, Fuminobu; Beppu, Shintaro; Ueda, Hiroaki; Nehra, Ajay; Khandheria, Bijoy K

    2008-01-01

    The purpose of this study was to evaluate the effect of sildenafil citrate (Viagra) on coronary function in normal subjects. The study assessed mean blood pressure, left anterior descending coronary artery (LAD) flow, and echocardiographic variables before and 30 and 60 minutes after taking 50 mg of sildenafil citrate. The mean velocity of LAD flow was assessed with Doppler flow imaging. The study subjects were 6 healthy male volunteers (mean age 37 years). The mean velocity of LAD flow increased 60 minutes after taking sildenafil citrate, but there were no other changes. Two volunteers felt mild flashing and one had mild headache during the study. Sildenafil citrate caused vasodilatation in a normal coronary artery without systemic pressure drops. These results suggest that the agent itself did not have negative effects on the heart in normal subjects.

  9. Deflection of atomic beams with isotope separation by optical resonance radiation using stimulated emission and the ac stark effect

    International Nuclear Information System (INIS)

    Bjorkholm, J.E.; Liao, P.F.H.

    1977-01-01

    Improved atomic beam deflection and improved isotope separation, even in vapors, is proposed by substituting the A.C. Stark effect for the baseband chirp of the pushing beam in the prior proposal by I. Nebenzahl et al., Applied Physics Letters, Vol. 25, page 327 (September 1974). The efficiency inherent in re-using the photons as in the Nebenzahl et al proposal is retained; but the external frequency chirpers are avoided. The entire process is performed by two pulses of monochromatic coherent light, thereby avoiding the complication of amplifying frequency-modulated light pulses. The A.C. Stark effect is provided by the second beam of coherent monochromatic light, which is sufficiently intense to chirp the energy levels of the atoms or isotopes of the atomic beam or vapor. Although, in general, the A.C. Stark effect will alter the isotope shift somewhat, it is not eliminated. In fact, the appropriate choice of frequencies of the pushing and chirping beams may even relax the requirements with respect to the isotope absorption line shift for effective separation. That is, it may make the isotope absorption lines more easily resolvable

  10. Toxic effect of C60 fullerene-doxorubicin complex towards tumor and normal cells in vitro

    Directory of Open Access Journals (Sweden)

    Prylutska S. V.

    2014-09-01

    Full Text Available Creation of new nanostructures possessing high antitumor activity is an important problem of modern biotechnology. Aim. To evaluate cytotoxicity of created complex of pristine C60 fullerene with the anthracycline antibiotic doxorubicin (Dox, as well as of free C60 fullerene and Dox, towards different cell types – tumor, normal immunocompetent and hepatocytes. Methods. Measurement of size distribution for particles in C60 + Dox mixture was performed by a dynamic light scattering (DLS technique. Toxic effect of C60 + Dox complex in vitro towards tumor and normal cells was studied using the MTT assay. Results. DLS experiment demonstrated that the main fraction of the particles in C60 + Dox mixture had a diameter in the range of about 132 nm. The toxic effect of C60 + Dox complex towards normal (lymphocytes, macrophages, hepatocytes and tumor (Ehrlich ascites carcinoma, leukemia L1210, Lewis lung carcinoma cells was decreased by ~10–16 % and ~7–9 %, accordingly, compared with the same effect of free Dox. Conclusions. The created C60 + Dox composite may be considered as a new pharmacological agent that kills effectively tumor cells in vitro and simultaneously prevents a toxic effect of the free form of Dox on normal cells.

  11. Investigations on the heterogenous catalytic hydrogenation using isotope effect and gamma- and neutron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Kudlacek, R; Cabicar, J [Ceske Vysoke Uceni Technicke, Prague (Czechoslovakia). Katedra Jaderne Chemie

    1976-01-01

    The kinetic and solvent isotope effects during the maleic acid heterogeneous catalytic hydrogenation and deuteration in light and heavy water have been studied. Also the effect of the gamma and neutron irradiation on the Ni-ZnO catalysts (with various ratios of components) on the reaction kinetics and mechanism has been measured, as well as the effect of pH on the adsorption behaviour of maleic acid and the temperature dependence of the reaction rate. Existence of different adsorption centers for hydrogen and maleic acid could be deduced from these experiments. A reaction mechanism based on the two-dimensional diffusion of components in the surface is proposed. The catalyst is formed from Ni and ZnO-microspheres. Hydrogen is bound to nickel and maleic acid is adsorbed on the ZnO-microspheres. The reaction takes place on the boundary layers of these microspheres.

  12. Comparison of effective atomic numbers of the cancerous and normal kidney tissue

    International Nuclear Information System (INIS)

    Manjunatha, H.C.

    2015-01-01

    The effective atomic number (Z eff ) and electron density (N e ) of normal kidney and cancerous kidney have been computed for total and partial photon interactions by computing the molecular, atomic, and electronic cross section in the wide energy range of 1 keV-100 GeV using WinXCOM. The mean Z eff and N e of normal kidney and cancerous kidney in the various energy ranges and for total and partial photon interactions are tabulated. The variation of effective N e with energy is shown graphically for all photon interactions. In addition to this computer tomography (CT), numbers of normal kidney and cancerous kidney for photon interaction and energy absorption is also computed. The role of Z eff in the dual-energy dividing radiography is also discussed. The values of Z eff and N e for cancerous kidney are higher than normal kidney. This is due to the levels of elements K, Ca, Fe, Ni, and Se are lower and those of the elements Ti, Co, Zn, As, and Cd are higher in the cancer tissue of kidney than those observed in the normal tissue. The soft tissue and cancerous tissue are very similar, but their atomic number differs. The cancerous tissue exhibits a higher Z eff than the normal tissue. This fact helps in the dual-energy dividing radiography which enables to improve the diagnosis of the kidney cancer. Hence, the computed values may be useful in the diagnosis of the kidney cancer. CT numbers for normal kidney are higher than cancerous kidney. (author)

  13. Groundwater Inputs to Rivers: Hydrological, Biogeochemical and Ecological Effects Inferred by Environmental Isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Stellato, L. [Centre for Isotopic Research on Cultural and Environmental heritage (CIRCE), Seconda Universita degli Studi di Napoli, Caserta (Italy); Newman, B. D. [Isotope Hydrology Section, International Atomic Energy Agency, Vienna (Austria)

    2013-05-15

    In an effort to improve river management, numerous studies over the past two decades have supported the concept that river water and groundwater need to be considered together, as part of a hydrologic continuum. In particular, studies of the interface between surface water and groundwater (the hyporheic zone) have seen the tight collaboration of catchment hydrologists and stream ecologists in order to elucidate processes affecting stream functioning. Groundwater and surface waters interact at different spatial and temporal scales depending on system hydrology and geomorphology, which in turn influence nutrient cycling and in-stream ecology in relation to climatic, geologic, biotic and anthropogenic factors. In this paper, groundwater inputs to rivers are explored from two different and complementary perspectives: the hydrogeological, describing the generally acknowledged mechanisms of streamflow generation and the main factors controlling stream-aquifer interactions, and the ecologic, describing the processes occurring at the hyporheical and the riparian zones and their possible effects on stream functioning and on nutrient cycling, also taking into consideration the impact of human activities. Groundwater inflows to rivers can be important controls on hot moment/hot spot type biogeochemical behaviors. A description of the common methods used to assess these processes is provided emphasizing tracer methods (including physical, chemical and isotopic). In particular, naturally occurring isotopes are useful tools to identify stream discharge components, biogeochemical processes involved in nutrient cycling (such as N and P dynamics), nutrient sources and transport to rivers, and subsurface storage zones and residence times of hyporheic water. Several studies which have employed isotope techniques to clarify the processes occurring when groundwater enters the river,are reported in this chapter, with a view to highlighting both the advantages and limitations of these

  14. Study on the metabolism of physiological amounts of Cr(III) intragastrical administration in normal rats using activable enriched stable isotope Cr-50 compound as a tracer

    International Nuclear Information System (INIS)

    Feng, W.Y.; Ding, W.J.; Qian, Q.F.; Chai, Z.F.

    1998-01-01

    In order to study the metabolism of physiological amounts of 51 Cr (10μg/100 g of body wt.) intragastrically administered in rats, the activable enriched stable isotope Cr-50 compound Cr 2 O 3 was used as a tracer. The absorption and distribution of 51 Cr(III) in rats with time were studied. Significant 51 Cr contents were found in all the organs and tissues of interest. The kidney, liver and bone contain higher amounts of 51 Cr than others. The fact that specific activities of 51 Cr are notably high in kidney, bone, spleen and pancreas and decrease gradually with time suggests that there are tighter binding of chromium in these organs. The excretion of 51 Cr at various time intervals was also studied. Almost totally intragastrically administered dose was excreted in the feces. The increased urinary excretion of 51 Cr with time indicates that the urine-chromium is the metabolic derivative of organism. In view of the tissues distribution and excretion, it can be concluded that no more than 1% of the dose was absorbed from the gastrointestinal tract. (author)

  15. 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

  16. ALERT. Adverse late effects of cancer treatment. Vol. 2. Normal tissue specific sites and systems

    Energy Technology Data Exchange (ETDEWEB)

    Rubin, Philip; Constine, Louis S. [Univ. Rochester Medical Center, NY (United States). Dept. of Radiation Oncology; Marks, Lawrence B. (ed.) [Univ. North Carolina and Lineberger, Comprehensive Cancer Center, Chapel Hill, NC (United States). Dept. of Radiation Oncology

    2014-09-01

    Comprehensively documents potential late effects in all the normal tissue sites in the human body. Considers in detail the detection, diagnosis, management and prevention of effects and discusses prognostic outcomes. Clearly presents radiation risk factors and interactions with chemotherapy effects. Provides the most current evidence-based medicine for cancer care survivorship guidelines. The literature on the late effects of cancer treatment is widely scattered in different journals since all major organ systems are affected and management is based on a variety of medical and surgical treatments. The aim of ALERT - Adverse Late Effects of Cancer Treatment is to offer a coherent multidisciplinary approach to the care of cancer survivors. The central paradigm is that cytotoxic multimodal therapy results in a perpetual cascade of events that affects each major organ system differently and is expressed continually over time. Essentially, radiation and chemotherapy are intense biologic modifiers that allow for cancer cure and cancer survivorship but accelerate senescence of normal tissues and increase the incidence of age-related diseases and second malignant tumors. Volume 2 of this two-volume work comprehensively documents potential late effects in all the normal tissue anatomic sites in the human body. The detection, diagnosis, management and prevention of effects are all considered in detail, and prognostic outcomes are discussed. Radiation risk factors and interactions with chemotherapy effects are clearly presented. The text is accompanied by numerous supportive illustrations and tables.

  17. Deduction of kinetic mechanism in multisubstrate enzyme reactions from tritium isotope effects. Application to dopamine beta-hydroxylase

    International Nuclear Information System (INIS)

    Klinman, J.P.; Humphries, H.; Voet, J.G.

    1980-01-01

    Primary tritium isotope effects have been measured for the hydroxylation of [2-3H] dopamine catalyzed by dopamine beta-hydroxylase. Experimental values vary from 8.8 +/- 1.4 at 0.02 mM oxygen to 4.1 +/- 0.6 at 1.0 mM oxygen. It is shown that the observed dependence of the isotope effect on oxygen concentration provides unequivocal evidence for a kinetically significant dissociation of both dopamine and oxygen from enzyme, ternary complex. This approach, which is applicable to any multisubstrate enzyme characterized by detectable kinetic isotope effects, provides an alternate to classical methods for the elucidation of kinetic order in enzyme-catalyzed reactions

  18. The effects of normal aging on multiple aspects of financial decision-making.

    Directory of Open Access Journals (Sweden)

    Dorien F Bangma

    Full Text Available Financial decision-making (FDM is crucial for independent living. Due to cognitive decline that accompanies normal aging, older adults might have difficulties in some aspects of FDM. However, an improved knowledge, personal experience and affective decision-making, which are also related to normal aging, may lead to a stable or even improved age-related performance in some other aspects of FDM. Therefore, the present explorative study examines the effects of normal aging on multiple aspects of FDM.One-hundred and eighty participants (range 18-87 years were assessed with eight FDM tests and several standard neuropsychological tests. Age effects were evaluated using hierarchical multiple regression analyses. The validity of the prediction models was examined by internal validation (i.e. bootstrap resampling procedure as well as external validation on another, independent, sample of participants (n = 124. Multiple regression and correlation analyses were applied to investigate the mediation effect of standard measures of cognition on the observed effects of age on FDM.On a relatively basic level of FDM (e.g., paying bills or using FDM styles no significant effects of aging were found. However more complex FDM, such as making decisions in accordance with specific rules, becomes more difficult with advancing age. Furthermore, an older age was found to be related to a decreased sensitivity for impulsive buying. These results were confirmed by the internal and external validation analyses. Mediation effects of numeracy and planning were found to explain parts of the association between one aspect of FDM (i.e. Competence in decision rules and age; however, these cognitive domains were not able to completely explain the relation between age and FDM.Normal aging has a negative influence on a complex aspect of FDM, however, other aspects appear to be unaffected by normal aging or improve.

