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Sample records for heavy-atom kinetic isotope

  1. Newtonian kinetic isotope effects. Observation, prediction, and origin of heavy-atom dynamic isotope effects.

    Science.gov (United States)

    Kelly, Kelmara K; Hirschi, Jennifer S; Singleton, Daniel A

    2009-06-24

    Intramolecular (13)C kinetic isotope effects were determined for the dimerization of cyclopentadiene. Substantial isotope effects were observed in three positions, despite the C(2) symmetry of the cycloaddition transition state and the absence of dynamical bottlenecks after this transition state. The observed isotope effects were predicted well from trajectory studies by extrapolating the outcomes of trajectories incorporating superheavy isotopes of carbon, ranging from (20)C to (140)C. Trajectory studies suggest that the isotope effects are unrelated to zero-point energy or the geometrical and momentum properties of the transition state. However, steepest-descent paths in mass-weighted coordinates correctly predict the direction of the isotope effects, supporting a novel origin in Newton's second law of motion.

  2. Heavy atom isotope effects on enzymatic reactions

    Science.gov (United States)

    Paneth, Piotr

    1994-05-01

    The theory of isotope effects, which has proved to be extremely useful in providing geometrical details of transition states in a variety of chemical reactions, has recently found an application in studies of enzyme-catalyzed reactions. These reactions are multistep in nature with few steps being partially rate-limiting, thus interpretation of these isotope effects is more complex. The theoretical framework of heavy-atom isotope effects on enzymatic reactions is critically analyzed on the basis of recent results of: carbon kinetic isotope effects on carbonic anhydrase and catalytic antibodies; multiple carbon, deuterium isotope effects on reactions catalyzed by formate decarboxylase; oxygen isotope effects on binding processes in reactions catalyzed by pyruvate kinase; and equilibrium oxygen isotope effect on binding an inhibitor to lactate dehydrogenase. The advantages and disadvantages of reaction complexity in learning details of formal and molecular mechanisms are discussed in the examples of reactions catalyzed by phosphoenolpyruvate carboxylase, orotidine decarboxylase and glutamine synthetase.

  3. Kinetic isotope effects in the OH and Cl reactions of the clumped methane species 13CH3D

    DEFF Research Database (Denmark)

    Joelsson, Magnus

    a heavy atom vibrates slower than a light atom, the substitution to heavier isotopes in a molecular bond leads to lower Zero-Point Energy (ZPE) and thus amore stable bond. Fromstatistical thermodynamics we know that the influence of ZPE is largest at low temperatures, therefore the clumping of isotopes....... In Papers I and II, isotopically-labeled methane was used and the reactions were studied using Fourier Transform Infrared spectroscopy (FTIR). In Paper III; natural abundance methane was used and only the reaction yield was measured with FTIR spectroscopy. Meanwhile, the isotopic compositions were measured...... the clumping effect by a reaction, the apparent clumpiness is defined as the deviation of the Kinetic Isotope Effect (KIE) of the reaction with the clumped isotope (13CH3D) from the combination of KIEs of reactions with the single substituted isotopologues (13CH4 and 12CH3D). If the KIE of the reaction with 13...

  4. Role of Heavy Atom Tunneling in Myers-Saito Cyclization of Cyclic Enyne-Cumulene Systems.

    Science.gov (United States)

    Karmakar, Sharmistha; Datta, Ayan

    2016-02-11

    Direct dynamics calculation using canonical variational transtition state theory (CVT) inclusive of small curvature tunneling (SCT) reveals heavy atom tunneling in Myers-Saito cyclization of 10- and 9-membered cyclic enyne-cumulene systems like 1,6-didehydro[10]annulene and derivative of neocarzinostatin, respectively. The pure density functional theory functional, BLYP at a 6-31+G (d,p) basis set reproduce the observed reaction energies and barriers within 1.0 kcal/mol. The calculated rate constants of cyclization inclusive of heavy atom tunneling (k(CVT+SCT) = 3.26 × 10(-4) s(-1) at 222 K; t1/2 = 35 min) are in excellent agreement with experiments (t1/2 ∼ 21-31 min). Both primary and secondary kinetic isotope effect (KIE) become enhanced significantly upon inclusion of quantum mechanical tunneling. An Arrhenius plot of KIE shows measurable curvature at the experimental temperature of 222 K. The translation vector for the cyclization reactions in the transition-states (TS) show significant motion of primary and secondary carbon atoms explaining the origin of large KIE.

  5. The UKB prescription and the heavy atom effects on the nuclear magnetic shielding of vicinal heavy atoms.

    Science.gov (United States)

    Maldonado, Alejandro F; Aucar, Gustavo A

    2009-07-21

    Fully relativistic calculations of NMR magnetic shielding on XYH3 (X = C, Si, Ge and Sn; Y = Br, I), XHn (n = 1-4) molecular systems and noble gases performed with a fully relativistic polarization propagator formalism at the RPA level of approach are presented. The rate of convergence (size of basis set and time involved) for calculations with both kinetic balance prescriptions, RKB and UKB, were investigated. Calculations with UKB makes it feasible to obtain reliable results for two or more heavy-atom-containing molecules. For such XYH3 systems, the influence of heavy vicinal halogen atoms on sigma(X) is such that heavy atom effects on heavy atoms (vicinal plus their own effects or HAVHA + HAHA effects) amount to 30.50% for X = Sn and Y = I; being the HAHA effect of the order of 25%. So the vicinal effect alone is of the order of 5.5%. The vicinal heavy atom effect on light atoms (HALA effect) is of the order of 28% for X = C and Y = I. A similar behaviour, but of opposite sign, is observed for sigma(Y) for which sigmaR-NR (I; X = C) (HAHA effect) is around 27% and sigmaR-NR(I; X = Sn) (HAVHA + HAHA effects) is close to 21%. Its electronic origin is paramagnetic for halogen atoms but both dia- and paramagnetic for central atoms. The effect on two bond distant hydrogen atoms is such that the largest variation of sigma(H) within the same family of XYH3 molecules appears for X = Si and Y = I: around 20%. In this case sigma(H; X = Sn, Y = I) = 33.45 ppm and sigma(H; X = Sn, Y = H) = 27.82 ppm.

  6. 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.

  7. Photoelectron spectroscopy of heavy atoms and molecules

    Energy Technology Data Exchange (ETDEWEB)

    White, M.G.

    1979-07-01

    The importance of relativistic interactions in the photoionization of heavy atoms and molecules has been investigated by the technique of photoelectron spectroscopy. In particular, experiments are reported which illustrate the effects of the spin-orbit interaction in the neutral ground state, final ionic states and continuum states of the photoionization target.

  8. Relativistic heavy-atom effects on heavy-atom nuclear shieldings

    Science.gov (United States)

    Lantto, Perttu; Romero, Rodolfo H.; Gómez, Sergio S.; Aucar, Gustavo A.; Vaara, Juha

    2006-11-01

    The principal relativistic heavy-atom effects on the nuclear magnetic resonance (NMR) shielding tensor of the heavy atom itself (HAHA effects) are calculated using ab initio methods at the level of the Breit-Pauli Hamiltonian. This is the first systematic study of the main HAHA effects on nuclear shielding and chemical shift by perturbational relativistic approach. The dependence of the HAHA effects on the chemical environment of the heavy atom is investigated for the closed-shell X2+, X4+, XH2, and XH3- (X =Si-Pb) as well as X3+, XH3, and XF3 (X =P-Bi) systems. Fully relativistic Dirac-Hartree-Fock calculations are carried out for comparison. It is necessary in the Breit-Pauli approach to include the second-order magnetic-field-dependent spin-orbit (SO) shielding contribution as it is the larger SO term in XH3-, XH3, and XF3, and is equally large in XH2 as the conventional, third-order field-independent spin-orbit contribution. Considering the chemical shift, the third-order SO mechanism contributes two-thirds of the difference of ˜1500ppm between BiH3 and BiF3. The second-order SO mechanism and the numerically largest relativistic effect, which arises from the cross-term contribution of the Fermi contact hyperfine interaction and the relativistically modified spin-Zeeman interaction (FC/SZ-KE), are isotropic and practically independent of electron correlation effects as well as the chemical environment of the heavy atom. The third-order SO terms depend on these factors and contribute both to heavy-atom shielding anisotropy and NMR chemical shifts. While a qualitative picture of heavy-atom chemical shifts is already obtained at the nonrelativistic level of theory, reliable shifts may be expected after including the third-order SO contributions only, especially when calculations are carried out at correlated level. The FC/SZ-KE contribution to shielding is almost completely produced in the s orbitals of the heavy atom, with values diminishing with the principal

  9. Effect of heavy atoms in bioluminescent reactions.

    Science.gov (United States)

    Kirillova, Tamara N; Kudryasheva, Nadezhda S

    2007-03-01

    Bioluminescent reactions of luminous organisms are excellent models for studying the effects of heavy atoms on enzymatic processes. The effects of potassium halides with halide anions of different atomic weight were compared in bioluminescent reactions of the firefly (Luciola mingrelica), a marine coelenterate (Obelia longissima), and a marine bacterium (Photobacterium leiognathi). Two mechanisms of the effects of the halides were examined-the physicochemical effect of the external heavy atom, based on spin-orbit interactions in electron-excited structures, and the biochemical effect, i.e. interactions with the enzymes resulting in changes of enzymatic activity. The physicochemical effect was evaluated by using photoexcitation of model fluorescent compounds (flavin mononucleotide, firefly luciferin, and coelenteramide) of similar structure to the bioluminescence emitters. The bioluminescent and photoluminescent inhibition coefficients were calculated and compared for the luminous organisms to evaluate the relative contributions of the two mechanisms. The biochemical mechanism was found to be dominant. Hence, the bioluminescent reactions can be used as assays to monitor enzyme inhibition, in metabolic processes, by Br or I-containing compounds.

  10. Microbially Mediated Kinetic Sulfur Isotope Fractionation: Reactive Transport Modeling Benchmark

    Science.gov (United States)

    Wanner, C.; Druhan, J. L.; Cheng, Y.; Amos, R. T.; Steefel, C. I.; Ajo Franklin, J. B.

    2014-12-01

    Microbially mediated sulfate reduction is a ubiquitous process in many subsurface systems. Isotopic fractionation is characteristic of this anaerobic process, since sulfate reducing bacteria (SRB) favor the reduction of the lighter sulfate isotopologue (S32O42-) over the heavier isotopologue (S34O42-). Detection of isotopic shifts have been utilized as a proxy for the onset of sulfate reduction in subsurface systems such as oil reservoirs and aquifers undergoing uranium bioremediation. Reactive transport modeling (RTM) of kinetic sulfur isotope fractionation has been applied to field and laboratory studies. These RTM approaches employ different mathematical formulations in the representation of kinetic sulfur isotope fractionation. In order to test the various formulations, we propose a benchmark problem set for the simulation of kinetic sulfur isotope fractionation during microbially mediated sulfate reduction. The benchmark problem set is comprised of four problem levels and is based on a recent laboratory column experimental study of sulfur isotope fractionation. Pertinent processes impacting sulfur isotopic composition such as microbial sulfate reduction and dispersion are included in the problem set. To date, participating RTM codes are: CRUNCHTOPE, TOUGHREACT, MIN3P and THE GEOCHEMIST'S WORKBENCH. Preliminary results from various codes show reasonable agreement for the problem levels simulating sulfur isotope fractionation in 1D.

  11. Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

    Energy Technology Data Exchange (ETDEWEB)

    Matsuyama, M.; Kondo, M.; Noda, N. [Hydrogen Isotope Research Center, University of Toyama, Gofuku, Toyama (Japan); Tanaka, M.; Nishimura, K. [National Institute for Fusion Science, Toki-shi, Gifu (Japan)

    2015-03-15

    In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel is limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)

  12. Calcium kinetics with microgram stable isotope doses and saliva sampling

    Science.gov (United States)

    Smith, S. M.; Wastney, M. E.; Nyquist, L. E.; Shih, C. Y.; Wiesmann, H.; Nillen, J. L.; Lane, H. W.

    1996-01-01

    Studies of calcium kinetics require administration of tracer doses of calcium and subsequent repeated sampling of biological fluids. This study was designed to develop techniques that would allow estimation of calcium kinetics by using small (micrograms) doses of isotopes instead of the more common large (mg) doses to minimize tracer perturbation of the system and reduce cost, and to explore the use of saliva sampling as an alternative to blood sampling. Subjects received an oral dose (133 micrograms) of 43Ca and an i.v. dose (7.7 micrograms) of 46Ca. Isotopic enrichment in blood, urine, saliva and feces was well above thermal ionization mass spectrometry measurement precision up to 170 h after dosing. Fractional calcium absorptions determined from isotopic ratios in blood, urine and saliva were similar. Compartmental modeling revealed that kinetic parameters determined from serum or saliva data were similar, decreasing the necessity for blood samples. It is concluded from these results that calcium kinetics can be assessed with micrograms doses of stable isotopes, thereby reducing tracer costs and with saliva samples, thereby reducing the amount of blood needed.

  13. Kinetic Isotope Effects in the Reduction of Methyl Iodide

    DEFF Research Database (Denmark)

    Holm, Torkil

    1999-01-01

    a-Deuterium kinetic isotope effects (KIE's) have been determined for the reaction of methyl iodide with a series of reducing agents. Reagents which transfer hydride ion in an SN2 reaction show small inverse or small normal KIE's. Reagents which transfer an electron to methyl iodide to produce...