  19. Effect of utilizing unground and ground normal and black rice husk ...

    Indian Academy of Sciences (India)

    The aim of the present study is to investigate the effects of utilizing different processings of normal rice husk ash (RHA) and black rice husk ash (BRHA) on the mechanical and durability properties of high strength concrete (HSC). Mechanical and durability properties of HSC were evaluated on concrete mixes containing ...

  20. Hall effect in the normal phase of the organic superconductor (TMTSF)2PF6

    DEFF Research Database (Denmark)

    Moser, J.; Cooper, J.R.; Jerome, D.

    2000-01-01

    We report accurate Hall effect measurements performed in the normal phase of the quasi-one-dimensional organic conductor (TMTSF)(2)PF(6) at ambient pressure. The Hall coefficient is found to be strongly temperature dependent all the way from 300 K down to the spin density wave onset arising aroun...

  1. Effect of annealing treatments on normal state resistivity of YBa 2 ...

    African Journals Online (AJOL)

    Samples of YBa2(Cu1-xTix)3Oy superconductor with x=0.00 , 0.01, 0.03 have been prepared by solide state reaction method. The effect of annealing treatments on normal electrical resistivity has been done using the bipolaron model. The results of this study show the increase of localized charge when the dopant content ...

  2. Effect of normal stress under an excitation in poroelastic flat slabs

    African Journals Online (AJOL)

    user

    Biot's poroelastic theory is employed to investigate stresses under an ... Keywords: Flat slab, radial normal stress, pervious surface, impervious ... warranted, because of above mentioned applications. ...... M.Tajuddin, and G. Narayan Reddy, Effect of boundaries on the dynamic interaction of a liquid filled porous layer and a.

  3. The effect of ascorbic acid and propranolol on normal sleep and ...

    African Journals Online (AJOL)

    This study was designed to investigate the possible effects of ascorbic acid on open field locomotor activity and normal sleep in healthy adult rats and evaluate how these correlate with those of propranolol. MethodS: Eighty healthy adult Wistar rats of both sexes were divided into two groups of 40 animals each group.

  4. Molybdenum isotope variations in calc-alkaline lavas from the Banda arc, Indonesia: Assessing the effect of crystal fractionation in creating isotopically heavy continental crust

    NARCIS (Netherlands)

    Wille, Martin; Nebel, Oliver; Pettke, Thomas; Vroon, Pieter Z.; König, Stephan; Schoenberg, Ronny

    2018-01-01

    Recent studies report a large Mo isotope variability of up to 1‰ (expressed in δ98/95MoNIST3134) in convergent margin lavas. These isotopic variations have been associated with subduction zone processes and ultimately may account for heavy and variable isotope signatures in evolved continental

  5. Differential Effects of Tea Extracts on Growth and Cytokine Production by Normal and Leukemic Human Leukocytes

    Directory of Open Access Journals (Sweden)

    Diana Bayer

    2012-04-01

    Full Text Available Background: Tea is one of the world’s most highly consumed beverages, second only to water. It is affordable and abundant and thus has great potential for improving health of those in both developed and developing areas. Green, oolong, and black teas differ in the extent of fermentation and types of bioactive polyphenols produced. Green tea and its major polyphenol decrease growth of some cancer cells and effect production of immune system cytokines. This study compares the effects of different types of tea extracts on viability and cytokine production by normal and leukemic human T lymphocytes. Generation of the toxic reactive oxygen species H2O2 by extracts was also examined.Methods: The Jurkat T lymphoblastic leukemia cells and mitogen-stimulated normal human peripheral blood mononuclear cells were used in this study. Cell viability was determined by (3-4,5-dimethylthiamizol-2-yl-diphenyltetrazolium bromide assay and production of interleukin-2 by Enzyme-Linked ImmunoSorbent Assay. Levels of H2O2 generated by tea extracts were determined using the xylenol-orange method.Results: We found that green, oolong, and black tea extracts differentially effect the growth and viability of T lymphoblastic leukemia cells and normal peripheral blood mononuclear cells, substantially decreasing both growth and viability of leukemic T lymphocytes and having much lesser effects on their normal counterparts. Tea extracts also had differential effects on the production of the T lymphocyte growth factor interleukin-2, significantly decreasing production by leukemic cells while having only minor effects on normal cells. All three extracts induced H2O2 generation, with green and oolong tea extracts having the greatest effect. Leukemic cells were much more susceptible to growth inhibition and killing by H2O2 than normal lymphocytes.Functional Foods in Health and Disease 2012, 2(4:72-85 Conclusions: The three tea extracts studied altered leukemic T lymphocyte

  6. Isotope effect in the carbonyl sulfide reaction with O(3P)

    DEFF Research Database (Denmark)

    Hattori, Shohei; Schmidt, Johan Albrecht; Mahler, Denise W.

    2012-01-01

    The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O((3)P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear...... least-squares spectral fitting procedure with line parameters from the HITRAN database. The ratio of the rate of the reaction of OC(34)S relative to OC(32)S was found to be 0.9783 ± 0.0062 ((34)e = (-21.7 ± 6.2)‰). The KIE was also calculated using quantum chemistry and classical transition state theory......; at 300 K, the isotopic fractionation was found to be (34)e = -14.8‰. The OCS sink reaction with O((3)P) cannot explain the large fractionation in (34)S, over +73‰, indicated by remote sensing data. In addition, (34)e in OCS photolysis and OH oxidation are not larger than 10‰, indicating that...

  7. Isotope effect on hydrated electron relaxation dynamics studied with time-resolved liquid jet photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Elkins, Madeline H.; Williams, Holly L. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Neumark, Daniel M., E-mail: dneumark@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2016-05-14

    The excited state relaxation dynamics of the solvated electron in H{sub 2}O and D{sub 2}O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H{sub 2}O and 102 ± 8 fs in D{sub 2}O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.

  8. Lithium isotope effects in chemical exchange with (2,2,1) cryptand

    International Nuclear Information System (INIS)

    Jepson, B.E.; Cairns, G.A.

    1979-01-01

    Equilibrium single-stage separation factors were determined for three lithium - (2,2,1) cryptand two-phase chemical exchange systems. The equilibrated phases consisted of an aqueous solution of a lithium salt and a chloroform solution of lithium cryptate salt complex. Lithium-6 concentrated in the organic phase in all cases, and the lithium isotope exchange rate with (2,2,1) cryptand was rapid. The separation factors were α = 1.026 +- 0.006 (LiBr exchange), α = 1.035 +- 0.003 (LiTFA), and α = 1.041 +- 0.006 (LiTFA + HTFA), where TFA represents trifluoroacetate. These values were compared with separation factors of other lithium chemical exchange systems. This work has shown that separation factors are influenced by the choice of chemical species and parameters. It has also demonstrated that significant lithium isotope effects can be obtained without a valence change of the metal exchanging between the aquo and cryptate complexes

  9. 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

  10. Isotope effect in heavy/light water suspensions of optically active gold nanoparticles

    Science.gov (United States)

    Kutsenko, V. Y.; Artykulnyi, O. P.; Petrenko, V. I.; Avdeev, M. V.; Marchenko, O. A.; Bulavin, L. A.; Snegir, S. V.

    2018-04-01

    Aqueous suspensions of optically active gold nanoparticles coated with trisodium citrate were synthesized in light (H2O) water and mixture of light and heavy (H2O/D2O) water using the modified Turkevich protocol. The objective of the paper was to verify sensitivity of neutron scattering methods (in particular, neutron reflectometry) to the potential isotope H/D substitution in the stabilizing organic shell around particles in colloidal solutions. First, the isotope effect was studied with respect to the changes in the structural properties of metal particles (size, shape, crystalline morphology) in solutions by electron microscopy including high-resolution transmission electron microscopy from dried systems. The structural factors determining the variation in the adsorption spectra in addition to the change in the optical properties of surrounding medium were discussed. Then, neutron reflectometry was applied to the layered nanoparticles anchored on a silicon wafer via 3-aminopropyltriethoxysilane molecules to reveal the presence of deuterated water molecules in the shell presumably formed by citrate molecules around the metallic core.

  11. Shell and isotopic effects in neutron interaction with nuclei. [Optical model and nucleus asymmetry correlations

    Energy Technology Data Exchange (ETDEWEB)

    Pasechnik, M V

    1978-01-01

    Major results of investigations into the shell structure of deformed nuclei with the number of neutrons of approximately 100, as well as new isotopic effects in the inelastic scattering of fast neutrons with nuclei are reported. The experiments conducted at the WWR-M research reactor have shown a substantial dependence of the nuclear excited energy-level density on the mass number and the number of neutrons. The fact resulted in a conclusion that the deformed nuclei possess filled shells, that was an incentive to revise the whole nuclear shell concept. In particular it was established that the property of magicity rests not only on the sphericity of nuclei but it may be also observed in strongly deformed nuclei. The isotope-spin dependence of the nuclear potential was studied at the AG-5 pulse electrostatic generator. The parameters of the potential were determined by comparing the experimental data on inelastic scattering and polarization of fast neutrons by nuclei from /sup 48/Ti to /sup 209/Bi with the calculations in terms of the optical model. Simple correlations were established between the optical potential and the nucleus asymmetry parameter ..cap alpha..=N-Z/A in wide ranges of mass numbers and neutron energy.

  12. Use of normalized total dose to represent the biological effect of fractionated radiotherapy

    International Nuclear Information System (INIS)

    Flickinger, J.C.; Kalend, A.

    1990-01-01

    There are currently a number of radiobiological models to account for the effects of dose fractionation and time. Normalized total dose (NTD) is not another new model but is a previously reported, clinically useful form in which to represent the biological effect, determined by any specific radiobiological dose-fractionation model, of a course of radiation using a single set of standardized, easily understood terminology. The generalized form of NTD reviewed in this paper describes the effect of a course of radiotherapy administered with nonstandard fractionation as the total dose of radiation in Gy that could be administered with a given reference fractionation such as 2 Gy per fraction, 5 fractions per week that would produce an equivalent biological effect (probability of complications or tumor control) as predicted by a given dose-fractionation formula. The use of normalized total dose with several different exponential and linear-quadratic dose-fraction formulas is presented. (author). 51 refs.; 1 fig.; 1 tab

  13. Picture superiority in free recall: the effects of normal aging and primary degenerative dementia.

    Science.gov (United States)

    Rissenberg, M; Glanzer, M

    1986-01-01

    A key factor in the decline of memory with age may be a breakdown of communication in the information network involved in memory and cognitive processing. A special case of this communication is assumed to underlie the picture superiority effect in recall. From this hypothesis it follows that the picture superiority effect should lessen with age. In Experiment 1, three groups of adults (young, old normal, and old memory-impaired) were tested in free recall of pictures and word lists. As predicted, the picture superiority effect declined with age. Experiment 2 replicated these findings and showed, moreover, that the picture superiority effect can be reestablished in normal old adults by instructing them to verbalize overtly during item presentation.

  14. Use of normalized total dose to represent the biological effect of fractionated radiotherapy

    Energy Technology Data Exchange (ETDEWEB)

    Flickinger, J C; Kalend, A [Pittsburgh University School of Medicine (USA). Department of Radiation Oncology Pittsburg Cancer Institute (USA)

    1990-03-01

    There are currently a number of radiobiological models to account for the effects of dose fractionation and time. Normalized total dose (NTD) is not another new model but is a previously reported, clinically useful form in which to represent the biological effect, determined by any specific radiobiological dose-fractionation model, of a course of radiation using a single set of standardized, easily understood terminology. The generalized form of NTD reviewed in this paper describes the effect of a course of radiotherapy administered with nonstandard fractionation as the total dose of radiation in Gy that could be administered with a given reference fractionation such as 2 Gy per fraction, 5 fractions per week that would produce an equivalent biological effect (probability of complications or tumor control) as predicted by a given dose-fractionation formula. The use of normalized total dose with several different exponential and linear-quadratic dose-fraction formulas is presented. (author). 51 refs.; 1 fig.; 1 tab.

  15. Alpha heating and isotopic mass effects in JET plasmas with sawteeth

    Energy Technology Data Exchange (ETDEWEB)

    Budny, R. V. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); Team, JET [EUROfusion Consortium, JET, Culham Science Centre, Abingdon, OX14 3DB, UK

    2016-02-09

    The alpha heating experiment in the Joint European Torus (JET) 1997 DTE1 campaign is re-examined. Several effects correlated with tritium content and thermal hydrogenic isotopic mass < A> weaken the conclusion that alpha heating was clearly observed. These effects delayed the occurrence of significant sawtooth crashes allowing the electron and ion temperatures T e and T i to achieve higher values. Under otherwise equal circumstances T e and T i were typically higher for discharges with higher < A >, and significant scaling of T i, T e, and total stored energy with < A > were observed. The higher T i led to increased ion–electron heating rates with magnitudes comparable to those computed for alpha electron heating. Rates of other heating/loss processes also had comparable magnitudes. Simulations of T e assuming the observed scaling of T i are qualitatively consistent with the measured profiles, without invoking alpha heating

  16. 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)

  17. 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...