  14. An overview of heavy-atom derivatization of protein crystals.

    Science.gov (United States)

    Pike, Ashley C W; Garman, Elspeth F; Krojer, Tobias; von Delft, Frank; Carpenter, Elisabeth P

    2016-03-01

    Heavy-atom derivatization is one of the oldest techniques for obtaining phase information for protein crystals and, although it is no longer the first choice, it remains a useful technique for obtaining phases for unknown structures and for low-resolution data sets. It is also valuable for confirming the chain trace in low-resolution electron-density maps. This overview provides a summary of the technique and is aimed at first-time users of the method. It includes guidelines on when to use it, which heavy atoms are most likely to work, how to prepare heavy-atom solutions, how to derivatize crystals and how to determine whether a crystal is in fact a derivative.

  15. Kinetic 15N-isotope effects on algal growth

    Science.gov (United States)

    Andriukonis, Eivydas; Gorokhova, Elena

    2017-03-01

    Stable isotope labeling is a standard technique for tracing material transfer in molecular, ecological and biogeochemical studies. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism metabolism and growth, which is not consistent with current theoretical and empirical knowledge on kinetic isotope effects. Here, we demonstrate profound changes in growth dynamics of the green alga Raphidocelis subcapitata grown in 15N-enriched media. With increasing 15N concentration (0.37 to 50 at%), the lag phase increased, whereas maximal growth rate and total yield decreased; moreover, there was a negative relationship between the growth and the lag phase across the treatments. The latter suggests that a trade-off between growth rate and the ability to adapt to the high 15N environment may exist. Remarkably, the lag-phase response at 3.5 at% 15N was the shortest and deviated from the overall trend, thus providing partial support to the recently proposed Isotopic Resonance hypothesis, which predicts that certain isotopic composition is particularly favorable for living organisms. These findings confirm the occurrence of KIE in isotopically enriched algae and underline the importance of considering these effects when using stable isotope labeling in field and experimental studies.

  16. Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

    Science.gov (United States)

    Ni, Y.; Ma, Q.; Ellis, G.S.; Dai, J.; Katz, B.; Zhang, S.; Tang, Y.

    2011-01-01

    Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using ??D values in ethane from several basins in the world are in close agreement with similar predictions based on the ??13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that ??D values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that ??D values in ethane might be more suitable for modeling than comparable values in methane and propane. ?? 2011 Elsevier Ltd.

  17. Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

    Science.gov (United States)

    Ni, Yunyan; Ma, Qisheng; Ellis, Geoffrey S.; Dai, Jinxing; Katz, Barry; Zhang, Shuichang; Tang, Yongchun

    2011-05-01

    Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ 13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.

  18. Kinetic isotope effects for fast deuterium and proton exchange rates.

    Science.gov (United States)

    Canet, Estel; Mammoli, Daniele; Kadeřávek, Pavel; Pelupessy, Philippe; Bodenhausen, Geoffrey

    2016-04-21

    By monitoring the effect of deuterium decoupling on the decay of transverse (15)N magnetization in D-(15)N spin pairs during multiple-refocusing echo sequences, we have determined fast D-D exchange rates kD and compared them with fast H-H exchange rates kH in tryptophan to determine the kinetic isotope effect as a function of pH and temperature.

  19. Retention of Halogenated Solutes on Stationary Phases Containing Heavy Atoms

    Directory of Open Access Journals (Sweden)

    Toshio Miwa

    2013-05-01

    Full Text Available To examine the effects of weak intermolecular interactions on solid-phase extraction (SPE and chromatographic separation, we synthesized some novel stationary phases with a heavy atom effect layer by immobilizing halogenated aromatic rings and hydroxyl groups onto the surface of a hydrophilic base polymer. Using SPE cartridges packed with the functionalized materials, we found that the heavy atom stationary phases could selectively retain halophenols in organic solvents, such as 1-propanol which blocks the hydrogen bonding, or acetonitrile which blocks the p-p interaction. The extraction efficiency of the materials toward the halophenols depended on the dipole moments of phenoxy groups present as functional groups. On the other hand, the extraction efficiency of solutes toward the functional group depended on their molar refractions, i.e., induced dipole moments. The retention of the solutes to the stationary phase ultimately depended on not only strong intermolecular interactions, but also the effects of weak interactions such as the dispersion force.

  20. Magnetic ordering and anisotropy in heavy atom radicals.

    Science.gov (United States)

    Winter, Stephen M; Hill, Stephen; Oakley, Richard T

    2015-03-25

    Recent developments in stable radical chemistry have afforded "heavy atom" radicals, neutral open-shell (S = 1/2) molecular species containing heavy p-block elements (S, Se), which display solid-state magnetic properties once considered exclusive to conventional metal-based magnets. These highly spin-delocalized radicals do not associate in the solid state and yet display extensive networks of close intermolecular interactions. Spin density on the heavy atoms allows for increased isotropic and spin-orbit mediated anisotropic exchange effects. Structural variations induced by chemical modification and physical pressure, coupled with ab-initio methods to estimate exchange energies, have facilitated the development of predictive structure/property relationships. These results, coupled with detailed theoretical analyses and magnetic resonance spectroscopic measurements, have provided insight into the magnetic structure of ferromagnetic and spin-canted antiferromagnetic ordered materials as well as an understanding of the importance of spin-orbit coupling contributions to magnetic hysteresis and anisotropy. Isotropic and anisotropic ferromagnetic exchange can also be enhanced indirectly by the incorporation of heavy atoms into nonspin-bearing sites, where they can contribute to multi-orbital spin-orbit coupling.

  1. QED radiative corrections to parity nonconservation in heavy atoms.

    Science.gov (United States)

    Kuchiev, M Yu; Flambaum, V V

    2002-12-31

    The self-energy and vertex QED radiative corrections [approximately Zalpha2f(Zalpha)] are shown to give a large negative contribution to the parity nonconserving (PNC) amplitude in heavy atoms. The correction -0.73(20)% found for the 6s-7s PNC amplitude in 133Cs brings the experimental result for this transition into agreement with the standard model. The calculations are based on a new relation that expresses the radiative corrections to the PNC matrix element via corrections to the energy shifts induced by the finite nuclear size.

  2. Variation of kinetic isotope effect in multiple proton transfer reactions

    Indian Academy of Sciences (India)

    B Saritha; M Durga Prasad

    2012-01-01

    Recently, we had suggested that the motion along the promoter mode in the first part of the IRC of proton transfer reaction enhances the delocalization of electrons on the acceptor atom into the * orbital of the donor-hydrogen covalent bond, and as a consequence weakens it. This leads to a reduction of the barrier to the proton transfer as well as the stretching frequency of donor-hydrogen bond. An extension of this to the concerted multiple proton transfer reactions implies that the kinetic isotope effect in such reaction depends exponentially on the number of protons that are being transferred. Computational evidence on three systems, (HF)3, formic acid dimer, and (H2O) clusters is provided to support this assertion.

  3. Initiating Heavy-atom Based Phasing by Multi-Dimensional Molecular Replacement

    DEFF Research Database (Denmark)

    Pedersen, Bjørn Panyella; Gourdon, Pontus; Liu, Xiangyu;

    2014-01-01

    To obtain an electron-density map from a macromolecular crystal the phase-problem needs to be solved, which often involves the use of heavy-atom derivative crystals and concomitantly the determination of the heavy atom substructure. This is customarily done by direct methods or Patterson-based ap......To obtain an electron-density map from a macromolecular crystal the phase-problem needs to be solved, which often involves the use of heavy-atom derivative crystals and concomitantly the determination of the heavy atom substructure. This is customarily done by direct methods or Patterson...

  4. An improved pyrite pretreatment protocol for kinetic and isotopic studies

    Science.gov (United States)

    Mirzoyan, Natella; Kamyshny, Alexey; Halevy, Itay

    2014-05-01

    An improved pyrite pretreatment protocol for kinetic and isotopic studies Natella Mirzoyan1, Alexey Kamyshny Jr.2, Itay Halevy1 1Earth and Planetary Sciences, Weizmann Institute of Science, Rehovot 76100, Israel 2Geological and Environmental Sciences, Ben-Gurion University of the Negev, Beer Sheva 84105, Israel Pyrite is one of the most abundant and widespread of the sulfide minerals with a central role in biogeochemical cycles of iron and sulfur. Due to its diverse roles in the natural and anthropogenic sulfur cycle, pyrite has been extensively studied in various experimental investigations of the kinetics of its dissolution and oxidation, the isotopic fractionations associated with these reactions, and the microbiological processes involved. Pretreatment of pyrite for removal of oxidation impurities to prevent experimental artifacts and inaccuracies is often practiced. While numerous pyrite-cleaning methods have been used in experiments, a common pyrite pretreatment method, often used to investigate pyrite chemistry by the isotopic fractionations associated with it, includes several rinses by HCl, acetone and deionized water. Elemental sulfur (S0) is a common product of incomplete pyrite oxidation. Removal of S0 is desirable to avoid experimental biases associated with its participation in pyrite transformations, but is more complicated than the removal of sulfate. Although rinsing with an organic solvent is in part aimed at removing S0, to the best of our knowledge, the extraction efficiency of S0 in existing protocols has not been assessed. We have developed and tested a new protocol for elemental sulfur removal from the surface of pyrite by ultrasonication with warm acetone. Our data demonstrate the presence of large fractions of S0 on untreated pyrite particle surfaces, of which only approximately 60% was removed by the commonly used pretreatment method. The new protocol described here was found to be more efficient at S0 removal than the commonly used method

  5. A rapid and rational approach to generating isomorphous heavy-atom phasing derivatives.

    Science.gov (United States)

    Lu, Jinghua; Sun, Peter D

    2014-09-01

    In attempts to replace the conventional trial-and-error heavy-atom derivative search method with a rational approach, we previously defined heavy metal compound reactivity against peptide ligands. Here, we assembled a composite pH- and buffer-dependent peptide reactivity profile for each heavy metal compound to guide rational heavy-atom derivative search. When knowledge of the best-reacting heavy-atom compound is combined with mass spectrometry assisted derivatization, and with a quick-soak method to optimize phasing, it is likely that the traditional heavy-atom compounds could meet the demand of modern high-throughput X-ray crystallography. As an example, we applied this rational heavy-atom phasing approach to determine a previously unknown mouse serum amyloid A2 crystal structure.

  6. EQUILIBRIUM AND KINETIC NITROGEN AND OXYGEN-ISOTOPE FRACTIONATIONS BETWEEN DISSOLVED AND GASEOUS N2O

    NARCIS (Netherlands)

    INOUE, HY; MOOK, WG

    1994-01-01

    Experiments were performed to determine the equilibrium as well as kinetic stable nitrogen and oxygen isotope fractionations between aqueous dissolved and gaseous N2O. The equilibrium fractionations, defined as the ratio of the isotopic abundance ratios (15R and 18R, respectively) of gaseous and

  7. 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.

  8. Isotope exchange kinetics in metal hydrides I : TPLUG model.

    Energy Technology Data Exchange (ETDEWEB)

    Larson, Rich; James, Scott Carlton; Nilson, Robert H.

    2011-05-01

    A one-dimensional isobaric reactor model is used to simulate hydrogen isotope exchange processes taking place during flow through a powdered palladium bed. This simple model is designed to serve primarily as a platform for the initial development of detailed chemical mechanisms that can then be refined with the aid of more complex reactor descriptions. The one-dimensional model is based on the Sandia in-house code TPLUG, which solves a transient set of governing equations including an overall mass balance for the gas phase, material balances for all of the gas-phase and surface species, and an ideal gas equation of state. An energy equation can also be solved if thermodynamic properties for all of the species involved are known. The code is coupled with the Chemkin package to facilitate the incorporation of arbitrary multistep reaction mechanisms into the simulations. This capability is used here to test and optimize a basic mechanism describing the surface chemistry at or near the interface between the gas phase and a palladium particle. The mechanism includes reversible dissociative adsorptions of the three gas-phase species on the particle surface as well as atomic migrations between the surface and the bulk. The migration steps are more general than those used previously in that they do not require simultaneous movement of two atoms in opposite directions; this makes possible the creation and destruction of bulk vacancies and thus allows the model to account for variations in the bulk stoichiometry with isotopic composition. The optimization code APPSPACK is used to adjust the mass-action rate constants so as to achieve the best possible fit to a given set of experimental data, subject to a set of rigorous thermodynamic constraints. When data for nearly isothermal and isobaric deuterium-to-hydrogen (D {yields} H) and hydrogen-to-deuterium (H {yields} D) exchanges are fitted simultaneously, results for the former are excellent, while those for the latter show

  9. Isotope exchange kinetics in metal hydrides I : TPLUG model.

    Energy Technology Data Exchange (ETDEWEB)

    Larson, Rich; James, Scott Carlton; Nilson, Robert H.

    2011-05-01

    A one-dimensional isobaric reactor model is used to simulate hydrogen isotope exchange processes taking place during flow through a powdered palladium bed. This simple model is designed to serve primarily as a platform for the initial development of detailed chemical mechanisms that can then be refined with the aid of more complex reactor descriptions. The one-dimensional model is based on the Sandia in-house code TPLUG, which solves a transient set of governing equations including an overall mass balance for the gas phase, material balances for all of the gas-phase and surface species, and an ideal gas equation of state. An energy equation can also be solved if thermodynamic properties for all of the species involved are known. The code is coupled with the Chemkin package to facilitate the incorporation of arbitrary multistep reaction mechanisms into the simulations. This capability is used here to test and optimize a basic mechanism describing the surface chemistry at or near the interface between the gas phase and a palladium particle. The mechanism includes reversible dissociative adsorptions of the three gas-phase species on the particle surface as well as atomic migrations between the surface and the bulk. The migration steps are more general than those used previously in that they do not require simultaneous movement of two atoms in opposite directions; this makes possible the creation and destruction of bulk vacancies and thus allows the model to account for variations in the bulk stoichiometry with isotopic composition. The optimization code APPSPACK is used to adjust the mass-action rate constants so as to achieve the best possible fit to a given set of experimental data, subject to a set of rigorous thermodynamic constraints. When data for nearly isothermal and isobaric deuterium-to-hydrogen (D {yields} H) and hydrogen-to-deuterium (H {yields} D) exchanges are fitted simultaneously, results for the former are excellent, while those for the latter show

  10. Determination of urea kinetics by isotope dilution with [C-13]urea and gas chromatography isotope ratio mass spectrometry (GC-IRMS) analysis

    NARCIS (Netherlands)

    Kloppenburg, Wybe; Wolthers, BG; Stellaard, F; Elzinga, H; Tepper, T; deJong, PE; Huisman, RM

    1997-01-01

    1. Stable urea isotopes can be used to study urea kinetics in humans, The use of stable urea isotopes far studying urea kinetic parameters in humans on a large scale is hampered by the high costs of the labelled material, We devised a urea dilution for measurement of the distribution volume, product

  11. Initiating Heavy-atom Based Phasing by Multi-Dimensional Molecular Replacement

    DEFF Research Database (Denmark)

    Pedersen, Bjørn Panyella; Gourdon, Pontus Emanuel; Liu, Xiangyu

    2014-01-01

    approaches, which however may fail when only poorly diffracting derivative crystals are available, as often the case for e.g. membrane proteins. Here we present an approach for heavy atom site identification based on a Molecular Replacement Parameter Matrix (MRPM) search. It involves an n-dimensional search......To obtain an electron-density map from a macromolecular crystal the phase-problem needs to be solved, which often involves the use of heavy-atom derivative crystals and concomitantly the determination of the heavy atom substructure. This is customarily done by direct methods or Patterson-based...... to test a wide spectrum of molecular replacement parameters, such as clusters of different conformations. The result is scored by the ability to identify heavy-atom positions, from anomalous difference Fourier maps, that allow meaningful phases to be determined. The strategy was successfully applied...

  12. The modeling of carbon isotope kinetics and its application to the evaluation of natural gas

    Institute of Scientific and Technical Information of China (English)

    Xianqing LI; Xianming XIAO; Yongchun TANG; Hui TIAN; Qiang ZHOU; Yunfeng YANG; Peng DONG; Yan WANG; Zhihong SONG

    2008-01-01

    The modeling of carbon isotope kinetics of natural gas is an issue driving pioneering research in the oil and gas geochemistry in China and internationally.Combined with the sedimentary burial history and basin geothermal history,the modeling of carbon isotope kinetics provides a new and effective means for the determination of the origin and accumulation history of natural gas pools.In this paper,we introduce the modeling of carbon isotope kinetics of natural gas formation and its applications to the assessment of natural gas maturity,the determination of the gas source,the history of gas accumulation,and the oil-gas ratio.It is shown that this approach is of great value for these applications.The carbon isotopic characteristics of natural gas are not only affected by the gas source and maturity of the source rock,but also are related to the accumulation condition and geothermal gradient in a basin.There are obvious differences in the characteristics of carbon isotope ratios between instantaneous gas and cumulative gas.Different basins have different kinetic models of carbon isotope fractionation,which depends on the gas source condition,the accumulation history and the sedimentary-tectonic history.Since the origin of natural gas in the superimposed basin in China is very complicated,and the natural gas pool is characterized by multiphase and variable gas-sources,this paper may provide a new perspective on the study and evaluation of natural gas.

  13. Determination of absolute configuration using heavy atom based co-crystallization method: Halogen atom effects

    Science.gov (United States)

    Wang, Jian-Rong; Fan, Xiaowu; Ding, Qiaoce; Mei, Xuefeng

    2016-09-01

    Heavy atom (chloride, bromide, and iodide) based co-crystals for determination of absolute configuration (AC) for chiral molecules were synthesized and evaluated. Co-crystals of cholestanol and L-ascorbic acid were analysed and the effects and potential benefits of varying the heavy atom are discussed. Changing the halogen atoms (chloride, bromide, or iodide) affects the co-crystal formation, X-ray absorption, and anomalous dispersion, and hence the ability to determine AC.

  14. Equilibrium and kinetic Si isotope fractionation factors and their implications on Si isotope distributions in the Earth's surface environments

    Science.gov (United States)

    Tang, M.; Zhang, S.; Liu, Y.

    2015-12-01

    Several important equilibrium Si isotope fractionation factors among minerals, organic molecules and the H4SiO4 solution are complemented to facilitate explanation of distributions of Si isotope in the Earth's surface environments. The results reveal that heavy Si isotopes will be significantly enriched in the secondary silicate minerals in comparison to aqueous H4SiO4. On the contrary, quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution. The extent of 28Si-enrichment in hyper-coordinated organosilicon complexes is found the largest. In addition, the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer is calculated and the result supports previous statement that highly 28Si-enrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations. With equilibrium Si isotope fractionation factors provided here, Si isotope distributions in many surface systems of the Earth can be explained. For example, the change of bulk soil δ30Si can be predicted as a concave pattern with respect to weathering degree, with the minimum value where allophane completely dissolves and the total amount of sesqui-oxides and poorly crystalline minerals reaches its maximum. When well-crystallized clays start to precipitate from pore solutions under equilibrium conditions, the bulk soil δ30Si will increase again and reach a constant value. Similarly, the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain δ30Si variations in the ground water profile. Equilibrium Si isotope fractionations among quadra-coordinated organosilicon complexes and the H4SiO4 solution may also shed the light on the Si isotope distributions in Si-accumulating plants.

  15. Kinetic control on Zn isotope signatures recorded in marine diatoms

    Science.gov (United States)

    Köbberich, Michael; Vance, Derek

    2017-08-01

    Marine diatoms dominate the oceanic cycle of the essential micronutrient zinc (Zn). The stable isotopes of zinc and other metals are increasingly used to understand trace metal micronutrient cycling in the oceans. One clear feature of the early isotope data is the heavy Zn isotope signature of the average oceanic dissolved pool relative to the inputs, potentially driven by uptake of light isotopes into phytoplankton cells and export to sediments. However, despite the fact that diatoms strip Zn from surface waters across the Antarctic polar front in the Southern Ocean, the local upper ocean is not isotopically heavy. Here we use culturing experiments to quantify the extent of Zn isotope fractionation by diatoms and to elucidate the mechanisms driving it. We have cultured two different open-ocean diatom species (T. oceanica and Chaetoceros sp.) in a series of experiments at constant medium Zn concentration but at bioavailable medium Fe ranging from limiting to replete. We find that T. oceanica can maintain high growth rates and Zn uptake rates over the full range of bioavailable iron (Fe) investigated, and that the Zn taken up has a δ66Zn that is unfractionated relative to that of the bioavailable free Zn in the medium. The studied representative of the genus Chaetoceros, on the other hand, shows more significantly reduced Zn uptake rates at low Fe and records more variable biomass δ66Zn signatures, of up to 0.85‰ heavier than the medium. We interpret the preferential uptake of heavy isotopes at extremely low Zn uptake rates as potentially due to either of the following two mechanisms. First, the release of extracellular polymeric substances (EPS), at low Fe levels, may preferentially scavenge heavy Zn isotopes. Second, the Zn uptake rate may be slow enough to establish pseudo-equilibrium conditions at the transporter site, with heavy Zn isotopes forming more stable surface complexes. Thus we find that, in our experiments, Fe-limitation exerts a key control that

  16. Kinetic and solvent deuterium isotope effects in the oxidation of putrescine catalysed by enzyme diamine oxidase.

    Science.gov (United States)

    Pałka, Katarzyna; Szymańska, Jolanta; Kańska, Marianna

    2013-01-01

    In this study, the kinetic isotope effects and solvent isotope effects in the reaction of the deamination of [(1R)-(2)H ] putrescine--catalysed by enzyme diamine oxidase (EC 1.4.3.6)--were determined using a non-competitive spectroscopic method. Putrescine, stereospecifically labelled with deuterium, was obtained by enzymatic decarboxylation of l-ornithine that was carried out in a fully deuteriated incubation medium.

  17. Predictive Framework and Experimental Tests of the Kinetic Isotope Effect at Redox-Active Interfaces

    Science.gov (United States)

    Kavner, A.; John, S.; Black, J. R.

    2013-12-01

    Electrochemical reactions provide a compelling framework to study kinetic isotope effects because redox-related processes are important for a wide variety of geological and environmental processes. In the laboratory, electrochemical reaction rates can be electronically controlled and measured in the laboratory using a potentiostat. This enables variation of redox reactions rates independent of changes in chemistry and, and the resulting isotope compositions of reactants and products can be separated and analyzed. In the past years, a series of experimental studies have demonstrated a large, light, and tunable kinetic isotope effect during electrodeposition of metal Fe, Zn, Li, Cu, and Mo from a variety of solutions (e.g. Black et al., 2009, 2010, 2011). A theoretical framework based on Marcus kinetic theory predicts a voltage-dependent kinetic isotope effect (Kavner et al., 2005, 2008), however while this framework was able to predict the tunable nature of the effect, it was not able to simultaneously predict absolute reaction rates and relative isotope rates. Here we present a more complete development of a statistical mechanical framework for simple interfacial redox reactions, which includes isotopic behavior. The framework is able to predict a kinetic isotope effect as a function of temperature and reaction rate, starting with three input parameters: a single reorganization energy which describes the overall kinetics of the electron transfer reaction, and the equilibrium reduced partition function ratios for heavy and light isotopes in the product and reactant phases. We show the framework, elucidate some of the predictions, and show direct comparisons against isotope fractionation data obtained during laboratory and natural environment redox processes. A. Kavner, A. Shahar, F. Bonet, J. Simon and E. Young (2005) Geochim. Cosmochim. Acta, 69(12), 2971-2979. A. Kavner, S. G. John, S. Sass, and E. A. Boyle (2008), Geochim. Cosmochim. Acta, vol 72, pp. 1731

  18. Kinetic Isotopic Fractionation During Diffusion of Ionic Speciesin Water

    Energy Technology Data Exchange (ETDEWEB)

    Richter, Frank M.; Mendybaev, Ruslan A.; Christensen, John; Hutcheon, Ian D.; Williams, Ross W.; Sturchio, Neil C.; Beloso Jr.,Abelardo D.

    2005-06-09

    Experiments specifically designed to measure the ratio of the diffusivities of ions dissolved in water were used to determine D{sub Li}/D{sub K}, D{sub 7{sub Li}}/D{sub 6{sub Li}}, D{sub 25{sub Mg}}/D{sub 24{sub Mg}}, D{sub 26{sub Mg}}/D{sub 25{sub Mg}}, and D{sub 37{sub Cl}}/D{sub 35{sub Cl}}. The measured ratio of the diffusion coefficients for Li and K in water (D{sub Li}/D{sub K} = 0.6) is in good agreement with published data, providing evidence that the experimental design being used resolves the relative mobility of ions with adequate precision to also be used for determining the fractionation of isotopes by diffusion in water. In the case of Li we found measurable isotopic fractionation associated with the diffusion of dissolved LiCl (D{sub 7{sub Li}}/D{sub 6{sub Li}} = 0.99772 {+-} 0.00026). This difference in the diffusion coefficient of {sup 7}Li compared to {sup 6}Li is significantly less than reported in an earlier study, a difference we attribute to the fact that in the earlier study Li diffused through a membrane separating the water reservoirs. Our experiments involving Mg diffusing in water found no measurable isotopic fractionation (D{sub 25{sub Mg}}/D{sub 24{sub Mg}} = 1.00003 {+-} 0.00006). Cl isotopes were fractionated during diffusion in water (D{sub 37{sub Cl}}/D{sub 35{sub Cl}} = 0.99857 {+-} 0.00080) whether or not the co-diffuser (Li or Mg) was isotopically fractionated. The isotopic fractionation associated with the diffusion of ions in water is much smaller than values we found previously for the isotopic fractionation of Li and Ca isotopes by diffusion in molten silicate liquids. A major distinction between water and silicate liquids is that water, being a polar liquid, surrounds dissolved ions with hydration shells, which very likely play an important but still poorly understood role in reducing isotopic fractionation associated with diffusion.

  19. Kinetic secondary deuterium isotope effects for substituted benzaldehyde cyanohydrin formation

    Energy Technology Data Exchange (ETDEWEB)

    Okano, V.; do Amaral, L.; Cordes, E.H.