  18. 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.)

  19. Sentiment Classification of Documents in Serbian: The Effects of Morphological Normalization and Word Embeddings

    Directory of Open Access Journals (Sweden)

    V. Batanović

    2017-11-01

    Full Text Available An open issue in the sentiment classification of texts written in Serbian is the effect of different forms of morphological normalization and the usefulness of leveraging large amounts of unlabeled texts. In this paper, we assess the impact of lemmatizers and stemmers for Serbian on classifiers trained and evaluated on the Serbian Movie Review Dataset. We also consider the effectiveness of using word embeddings, generated from a large unlabeled corpus, as classification features.

  20. Effects of tracheal occlusion with retinoic acid administration on normal lung development.

    Science.gov (United States)

    Delabaere, Amélie; Marceau, Geoffroy; Coste, Karen; Blanchon, Loïc; Déchelotte, Pierre-Jean; Blanc, Pierre; Sapin, Vincent; Gallot, Denis

    2017-05-01

    Tracheal occlusion (TO) is an investigational therapy for severe congenital diaphragmatic hernia that decreases pulmonary hypoplasia, but sustained TO also induces deficient surfactant synthesis. Intramuscular maternal administration of retinoic acid (RA) in a surgical rabbit model of congenital diaphragmatic hernia showed a beneficial effect on lung maturation. We evaluated the potential of RA delivery into the trachea and studied the combined effects of TO and RA on normal lung development. Experiments were performed on normal rabbit fetuses. Liposomes and capric triglyceride (Miglyol ® ), alone and with RA, were administered in the trachea just before TO (d26). Lung morphology and surfactant production were studied at term (d30). Tracheal occlusion increased lung weight and enhanced alveolar development but increased apoptotic activity and decreased surfactant expression. Tracheal injection of RA improved surfactant production to levels of normal controls. We established the potential of liposome and Miglyol as RA vehicle for delivering this bioactive molecule in the fetal airways. Tracheal RA injection seems to oppose the effects of TO in fetuses with normal lungs. © 2017 John Wiley & Sons, Ltd. © 2017 John Wiley & Sons, Ltd.

  1. Effects of hyperthermia and ionizing radiation in normal and ataxia telangiectasia human fibroblast lines

    International Nuclear Information System (INIS)

    Mitchel, R.E.J.; Chan, A.; Smith, B.P.; Child, S.D.; Paterson, M.C.

    1984-01-01

    The effects of 45 0 C hyperthermia and γ radiation have been studied in three normal human fibroblast lines (GM38, GM730, WI38) and compared to the effects in two lines derived from patients with the hereditary disease ataxia telangiectasia (AR3BI, AT5BI). All lines, both normal and γ-sensitive AT, showed a similar resistance to killing by heat alone, suggesting that the defect responsible for the increased radiation sensitivity in AT lines does not confer increased heat sensitivity. Shouldered survival curves were obtained in each case indicating the ability to accumulate sublethal heat damage. All normal and AT cell lines exhibited increased resistance to the lethal effects of heat in response to a thermal stress, indicating that the defect that causes radiosensitivity in AT cell lines does not prevent the induction of thermotolerance. It was hypothesized that in normal cells, this heat treatment inactivates the process which is already defective in AT lines, and that this process may be required for the proper rejoining of double-strand breaks produced during the repair of other radiation-induced lesions

  2. A comparison of the effects of caffeine following abstinence and normal caffeine use.

    Science.gov (United States)

    Addicott, Merideth A; Laurienti, Paul J

    2009-12-01

    Caffeine typically produces positive effects on mood and performance. However, tolerance may develop following habitual use, and abrupt cessation can result in withdrawal symptoms, such as fatigue. This study investigated whether caffeine has a greater stimulant effect in a withdrawn state compared to a normal caffeinated state, among moderate daily caffeine consumers. Using a within-subjects design, 17 caffeine consumers (mean +/- sd = 375 +/- 101 mg/day) ingested placebo or caffeine (250 mg) following 30-h of caffeine abstention or normal dietary caffeine use on four separate days. Self-reported mood and performance on choice reaction time, selective attention, and memory tasks were measured. Caffeine had a greater effect on mood and choice reaction time in the abstained state than in the normal caffeinated state, but caffeine improved selective attention and memory in both states. Although improvements in mood and reaction time may best explained as relief from withdrawal symptoms, other performance measures showed no evidence of withdrawal and were equally sensitive to an acute dose of caffeine in the normal caffeinated state.

  3. Effect of a Modest Weight Loss in Normalizing Blood Pressure in Obese Subjects on Antihypertensive Drugs

    Directory of Open Access Journals (Sweden)

    Luisa Gilardini

    2016-07-01

    Full Text Available Objective: To assess the effect of a lifestyle intervention in lowering/normalizing blood pressure (BP levels in hypertensive (controlled or not obese patients. Methods: In this prospective observational study, 490 obese hypertensive patients, 389 controlled (BP Results: 18.9% of CH and 20.0% of UH were on ≥ 3 antihypertensive drugs. Weight change (average -4.9 ± 2.7% was independent of the antihypertensive drugs employed. Systolic BP (SBP decreased by 23 mm Hg and diastolic BP (DBP by 9 mm Hg, in patients with UH most of whom (89% normalized BP levels (in 49% after a weight loss Conclusion: Lifestyle interventions are useful for all obese hypertensive patients in most of whom a modest weight loss is sufficient to normalize BP levels avoiding the aggressive use of multiple antihypertensive drugs.

  4. Mass-dependent and non-mass-dependent isotope effects in ozone photolysis: Resolving theory and experiments

    International Nuclear Information System (INIS)

    Cole, Amanda S.; Boering, Kristie A.

    2006-01-01

    In addition to the anomalous 17 O and 18 O isotope effects in the three-body ozone formation reaction O+O 2 +M, isotope effects in the destruction of ozone by photolysis may also play a role in determining the isotopic composition of ozone and other trace gases in the atmosphere. While previous experiments on ozone photolysis at 254 nm were interpreted as evidence for preferential loss of light ozone that is anomalous (or 'non-mass-dependent'), recent semiempirical theoretical calculations predicted a preferential loss of heavy ozone at that wavelength that is mass dependent. Through photochemical modeling results presented here, we resolve this apparent contradiction between experiment and theory. Specifically, we show that the formation of ozone during the UV photolysis experiments is not negligible, as had been assumed, and that the well-known non-mass-dependent isotope effects in ozone formation can account for the non-mass-dependent enrichment of the heavy isotopologs of ozone observed in the experiment. Thus, no unusual non-mass-dependent fractionation in ozone photolysis must be invoked to explain the experimental results. Furthermore, we show that theoretical predictions of a mass-dependent preferential loss of the heavy isotopologs of ozone during UV photolysis are not inconsistent with the experimental data, particularly if mass-dependent isotope effects in the chemical loss reactions of ozone during the photolysis experiments or experimental artifacts enrich the remaining ozone in 17 O and 18 O. Before the calculated fractionation factors can be quantitatively evaluated, however, further investigation of possible mass-dependent isotope effects in the reactions of ozone with O( 1 D), O( 3 P), O 2 ( 1 Δ), and O 2 ( 1 Σ) is needed through experiments we suggest here

  5. Effect of friction on vibrotactile sensation of normal and dehydrated skin.

    Science.gov (United States)

    Chen, S; Ge, S; Tang, W; Zhang, J

    2016-02-01

    Vibrotactile sensation mediated is highly dependent on surface mechanical and frictional properties. Dehydration of skin could change these properties. To investigate the relationship between friction and vibrotactile sensation of normal and dehydrated skin. Vibrations were firstly measured during surface exploration using a biomimetic sensor. Piglet skin was used as human skin model to study frictional properties for both normal and dehydrated skin using an atomic force microscope on nanoscale and a pin-on-disk tribometer on macroscale. Effect of vibrational frequency on friction and vibrotactile perception was also observed on nano and macro scale for normal and dehydrated skin. The result indicated that dehydrated skin was less sensitive than normal skin. The coefficient of friction of dehydrated skin is smaller than that of normal skin on both nano and macro scale. The coefficient of friction increases as increasing scanning frequencies. There is a positive correlation between coefficient of friction and vibrotactile sensation on nanoscale and macroscale. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  6. Possibilities and scope of the double isotope effect method in the elucidation of mechanisms of enzyme catalyzed reactions

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, H L; Medina, R [Technische Univ. Muenchen, Freising (Germany, F.R.). Lehrstuhl fuer Allgemeine Chemie und Biochemie

    1991-01-01

    Kinetic isotope effects on enzyme catalyzed reactions are indicative for the first irreversible in a sequence of individual steps. Hints on the relative velocities of other steps can only be obtained from the partitioning factor R and its dependence on external reaction conditions. In general, the experimental data needed are obtained from isotope abundance measurements in a defined position of the substrate or product as a function of turnover. This method does not reveal events dealing with neighbour atoms or preceding the main isotope sensitive step. In the method presented here, the analytical measurement is extended to the second atom involved in a bond fission of formation (Double Isotope Effect Method). It is shown that the additional results obtained support the identification of the main isotopically sensitive step and its relative contribution to the overall reaction rate, the identification of other kinetically significant steps and the differentiation between stepwise and concerted reaction mechanisms. The method and its advantages are demonstrated on reactions comprising C-N-bond splitting (urease and arginase reaction), C-C-bound fission (reactions catalyzed by pyruvate-dehydrogenase, pyruvate-formiate-lyase and lactate-oxidase), C-O-bound formation (ribulose-bisphosphate-oxygenase reaction), and N-O-bond fission (nitrate- and nitrite-reductase reactions). (orig.).

  7. The effect of warming on grassland evapotranspiration partitioning using laser-based isotope monitoring techniques

    KAUST Repository

    Wang, Lixin; Niu, Shuli; Good, Stephen P.; Soderberg, Keir; McCabe, Matthew; Sherry, Rebecca A.; Luo, Yiqi; Zhou, Xuhui; Xia, Jianyang; Caylor, Kelly K.

    2013-01-01

    The proportion of transpiration (T) in total evapotranspiration (ET) is an important parameter that provides insight into the degree of biological influence on the hydrological cycles. Studies addressing the effects of climatic warming on the ecosystem total water balance are scarce, and measured warming effects on the T/ET ratio in field experiments have not been seen in the literature. In this study, we quantified T/ET ratios under ambient and warming treatments in a grassland ecosystem using a stable isotope approach. The measurements were made at a long-term grassland warming site in Oklahoma during the May-June peak growing season of 2011. Chamber-based methods were used to estimate the δ2H isotopic composition of evaporation (δE), transpiration (δT) and the aggregated evapotranspiration (δET). A modified commercial conifer leaf chamber was used for δT, a modified commercial soil chamber was used for δE and a custom built chamber was used for δET. The δE, δET and δT were quantified using both the Keeling plot approach and a mass balance method, with the Craig-Gordon model approach also used to calculate δE. Multiple methods demonstrated no significant difference between control and warming plots for both δET and δT. Though the chamber-based estimates and the Craig-Gordon results diverged by about 12‰, all methods showed that δE was more depleted in the warming plots. This decrease in δE indicates that the evaporation flux as a percentage of total water flux necessarily decreased for δET to remain constant, which was confirmed by field observations. The T/ET ratio in the control treatment was 0.65 or 0.77 and the ratio found in the warming treatment was 0.83 or 0.86, based on the chamber method and the Craig-Gordon approach. Sensitivity analysis of the Craig-Gordon model demonstrates that the warming-induced decrease in soil liquid water isotopic composition is the major factor responsible for the observed δE depletion and the temperature

  8. The effect of warming on grassland evapotranspiration partitioning using laser-based isotope monitoring techniques

    KAUST Repository

    Wang, Lixin

    2013-06-01

    The proportion of transpiration (T) in total evapotranspiration (ET) is an important parameter that provides insight into the degree of biological influence on the hydrological cycles. Studies addressing the effects of climatic warming on the ecosystem total water balance are scarce, and measured warming effects on the T/ET ratio in field experiments have not been seen in the literature. In this study, we quantified T/ET ratios under ambient and warming treatments in a grassland ecosystem using a stable isotope approach. The measurements were made at a long-term grassland warming site in Oklahoma during the May-June peak growing season of 2011. Chamber-based methods were used to estimate the δ2H isotopic composition of evaporation (δE), transpiration (δT) and the aggregated evapotranspiration (δET). A modified commercial conifer leaf chamber was used for δT, a modified commercial soil chamber was used for δE and a custom built chamber was used for δET. The δE, δET and δT were quantified using both the Keeling plot approach and a mass balance method, with the Craig-Gordon model approach also used to calculate δE. Multiple methods demonstrated no significant difference between control and warming plots for both δET and δT. Though the chamber-based estimates and the Craig-Gordon results diverged by about 12‰, all methods showed that δE was more depleted in the warming plots. This decrease in δE indicates that the evaporation flux as a percentage of total water flux necessarily decreased for δET to remain constant, which was confirmed by field observations. The T/ET ratio in the control treatment was 0.65 or 0.77 and the ratio found in the warming treatment was 0.83 or 0.86, based on the chamber method and the Craig-Gordon approach. Sensitivity analysis of the Craig-Gordon model demonstrates that the warming-induced decrease in soil liquid water isotopic composition is the major factor responsible for the observed δE depletion and the temperature

  9. CURED I - LENT. Late effects of cancer treatment on normal tissues

    International Nuclear Information System (INIS)

    Rubin, P.; Okunieff, P.; Constine, L.S.; Rochester Univ. School of Medicine and Dentistry, Rochester, NY; Marks, L.B.