    1976-07-07

    ..cap alpha.. secondary deuterium isotope effects have been measured for the observed rate constants for addition of cyanide ion to a series of substituted benzaldehydes in aqueous solution at 25/sup 0/C. Under the experimental conditions employed, these reactions did not proceed to completion, and the observed isotope effects were corrected to account for the influence of the reverse reaction employing measured equilibrium constants for cyanohydrin formation and previously determined secondary deuterium isotope effect for the equilibrium constant for 4-methoxybenzaldehyde cyanohydrin formation. In the four cases studied, values of k/sub D//k/sub H/ varied from 1.15 to 1.20, only slightly lower than the calculated maximal value for complete formation of the anionic tetrahedral species which is the immediate product of the rate-determining step, 1.21. A trend in isotope effect as a function of substrate reactivity could not be definitively established. The results suffice to establish that addition of cyanide to benzaldehydes proceeds via transition states in which rehybridization of carbonyl carbon to the tetrahedral geometry is nearly complete.

  20. Effect of heavy atoms on the thermal stability of α-amylase from Aspergillus oryzae.

    Directory of Open Access Journals (Sweden)

    Michihiro Sugahara

    Full Text Available Currently, there are no versatile and established methods for improving stability of proteins. In an entirely different approach from conventional techniques such as mutagenesis, we attempted to enhance enzyme stability of α-amylase from Aspergillus oryzae using a heavy-atom derivatization technique. We evaluated changes in stability using differential scanning calorimetry (DSC. Candidate heavy atoms were identified using the Heavy-Atom Database System HATODAS, a Web-based tool designed to assist in heavy-atom derivatization of proteins for X-ray crystallography. The denaturation temperature of α-amylase derivatized with gadolinium (Gd or samarium (Sm ions increased by 6.2 or 5.7°C, respectively, compared to that of the native protein (60.6°C. The binding of six Gd ions was confirmed by X-ray crystallography of the enzyme at 1.5 Å resolution. DSC and dynamic light-scattering data revealed a correlation between stability and the aggregation state upon addition of Gd ions. These results show that HATODAS search is an effective tool for selecting heavy atoms for stabilization of this protein.

  1. Initiating heavy-atom-based phasing by multi-dimensional molecular replacement.

    Science.gov (United States)

    Pedersen, Bjørn Panyella; Gourdon, Pontus; Liu, Xiangyu; Karlsen, Jesper Lykkegaard; Nissen, Poul

    2016-03-01

    To obtain an electron-density map from a macromolecular crystal the phase problem needs to be solved, which often involves the use of heavy-atom derivative crystals and concomitant heavy-atom substructure determination. This is typically performed by dual-space methods, direct methods or Patterson-based approaches, which however may fail when only poorly diffracting derivative crystals are available. This is often the case for, for example, membrane proteins. Here, an approach for heavy-atom site identification based on a molecular-replacement parameter matrix (MRPM) is presented. It involves an n-dimensional search to test a wide spectrum of molecular-replacement parameters, such as different data sets and search models with different conformations. Results are scored by the ability to identify heavy-atom positions from anomalous difference Fourier maps. The strategy was successfully applied in the determination of a membrane-protein structure, the copper-transporting P-type ATPase CopA, when other methods had failed to determine the heavy-atom substructure. MRPM is well suited to proteins undergoing large conformational changes where multiple search models should be considered, and it enables the identification of weak but correct molecular-replacement solutions with maximum contrast to prime experimental phasing efforts.

  2. Determination of Kinetic Isotope Effects in Yeast Alcohol Dehydrogenase Using Transition Path Sampling

    Science.gov (United States)

    Varga, Matthew; Schwartz, Steven

    2015-03-01

    The experimental determination of kinetic isotope effects in enzymatic systems can be a difficult, time-consuming, and expensive process. In this study, we use the Chandler-Bolhius method for the determination of reaction rates within transition path sampling (rTPS) to determine the primary kinetic isotope effect in yeast alcohol dehydrogenase (YADH). In this study, normal mode centroid molecular dynamics (CMD) was applied to the transferring hydride/deuteride in order to correctly incorporate quantum effects into the molecular simulations. Though previous studies have used rTPS to calculate reaction rate constants in various model and real systems, it has not been applied to a system as large as YADH. Due to the fact that particle transfer is not wholly indicative of the chemical step, this method cannot be used to determine reaction rate constants in YADH. However, it is possible to determine the transition rate constant of the particle transfer, and the kinetic isotope effect of that step. This method provides a set of tools to determine kinetic isotope effects with the atomistic detail of molecular simulations.

  3. You Are What You Eat: Mass spectrometry in paediatric kinetic studies using stable isotopes

    NARCIS (Netherlands)

    H. Schierbeek (Henk)

    2009-01-01

    textabstractAn overview will be presented about applications of stable isotopes in paediatric research. Mass spectrometry has proven to be an essential tool for unravelling kinetic studies in a large range of different research disciplines related to intestinal diseases, obesities, severe cerebral p

  4. Kinetic and geometric isotope effects originating from different adsorption potential energy surfaces: cyclohexane on Rh(111).

    Science.gov (United States)

    Koitaya, Takanori; Shimizu, Sumera; Mukai, Kozo; Yoshimoto, Shinya; Yoshinobu, Jun

    2012-06-07

    Novel isotope effects were observed in desorption kinetics and adsorption geometry of cyclohexane on Rh(111) by the use of infrared reflection absorption spectroscopy, temperature programmed desorption, photoelectron spectroscopy, and spot-profile-analysis low energy electron diffraction. The desorption energy of deuterated cyclohexane (C(6)D(12)) is lower than that of C(6)H(12). In addition, the work function change by adsorbed C(6)D(12) is smaller than that by adsorbed C(6)H(12). These results indicate that C(6)D(12) has a shallower adsorption potential than C(6)H(12) (vertical geometric isotope effect). The lateral geometric isotope effect was also observed in the two-dimensional cyclohexane superstructures as a result of the different repulsive interaction between interfacial dipoles. The observed isotope effects should be ascribed to the quantum nature of hydrogen involved in the C-H···metal interaction.

  5. Site specific incorporation of heavy atom-containing unnatural amino acids into proteins for structure determination

    Science.gov (United States)

    Xie, Jianming; Wang, Lei; Wu, Ning; Schultz, Peter G.

    2008-07-15

    Translation systems and other compositions including orthogonal aminoacyl tRNA-synthetases that preferentially charge an orthogonal tRNA with an iodinated or brominated amino acid are provided. Nucleic acids encoding such synthetases are also described, as are methods and kits for producing proteins including heavy atom-containing amino acids, e.g., brominated or iodinated amino acids. Methods of determining the structure of a protein, e.g., a protein into which a heavy atom has been site-specifically incorporated through use of an orthogonal tRNA/aminoacyl tRNA-synthetase pair, are also described.

  6. Microscopic Observation of Kinetic Molecular Sieving of Hydrogen Isotopes in a Nanoporous Material

    Science.gov (United States)

    Nguyen, T. X.; Jobic, H.; Bhatia, S. K.

    2010-08-01

    We report quasielastic neutron scattering studies of H2-D2 diffusion in a carbon molecular sieve, demonstrating remarkable quantum effects, with the heavier isotope diffusing faster below 100 K, confirming our recent predictions. Our transition state theory and molecular dynamics calculations show that while it is critical for this effect to have narrow windows of size comparable to the de Broglie wavelength, high flux requires that the energy barrier be reduced through small cages. Such materials will enable novel processes for kinetic molecular sieving of hydrogen isotopes.

  7. Initiating heavy-atom-based phasing by multi-dimensional molecular replacement

    DEFF Research Database (Denmark)

    Pedersen, Bjørn Panyella; Gourdon, Pontus; Liu, Xiangyu;

    2016-01-01

    -dimensional search to test a wide spectrum of molecular-replacement parameters, such as different data sets and search models with different conformations. Results are scored by the ability to identify heavy-atom positions from anomalous difference Fourier maps. The strategy was successfully applied...... the identification of weak but correct molecular-replacement solutions with maximum contrast to prime experimental phasing efforts....

  8. 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....

  9. An experimental system to investigate kinetics and isotopic properties of the electrolytic metal hydride formation

    Energy Technology Data Exchange (ETDEWEB)

    Leardini, F. [Dpto. Fisica de Materiales, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain)]. E-mail: fabrice.leardini@uam.es; Bodega, J. [Dpto. Fisica de Materiales, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Fernandez, J.F. [Dpto. Fisica de Materiales, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Sanchez, C. [Dpto. Fisica de Materiales, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain)

    2005-12-08

    We present in this paper an experimental set-up based in a mass spectrometer connected to a closed electrolytic cell. Calibrations accomplished with a Pt cathode and H{sub 2}O/D{sub 2}O mixtures have shown new kinetics in galvanostatic electrolysis. These findings may be relevant in some important processes such as the hydrogen evolution reaction, isotopic separation factors or the electrolytic formation of metal hydrides.

  10. Enzymatic Kinetic Isotope Effects from Path-Integral Free Energy Perturbation Theory.

    Science.gov (United States)

    Gao, J

    2016-01-01

    Path-integral free energy perturbation (PI-FEP) theory is presented to directly determine the ratio of quantum mechanical partition functions of different isotopologs in a single simulation. Furthermore, a double averaging strategy is used to carry out the practical simulation, separating the quantum mechanical path integral exactly into two separate calculations, one corresponding to a classical molecular dynamics simulation of the centroid coordinates, and another involving free-particle path-integral sampling over the classical, centroid positions. An integrated centroid path-integral free energy perturbation and umbrella sampling (PI-FEP/UM, or simply, PI-FEP) method along with bisection sampling was summarized, which provides an accurate and fast convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. The PI-FEP method is illustrated by a number of applications, to highlight the computational precision and accuracy, the rule of geometrical mean in kinetic isotope effects, enhanced nuclear quantum effects in enzyme catalysis, and protein dynamics on temperature dependence of kinetic isotope effects.

  11. The power of integrating kinetic isotope effects into the formalism of the Michaelis-Menten equation.

    Science.gov (United States)

    Klinman, Judith P

    2014-01-01

    The final arbiter of enzyme mechanism is the ability to establish and test a kinetic mechanism. Isotope effects play a major role in expanding the scope and insight derived from the Michaelis-Menten equation. The integration of isotope effects into the formalism of the Michaelis-Menten equation began in the 1970s and has continued until the present. This review discusses a family of eukaryotic copper proteins, including dopamine β-monooxygenase, tyramine β-monooxygenase and peptidylglycine α-amidating enzyme, which are responsible for the synthesis of neuroactive compounds, norepinephrine, octopamine and C-terminally carboxamidated peptides, respectively. The review highlights the results of studies showing how combining kinetic isotope effects with initial rate parameters permits the evaluation of: (a) the order of substrate binding to multisubstrate enzymes; (b) the magnitude of individual rate constants in complex, multistep reactions; (c) the identification of chemical intermediates; and (d) the role of nonclassical (tunnelling) behaviour in C-H activation. © 2013 FEBS.

  12. Local group modes and the dynamics of intramolecular energy transfer across a heavy atom

    OpenAIRE

    Lopez, Vicente; Fairen, Victor; Lederman, Steven M.; Marcus, R.A

    1986-01-01

    The dynamics of energy transfer is discussed for a model system in which two ligands are separated by a heavy atom. Numerical and analytical results are given for the case that each ligand is a CC. In the quasiperiodic regime, the dynamics are interpreted using perturbation theory. Local group modes involved in an intramolecular energy localization which can occur in this regime are identified. An approximate separation of the primarily ligand–ligand motions from the primarily ligand–metal–li...

  13. The Relativistic Effects on the Carbon-Carbon Coupling Constants Mediated by a Heavy Atom.

    Science.gov (United States)

    Wodyński, Artur; Malkina, Olga L; Pecul, Magdalena

    2016-07-21

    The (2)JCC, (3)JCC, and (4)JCC spin-spin coupling constants in the systems with a heavy atom (Cd, In, Sn, Sb, Te, Hg, Tl, Pb, Bi, and Po) in the coupling path have been calculated by means of density functional theory. The main goal was to estimate the relativistic effects on spin-spin coupling constants and to explore the factors which may influence them, including the nature of the heavy atom and carbon hybridization. The methods applied range, in order of reduced complexity, from the Dirac-Kohn-Sham (DKS) method (density functional theory with four-component Dirac-Coulomb Hamiltonian), through DFT with two- and one-component zeroth-order regular approximation (ZORA) Hamiltonians, to scalar effective core potentials (ECPs) with the nonrelativistic Hamiltonian. The use of DKS and ZORA methods leads to very similar results, and small-core ECPs of the MDF and MWB variety reproduce correctly the scalar relativistic effects. Scalar relativistic effects usually are larger than the spin-orbit coupling effects. The latter tend to influence the most the coupling constants of the sp(3)-hybridized carbon atoms and in compounds of the p-block heavy atoms. Large spin-orbit coupling contributions for the Po compounds are probably connected with the inverse of the lowest triplet excitation energy.

  14. Impact of historical mining assessed in soils by kinetic extraction and lead isotopic ratios

    Energy Technology Data Exchange (ETDEWEB)

    Camizuli, E., E-mail: estelle.camizuli@u-bourgogne.fr [UMR 6298, ArTeHiS, Université de Bourgogne — CNRS — Culture, 6 bd Gabriel, Bat. Gabriel, 21000 Dijon (France); Monna, F. [UMR 6298, ArTeHiS, Université de Bourgogne — CNRS — Culture, 6 bd Gabriel, Bat. Gabriel, 21000 Dijon (France); Bermond, A.; Manouchehri, N.; Besançon, S. [Institut des sciences et industries du vivant et de l' environnement (AgroParisTech), Laboratoire de Chimie Analytique, 16, rue Claude Bernard, 75231 Paris Cedex 05 (France); Losno, R. [UMR 7583, LISA, Universités Paris 7-Paris 12 — CNRS, 61 av. du Gal de Gaulle, 94010 Créteil Cedex (France); Oort, F. van [UR 251, Pessac, Institut National de la Recherche Agronomique, Centre de Versailles-Grignon, RD 10, 78026 Versailles Cedex (France); Labanowski, J. [UMR 7285, IC2MP, Université de Poitiers — CNRS, 4, rue Michel Brunet, 86022 Poitiers (France); Perreira, A. [UMR 6298, ArTeHiS, Université de Bourgogne — CNRS — Culture, 6 bd Gabriel, Bat. Gabriel, 21000 Dijon (France); Chateau, C. [UFR SVTE, Université de Bourgogne, 6 bd Gabriel, Bat. Gabriel, 21000 Dijon (France); Alibert, P. [UMR 6282, Biogeosciences, Université de Bourgogne — CNRS, 6 bd Gabriel, Bat. Gabriel, 21000 Dijon (France)

    2014-02-01

    The aim of this study is to estimate the long-term behaviour of trace metals, in two soils differently impacted by past mining. Topsoils from two 1 km{sup 2} zones in the forested Morvan massif (France) were sampled to assess the spatial distribution of Cd, Cu, Pb and Zn. The first zone had been contaminated by historical mining. As expected, it exhibits higher trace-metal levels and greater spatial heterogeneity than the second non-contaminated zone, supposed to represent the local background. One soil profile from each zone was investigated in detail to estimate metal behaviour, and hence, bioavailability. Kinetic extractions were performed using EDTA on three samples: the A horizon from both soil profiles and the B horizon from the contaminated soil. For all three samples, kinetic extractions can be modelled by two first-order reactions. Similar kinetic behaviour was observed for all metals, but more metal was extracted from the contaminated A horizon than from the B horizon. More surprising is the general predominance of the residual fraction over the “labile” and “less labile” pools. Past anthropogenic inputs may have percolated over time through the soil profiles because of acidic pH conditions. Stable organo-metallic complexes may also have been formed over time, reducing metal availability. These processes are not mutually exclusive. After kinetic extraction, the lead isotopic compositions of the samples exhibited different signatures, related to contamination history and intrinsic soil parameters. However, no variation in lead signature was observed during the extraction experiment, demonstrating that the “labile” and “less labile” lead pools do not differ in terms of origin. Even if trace metals resulting from past mining and metallurgy persist in soils long after these activities have ceased, kinetic extractions suggest that metals, at least for these particular forest soils, do not represent a threat for biota. - Highlights: • Trace

  15. Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    DePaolo, D.

    2010-10-15

    A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R{sub p}) to the gross forward precipitation rate (R{sub f}), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R{sub p} has been experimentally measured under varying conditions, but the magnitude of R{sub f} is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R{sub f} can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R{sub b} or k{sub b}), since at equilibrium R{sub f} = R{sub b}, and R{sub p} = 0. Hence it can be inferred that R{sub f} {approx} R{sub p} + R{sub b}. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R{sub p} (= R{sub f} - R{sub b}) << R{sub b}. For precipitation rates high enough that R{sub p} >> R{sub b}, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R{sub p} {approx} R{sub b} for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R{sub f} for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R{sub p

  16. 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

    The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically-symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over- saturation, determines crystal morphology, there are no quantitative models that relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be direct relationships between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D lattice Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. Crystal growth patterns can be varied between random growth and deterministic growth (along the maximum concentration gradient for example). The input parameters needed are the isotope- dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the condensation coefficient for ice is uncertain. The ratio D/k is a length (order 1 micron) that determines the minimum scale of dendritic growth features

  17. Ruthenium tetraoxide oxidations of alkanes: DFT calculations of barrier heights and kinetic isotope effects.

    Science.gov (United States)

    Drees, Markus; Strassner, Thomas

    2006-03-03

    The oxidation of C-H and C-C bonds by metal-oxo compounds is of general interest. We studied the RuO4-mediated catalytic oxidation of several cycloalkanes such as adamantane and cis- and trans-decalin as well as methane. B3LYP/6-31G(d) calculations on the experimentally proposed (3+2) mechanism are in good agreement with known experimental results. Comparison of experimental and theoretical kinetic isotope effects confirms the proposed mechanism. Besides RuO4, we also looked at RuO4(OH)- as a potential active species to account for ruthenium tetraoxide oxidations under strong basic conditions.

  18. Probing reversible chemistry in coenzyme B12 -dependent ethanolamine ammonia lyase with kinetic isotope effects.

    Science.gov (United States)

    Jones, Alex R; Rentergent, Julius; Scrutton, Nigel S; Hay, Sam

    2015-06-08

    Coenzyme B12 -dependent enzymes such as ethanolamine ammonia lyase have remarkable catalytic power and some unique properties that enable detailed analysis of the reaction chemistry and associated dynamics. By selectively deuterating the substrate (ethanolamine) and/or the β-carbon of the 5'-deoxyadenosyl moiety of the intrinsic coenzyme B12 , it was possible to experimentally probe both the forward and reverse hydrogen atom transfers between the 5'-deoxyadenosyl radical and substrate during single-turnover stopped-flow measurements. These data are interpreted within the context of a kinetic model where the 5'-deoxyadenosyl radical intermediate may be quasi-stable and rearrangement of the substrate radical is essentially irreversible. Global fitting of these data allows estimation of the intrinsic rate constants associated with CoC homolysis and initial H-abstraction steps. In contrast to previous stopped-flow studies, the apparent kinetic isotope effects are found to be relatively small.

  19. Temperature dependence of the kinetic isotope effect in β-pinene ozonolysis

    Science.gov (United States)

    Gensch, Iulia; Laumer, Werner; Stein, Olaf; Kammer, Beatrix; Hohaus, Thorsten; Saathoff, Harald; Wegener, Robert; Wahner, Andreas; Kiendler-Scharr, Astrid

    2011-10-01

    The temperature dependence of the kinetic isotope effect (KIE) of β-pinene ozonolysis was investigated experimentally at 258, 273 and 303 K in the AIDA atmospheric simulation chamber. Compound specific carbon isotopic analysis of gas phase samples was performed off-line with a Thermo Desorption-Gas Chromatography-Isotope Ratio Mass Spectrometry (TD-GC-IRMS) system. From the temporal behavior of the δ13C of β-pinene a KIE of 1.00358 ± 0.00013 was derived at 303 K, in agreement with literature data. Furthermore, KIE values of 1.00380 ± 0.00014 at 273 K and 1.00539 ± 0.00012 at 258 K were determined, showing an increasing KIE with decreasing temperature. A parameterization of the observed KIE temperature dependence was deduced and used in a sensitivity study carried out with the global chemistry transport model MOZART-3. Two scenarios were compared, the first neglecting, the second implementing the KIE temperature dependence in the simulations. β-Pinene stable carbon isotope ratio and concentration were computed, with emphasis on boreal zones. For early spring it is shown that when neglecting the temperature dependence of KIE, the calculated average age of β-pinene in the atmosphere can be up to two times over- or underestimated. The evolution of the isotopic composition of the major β-pinene oxidation product, nopinone, was examined using Master Chemical Mechanism (MCM) simulations. The tested hypothesis that formation of nopinone and its associated KIE are the determining factors for the observed δ13C values of nopinone is supported at high β-pinene conversion levels.

  20. Kinetic and metabolic isotope effects in coral skeletal carbon isotopes: A re-evaluation using experimental coral bleaching as a case study

    Science.gov (United States)

    Schoepf, Verena; Levas, Stephen J.; Rodrigues, Lisa J.; McBride, Michael O.; Aschaffenburg, Matthew D.; Matsui, Yohei; Warner, Mark E.; Hughes, Adam D.; Grottoli, Andréa G.

    2014-12-01

    Coral skeletal δ13C can be a paleo-climate proxy for light levels (i.e., cloud cover and seasonality) and for photosynthesis to respiration (P/R) ratios. The usefulness of coral δ13C as a proxy depends on metabolic isotope effects (related to changes in photosynthesis) being the dominant influence on skeletal δ13C. However, it is also influenced by kinetic isotope effects (related to calcification rate) which can overpower metabolic isotope effects and thus compromise the use of coral skeletal δ13C as a proxy. Heikoop et al. (2000) proposed a simple data correction to remove kinetic isotope effects from coral skeletal δ13C, as well as an equation to calculate P/R ratios from coral isotopes. However, despite having been used by other researchers, the data correction has never been directly tested, and isotope-based P/R ratios have never been compared to P/R ratios measured using respirometry. Experimental coral bleaching represents a unique environmental scenario to test this because bleaching produces large physiological responses that influence both metabolic and kinetic isotope effects in corals. Here, we tested the δ13C correction and the P/R calculation using three Pacific and three Caribbean coral species from controlled temperature-induced bleaching experiments where both the stable isotopes and the physiological variables that cause isotopic fractionation (i.e., photosynthesis, respiration, and calcification) were simultaneously measured. We show for the first time that the data correction proposed by Heikoop et al. (2000) does not effectively remove kinetic effects in the coral species studied here, and did not improve the metabolic signal of bleached and non-bleached corals. In addition, isotope-based P/R ratios were in poor agreement with measured P/R ratios, even when the data correction was applied. This suggests that additional factors influence δ13C and δ18O, which are not accounted for by the data correction. We therefore recommend that the

  1. An Isotopic Exchange Kinetic Model to Assess the Speciation of Metal Available Pool in Soil: The Case of Nickel.

    Science.gov (United States)

    Zelano, I O; Sivry, Y; Quantin, C; Gélabert, A; Maury, A; Phalyvong, K; Benedetti, M F

    2016-12-06

    In this study an innovative approach is proposed to predict the relative contribution of each mineral phase to the total metal availability in soils, which, in other words, could be called the available metal fractionation. Through the use of isotopic exchange kinetics (IEK) performed on typical Ni bearing phases (i.e., two types of serpentines, chlorite, smectite, goethite, and hematite) the isotopic exchange and metal-solid interaction processes are connected, considering both the thermodynamic and kinetic aspects. Results of Ni IEK experiments on mineral phases are fitted with a pseudo-first order kinetic model. For each Ni bearing phase, this allows to (i) determine the number and size of exchangeable pools (ENi(i)), (ii) assess their corresponding kinetic constants (k(i)), and (iii) discuss the mechanism of Ni isotopic exchange at mineral surfaces. It is shown that all the phases investigated, with the only exception of hematite, present at least two distinct reactive pools with significantly different k(i) values. Results suggest also that metal involved in outer-sphere complexes would display isotopic exchange between 100 and 1000 times faster than metal involved in inner-sphere complexes, and that the presence of high and low affinity sites may influence the rate of isotopic exchange up to 1 order of magnitude. Moreover, the method developed represents a tool to predict and estimate Ni mobility and availability in natural soil samples on the basis of soil mineral composition, providing information barely obtained with other techniques.

  2. Inner Sphere and Outer Sphere Electron Transfer to Methyl Iodide. Deuterium and 13C Kinetic Isotope Effects

    DEFF Research Database (Denmark)

    Holm, Torkil; Crossland, Ingolf

    1996-01-01

    Deuterium and 13C kinetic isotope effects (KIEs) have been determined for the conversion of methyl iodide into methyl radical via inner sphere ET (electron transfer) and via outer sphere ET. The alfa-deuterium KIE was found to be very high for in......Deuterium and 13C kinetic isotope effects (KIEs) have been determined for the conversion of methyl iodide into methyl radical via inner sphere ET (electron transfer) and via outer sphere ET. The alfa-deuterium KIE was found to be very high for in...

  3. Proton-induced alginment of the L/sub 3/-subshell in heavy atoms

    Energy Technology Data Exchange (ETDEWEB)

    Jitschin, W.; Kaschuba, A.; Kleinpoppen, H.; Lutz, H.O.

    1982-01-01

    The proton-induced alignment of the L-shell in heavy atoms (54 <= Z <= 92) has been studied my measuring the anisotropy of the emitted x radiation. The proton energies ranged from 150 keV to 10 MeV. The alignment in different target atoms was found to approximately follow a universal curve. Calculations in Born approximation as well as in the semiclassical approach give a good description of the observed alignment at high projectile velocities. In the low energy regime the deflection of the projectile in the Coulomb field of the target nucleus has to be taken into account to obtain agreement between theory and experiment.

  4. Kinetic isotope effects in the OH and Cl reactions of the clumped methane species 13CH3D

    DEFF Research Database (Denmark)

    Joelsson, Magnus

    Methane is an potent greenhouse gas, second only to carbon dioxide of the anthropogenic greenhouse gases in its influence on Earth’s radiative budget. Although less abundant in the atmosphere, methane’s global warming potential is about twentyeight times that of carbon dioxide. Sources of methane...... at significantly different temperatures, therefore, the clumped isotope signatures of methane can be used to identify the process by which the gas was formed. Clumped isotopes can thus be a helpful tool in refining the budget of atmospheric methane. However, the isotopic composition of the atmospheric methane pool....... 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...