    2008-01-01

    The search for the most favorable therapeutic ratio - at which ablation of cancer is achieved while normal tissues are conserved - has been modern radiation oncology's equivalent of the quest for the Holy Grail. Our awareness of the late effects of radiation grew during the past century as new modalities were introduced. Heightened normal tissue reactions accompanied the higher rates of cancer ablation achieved by escalation of radiation doses, accelerated fractionated radiotherapy, and aggressive concurrent chemotherapy and radiation regimens. This volume is based on the LENT V NCI-sponsored meeting held in May 2004 and the CURED I conference held in 2006. Written by experts in the field, it addresses a number of critical topics relating to late effects, such as mechanisms of injury, the role of screening, options for interventions, second malignancies, and prevention. It is hoped that it will assist the reader in understanding how to prevent and treat the long-term side-effects of irradiation. (orig.)

  10. Mechanism of Nitrogenase H 2 Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects

    Energy Technology Data Exchange (ETDEWEB)

    Khadka, Nimesh [Department of Chemistry; Milton, Ross D. [Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States; Shaw, Sudipta [Department of Chemistry; Lukoyanov, Dmitriy [Department; Dean, Dennis R. [Department of Biochemistry, Virginia Tech, Blacksburg, Virginia 24061, United States; Minteer, Shelley D. [Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States; Raugei, Simone [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Hoffman, Brian M. [Department; Seefeldt, Lance C. [Department of Chemistry

    2017-09-15

    Nitrogenase catalyzes the reduction of dinitrogen (N2) to ammonia (NH3) with obligatory reduction of protons (H+) to dihydrogen (H2) through a mechanism involving reductive elimination of two [Fe-H-Fe] bridging hydrides at its active site FeMo-cofactor. The overall rate-limiting step is associated with ATP-driven electron delivery from Fe protein, precluding isotope effect measurements on substrate reduction steps. Here, we use mediated bioelectrocatalysis to drive electron delivery to MoFe protein without Fe protein and ATP hydrolysis, thereby eliminating the normal rate-limiting step. The ratio of catalytic current in mixtures of H2O and D2O, the proton inventory, changes linearly with the D2O/H2O ratio, revealing that a single H/D is involved in the rate limiting step. Kinetic models, along with measurements that vary the electron/proton delivery rate and use different substrates, reveal that the rate-limiting step under these conditions is the H2 formation reaction. Altering the chemical environment around the active site FeMo-cofactor in the MoFe protein either by substituting nearby amino acids or transferring the isolated FeMo-cofactor into a different peptide matrix, changes the net isotope effect, but the proton inventory plot remains linear, consistent with an unchanging rate-limiting step. Density functional theory predicts a transition state for H2 formation where the proton from S-H+ moves to the hydride in Fe-H-, predicting the number and magnitude of the observed H/D isotope effect. This study not only reveals the mechanism of H2 formation, but also illustrates a strategy for mechanistic study that can be applied to other enzymes and to biomimetic complexes.

  11. Isotope separation of 22Na and 24Na with using light induced drift effect

    International Nuclear Information System (INIS)

    Hradecny, C.; Tethal, T.; Ermolaev, I.M.; Zemlyanoj, S.G.; Zuzaan, P.

    1993-01-01

    The LIDIS (Light Drift Isotope Separation) separator without a gas flow is discussed. It is shown, that atomization degree of the separated isotopes limited real separation coefficient. The better buffer gas purification allowed to increase the experimental separation factor of 22 Na and 24 Na isotopes up to 25. The new experimental set up allow to increase the separation efficiency up to 50%. 12 refs.; 5 figs

  12. The nitrogen isotope effect of benthic remineralization-nitrification-denitrification coupling in an estuarine environment

    Directory of Open Access Journals (Sweden)

    M. Alkhatib

    2012-05-01

    Full Text Available The nitrogen (N stable isotopic composition of pore water nitrate and total dissolved N (TDN was measured in sediments of the St. Lawrence Estuary and the Gulf of St. Lawrence. The study area is characterized by gradients in organic matter reactivity, bottom water oxygen concentrations, as well as benthic respiration rates. N isotope effects on the water column associated with the benthic exchange of nitrate (εapp and TDN (εsed during benthic nitrification-denitrification coupling were investigated. The sediments were a major sink for nitrate and a source of reduced dissolved N (RDN = DON + NH4+. We observed that both the pore water nitrate and RDN pools were enriched in 15N relative to the water column, with increasing δ15N downcore in the sediments. As in other marine environments, the biological nitrate isotope fractionation of net fixed N loss was barely expressed at the scale of sediment-water exchange, with ϵapp values <3‰. The strongest under-expression (i.e. lowest εapp of the biological N isotope fractionation was observed at the most oxygenated sites with the least reactive organic matter, indicating that, through their control on the depth of the denitrification zone, bottom water oxygen concentrations and the organic matter reactivity can modulate εapp. For the first time, actual measurements of δ15N of pore water RDN were included in the calculations of εsed. We argue that large fractions of the sea-floor-derived DON are reactive and, hence, involved in the development of the δ15N of dissolved inorganic N (DIN in the water column. In the St. Lawrence sediments, the combined benthic N transformations yield a flux of 15N-enriched RDN that can significantly elevate εsed above εapp. Calculated εsed values were within the range of 4.6 ± 2

  13. 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)

  14. The effect of serum from obese and normal weight men on glucose metabolism in leucocytes

    International Nuclear Information System (INIS)

    Myking, O.; Kjoesen, B.; Bassoee, H.H.

    1980-01-01

    The influence of pooled serum from either obese or normal weight males on glucose metabolism in human leucocytes has been studied. Leucocytes from normal weight males were incubated with 10-90% pooled serum and either [U- 14 C], or [1- 14 C]glucose. Compared to serum from the normal weight males, serum from the obese group had a more stimulating effect on the 14 CO 2 and [ 14 C]lactate production from [U- 14 C]glucose and on the 14 CO 2 production from [1- 14 C]glucose. The two serum pools had the same stimulating effect on the Embden-Meyerhof pathway as indicated by the formation of [ 14 C]lactate from [l- 14 C]glucose. Calculations revealed that the activity in the pentose phosphate pathway was stimulated more by serum from obese, than from normal weight males. It is a possibility that increased stimulation of the pentose phosphate pathway may contribute to the development of overweight. (author)

  15. Estimation of the specific mass effect in the isotope shifts of energy levels in the optical spectrum of Ba I and Ba II

    International Nuclear Information System (INIS)

    Pendrill, L.R.

    1984-01-01

    A graphical method for separating mass and volume effects from purely optical isotope shift data is presented and compared with King's ''bunching'' method. Recent experimental data on isotope shifts for a wide range of spectral lines in the naturally abundant isotopes of Ba I and Ba II are analysed. Some agreement is found with muonic X-ray data concerning the nuclear size for the isotopes 136, 137 and 138, but there is disagreement (over 20%) for the other isotopes. The level isotope shifts are further parameterised in terms of a linear model, and the specific mass effect is decomposed into sums of one-electron and two-electron shift parameters with respect to the inert-gas like ground state of Ba III. (orig.)

  16. Comparison of greenhouse and 32P isotopic laboratory methods for evaluating the agronomic effectiveness of natural and modified rock phosphates in some acid soils of Ghana

    International Nuclear Information System (INIS)

    Owusu-Bennoah, E.; Zapata, F.; Fardeau, J.C.

    2002-01-01

    Phosphorus deficiency is one of the major constraints for normal plant growth and crop yields in the acid soils of Ghana and therefore addition of P inputs is required for sustainable crop production. This is often difficult, if not impossible for small-scale farmers due to the high cost of mineral P fertilizers and limited access to fertilizer supplies. Direct application of finely ground phosphate rocks (PRs) and their modified forms have been recommended as alternatives for P fertilization. The direct application of the natural and modified PRs to these acid soils implies the need to predict their agronomic effectiveness of the PRs in the simplest and most cost-effective manner. In this study the classical greenhouse pot experiment was compared to the 32 P isotopic kinetics laboratory method for evaluating the agronomic effectiveness of natural and modified Togo PR in six highly weathered Oxisols from southwest Ghana. In the 32 P isotopic kinetics laboratory experiment the six soil samples were each fertilised at the rate of 50 mg P kg -1 soil in the form of triple superphosphate (TSP), Togo PAPR-50%, and Togo PR, respectively. Controls without P amendment were also included. Isotopic exchange kinetics experiments were carried out on two sets of samples, immediately after P fertilizer additions (without incubation) and after 6 weeks of incubation under wet conditions and at a room temperature of 25 deg C. In the greenhouse pot experiment, P fertilizers in the form of Togo PR, Togo PAPR, Mali PR and TSP were each applied to the six soils at rates equivalent to 0, 30, 60, and 120 kg P ha -1 , respectively. The P fertilizers were mixed with the soils and maize (Zea mays L.) variety Obatanpa was grown for 42 days before harvest. The isotopic kinetics data of the control samples indicated that 5 of the studied soils had very low P fertility status as reflected by their low P concentrations in solution (C P -1 ) and low exchangeable P (E 1 min -1 ). The capacity

  17. Simulating the effect of muscle weakness and contracture on neuromuscular control of normal gait in children.

    Science.gov (United States)

    Fox, Aaron S; Carty, Christopher P; Modenese, Luca; Barber, Lee A; Lichtwark, Glen A

    2018-03-01

    Altered neural control of movement and musculoskeletal deficiencies are common in children with spastic cerebral palsy (SCP), with muscle weakness and contracture commonly experienced. Both neural and musculoskeletal deficiencies are likely to contribute to abnormal gait, such as equinus gait (toe-walking), in children with SCP. However, it is not known whether the musculoskeletal deficiencies prevent normal gait or if neural control could be altered to achieve normal gait. This study examined the effect of simulated muscle weakness and contracture of the major plantarflexor/dorsiflexor muscles on the neuromuscular requirements for achieving normal walking gait in children. Initial muscle-driven simulations of walking with normal musculoskeletal properties by typically developing children were undertaken. Additional simulations with altered musculoskeletal properties were then undertaken; with muscle weakness and contracture simulated by reducing the maximum isometric force and tendon slack length, respectively, of selected muscles. Muscle activations and forces required across all simulations were then compared via waveform analysis. Maintenance of normal gait appeared robust to muscle weakness in isolation, with increased activation of weakened muscles the major compensatory strategy. With muscle contracture, reduced activation of the plantarflexors was required across the mid-portion of stance suggesting a greater contribution from passive forces. Increased activation and force during swing was also required from the tibialis anterior to counteract the increased passive forces from the simulated dorsiflexor muscle contracture. Improvements in plantarflexor and dorsiflexor motor function and muscle strength, concomitant with reductions in plantarflexor muscle stiffness may target the deficits associated with SCP that limit normal gait. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. 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.

  19. Isotope and Electric Field Effects in Dissociative Recombination of D3+

    International Nuclear Information System (INIS)

    Larsson, M.; Rosen, S.; Danared, H.; Larson, A.; Le Padellec, A.; Semaniak, J.; Stroemholm, C.; Peterson, J.R.

    1997-01-01

    The cross section for dissociative recombination of vibrationally cold D 3 + has been measured at the ion storage ring CRYRING. The rate constant at 300K, α=2.7x10 -8 cm 3 s -1 , is a factor of 4.3 smaller than the corresponding value for H 3 + measured earlier in CRYRING. An electric field of 30V/cm was introduced in the electron-ion interaction region. This had no measurable effect on the dissociative recombination cross section. This suggests that the cross sections measured in storage rings for H 3 + and its isotopic variants can be directly compared with theoretical results once such results become available. copyright 1997 The American Physical Society

  20. Isotope substitution effects on preferred conformations of some hydrocarbon radical cations

    International Nuclear Information System (INIS)

    Lunell, S.; Eriksson, L.A.

    1992-01-01

    The stability of different conformational isomers of partially deuterated radical cations of ethane, butane, and cyclopropane is studied at the HF/6-31G** and MP2/6-31G** levels. It is shown that the superposition patterns of spectra corresponding to different isomers, observed in ESR spectroscopy, are accurately reproduced by Boltzmann statistics based on differences in vibrational zero-point energies (ZPE), provided that the temperature is high enough to overcome existing barriers toward internal pseudorotation in the cations. For the ethane and butane cations, the most stable conformations are, as expected, those which are deuterated in the short CH bonds, while this is found not to be the case for the cyclopropane cation. The latter result is explained by shifts in the low-frequency bending modes, which counteract the anticipated isotope effect on the C H stretching modes

  1. The short range effective interaction and the spectra of calcium isotopes in (f-p) space

    International Nuclear Information System (INIS)

    Qing-ying, Z.; Shen-wu, L.; Jian-xin, W.