  5. External Heavy-Atom Effect via Orbital Interactions Revealed by Single-Crystal X-ray Diffraction.

    Science.gov (United States)

    Sun, Xingxing; Zhang, Baicheng; Li, Xinyang; Trindle, Carl O; Zhang, Guoqing

    2016-07-28

    Enhanced spin-orbit coupling through external heavy-atom effect (EHE) has been routinely used to induce room-temperature phosphorescence (RTP) for purely organic molecular materials. Therefore, understanding the nature of EHE, i.e., the specific orbital interactions between the external heavy atom and the luminophore, is of essential importance in molecular design. For organic systems, halogens (e.g., Cl, Br, and I) are the most commonly seen heavy atoms serving to realize the EHE-related RTP. In this report, we conduct an investigation on how heavy-atom perturbers and aromatic luminophores interact on the basis of data obtained from crystallography. We synthesized two classes of molecular systems including N-haloalkyl-substituted carbazoles and quinolinium halides, where the luminescent molecules are considered as "base" or "acid" relative to the heavy-atom perturbers, respectively. We propose that electron donation from a π molecular orbital (MO) of the carbazole to the σ* MO of the C-X bond (π/σ*) and n electron donation to a π* MO of the quinolinium moiety (n/π*) are responsible for the EHE (RTP) in the solid state, respectively.

  6. Effect of parent body evolution on equilibrium and kinetic isotope fractionation: a combined Ni and Fe isotope study of iron and stony-iron meteorites

    Science.gov (United States)

    Chernonozhkin, Stepan M.; Goderis, Steven; Costas-Rodríguez, Marta; Claeys, Philippe; Vanhaecke, Frank

    2016-08-01

    Various iron and stony-iron meteorites have been characterized for their Ni and Fe isotopic compositions using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) after sample digestion and chromatographic separation of the target elements in an attempt to further constrain the planetary differentiation processes that shifted these isotope ratios and to shed light on the formational history and evolution of selected achondrite parent body asteroids. Emphasis was placed on spatially resolved isotopic analysis of iron meteorites, known to be inhomogeneous at the μm to mm scale, and on the isotopic characterization of adjacent metal and silicate phases in main group pallasites (PMG), mesosiderites, and the IIE and IAB complex silicate-bearing iron meteorites. In a 3-isotope plot of 60/58Ni versus62/58Ni, the slope of the best-fitting straight line through the laterally resolved Ni isotope ratio data for iron meteorites reveals kinetically controlled isotope fractionation (βexper = 1.981 ± 0.039, 1 SD), predominantly resulting from sub-solidus diffusion (with the fractionation exponent β connecting the isotope fractionation factors, as α62/58 =α60/58β). The observed relation between δ56/54Fe and Ir concentration in the metal fractions of PMGs and in IIIAB iron meteorites indicates a dependence of the bulk Fe isotopic composition on the fractional crystallization of an asteroidal metal core. No such fractional crystallization trends were found for the corresponding Ni isotope ratios or for other iron meteorite groups, such as the IIABs. In the case of the IIE and IAB silicate-bearing iron meteorites, the Fe and Ni isotopic signatures potentially reflect the influence of impact processes, as the degree of diffusion-controlled Ni isotope fractionation is closer to that of Fe compared to what is observed for magmatic iron meteorite types. Between the metal and olivine counterparts of pallasites, the Fe and Ni isotopic compositions show clearly

  7. Reaction Rates and Kinetic Isotope Effects of H$_2$ + OH $\\rightarrow$ H$_2$O + H

    CERN Document Server

    Meisner, Jan

    2016-01-01

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

  8. 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...

  9. Simulation Experiments on the Reaction of CH4-CaSO4 and Its Carbon Kinetic Isotope Fractionation

    Institute of Scientific and Technical Information of China (English)

    YueChangtao; LiShuyuan; DingKangle; ZhongNingning

    2005-01-01

    Thermochemical sulfate reduction (TSR) in geological deposits can account for the accumulation of H,S in deep sour gas reservoirs. In this paper, thermal simulation experiments on the reaction of CH4-CaSO4 were carried out using an autoclave at high temperatures and high pressures. The products were characterized with analytical methods including carbon isotope analysis. It is found that the reaction can proceed to produce H2S, H2O and CaCO3 as the main products. Based on the experimental results, the carbon kinetic isotope fractionation was investigated, and the value of Ki(kinetic isotope effect) was calculated. The results obtained in this paper can provide useful information to explain the occurrence of H2S in deep carbonate gas reservoirs.

  10. Use of chlorine kinetic isotope effects for evaluating ion pairing in nucleophilic displacements at saturated carbon

    Energy Technology Data Exchange (ETDEWEB)

    Graczyk, D.G.; Taylor, J.W.; Turnquist, C.R.

    1978-11-08

    Use of the Winstein scheme to describe ion pairing leads to the conclusion that chlorine kinetic isotope effects (KIE) are primarily responsive to processes involving the covalently bound chlorine and less indicative of reactions which occur after the formation of the initial ion pair. This conclusion has been tested by showing that the calculated equilibrium isotope effect (1.0057) and observed (1.0059/sub 6/ +- 0.0001/sub 1/) KIE are nearly identical when the solvolysis of p-methylbenzyl chloride is forced toward a limiting case with 97% trifluoroethanol as solvent. The reaction of p-phenoxybenzyl chloride showed similar behavior with an equilibrium KIE value of 1.0058/sub 4/ +- 0.0001/sub 1/. These results suggest that competing ion-pair and S/sub N/2 processes may be one factor contributing to Hammett plot curvature for these nucleophilic displacement reactions. Chloride KIE values for the reaction of n-butyl chloride with thiophenoxide anion, where ion pairing does not occur, show little variation with a wide variety of solvents. 3 tables.

  11. A kinetic chemistry tagging technique and its application to modelling the stable isotopic composition of atmospheric trace gases

    Directory of Open Access Journals (Sweden)

    S. Gromov

    2010-02-01

    Full Text Available Isotope composition, in many cases, holds unique information on sources, chemical modification and sinks of atmospheric trace gases. Vital to the interpretation and use of an increasing number of isotope analyses is appropriate modelling. However, the exact implementation of isotopic information is a challenge, and often studies use simplifications which limit their applicability. Here we confer a thorough isotopic extension to MECCA, a comprehensive kinetic chemistry sub-model. To this end, we devise a generic tagging technique for the kinetic chemistry mechanisms implemented as the sub-submodel MECCA-TAG. The technique constitutes a diagnostic tool that can benefit the investigation of various aspects of kinetic chemistry schemes; at the same time, the designed numerical optimisation reduces the computational effort while keeping important details unaffected. We further focus specifically on the modelling of stable isotopic composition, including the required extensions of the approach. The results of MECCA-TAG are evaluated against the reference sub-submodel MECCA-DBL, which is implicitly full-detailed, but necessarily is sub-optimal in practical applications due to its high computational demands. Furthermore, we evaluate the elaborate carbon and oxygen isotopic mechanism by simulating the multi-isotope composition of CO and other trace gases in the CAABA/MECCA box-model. The mechanism realistically simulates the oxygen isotope composition of key species resulting from the interchange with ozone and main atmospheric reservoirs, as well as the carbon isotope signature transfer. The model adequately reproduces the isotope chemistry features for CO under the limitation of the modelling domain. In particular, the mass-independently fractionated (MIF composition of CO due to reactions of ozone with unsaturated hydrocarbons (a source effect versus its intrinsic MIF enrichment induced in the removal reaction via oxidation by OH is assessed. As for

  12. A kinetic chemistry tagging technique and its application to modelling the stable isotopic composition of atmospheric trace gases

    Directory of Open Access Journals (Sweden)

    S. Gromov

    2010-08-01

    Full Text Available Isotope composition, in many cases, holds unique information on the sources, chemical modification and sinks of atmospheric trace gases. Vital to the interpretation and use of an increasing number of isotope analyses is appropriate modelling. However, the exact implementation of isotopic information in chemistry-climate models is a challenge, and often studies use simplifications which limit their applicability. Here we implement a thorough isotopic extension in MECCA, a comprehensive kinetic chemistry sub-model. To this end, we devise a generic tagging technique for the kinetic chemistry mechanisms implemented as the sub-submodel MECCA-TAG. The technique is diagnostic and numerically efficient and supports the investigation of various aspects of kinetic chemistry schemes. We focus specifically on the application to the modelling of stable isotopic composition. The results of MECCA-TAG are evaluated against the reference sub-submodel MECCA-DBL, which is implicitly full-detailed, but computationally expensive and thus sub-optimal in practical applications. Furthermore, we evaluate the elaborate carbon and oxygen isotopic mechanism by simulating the multi-isotope composition of CO and other trace gases in the CAABA/MECCA box-model. The mechanism realistically simulates the oxygen isotope composition of key species, as well as the carbon isotope signature transfer. The model adequately reproduces the isotope chemistry features for CO, taking into account the limits of the modelling domain. In particular, the mass-independently fractionated (MIF composition of CO due to reactions of ozone with unsaturated hydrocarbons (a source effect versus its intrinsic MIF enrichment induced in the removal reaction via oxidation by OH is assessed. The simulated ozone source effect was up to +1‰ in Δ17O(CO. The versatile modelling framework we employ (the Modular Earth Submodel System, MESSy opens the way for implementation of the novel detailed

  13. The isotopic effects in the scattering and the kinetics of the atomic cascade

    CERN Document Server

    Popov, V P

    2016-01-01

    {\\it Ab initio} quantum-mechanical calculations of the differential and integrated cross sections of the elastic scattering, Stark transitions, and Coulomb de-excitation at collisions of excited $\\mu^- p$ and $\\mu^- d$ atoms with hydrogen isotope atoms in the ground state are performed. The scattering processes are treated in a unified manner in the framework of the close-coupling approach. The used basis includes both open and closed channels corresponding to all exotic atom states with principal quantum numbers from $n=1$ up to $n_{\\rm max}=20$. The energy shifts of $ns$ states due to electron vacuum polarization and finite nuclear size are taken into account. The kinetics of atomic cascade of $\\mu^- p$ and $\\mu^- d$ atoms are studied in a wide range of relative target densities ($\\varphi = 10^{-8} -1$) within the improved version of the extended cascade model. The results of the numerical quantum-mechanical calculations of the cross sections for quantum numbers and kinetic energies of muonic atoms, that ar...

  14. Collisional cooling of light ions by co-trapped heavy atoms

    CERN Document Server

    Dutta, Sourav; Rangwala, S A

    2015-01-01

    The most generic cooling and thermalization pathway at the lowest temperatures is via elastic collisions. In hybrid ion-atom traps, ion cooling to temperatures where low partial wave collisions dominate require the collisional cooling mechanism to be well understood and controlled. There exists great uncertainty on whether cooling of light ions by heavier neutral atoms is possible. Here we experimentally demonstrate the cooling of light ions by co-trapped heavy atoms for the first time. We show that trapped 39K+ ions are cooled by localized ultracold neutral 85Rb atoms for an ion-atom mass ratio where most theoretical models predict ion heating. We demonstrate, based on detailed numerical simulation of our ion-cooling model, which is in excellent agreement with experiments, that cooling of ions by localized cold atoms is possible for any mass ratio. Our result opens up the possibility of studying quantum collisions and chemistry in trapped atom-ion systems.

  15. Insight on RDX degradation mechanism by Rhodococcus strains using 13C and 15N kinetic isotope effects.

    Science.gov (United States)

    Bernstein, Anat; Ronen, Zeev; Gelman, Faina

    2013-01-02

    The explosive Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is known to be degraded aerobically by various isolates of the Rhodococcus species, with denitration being the key step, mediated by Cytochrome P450. Our study aimed at gaining insight into the RDX degradation mechanism by Rhodococcus species and comparing isotope effects associated with RDX degradation by distinct Rhodococcus strains. For these purposes, enrichment in (13)C and (15)N isotopes throughout RDX denitration was studied for three distinct Rhodococcus strains, isolated from soil and groundwater in an RDX-contaminated site. The observable (15)N enrichment throughout the reaction, together with minor (13)C enrichment, suggests that N-N bond cleavage is likely to be the key rate-limiting step in the reaction. The similarity in the kinetic (15)N isotope effect between the three tested strains suggests that either isotope-masking effects are negligible, or are of a similar extent for all tested strains. The lack of variability in the kinetic (15)N isotope effect allows the interpretation of environmental studies with greater confidence.

  16. Structural and Kinetic Isotope Effect Studies of Nicotinamidase (Pnc1) from Saccharomyces cerevisiae

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Brian C.; Anderson, Mark A.; Hoadley, Kelly A.; Keck, James L.; Cleland, W. Wallace; Denu, John M. (UW)

    2012-05-08

    Nicotinamidases catalyze the hydrolysis of nicotinamide to nicotinic acid and ammonia. Nicotinamidases are absent in mammals but function in NAD{sup +} salvage in many bacteria, yeast, plants, protozoa, and metazoans. We have performed structural and kinetic investigations of the nicotinamidase from Saccharomyces cerevisiae (Pnc1). Steady-state product inhibitor analysis revealed an irreversible reaction in which ammonia is the first product released, followed by nicotinic acid. A series of nicotinamide analogues acting as inhibitors or substrates were examined, revealing that the nicotinamide carbonyl oxygen and ring nitrogen are critical for binding and reactivity. X-ray structural analysis revealed a covalent adduct between nicotinaldehyde and Cys167 of Pnc1 and coordination of the nicotinamide ring nitrogen to the active-site zinc ion. Using this structure as a guide, the function of several residues was probed via mutagenesis and primary {sup 15}N and {sup 13}C kinetic isotope effects (KIEs) on V/K for amide bond hydrolysis. The KIE values of almost all variants were increased, indicating that C-N bond cleavage is at least partially rate limiting; however, a decreased KIE for D51N was indicative of a stronger commitment to catalysis. In addition, KIE values using slower alternate substrates indicated that C-N bond cleavage is at least partially rate limiting with nicotinamide to highly rate limiting with thionicotinamide. A detailed mechanism involving nucleophilic attack of Cys167, followed by elimination of ammonia and then hydrolysis to liberate nicotinic acid, is discussed. These results will aid in the design of mechanism-based inhibitors to target pathogens that rely on nicotinamidase activity.

  17. Assessing chromate availability in tropical ultramafic soils using isotopic exchange kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Garnier, Jeremie; Quantin, Cecile [Univ. Paris Sud CNRS, Orsay (France); Echevarria, Guillaume [ENSAIA-INPL-INRA, Vandoeuvre-les-Nancy (France); Becquer, Thierry [IRD - Univ. Paris VI and XII, Montpellier (France)

    2009-10-15

    Background, aim, and scope The presence of labile chromate in the soils is an environmental problem because of its high toxicity. The isotopic exchange kinetics (IEK) methods have been shown to be a useful tool to measure the phytoavailability of major (P, K) and trace elements (Cd, Zn, Ni, Pb) in soils. This study focused on the potential of applying IEK for chromate to characterize its availability in two tropical ultramafic Ferralsols. Materials and methods Two Ferralsols (NIQ II and NIQ III) of the ultramafic complex of Niquelandia (Goias, Brazil), known to have a high content of extractable chromate, were investigated. We adapted IEK for chromate in order to distinguish different pools of available chromate according to their rate of exchange kinetic. Results The extractable Cr(III) ranged from 9 to 132 mg kg{sup -1}, whereas extractable Cr(VI) ranged from 64 to 1,014 mg kg{sup -1}. The intensity factor, i.e., concentration of soluble Cr, ranged from 78 to 231 {mu}g L{sup -1} in profile NIQ II and from 6 to 141 {mu}g L{sup -1} in profile NIQ III. The highest concentrations were found in both topsoils and in the NIQ II-5 horizon. Most of the Cr(VI) was labile in short (E{sub 0-1} {sub min}) or medium-term (E{sub 1} {sub min-24} {sub h}) in both soils. The E{sub 0-1} {sub min} and E{sub 1} {sub min-24} {sub h} represented 39 to 83% of labile Cr (VI) in NIQ II and 69 to 80% in NIQ III. A high quantity of Cr(VI) was thus extremely labile and highly available, particularly in NIQ II. Moreover, both soils had a high buffering capacity of soluble Cr(VI) by labile pools. (orig.)

  18. Suitability of Isotope Kinetic Approach to Assess Phos—phorus Status and Bioavailability of Major Acidic Soils in Subtropical China

    Institute of Scientific and Technical Information of China (English)

    XIONGLIMING; J.C.FARDEAU

    1997-01-01

    A 32P isotope kinetic approach was used to describe the chemical status and bioavailability of phosphorus in 32 acidic soils from subtropical China.By determining the residual radoactivity,rt,in soil solution at different time,t,after introduction of the isotope in an amount of R into the steady soil-water system,a well-defined isotope kinetic model was established,and upon this model the decrease rate ,n,of log(rt/R) with respect to logt,the mean sojourn time of phosphate ions in solution,the mean exchange rate and the mean flux of phosphate ions between soil solid and solution phases were calculated.Other parameters,such as the exchangeable P within the first minute of isotope exchange(E1),and P in various compartments that could be exchanged with solution phosphte ions at different perods of time,were also obtained.For these acidic soils,the r1/R had a significant correlation with the contents of clay and free Al2O3 where r1 is the radioactivity in solution 1 minute after introduction of the isotope into the system.Parameter n also had a significant correlation with clay content and a neagtive correlation with soil pH,E1 values and Cp,the P concentration in soil solution,also Significantly correlated with clay and sesquioxide contents of the soils.these indicated that these isotope kinetic parameters were largely influenced by P-fixing components of the soils.For the soils with strong P-fixing ability,the E1 values overestimated labile P pools and hence their correlations with A values and plant P uptake were not significant .The other iostope kinetic parameters also had no significant correlation with plant P uptak.On the other hand,the convetional chemical-extracted p correlated better with plant P uptake .It was concluded that the iostope kinetic method could assess the p chemical status yet it would inappropriate in predicting plant available P for soils with a high P-fixing ability as the problem of an overestimation of soil lable P in these soils was

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1992-02-01

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

  20. 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.

  1. Kinetic Isotope Effect on Transport Mediated by Clc-Type H+/CL- Exchangers

    Science.gov (United States)

    Picollo, Alessandra; Malvezzi, Mattia; Accardi, Alessio

    2013-01-01

    CLC transporters mediate the stoichiometric exchange of 2 Cl- ions for 1 H+ across the membranes of cellular compartments, mostly endosomes and lysosomes. Despite intense biophysical, structural and electrophysiological scrutiny the H+ transfer mechanism of these exchangers remains largely unknown. Previous work showed that two conserved Glutamates define the extremities of the H+ pathway in CLC exchangers. However, we don't know whether H+ transfer between these residues takes place along a series of protonatable moieties, via a Grotthuss mechanism and by diffusion of an H3+O cation and if at any step H+ tunneling plays a role. To differentiate between these possible mechanisms we measured the deuterium kinetic isotope effect on the transport rate of CLC-ec1 and CLC-5, respectively a prokaryotic and a eukaryotic CLC exchanger. We found that transport mediated by both proteins is slowed by ˜20-40% when H2O is replaced by D2O. This result suggests that the rate limiting step for H+ transport takes place along a hydrogen-bonded pathway, possibly formed by water molecules. However, we found that the voltage dependence of CLC-5 inhibition by extracellular H+ is eliminated by this substitution. This suggests that the voltage dependence of this process arises from a mechanism that is exquisitely sensitive to particle mass such as proton tunneling.

  2. Kinetic isotope effects in the characterization of catalysis by protein tyrosine phosphatases.

    Science.gov (United States)

    Hengge, Alvan C

    2015-11-01

    Although thermodynamically favorable, the uncatalyzed hydrolysis of phosphate monoesters is extraordinarily slow, making phosphatases among the most catalytically efficient enzymes known. Protein-tyrosine phosphatases (PTPs) are ubiquitous in biology, and kinetic isotope effects were one of the key mechanistic tools used to discern molecular details of their catalytic mechanism and the transition state for phosphoryl transfer. Later, the unique level of detail KIEs provided led to deeper questions about the potential role of protein motions in PTP catalysis. The recent discovery that such motions are responsible for different catalytic rates between PTPs arose from questions originating from KIE data showing that the transition states and chemical mechanisms are identical, combined with structural data demonstrating superimposable active sites. KIEs also reveal perturbations to the transition state as mutations are made to residues directly involved in chemistry, and to residues that affect protein motions essential for catalysis. This article is part of a Special Issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Reaction of dimethyl ether with hydroxyl radicals: kinetic isotope effect and prereactive complex formation.

    Science.gov (United States)

    Bänsch, Cornelie; Kiecherer, Johannes; Szöri, Milan; Olzmann, Matthias

    2013-09-05

    The kinetic isotope effect of the reactions OH + CH3OCH3 (DME) and OH + CD3OCD3 (DME-d6) was experimentally and theoretically studied. Experiments were carried out in a slow-flow reactor at pressures between 5 and 21 bar (helium as bath gas) with production of OH by laser flash photolysis of HNO3 and time-resolved detection of OH by laser-induced fluorescence. The temperature dependences of the rate coefficients obtained can be described by the following modified Arrhenius expressions: k(OH+DME) = (4.5 ± 1.3) × 10(-16) (T/K)(1.48) exp(66.6 K/T) cm(3) s(-1) (T = 292-650 K, P = 5.9-20.9 bar) and k(OH+DME-d6) = (7.3 ± 2.2) × 10(-23) (T/K)(3.57) exp(759.8 K/T) cm(3) s(-1) (T = 387-554 K, P = 13.0-20.4 bar). A pressure dependence of the rate coefficients was not observed. The agreement of our experimental results for k(OH+DME) with values from other authors is very good, and from a fit to all available literature data, we derived the following modified Arrhenius expression, which reproduces the values obtained in the temperature range T = 230-1500 K at pressures between 30 mbar and 21 bar to better than within ±20%: k(OH+DME) = 8.45 × 10(-18) (T/K)(2.07) exp(262.2 K/T) cm(3) s(-1). For k(OH+DME-d6), to the best of our knowledge, this is the first experimental study. For the analysis of the reaction pathway and the kinetic isotope effect, potential energy diagrams were calculated by using three different quantum chemical methods: (I) CCSD(T)/cc-pV(T,Q)Z//MP2/6-311G(d,p), (II) CCSD(T)/cc-pV(T,Q)Z//CCSD/cc-pVDZ, and (III) CBS-QB3. In all three cases, the reaction is predicted to proceed via a prereaction OH-ether complex with subsequent intramolecular hydrogen abstraction and dissociation to give the methoxymethyl radical and water. Overall rate coefficients were calculated by assuming a thermal equilibrium between the reactants and the prereaction complex and by calculating the rate coefficients of the hydrogen abstraction step from canonical transition state theory

  4. Metal Free Azide-Alkyne Click Reaction: Role of Substituents and Heavy Atom Tunneling.

    Science.gov (United States)

    Karmakar, Sharmistha; Datta, Ayan

    2015-09-03

    Metal free click reactions provide an excellent noninvasive tool to modify and understand the processes in biological systems. Release of ring strain in cyclooctynes on reaction with azides on the formation of triazoles results in small activation energies for various intermolecular Huisgen reactions (1-9). Substitution of difluoro groups at the α, α' position of the cyclooctyne ring enhances the rates of cycloadditions by 10 and 20 times for methyl azide and benzyl azide respectively at room temperature. The computed rate enhancement on difluoro substitution using direct dynamical calculations using the canonical variational transition state theory (CVT/CAG) with small curvature tunneling (SCT) corrections are in excellent agreement with the experimental results. For the intramolecular click reaction (10) notwithstanding its much higher activation energy, quantum mechanical tunneling (QMT) enhances the rate of cycloaddition significantly and increases the N(14)/N(15) primary kinetic isotope effect at 298 K. QMT is shown to be rather efficient in 10 due to a thin barrier of ∼2.4 Å. The present study shows that tunneling effects can be significant for intramolecular click reactions.

  5. Kinetically Relevant Steps and H2/D2 Isotope Effects in Fischer-Tropsch Synthesis on Fe and Co Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ojeda, Manuel; Li, Anwu; Nabar, Rahul P.; Nilekar, Anand U.; Mavrikakis, Manos; Iglesia, Enrique

    2010-11-25

    H2/D2 isotope effects on Fischer-Tropsch synthesis (FTS) rate and selectivity are examined here by combining measured values on Fe and Co at conditions leading to high C5+ yields with theoretical estimates on model Fe(110) and Co(0001) surfaces with high coverages of chemisorbed CO (CO*). Inverse isotope effects (rH/rD < 1) are observed on Co and Fe catalysts as a result of compensating thermodynamic (H2 dissociation to H*; H* addition to CO* species to form HCO*) and kinetic (H* reaction with HCO*) isotope effects. These isotopic effects and their rigorous mechanistic interpretation confirm the prevalence of H-assisted CO dissociation routes on both Fe and Co catalysts, instead of unassisted pathways that would lead to similar rates with H2 and D2 reactants. The small contributions from unassisted pathways to CO conversion rates on Fe are indeed independent of the dihydrogen isotope, as is also the case for the rates of primary reactions that form CO2 as the sole oxygen rejection route in unassisted CO dissociation paths. Isotopic effects on the selectivity to C5+ and CH4 products are small, and D2 leads to a more paraffinic product than does H2, apparently because it leads to preference for chain termination via hydrogen addition over abstraction. These results are consistent with FTS pathways limited by H-assisted CO dissociation on both Fe and Co and illustrate the importance of thermodynamic contributions to inverse isotope effects for reactions involving quasi-equilibrated H2 dissociation and the subsequent addition of H* in hydrogenation catalysis, as illustrated here by theory and experiment for the specific case of CO hydrogenation.

  6. Kinetic isotope effect for H2 and D2 quantum molecular sieving in adsorption/desorption on porous carbon materials.

    Science.gov (United States)

    Zhao, Xuebo; Villar-Rodil, Silvia; Fletcher, Ashleigh J; Thomas, K Mark

    2006-05-25

    Adsorption and desorption of H(2) and D(2) from porous carbon materials, such as activated carbon at 77 K, are usually fully reversible with very rapid adsorption/desorption kinetics. The adsorption and desorption of H(2) and D(2) at 77 K on a carbon molecular sieve (Takeda 3A), where the kinetic selectivity was incorporated by carbon deposition, and a carbon, where the pore structure was modified by thermal annealing to give similar pore structure characteristics to the carbon molecular sieve substrate, were studied. The D(2) adsorption and desorption kinetics were significantly faster (up to x1.9) than the corresponding H(2) kinetics for specific pressure increments/decrements. This represents the first experimental observation of kinetic isotope quantum molecular sieving in porous materials due to the larger zero-point energy for the lighter H(2), resulting in slower adsorption/desorption kinetics compared with the heavier D(2). The results are discussed in terms of the adsorption mechanism.