    1986-01-01

    In this work, the authors use a new type of extremely short range interaction, the double delta interaction (DDI) to calculate the low-lying spectra of calcium isotopes /sup 41/Ca through /sup 48/Ca. The configuration space (f-p) includes configurations ( f/sub 7/2//sup n/ ) and ( f/sub 7/2//sup n-1/2p/sub 3/2/). The calculated energies are compared with experimental data for 75 levels. For comparison, they also use usual modified surface delta interaction (MSDI) to calculate the same spectra aforementioned. It is clear that the results calculated with DDI are better than with MSDI. Therefore, in the short-range effective interaction the addition of body delta force to the modified surface delta force may improve the agreement with experiment. The authors believe that the conclusion will not be changed if one enlarges the shell model space

  2. Anomalous H/D isotope effect on 35Cl NQR frequencies in piperidinium p-chlorobenzoate

    International Nuclear Information System (INIS)

    Nakano, Ryo; Honda, Hisashi; Kimura, Taiki; Nakata, Eiichi; Takamizawa, Satoshi; Noro, Sumiko; Ishimaru, Shin'ichi

    2008-01-01

    Anomalous isotope effects were detected in the 35 Cl nuclear quadrupole resonance (NQR) frequency of piperidinium p-chlrobenzoate (C 5 H 10 NH. ClC 6 H 4 COOH) by deuteration of hydrogen atoms. The atoms were determined to form two kinds of N-H...O type H-bonds in the crystal structure. Large frequency shifts of the 35 Cl resonance lines reaching 288 kHz at 77 K and 278 kHz at room temperature were caused upon deuteration, in spite of the fact that the Cl atoms in the molecule do not form hydrogen bonds in the crystal. Results of single crystal X-ray diffraction measurements and density-functional-theorem calculations suggest that a dihedral-angle change of 1.8 o between benzene and the piperidine ring contributes to 35 Cl NQR anomalous frequency shifts.

  3. Catalytic recruitment in the inactivation of acetylcholinesterase by soman: temperature dependence of the solvent isotope effect

    International Nuclear Information System (INIS)

    Kovach, I.M.; Huber, J.H.A.; Schowen, R.L.

    1988-01-01

    3,3-Dimethyl-2-butyl methylphosphonofluoridate (soman) recruits at least 60-70% of the catalytic power of acetylcholinesterase during phosphonylation of the active-site serine, as compared with the acetylation by acetylcholine. The solvent isotope effect is 1.34 +/- 0.11 and is temperature independent within experimental error between 5 and 45 0 C. This observation is quite similar to what has been found for the reactions of aryl acetates and anilides. Average activation parameters for the same temperature range are ΔH* = 7.3 +/- 0.6 kcal/mol and ΔS* = -4 +/- 2 eu (H 2 O) and ΔH* = 7.1 +/- 0.4 kcal/mol and ΔS* = -6 +/- 1 eu (D 2 O). A rate-limiting process with 50% contribution of an induced-fit conformational change is supported by the data

  4. The role of symmetry in the mass independent isotope effect in ozone

    Science.gov (United States)

    Michalski, Greg; Bhattacharya, S. K.

    2009-01-01

    Understanding the internal distribution of “anomalous” isotope enrichments has important implications for validating theoretical postulates on the origin of these enrichments in molecules such as ozone and for understanding the transfer of these enrichments to other compounds in the atmosphere via mass transfer. Here, we present an approach, using the reaction NO2− + O3, for assessing the internal distribution of the Δ17O anomaly and the δ18O enrichment in ozone produced by electric discharge. The Δ17O results strongly support the symmetry mechanism for generating mass independent fractionations, and the δ18O results are consistent with published data. Positional Δ17O and δ18O enrichments in ozone can now be more effectively used in photochemical models that use mass balance oxygen atom transfer mechanisms to infer atmospheric oxidation chemistry. PMID:19307571

  5. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    Science.gov (United States)

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Variability in mesophyll conductance between barley genotypes, and effects on transpiration efficiency and carbon isotope discrimination.

    Science.gov (United States)

    Barbour, Margaret M; Warren, Charles R; Farquhar, Graham D; Forrester, Guy; Brown, Hamish

    2010-07-01

    Leaf internal, or mesophyll, conductance to CO(2) (g(m)) is a significant and variable limitation of photosynthesis that also affects leaf transpiration efficiency (TE). Genotypic variation in g(m) and the effect of g(m) on TE were assessed in six barley genotypes (four Hordeum vulgare and two H. bulbosum). Significant variation in g(m) was found between genotypes, and was correlated with photosynthetic rate. The genotype with the highest g(m) also had the highest TE and the lowest carbon isotope discrimination as recorded in leaf tissue (Delta(p)). These results suggest g(m) has unexplored potential to provide TE improvement within crop breeding programmes.

  7. Health effects of technologies for power generation: Contributions from normal operation, severe accidents and terrorist threat

    International Nuclear Information System (INIS)

    Hirschberg, Stefan; Bauer, Christian; Burgherr, Peter; Cazzoli, Eric; Heck, Thomas; Spada, Matteo; Treyer, Karin

    2016-01-01

    As a part of comprehensive analysis of current and future energy systems we carried out numerous analyses of health effects of a wide spectrum of electricity supply technologies including advanced ones, operating in various countries under different conditions. The scope of the analysis covers full energy chains, i.e. fossil, nuclear and renewable power plants and the various stages of fuel cycles. State-of-the-art methods are used for the estimation of health effects. This paper addresses health effects in terms of reduced life expectancy in the context of normal operation as well as fatalities resulting from severe accidents and potential terrorist attacks. Based on the numerical results and identified patterns a comparative perspective on health effects associated with various electricity generation technologies and fuel cycles is provided. In particular the estimates of health risks from normal operation can be compared with those resulting from severe accidents and hypothetical terrorist attacks. A novel approach to the analysis of terrorist threat against energy infrastructure was developed, implemented and applied to selected energy facilities in various locations. Finally, major limitations of the current approach are identified and recommendations for further work are given. - Highlights: • We provide state-of-the-art comparative assessment of energy health risks. • The scope of the analysis should to the extent possible cover full energy chains. • Health impacts from normal operation dominate the risks. • We present novel approach to analysis of terrorist threat. • Limitations include technology choices, geographical coverage and terrorist issues.

  8. Spectroscopic and Quantum Mechanical Calculation Study of the Effect of Isotopic Substitution on NIR Spectra of Methanol.

    Science.gov (United States)

    Grabska, Justyna; Czarnecki, Mirosław A; Beć, Krzysztof B; Ozaki, Yukihiro

    2017-10-19

    In this work, we studied methanol and its deuterated derivatives (CH 3 OH, CH 3 OD, CD 3 OH, CD 3 OD) by NIR spectroscopy and anharmonic quantum chemical calculations. Vibrational bands corresponding to up to three quanta transitions (first and second overtones, binary and ternary combination modes) were predicted by the use of the VPT2 route. The accuracy of prediction of NIR modes was evaluated through density functional theory (DFT) with selected density functionals and basis sets. On the basis of the theoretical NIR spectra, detailed band assignments for all studied molecules were proposed. It was found that the pattern of bands in NIR spectra of deuterated methanols can be used for identification of isotopically equalized forms. Calculations of NIR spectra of all possible forms of CXXXOX (X = H, D) molecules demonstrated that the isotopic contamination can be identified due to a coexistence of bands specific to OH and OD groups. Also, bands from partially deuterated methyl groups can be distinguished in NIR spectra. Since the VPT2 framework is known to be sensitive to inaccuracy in the case of highly anharmonic modes, we obtained an independent insight by numerical solving of the time-independent Schrödinger equation corresponding to the O-X stretching mode scanned within -0.4 to 2.0 Å over a dense grid of 0.005 Å. This way the energies of vibrational levels of the CX1X2X3OX4 (X = H, D) isotopomers and the corresponding transition frequencies were obtained with high accuracy (<0.1 cm -1 ). The change in normal coordinate influences the reduced mass of the oscillator and thus its frequency. Our results lead to a conclusion that the effect of deuterization of the methyl group introduces a very specific and consistent frequency shift of the first overtone of the O-X stretching mode depending on the substitution of X1, X2, or X3 positions (<2 cm -1 ). However, the pattern of this shift is not reproduced accurately and is also largely overestimated by VPT2

  9. 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

  10. 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

  11. The effects of the 'key' molar mass on the design of a cascade handling a multi-isotopic mixture

    International Nuclear Information System (INIS)

    Raichura, R.C.; Al-Janabi, M.A.M.

    1991-01-01

    The parameters required for describing the characteristics of separating units and cascades handling a multi-isotope mixture are first reviewed from previous work and then expressed in terms of a newly defined parameter called the 'Key' molar mass. The effects of the latter on the operating and economic parameters of a gas centrifuge cascade handling a multi-isotopic mixture are studied. Only cascades of the 'primitive' type, i.e. those in which the feed of a stage is made up of the light and heavy fractions of neighbouring stages, are considered. The costs incurred in obtaining outputs with specified concentrations are then discussed. (author)

  12. Numerical simulation of bellows effect on flow and separation of uranium isotopes in a supercritical gas centrifuge

    International Nuclear Information System (INIS)

    Borisevich, V.D.; Morozov, O.E.; Godisov, O.N.

    2000-01-01

    Numerical solving of the Navier-Stokes and convection-diffusion equations by the finite difference technique has been applied to study the influence of bellows on the flow and separation of uranium isotopes in a single supercritical gas centrifuge. Dependence of the separative power of a gas centrifuge on geometric parameters and position of a bellows on a rotor wall as well as the effect of scoop drag and feed flow on isotope separation in a gas centrifuge with a bellows have been obtained in computing experiments. It was demonstrated that increase of the separative power with increase of the gas centrifuge length is less considerable than predicted by the Dirac's law

  13. Density functional theory calculations of H/D isotope effects on polymer electrolyte membrane fuel cell operations

    Energy Technology Data Exchange (ETDEWEB)

    Yanase, Satoshi; Oi, Takao [Sophia Univ., Tokyo (Japan). Faculty of Science and Technology

    2015-10-01

    To elucidate hydrogen isotope effects observed between fuel and exhaust hydrogen gases during polymer electrolyte membrane fuel cell operations, H-to-D reduced partition function ratios (RPFRs) for the hydrogen species in the Pt catalyst phase of the anode and the electrolyte membrane phase of the fuel cell were evaluated by density functional theory calculations on model species of the two phases. The evaluation yielded 3.2365 as the value of the equilibrium constant of the hydrogen isotope exchange reaction between the two phases at 39 C, which was close to the experimentally estimated value of 3.46-3.99 at the same temperature. It was indicated that H{sup +} ions on the Pt catalyst surface of the anode and H species in the electrolyte membrane phase were isotopically in equilibrium with one another during fuel cell operations.

  14. The effect of fusion-relevant helium levels on the mechanical properties of isotopically tailored ferritic alloys

    Energy Technology Data Exchange (ETDEWEB)

    Hankin, G.L. [Loughborough Univ. (United Kingdom); Hamilton, M.L.; Gelles, D.S. [Pacific Northwest National Lab., Richland, WA (United States)] [and others

    1997-04-01

    The yield and maximum strengths of an irradiated series of isotopically tailored ferritic alloys were evaluated using the shear punch test. The composition of three of the alloys was Fe-12Cr-1.5Ni. Different balances of nickel isotopes were used in each alloy in order to produce different helium levels. A fourth alloy, which contained no nickel, was also irradiated. The addition of nickel at any isotopic balance to the Fe-12Cr base alloy significantly increased the shear yield and maximum strengths of the alloys, and as expected, the strength of the alloys decreased with increasing irradiation temperature. Helium itself, up to 75 appm over 7 dpa appears to have little effect on the mechanical properties of the alloys.

  15. Influence of Three-square-well Interaction Potential on Isotope Effect Coefficient of High-TC Superconductors

    International Nuclear Information System (INIS)

    Udomsamuthirun, P.; Dokkaemklang, S.; Kumvongsa, C.; Maneeratanakul, S.

    2005-10-01

    In this research, the exact formula of the isotope effect coefficient of s wave and d-wave superconductor in weak-coupling limit are derived by using a three square- well interaction potential that pairing interaction consists of 3 parts : an attractive electron-phonon interaction, an attractive non-electron-phonon interaction , and a repulsive Coulomb interaction . op ac , w w and c w is the characteristic energy cutoff of the Debye phonon , non-phonon ,and Coulomb respectively and 2 / 1 ac M- a w , and c op , w w do not depend on isotope mass(M). We find that, in all case of consideration, the isotope coefficient converges to 0.5 at lower value of Coulomb coupling constant and larger values of phonon and non-phonon coupling constant

  16. Effects of temperature and isotopic substitution on electron attachment dynamics of guanine–cytosine base pair: Ring-polymer and classical molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Minoshima, Yusuke; Seki, Yusuke [Department of Chemistry, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan); Takayanagi, Toshiyuki, E-mail: tako@mail.saitama-u.ac.jp [Department of Chemistry, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan); Shiga, Motoyuki [Center for Computational Science and E-Systems, Japan Atomic Energy Agency, 148-4, Kashiwanoha Campus, 178-4 Wakashiba, Kashiwa, Chiba 277-0871 (Japan)

    2016-06-15

    Highlights: • Dynamics of excess electron attachment to guanine–cytosine base pair. • Ring-polymer and classical molecular dynamics simulations are performed. • Temperature and isotope substitution effects are investigated. - Abstract: The dynamical process of electron attachment to a guanine–cytosine pair in the normal (h-GC) and deuterated (d-GC) forms has been studied theoretically by semiclassical ring-polymer molecular dynamics (RPMD) simulations using the empirical valence bond model. The initially formed dipole-bound anion is converted rapidly to the valence-bound anion within about 0.1 ps in both h-GC and d-GC. However, the subsequent proton transfer in h-GC occurs with a rate five times greater than the deuteron transfer in d-GC. The change of rates with isotopic substitution and temperature variation in the RPMD simulations are quantitatively and qualitatively different from those in the classical molecular dynamics (MD) simulations, demonstrating the importance of nuclear quantum effects on the dynamics of this system.

  17. Effects of temperature and isotopic substitution on electron attachment dynamics of guanine–cytosine base pair: Ring-polymer and classical molecular dynamics simulations

    International Nuclear Information System (INIS)

    Minoshima, Yusuke; Seki, Yusuke; Takayanagi, Toshiyuki; Shiga, Motoyuki

    2016-01-01

    Highlights: • Dynamics of excess electron attachment to guanine–cytosine base pair. • Ring-polymer and classical molecular dynamics simulations are performed. • Temperature and isotope substitution effects are investigated. - Abstract: The dynamical process of electron attachment to a guanine–cytosine pair in the normal (h-GC) and deuterated (d-GC) forms has been studied theoretically by semiclassical ring-polymer molecular dynamics (RPMD) simulations using the empirical valence bond model. The initially formed dipole-bound anion is converted rapidly to the valence-bound anion within about 0.1 ps in both h-GC and d-GC. However, the subsequent proton transfer in h-GC occurs with a rate five times greater than the deuteron transfer in d-GC. The change of rates with isotopic substitution and temperature variation in the RPMD simulations are quantitatively and qualitatively different from those in the classical molecular dynamics (MD) simulations, demonstrating the importance of nuclear quantum effects on the dynamics of this system.

  18. Isotopes in oxidation reactions

    International Nuclear Information System (INIS)

    Stewart, R.

    1976-01-01

    The use of isotopes in the study of organic oxidation mechanisms is discussed. The help provided by tracer studies to demonstrate the two-equivalent path - hydride transfer, is illustrated by the examples of carbonium oxidants and the Wacker reaction. The role of kinetic isotope effects in the study of the scission of carbon-hydrogen bonds is illustrated by hydride abstraction, hydrogen atom abstraction, proton abstraction and quantum mechanical tunnelling. Isotopic studies on the oxidation of alcohols, carbonyl compounds, amines and hydrocarbons are discussed. The role of isotopes in the study of biochemical oxidation is illustrated with a discussion on nicotinamide and flavin coenzymes. (B.R.H.)

  19. Studies on the effects of ionizing radiation on the normal and diseased liver in experimental animals

    International Nuclear Information System (INIS)

    Mahmoud, S.A.

    1981-01-01

    The experiments carried out in the present study primarily concerned with the effects of ionizing radiations on the normal and diseased liver in experimental animals (mice). Different radiation intensities and different exposure schemes were used to irradiate both healthy and schistosoma mansoni infected animals. A group of uninfected and unirradiated animals were used as controls. Follow up studies were performed every 6 weeks for 30 weeks. These included histopathological studies of the liver damage at every observation periods for all animal groups

  20. The cytogenetic estimate of the radioprotective effect of antioxydant on normal and defected human cells

    International Nuclear Information System (INIS)

    Zvereva, S.V.; Mutovina, G.R.; Khandogina, E.K.; Marchenko, L.F.; Neudakhin, E.V.; Artamonov, R.G.; Akif'ev, A.P.

    1993-01-01

    In studying the radioprotective action of natural and synthesised antioxydants a decreased yield of chromosome aberrations with respect to those in untreated cells was noted in normal cells irradiated in phase G 1 whereas no radioprotective effect was found in cells irradiated in G 0 . The addition of antioxydants into the cell cultures from patients with Turner's syndrome did not change their radiosensitivity. No adaptive response was induced in lymphocytes from patients with Down's syndrome cultivated with vitamine E

  1. Effect of a Modest Weight Loss in Normalizing Blood Pressure in Obese Subjects on Antihypertensive Drugs

    OpenAIRE

    Gilardini, Luisa; Redaelli, Gabriella; Croci, Marina; Conti, Antonio; Pasqualinotto, Lucia; Invitti, Cecilia

    2016-01-01

    Objective To assess the effect of a lifestyle intervention in lowering/normalizing blood pressure (BP) levels in hypertensive (controlled or not) obese patients. Methods In this prospective observational study, 490 obese hypertensive patients, 389 controlled (BP < 140/90 mm Hg; CH) and 101 uncontrolled (BP ≥ 140/90 mm Hg; UH) attended a 3-month lifestyle intervention. Before and after the intervention we assessed weight, waist circumference, fat mass, BP, metabolic and renal variables, and ph...

  2. Age and Gender Effects on Wideband Absorbance in Adults with Normal Outer and Middle Ear Function

    Science.gov (United States)

    Mazlan, Rafidah; Kei, Joseph; Ya, Cheng Li; Yusof, Wan Nur Hanim Mohd; Saim, Lokman; Zhao, Fei

    2015-01-01

    Purpose: This study examined the effects of age and gender on wideband energy absorbance in adults with normal middle ear function. Method: Forty young adults (14 men, 26 women, aged 20-38 years), 31 middle-aged adults (16 men, 15 women, aged 42-64 years), and 30 older adults (20 men, 10 women, aged 65-82 years) were assessed. Energy absorbance…

  3. Fractionation in position-specific isotope composition during vaporization of environmental pollutants measured with isotope ratio monitoring by 13C nuclear magnetic resonance spectrometry

    International Nuclear Information System (INIS)

    Julien, Maxime; Parinet, Julien; Nun, Pierrick; Bayle, Kevin; Höhener, Patrick; Robins, Richard J.; Remaud, Gérald S.

    2015-01-01

    Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by 13 C NMR (irm- 13 C NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources. - Highlights: • Position-Specific Isotope Analysis (PSIA) by 13 C NMR spectrometry. • PSIA on isotope fractionation during several vaporization processes. • PSIA for isotope profiling in environment pollutants. • Intramolecular 13 C reveal normal and inverse effects, bulk values being unchanged. - PSIA in pollutants during evaporation processes shows more detailed information for discerning the nature of the process involved than does bulk isotope measurements

  4. Effects of Wall-Normal and Angular Momentum Injections in Airfoil Separation Control

    Science.gov (United States)

    Munday, Phillip M.; Taira, Kunihiko

    2018-05-01

    The objective of this computational study is to quantify the influence of wall-normal and angular momentum injections in suppressing laminar flow separation over a canonical airfoil. Open-loop control of fully separated, incompressible flow over a NACA 0012 airfoil at $\\alpha = 9^\\circ$ and $Re = 23,000$ is examined with large-eddy simulations. This study independently introduces wall-normal momentum and angular momentum into the separated flow using swirling jets through model boundary conditions. The response of the flow field and the surface vorticity fluxes to various combinations of actuation inputs are examined in detail. It is observed that the addition of angular momentum input to wall-normal momentum injection enhances the suppression of flow separation. Lift enhancement and suppression of separation with the wall-normal and angular momentum inputs are characterized by modifying the standard definition of the coefficient of momentum. The effect of angular momentum is incorporated into the modified coefficient of momentum by introducing a characteristic swirling jet velocity based on the non-dimensional swirl number. With this single modified coefficient of momentum, we are able to categorize each controlled flow into separated, transitional, and attached flows.

  5. Investigation of the enzymatic mechanism of yeast orotidine-5'-monophosphate decarboxylase using 13C kinetic isotope effects

    International Nuclear Information System (INIS)

    Smiley, J.A.; Bell, J.B.; Jones, M.E.; Paneth, P.; O'Leary, M.H.

    1991-01-01

    Orotidine-5'-monophosphate decarboxylase (ODCase) from Saccharomyces cerevisiae displays an observed 13 C kinetic isotope effect of 1.0247 ± 0.0008 at 25 C, pH 6.8. The observed isotope effect is sensitive to changes in the reaction medium, such as pH, temperature, or glycerol content. The value of 1.0494 ± 0.0006 measured at pH 4.0, 25 C, is not altered significantly by temperature or glycerol, and thus the intrinsic isotope effect for the reaction is apparently being observed under these conditions and decarboxylation is almost entirely rate-determining. These data require a catalytic mechanism with freely reversible binding and one in which a very limited contribution to the overall rate is made by chemical steps preceding decarboxylation; the zwitterion mechanism of Beak and Siegel, which involves only protonation of the pyrimidine ring, is such a mechanism. With use of an intrinsic isotope effect of 1.05, a partitioning factor of less than unity is calculated for ODCase at pH 6.0, 25 C. A quantitative kinetic analysis using this result excludes the possibility of an enzymatic mechanism involving covalent attachment of an enzyme nucleophile to C-5 of the pyrimidine ring. These data fit a kinetic model in which an enzyme proton necessary for catalysis is titrated at high pH, thus providing evidence for the catalytic mechanism of Beak and Siegal

  6. The structure of active centers and the kinetic isotopic effect in the ionic polymerization of heterocyclic compounds

    International Nuclear Information System (INIS)

    Ponomarienko, W.A.; Berman, E.L.

    1979-01-01

    The method of kinetic isotopic effect has been applied to the elucidation of the structure of the active growth centres in the polymerization of some selected heterocyclic compounds. The cationic polymerization of ehtylene oxide, tetrahydrofuran and 1.3-dioxolane as well as the anionic and coordination polymerization of ethylene oxide have been discussed. (author)

  7. Effect of leaf litter degradation and seasonality on D/H isotope ratios of n-alkane biomarkers

    NARCIS (Netherlands)

    Zech, M.; Pedentchouk, N.; Buggle, B.; Leiber, K.; Kalbitz, K.; Markovic, S.B.; Glaser, B.

    2011-01-01

    During the last decade, compound-specific hydrogen isotope analysis of plant leaf-wax and sedimentary n-alkyl lipids has become a promising tool for paleohydrological reconstructions. However, with the exception of several previous studies, there is a lack of knowledge regarding possible effects of

  8. Determination of isotope fractionation effect using a double spike (242Pu+240Pu) during the mass spectrometric analysis of plutonium

    International Nuclear Information System (INIS)

    Chitambar, S.A.; Parab, A.R.; Khodade, P.S.; Jain, H.C.

    1986-01-01

    Isotope fractionation effect during the mass spectrometric analysis of plutonium has been investigated using a double spike ( 242 Pu+ 240 Pu) and the determination of concentration of plutonium in dissolver solution of irradiated fuel is reported. (author). 6 refs., 2 tables

  9. Crystal-plastic deformation of zircon : effects on microstructures, textures, microchemistry and the retention of radiogenic isotopes

    International Nuclear Information System (INIS)

    Kovaleva, E.

    2015-01-01

    Dating of deep-crustal deformation events potentially can be achieved by using plastically-deformed accessory minerals found in high-temperature shear zones. Deformation microstructures, such as dislocations and low-angle boundaries, form due to plastic deformation in the crystal lattice and act as fluid migration pathways and trace element (e.g. Pb, Ti, U, Th, REE) diffusion pathways through so-called “pipe diffusion”. Deformation microstructures can alter the chemical and isotopic composition of certain grain parts and may lead to complete or partial isotopic resetting of certain geochronometers (e.g. U/Th/Pb, K/Ar, Rb/Sr) in the mineral domains. This work aims to better understand the processes of crystal-plastic deformation and associated trace element redistribution and the resetting of isotopic systems in zircon. This study finds that: a) there are three general finite deformation patterns in deformed zircons; b) suggests that it is possible to reconstruct the macroscopic kinematic framework of the shear zone based on the orientation of deformed zircon grains and the operating misorientation axes; c) and demonstrates the effect of deformation microstructures on trace elements and Pb isotopes in zircon. The final goal of this project is to develop a tool for isotopic dating of high-temperature deformation events in the deep crust. In addition to these results, zircon grains with planar deformation bands have been discovered in paleo-seismic zones; these deformation features have been described in detail and a possible mechanism of their origin and formation is suggested. The effect of planar deformation bands on trace element and isotopic behavior has also been investigated. (author) [de

  10. Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

    Science.gov (United States)

    Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

    2015-04-01

    Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

  11. Effect of cobratoxin binding on the normal mode vibration within acetylcholine binding protein.

    Science.gov (United States)

    Bertaccini, Edward J; Lindahl, Erik; Sixma, Titia; Trudell, James R

    2008-04-01

    Recent crystal structures of the acetylcholine binding protein (AChBP) have revealed surprisingly small structural alterations upon ligand binding. Here we investigate the extent to which ligand binding may affect receptor dynamics. AChBP is a homologue of the extracellular component of ligand-gated ion channels (LGICs). We have previously used an elastic network normal-mode analysis to propose a gating mechanism for the LGICs and to suggest the effects of various ligands on such motions. However, the difficulties with elastic network methods lie in their inability to account for the modest effects of a small ligand or mutation on ion channel motion. Here, we report the successful application of an elastic network normal mode technique to measure the effects of large ligand binding on receptor dynamics. The present calculations demonstrate a clear alteration in the native symmetric motions of a protein due to the presence of large protein cobratoxin ligands. In particular, normal-mode analysis revealed that cobratoxin binding to this protein significantly dampened the axially symmetric motion of the AChBP that may be associated with channel gating in the full nAChR. The results suggest that alterations in receptor dynamics could be a general feature of ligand binding.

  12. Dose rate effect of 125I irradiation on normal rabbit eyes and experimental choroidal melanoma

    International Nuclear Information System (INIS)

    Yang, C.M.; Olsen, K.R.; Schwade, J.G.; Houdek, P.V.; Markoe, A.M.; Pisciotta, V.; Xiaodong Wu

    1993-01-01

    The dose rate effect of radiation by 125 I plaque on choroidal melanoma and normal intraocular tissue was studied. In the first part of the experiment, high activity plaques (HAP) and low activity plagues (LAP) were implanted on rabbit eyes with experimental Greene choroidal melanoma to deliver a total dose of 10 000 cGy to the tumor apex. The mean dose rate calculated at 0.5 mm from the inner sclera in eight eyes with high activity plaques was 3341.5 cGy hr -1 while that in ten eyes with low activity plaques was 239.9 cGy hr -1 . For tumors less than 1.0 mm in height, both groups showed complete tumor regression at the tumor implantation site after plaque treatment. For tumours more than 1.0 mm in height, two out of two eyes in the low activity plaque group and one of four eyes in the high activity plaque group failed to show complete tumor regression. In the second part of the experiment, 125 I plaques were implanted on the sclera of 12 normal rabbits' eyes. Six received high dose rate plaque treatment, while the other six received low dose rate plaque treatment. Clinical and histologic examinations demonstrated more damaging effects to the normal chorioretinal tissues at the plaque implantation site in the high dose rate plaque group. These results suggest that high dose rate plaques are more effective than low dose rate plaques when tumor height is statistically controlled. (Author)

  13. A study of hydrogen isotopes fuel control by wall effect in magnetic fusion devices

    Energy Technology Data Exchange (ETDEWEB)

    Motevalli, S.M., E-mail: motavali@umz.ac.ir; Safari, M.

    2016-11-15

    Highlights: • A particle balance model for the main plasma and wall inventory in magnetic fusion device has been represented. • The dependence of incident particles energy on the wall has been considered in 10–300 eV for the sputtering yield and recycling coefficient. • The effect of fueling methods on plasma density behavior has been studied. - Abstract: Determination of plasma density behavior in magnetic confinement system needs to study the plasma materials interaction in the facing components such as first wall, limiter and divertor. Recycling of hydrogen isotope is an effective parameter in plasma density rate and plasma fueling. Recycling coefficient over the long pulse operation, gets to the unity, so it has a significant effect on steady state in magnetic fusion devices. Typically, sputtered carbon atoms from the plasma facing components form hydrocarbons and they redeposit on the wall. In this case little rate of hydrogen loss occurs. In present work a zero dimensional particle equilibrium model has been represented to determine particles density rate in main plasma and wall inventory under recycling effect and codeposition of hydrogen in case of continues and discontinues fueling methods and effective parameters on the main plasma decay has been studied.

  14. Isotope effect in the photochemical decomposition of CO{sub 2} (ice) by Lyman-{alpha} radiation

    Energy Technology Data Exchange (ETDEWEB)

    Yuan Chunqing; Yates, John T. Jr. [Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904 (United States)

    2013-04-21

    The photochemical decomposition of CO{sub 2}(ice) at 75 K by Lyman-{alpha} radiation (10.2 eV) has been studied using transmission infrared spectroscopy. An isotope effect in the decomposition of the CO{sub 2} molecule in the ice has been discovered, favoring {sup 12}CO{sub 2} photodecomposition over {sup 13}CO{sub 2} by about 10%. The effect is caused by electronic energy transfer from the excited CO{sub 2} molecule to the ice matrix, which favors quenching of the heavier electronically-excited {sup 13}CO{sub 2} molecule over {sup 12}CO{sub 2}. The effect is similar to the Menzel-Gomer-Redhead isotope effect in desorption from adsorbed molecules on surfaces when electronically excited. An enhancement of the rate of formation of lattice-trapped CO and CO{sub 3} species is observed for the photolysis of the {sup 12}CO{sub 2} molecule compared to the {sup 13}CO{sub 2} molecule in the ice. Only 0.5% of the primary photoexcitation results in O-CO bond dissociation to produce trapped-CO and trapped-CO{sub 3} product molecules and the majority of the electronically-excited CO{sub 2} molecules return to the ground state. Here either vibrational relaxation occurs (majority process) or desorption of CO{sub 2} occurs (minority process) from highly vibrationally-excited CO{sub 2} molecules in the ice. The observation of the {sup 12}C/{sup 13}C isotope effect in the Lyman-{alpha} induced photodecomposition of CO{sub 2} (ice) suggests that over astronomical time scales the isotope enrichment effect may distort historical information derived from isotope ratios in space wherever photochemistry can occur.

  15. Effects of climatic seasonality on the isotopic composition of evaporating soil waters

    Directory of Open Access Journals (Sweden)

    P. Benettin

    2018-05-01

    Full Text Available Stable water isotopes are widely used in ecohydrology to trace the transport, storage, and mixing of water on its journey through landscapes and ecosystems. Evaporation leaves a characteristic signature on the isotopic composition of the water that is left behind, such that in dual-isotope space, evaporated waters plot below the local meteoric water line (LMWL that characterizes precipitation. Soil and xylem water samples can often plot below the LMWL as well, suggesting that they have also been influenced by evaporation. These soil and xylem water samples frequently plot along linear trends in dual-isotope space. These trend lines are often termed "evaporation lines" and their intersection with the LMWL is often interpreted as the isotopic composition of the precipitation source water. Here we use numerical experiments based on established isotope fractionation theory to show that these trend lines are often by-products of the seasonality in evaporative fractionation and in the isotopic composition of precipitation. Thus, they are often not true evaporation lines, and, if interpreted as such, can yield highly biased estimates of the isotopic composition of the source water.

  16. Lithium isotope effect during solvent extraction of LiCl with isoamyl alcohol

    International Nuclear Information System (INIS)

    Levkin, A.V.; Zhilov, V.I.; Marokin, O.V.; Demin, S.V.

    1991-01-01

    Method of extraction chromatography was used to measure the coefficient of lithium isotope separation (α) during extraction with isoamyl alcohol from concentrated LiCl aqueous solution. The α value is equal to 1.0036±0.0009; heavy 7 Li isotope is concentrated in organic phase at that

  17. Soil drying effects on the carbon isotope composition of soil respiration

    Science.gov (United States)

    Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opp...

  18. Applications of stable isotopes

    International Nuclear Information System (INIS)

    Gregg, C.T.

    1977-01-01

    Clinical applications include the galactose breath test which consists of oral administration of 13 C-labeled galactose and measurement of the 13 C content of respired CO 2 as a function of time in patients with cirrhotic livers for diagnosis of liver dysfunction. Another application was the breath test to study glucose metabolism in children. Respired 13 CO 2 from ingested glucose- 13 C was measured for normal and diabetic children. Studies on mice in which 60 percent of the body carbon was replaced with 13 C failed to show significant effects of the isotope. Studies on biochemical applications include nuclear magnetic resonance studies of 13 C-labeled amino acids from Chlorella pyrenoidosa; studies on 15 N nmr spectra of arginine-guanidino- 13 C-2,3-- 15 N 2 as a function of pH; and isolation of fatty acids from algae

  19. 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.

  20. Effect of 60Co-irradiation on normal and low protein diet fed rat brain

    International Nuclear Information System (INIS)

    Hasan, S.S.; Habibullah, M.

    1980-01-01

    The effect of whole-body irradiation (Co-60) on the brain tissue in Holtzmann strain adult male rats was studied. Two doses of irradiation (450 R,950 R) were tried on animals which were fed on normal as well as low protein diets over a period of 10 generations. In the normal rats, 450 R initially caused a lowered total protein. DNA and RNA content in the brain. After 7 days a tendency towards normalcy was observed. In the 950 R irradiated normal rats the diminution of protein content appeared irreversible. In malnourished 450 R irradiated rats, the protein content rose less steeply over the 7 days of observation. A higher dose of 950 R enhanced this effect on protein and also lowered the DNA content on day 5. The RNA content in the 950 R group with malnutrition showed a marked increase towards or beyond control perhaps as an expression of uncoupled feedback control. The paper gives evidence that protein deficiency may interfere with cellular regeneration in irradiated brain. (orig.) [de

  1. Effects of low dose irradiation on NK activity of normal individuals and patients with cancer

    International Nuclear Information System (INIS)

    Tian Hailin; Su Liaoyuan

    1994-10-01

    Effects of low dose irradiation on NK activity of lymphocytes and on K 562 cells were studied. The NK activity was determined by means of 3 H-TdR release assay. While 3 H-TdR incorporation was used to reflect functional changes of K 562 cells after low dose irradiation. 21 patients with cancer and 10 normal individuals were detected. The results indicated that the NK activity of lymphocytes in normal individuals increased significantly after 10 and 50 cGy γ-ray irradiation, while in patients with cancer the NK activity of lymphocytes increased only at the dose of 50 cGy irradiation. The increase of NK activity in normal individuals was higher than that in patients with cancer after same doses of irradiation. When K 562 cells were irradiated by 10 cGy γ-rays, the 3 H-TdR incorporation value increased. After exposed to over 50 cGy the stimulating effect disappeared

  2. Effect of /sup 60/Co-irradiation on normal and low protein diet fed rat brain

    Energy Technology Data Exchange (ETDEWEB)

    Hasan, S S [Garhwal Univ., Srinagar, Uttar Pradesh (India). Dept. of Zoology; Habibullah, M [Jawaharlal Nehru Univ., New Delhi (India). Neurobiology Lab.

    1980-06-01

    The effect of whole-body irradiation (Co-60) on the brain tissue in Holtzmann strain adult male rats was studied. Two doses of irradiation (450 R,950 R) were tried on animals which were fed on normal as well as low protein diets over a period of 10 generations. In the normal rats, 450 R initially caused a lowered total protein. DNA and RNA content in the brain. After 7 days a tendency towards normalcy was observed. In the 950 R irradiated normal rats the diminution of protein content appeared irreversible. In malnourished 450 R irradiated rats, the protein content rose less steeply over the 7 days of observation. A higher dose of 950 R enhanced this effect on protein and also lowered the DNA content on day 5. The RNA content in the 950 R group with malnutrition showed a marked increase towards or beyond control perhaps as an expression of uncoupled feedback control. The paper gives evidence that protein deficiency may interfere with cellular regeneration in irradiated brain.

  3. The normal and inverse magnetocaloric effect in RCu2 (R=Tb, Dy, Ho, Er) compounds

    International Nuclear Information System (INIS)

    Zheng, X.Q.; Xu, Z.Y.; Zhang, B.; Hu, F.X.; Shen, B.G.

    2017-01-01

    Orthorhombic polycrystalline RCu 2 (R=Tb, Dy, Ho and Er) compounds were synthesized and the magnetic properties and magnetocaloric effect (MCE) were investigated in detail. All of the RCu 2 compounds are antiferromagnetic (AFM) ordered. As temperature increases, RCu 2 compounds undergo an AFM to AFM transition at T t and an AFM to paramagnetic (PM) transition at T N . Besides of the normal MCE around T N , large inverse MCE around T t was found in TbCu 2 compound. Under a field change of 0–7 T, the maximal value of inverse MCE is even larger than the value of normal MCE around T N for TbCu 2 compound. Considering of the normal and inverse MCE, TbCu 2 shows the largest refrigerant capacity among the RCu 2 (R=Tb, Dy, Ho and Er) compounds indicating its potential applications in low temperature multistage refrigeration. - Highlights: • Large inverse magnetocaloric effect is observed in TbCu 2 compound. • The AFM to AFM transition is observed in RCu 2 (R=Tb, Dy, Ho, Er) compounds. • The MCE performance of TbCu 2 compound is evaluated in a more comprehensively way.

  4. Connection between effective-range expansion and nuclear vertex constant or asymptotic normalization coefficient

    International Nuclear Information System (INIS)

    Yarmukhamedov, R.; Baye, D.

    2011-01-01

    Explicit relations between the effective-range expansion and the nuclear vertex constant or asymptotic normalization coefficient (ANC) for the virtual decay B→A+a are derived for an arbitrary orbital momentum together with the corresponding location condition for the (A+a) bound-state energy. They are valid both for the charged case and for the neutral case. Combining these relations with the standard effective-range function up to order six makes it possible to reduce to two the number of free effective-range parameters if an ANC value is known from experiment. Values for the scattering length, effective range, and form parameter are determined in this way for the 16 O+p, α+t, and α+ 3 He collisions in partial waves where a bound state exists by using available ANCs deduced from experiments. The resulting effective-range expansions for these collisions are valid up to energies larger than 5 MeV.

  5. Isotopic clusters

    International Nuclear Information System (INIS)

    Geraedts, J.M.P.

    1983-01-01

    Spectra of isotopically mixed clusters (dimers of SF 6 ) are calculated as well as transition frequencies. The result leads to speculations about the suitability of the laser-cluster fragmentation process for isotope separation. (Auth.)

  6. Effects of preheated combustion air on laminar coflow diffusion flames under normal and microgravity conditions

    Science.gov (United States)

    Ghaderi Yeganeh, Mohammad

    Global energy consumption has been increasing around the world, owing to the rapid growth of industrialization and improvements in the standard of living. As a result, more carbon dioxide and nitrogen oxide are being released into the environment. Therefore, techniques for achieving combustion at reduced carbon dioxide and nitric oxide emission levels have drawn increased attention. Combustion with a highly preheated air and low-oxygen concentration has been shown to provide significant energy savings, reduce pollution and equipment size, and uniform thermal characteristics within the combustion chamber. However, the fundamental understanding of this technique is limited. The motivation of the present study is to identify the effects of preheated combustion air on laminar coflow diffusion flames. Combustion characteristics of laminar coflow diffusion flames are evaluated for the effects of preheated combustion air temperature under normal and low-gravity conditions. Experimental measurements are conducted using direct flame photography, particle image velocimetry (PIV) and optical emission spectroscopy diagnostics. Laminar coflow diffusion flames are examined under four experimental conditions: normal-temperature/normal-gravity (case I), preheated-temperature/normal gravity (case II), normal-temperature/low-gravity (case III), and preheated-temperature/low-gravity (case IV). Comparisons between these four cases yield significant insights. In our studies, increasing the combustion air temperature by 400 K (from 300 K to 700 K), causes a 37.1% reduction in the flame length and about a 25% increase in peak flame temperature. The results also show that a 400 K increase in the preheated air temperature increases CH concentration of the flame by about 83.3% (CH is a marker for the rate of chemical reaction), and also increases the C2 concentration by about 60% (C2 is a marker for the soot precursor). It can therefore be concluded that preheating the combustion air

  7. Effects of a primordial magnetic field with log-normal distribution on the cosmic microwave background

    International Nuclear Information System (INIS)

    Yamazaki, Dai G.; Ichiki, Kiyotomo; Takahashi, Keitaro

    2011-01-01

    We study the effect of primordial magnetic fields (PMFs) on the anisotropies of the cosmic microwave background (CMB). We assume the spectrum of PMFs is described by log-normal distribution which has a characteristic scale, rather than power-law spectrum. This scale is expected to reflect the generation mechanisms and our analysis is complementary to previous studies with power-law spectrum. We calculate power spectra of energy density and Lorentz force of the log-normal PMFs, and then calculate CMB temperature and polarization angular power spectra from scalar, vector, and tensor modes of perturbations generated from such PMFs. By comparing these spectra with WMAP7, QUaD, CBI, Boomerang, and ACBAR data sets, we find that the current CMB data set places the strongest constraint at k≅10 -2.5 Mpc -1 with the upper limit B < or approx. 3 nG.

  8. Numerical analysis of the effects induced by normal faults and dip angles on rock bursts

    Science.gov (United States)

    Jiang, Lishuai; Wang, Pu; Zhang, Peipeng; Zheng, Pengqiang; Xu, Bin

    2017-10-01

    The study of mining effects under the influences of a normal fault and its dip angle is significant for the prediction and prevention of rock bursts. Based on the geological conditions of panel 2301N in a coalmine, the evolution laws of the strata behaviors of the working face affected by a fault and the instability of the fault induced by mining operations with the working face of the footwall and hanging wall advancing towards a normal fault are studied using UDEC numerical simulation. The mechanism that induces rock burst is revealed, and the influence characteristics of the fault dip angle are analyzed. The results of the numerical simulation are verified by conducting a case study regarding the microseismic events. The results of this study serve as a reference for the prediction of rock bursts and their classification into hazardous areas under similar conditions.

  9. Studying the effect of different elements in gastric emptying that produce normal variations in `healthy` individuals

    Energy Technology Data Exchange (ETDEWEB)

    Hauser, L. [Sydney University, Sydney, NSW (Australia)

    1999-06-01

    Maintaining the rate of emptying solids and liquids at normal levels, is an essential component for the correct functioning of the entire gastro-intestinal tract. There is no single-test available which provides a `baseline` for all gastric emptying studies. This problem arises due to many elements which normally effect the rate of gastric emptying, such as those dealing with patient factors, the composition of the liquid/solid meal used and also which radiopharmaceutical is chosen. It is therefore recommended that each Nuclear Medicine practice needs to set-up guidelines which are able to be consistently reproduced. One such guideline may be in the form of a `liquid glucose meal` which provides consistent and accurate results for gastric emptying studies 18 refs., 2 figs.

  10. Kinetic isotope effects in the OH and Cl reactions of the clumped methane species 13CH3D

    DEFF Research Database (Denmark)

    Joelsson, Magnus

    . As is proven in the current research project, the clumped isotopes are removed by oxidation mechanisms at a slower rate. The residual methane pool is therefore enriched in clumped isotopes compared to the methane from the sources. In order to construct a top-down budget of methane, the clumped kinetic effect...... of the sinkmechanisms must be taken into account. The clumped kinetic effect in atmospheric oxidation of methane has been studied experimentally and theoretically in the three current papers: In Paper I the effect of oxidation by the chlorine radical at roomtemperature (25 ±C) was studied, in Paper II the effect...... of oxidation by the hydroxyl radical over a range of temperatures (5 ±C–40 ±C) was studied, and in Paper III the effect of both the chlorine and the hydroxyl radical at room temperature was studied. All the experiments were conducted in the smog chamber of the Department of Chemistry, University of Copenhagen...

  11. 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

  12. 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.

  13. Stable isotopes

    International Nuclear Information System (INIS)

    Evans, D.K.

    1986-01-01

    Seventy-five percent of the world's stable isotope supply comes from one producer, Oak Ridge Nuclear Laboratory (ORNL) in the US. Canadian concern is that foreign needs will be met only after domestic needs, thus creating a shortage of stable isotopes in Canada. This article describes the present situation in Canada (availability and cost) of stable isotopes, the isotope enrichment techniques, and related research programs at Chalk River Nuclear Laboratories (CRNL)

  14. Importance of isovector effects in reproducing neutron total cross section differences in the W isotopes

    International Nuclear Information System (INIS)

    Dietrich, F.S.; Anderson, J.D.; Bauer, R.W.; Grimes, S.M.; Finlay, R.W.; Abfalterer, W.P.; Bateman, F.B.; Haight, R.C.; Morgan, G.L.; Bauge, E.; Delaroche, J.-P.; Romain, P.

    2003-01-01

    Cross section differences among the isotopes 182,184,186 W have been measured as a part of a study of total cross sections in the 5-560 MeV energy range. These difference measurements show oscillations up to 150 mb between 5 and 100 MeV. Calculations with spherical and deformed phenomenological optical potentials employing standard radial and isospin dependences show much smaller oscillations than the experimental data. In a simple Ramsauer model, this discrepancy can be traced to a cancellation between radial and isospin effects. Understanding this problem requires a more detailed model that incorporates a realistic description of the neutron and proton density distributions. This has been done with the results of Hartree-Fock-Bogoliubov calculations using the Gogny force, together with a microscopic folding model employing a modification of the Jeukenne, Lejeune, and Mahaux potential as an effective interaction. This treatment yields a satisfactory interpretation of the observed total cross section differences up to 200 MeV. The calculations have been extended above that energy with a folding model based on an empirical effective interaction

  15. Barrier widths, barrier heights, and the origins of anomalous kinetic H/D isotope effects

    International Nuclear Information System (INIS)

    Wolfe, S.; Hoz, Shmaryahu; Kim, Chankyung; Yang, Kiyull

    1990-01-01

    Proton transfer between MeO - and HOMe has been studied using ab initio molecular orbital theory. At the highest level employed (MP2/6-31+G(d)//6-31G(d)+ZPE), -ΔH 298 and -ΔG 298 for the formation of the ion-molecule complex MeO - hor-ellipsis HOMe from the separated reactants are 26.3 and 15.2 kcal/mol, respectively. At the 6-31G(d)//6-31G(d) level of theory, the (MeO-H-OMe) - transition structure is 2.19 kcal/mol higher in energy than the ion-molecule complex (ΔE double-dagger = 2.19), but this barrier disappears when zero-point energies are taken into account. The performance of AM1 on this system is quantitatively different (-ΔH 298 = 13.3; -ΔG 298 = 6.9; ΔE double-dagger = 4.91; k H /k D = 5.13, increasing to 5.79 when quantum mechanical tunneling is invoked) but appears to be acceptable for the research envisaged in the title. The effect of an enforced separation of the heavy atoms upon proton transfer barriers and isotope effects (which simulates steric effects) has been studied briefly at the 6-31G(d) level and in some detail using AM1

  16. 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.

  17. Isospin splitting of nucleon effective mass and symmetry energy in isotopic nuclear reactions

    Science.gov (United States)

    Guo, Ya-Fei; Chen, Peng-Hui; Niu, Fei; Zhang, Hong-Fei; Jin, Gen-Ming; Feng, Zhao-Qing

    2017-10-01

    Within an isospin and momentum dependent transport model, the dynamics of isospin particles (nucleons and light clusters) in Fermi-energy heavy-ion collisions are investigated for constraining the isospin splitting of nucleon effective mass and the symmetry energy at subsaturation densities. The impacts of the isoscalar and isovector parts of the momentum dependent interaction on the emissions of isospin particles are explored, i.e., the mass splittings of and (). The single and double neutron to proton ratios of free nucleons and light particles are thoroughly investigated in the isotopic nuclear reactions of 112Sn+112Sn and 124Sn+124Sn at incident energies of 50 and 120 MeV/nucleon, respectively. It is found that both the effective mass splitting and symmetry energy impact the kinetic energy spectra of the single ratios, in particular at the high energy tail (larger than 20 MeV). The isospin splitting of nucleon effective mass slightly impacts the double ratio spectra at the energy of 50 MeV/nucleon. A soft symmetry energy with stiffness coefficient of γ s=0.5 is constrained from the experimental data with the Fermi-energy heavy-ion collisions. Supported by Major State Basic Research Development Program in China (2014CB845405, 2015CB856903), National Natural Science Foundation of China (11722546, 11675226, 11675066, U1332207) and Youth Innovation Promotion Association of Chinese Academy of Sciences

  18. 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

  19. Isotope separation

    International Nuclear Information System (INIS)

    Eerkens, J.W.

    1979-01-01

    A method of isotope separation is described which involves the use of a laser photon beam to selectively induce energy level transitions of an isotope molecule containing the isotope to be separated. The use of the technique for 235 U enrichment is demonstrated. (UK)

  20. Isotopic effect of the mean lifetimes of the NeAr2+ doubly charged rare-gas dimer

    International Nuclear Information System (INIS)

    Ben-Itzhak, I.; Bouhnik, J.P.; Chen, Z.; Gertner, I.; Heinemann, C.; Koch, W.; Lin, C.D.; Rosner, B.

    1995-01-01

    It has been suggested recently by Chen et al. [Phys. Rev. A 49, 3472 (1994)] that the measured long-lived NeAr 2+ formed in fast NeAr + + Ar charge-stripping collisions is mostly in its v=12 vibrational state bound to the electronic ground state, and that this molecular ion decays by tunneling through the potential barrier. Such a decay rate is expected to depend strongly on the reduced mass of the molecular ion leading to large isotopic effects. We have measured the mean lifetimes of the 20 Ne 40 Ar 2+ and 22 Ne 40 Ar 2+ isotopes in order to see this isotopic effect. Surprisingly, the mean lifetimes of both isotopes are similar to each other. Thus, it is suggested that the observed NeAr 2+ molecular ions do not decay via a tunneling mechanism, which would indicate that they reside in the metastable electronic ground state. Rather, electronic transitions from bound or metastable excited states into other repulsive states are the origin for the experimentally observed decay. Qualitative estimates for the shapes and ordering of these states in the electronic spectrum of NeAr 2+ are given