  7. Sub-Angstrom Atomic-Resolution Imaging of Heavy Atoms to Light Atoms

    Energy Technology Data Exchange (ETDEWEB)

    O' Keefe, Michael A.; Shao-Horn, Yang

    2003-05-23

    Three decades ago John Cowley and his group at ASU achieved high-resolution electron microscope images showing the crystal unit cell contents at better than 4Angstrom resolution. Over the years, this achievement has inspired improvements in resolution that have enabled researchers to pinpoint the positions of heavy atom columns within the cell. More recently, this ability has been extended to light atoms as resolution has improved. Sub-Angstrom resolution has enabled researchers to image the columns of light atoms (carbon, oxygen and nitrogen) that are present in many complex structures. By using sub-Angstrom focal-series reconstruction of the specimen exit surface wave to image columns of cobalt, oxygen, and lithium atoms in a transition metal oxide structure commonly used as positive electrodes in lithium rechargeable batteries, we show that the range of detectable light atoms extends to lithium. HRTEM at sub-Angstrom resolution will provide the essential role of experimental verification for the emergent nanotech revolution. Our results foreshadow those to be expected from next-generation TEMs with Cs-corrected lenses and monochromated electron beams.

  8. Mechanism of benzaldehyde lyase studied via thiamin diphosphate-bound intermediates and kinetic isotope effects.

    Science.gov (United States)

    Chakraborty, Sumit; Nemeria, Natalia; Yep, Alejandra; McLeish, Michael J; Kenyon, George L; Jordan, Frank

    2008-03-25

    Direct spectroscopic observation of thiamin diphosphate-bound intermediates was achieved on the enzyme benzaldehyde lyase, which carries out reversible and highly enantiospecific conversion of ( R)-benzoin to benzaldehyde. The key enamine intermediate could be observed at lambda max 393 nm in the benzoin breakdown direction and in the decarboxylase reaction starting with benzoylformate. With benzaldehyde as substrate, no intermediates could be detected, only formation of benzoin at 314 nm. To probe the rate-limiting step in the direction of ( R)-benzoin synthesis, the (1)H/ (2)H kinetic isotope effect was determined for benzaldehyde labeled at the aldehyde position and found to be small (1.14 +/- 0.03), indicating that ionization of the C2alphaH from C2alpha-hydroxybenzylthiamin diphosphate is not rate limiting. Use of the alternate substrates benzoylformic and phenylpyruvic acids (motivated by the observation that while a carboligase, benzaldehyde lyase could also catalyze the slow decarboxylation of 2-oxo acids) enabled the observation of the substrate-thiamin covalent intermediate via the 1',4'-iminopyrimidine tautomer, characteristic of all intermediates with a tetrahedral C2 substituent on ThDP. The reaction of benzaldehyde lyase with the chromophoric substrate analogue ( E)-2-oxo-4(pyridin-3-yl)-3-butenoic acid and its decarboxylated product ( E)-3-(pyridine-3-yl)acrylaldehyde enabled the detection of covalent adducts with both. Neither adduct underwent further reaction. An important finding of the studies is that all thiamin-related intermediates are in a chiral environment on benzaldehyde lyase as reflected by their circular dichroism signatures.

  9. Ab initio study of nitrogen and position-specific oxygen kinetic isotope effects in the NO + O3 reaction

    Science.gov (United States)

    Walters, Wendell W.; Michalski, Greg

    2016-12-01

    Ab initio calculations have been carried out to investigate nitrogen (k15/k14) and position-specific oxygen (k17/k16O & k18/k16) kinetic isotope effects (KIEs) for the reaction between NO and O3 using CCSD(T)/6-31G(d) and CCSD(T)/6-311G(d) derived frequencies in the complete Bigeleisen equations. Isotopic enrichment factors are calculated to be -6.7‰, -1.3‰, -44.7‰, -14.1‰, and -0.3‰ at 298 K for the reactions involving the 15N16O, 14N18O, 18O16O16O, 16O18O16O, and 16O16O18O isotopologues relative to the 14N16O and 16O3 isotopologues, respectively (CCSD(T)/6-311G(d)). Using our oxygen position-specific KIEs, a kinetic model was constructed using Kintecus, which estimates the overall isotopic enrichment factors associated with unreacted O3 and the oxygen transferred to NO2 to be -19.6‰ and -22.8‰, respectively, (CCSD(T)/6-311G(d)) which tends to be in agreement with previously reported experimental data. While this result may be fortuitous, this agreement suggests that our model is capturing the most important features of the underlying physics of the KIE associated with this reaction (i.e., shifts in zero-point energies). The calculated KIEs will useful in future NOx isotopic modeling studies aimed at understanding the processes responsible for the observed tropospheric isotopic variations of NOx as well as for tropospheric nitrate.

  10. Surface Kinetic Model for the Fractionation of Trace Elements and Isotopes in Calcite Precipitated from Aqueous Solution

    Science.gov (United States)

    Depaolo, D. J.; Ryerson, F. J.; Watkins, J. M.; Bourg, I. C.; Yang, W.; Nielsen, L. C.; Druhan, J. L.

    2010-12-01

    The isotopic and trace element concentrations in calcite and other carbonate minerals form the basis for several paleoceanographic and paleoenvironmental indicators. The chemical and isotopic composition of natural calcites is determined by a combination of equilibrium partitioning and kinetic fractionations. Currently there is no general model that describes when equilibrium applies and how kinetic effects depend on the circumstances and rates of mineral growth. A useful approach is to separate the growth of calcite from aqueous solutions into forward (f) and backward (b) reactions, and to consider the mechanisms and fractionations that may be associated with each. We are evaluating a model where the net precipitation rate of calcite (Rp) is expressed as the difference between a forward rate (Rf) and a backward (dissolution) rate (Rb). Dissolution is approached only as Rp/Rb->0. Much natural calcite, including biogenic, forms under conditions where Rp ≫ Rb, hence the isotopic and trace element partitioning is strongly influenced by the kinetics of the forward reaction. Assuming that there are kinetic fractionations associated with the forward and backward reactions, a simple model can be developed for the dependence of calcite composition on precipitation rate. This model can explain most available experimental data on Ca and O isotopes, as well as Sr/Ca and Mn/Ca in calcite, and can be used to infer the behavior of other trace and minor elements. The critical parameter in applying the model is the value of Rb which to first order can be estimated from mineral dissolution rates, but apparently is not a constant, but instead varies with solution chemistry, especially at saturation conditions close to equilibrium. The surface kinetic model requires three parameters that are measureable experimentally and potentially also predictable from molecular dynamics simulation approaches. In this way it differs from the surface entrapment model of Watson (2004) which

  11. The Application of Transient-State Kinetic Isotope Effects to the Resolution of Mechanisms of Enzyme-Catalyzed Reactions

    Directory of Open Access Journals (Sweden)

    Harvey F. Fisher

    2013-07-01

    Full Text Available Much of our understanding of the mechanisms of enzyme-catalyzed reactions is based on steady-state kinetic studies. Experimentally, this approach depends solely on the measurement of rates of free product appearance (d[P]/dt, a mechanistically and mathematically complex entity. Despite the ambiguity of this observed parameter, the method’s success is due in part to the elaborate rigorously derived algebraic theory on which it is based. Transient-state kinetics, on the other hand, despite its ability to observe the formation of intermediate steps in real time, has contributed relatively little to the subject due in, some measure, to the lack of such a solid mathematical basis. Here we discuss the current state of existing transient-state theory and the difficulties in its realistic application to experimental data. We describe a basic analytic theory of transient-state kinetic isotope effects in the form of three novel fundamental rules. These rules are adequate to define an extended mechanism, locating the isotope-sensitive step and identifying missing steps from experimental data. We demonstrate the application of these rules to resolved component time courses of the phenylalanine dehydrogenase reaction, extending the previously known reaction by one new prehydride transfer step and two new post hydride transfer steps. We conclude with an assessment of future directions in this area.

  12. A novel fluorescence "on-off-on" chemosensor for Hg(2+)via a water-assistant blocking heavy atom effect.

    Science.gov (United States)

    Wu, Chong; Zhao, Jiang-Lin; Jiang, Xue-Kai; Wang, Chuan-Zeng; Ni, Xin-Long; Zeng, Xi; Redshaw, Carl; Yamato, Takehiko

    2016-10-14

    Upper rim pyrene-functionalized hexahomotrioxacalix[3]arene L was synthesized via Click chemistry, and its fluorescence behaviors toward several common metal cations were investigated. L exhibited a significant fluorescence quenching response to Hg(2+) in CH3CN solution, which was unaffected by the coexistence of other competitive metal cations. Thus, L can be utilized as a highly selective and sensitive fluorescent chemosensor for Hg(2+) with a detection limit in the nM level. Interestingly, the quenched fluorescence emission can be successfully revived upon the addition of water. In this process, the heavy atom effect of Hg(2+) can be blocked by further coordination of a water molecule and resulted in the revival of the fluorescence emission of L/Hg(2+) complex. Particularly, other polar solvents such as CH3OH and CH3CH2OH also have the ability to revive the fluorescence emission of the L/Hg(2+) complex, but on a much smaller scale than observed for H2O. The heavy atom effect and blocking thereof were demonstrated within the same system by the use of a C3-symmetric homooxacalix[3]arene scaffold. The present studies provided further evidence for the blocking heavy atom effect.

  13. Kinetic Isotope Effects from QM/MM Subset Hessians: "Cut-Off" Analysis for SN2 Methyl Transfer in Solution.

    Science.gov (United States)

    Williams, Ian H

    2012-02-14

    Isotopic partition-function ratios and kinetic isotope effects for reaction of S-adenosylmethionine with catecholate in water are evaluated using a subset of 324 atoms within its surrounding aqueous environment at the AM1/TIP3P level. Two alternative methods for treating motion in the six librational degrees of freedom of the subset atoms relative to their environment are compared. A series of successively smaller subset Hessians are generated by cumulative deletion of rows and columns from the initial 972 × 972 Hessian. We find that it is better to treat these librations as vibrations than as translations and rotations and that there is no need to invoke the Teller-Redlich product rule. The validity of "cut-off" procedures for computation of isotope effects with truncated atomic subsets is assessed: to ensure errors in ln(KIE) < 1% (or 2% for the quantum-corrected KIE) for all isotopic substitutions considered, it is necessary to use a less-restrictive procedure than is suggested by the familiar two-bond cutoff rule.

  14. Heavy atom effect on magnetic anisotropy of matrix-isolated monobromine substituted septet trinitrene.

    Science.gov (United States)

    Misochko, Eugenii Ya; Masitov, Artem A; Akimov, Alexander V; Korchagin, Denis V; Chapyshev, Sergei V

    2015-03-19

    The heavy atom effect on the magnetic anisotropy of septet trinitrenes is reported. Septet 1-bromo-3,5-dichloro-2,4,6-trinitrenobenzene (S-1) was generated in a solid argon matrix by ultraviolet irradiation of 1,3,5-triazido-2-bromo-4,6-dichlorobenzene. This trinitrene displays an electron spin resonance (ESR) spectrum that drastically differs from ESR spectra of all previously studied septet trinitrenes. The zero-field splitting (ZFS) parameters, derived from the experimental spectrum, show the parameter |D| = 0.1237 cm(-1) and the unprecedentedly large ratio of E/D = 0.262 that is close to the rhombic limit E/D = 1/3 for high-spin molecules. The CASCI (based on state-averaged CASSCF) and DFT methods were applied to calculate the ZFS tensor focusing on the heavy (bromine) atom effects on the spin-orbit term. These calculations show that the multiconfigurational ab initio formalism and the CASCI method are the most successful for accurate predictions of the spin-orbit term in the ZFS tensor of high-spin nitrenes containing heavy bromine atoms. Due to the presence of the bromine atom in S-1, the contribution of the spin-orbit term to the total parameter D is dominant and responsible for the unusual orientation of the easy Z-axis lying in the molecular plane perpendicular to the C-Br bond. As a result, the principal values D(XX), D(YY), and D(ZZ) of the total tensor D̂(Tot) have such magnitudes and signs for which the ratio E/D is close to the rhombic limit, and the total parameter D is large in magnitude and positive in sign.

  15. Efficient estimators for quantum instanton evaluation of the kinetic isotope effects: application to the intramolecular hydrogen transfer in pentadiene.

    Science.gov (United States)

    Vanícek, Jirí; Miller, William H

    2007-09-21

    The quantum instanton approximation is used to compute kinetic isotope effects for intramolecular hydrogen transfer in cis-1,3-pentadiene. Due to the importance of skeleton motions, this system with 13 atoms is a simple prototype for hydrogen transfer in enzymatic reactions. The calculation is carried out using thermodynamic integration with respect to the mass of the isotopes and a path integral Monte Carlo evaluation of relevant thermodynamic quantities. Efficient "virial" estimators are derived for the logarithmic derivatives of the partition function and the delta-delta correlation functions. These estimators require significantly fewer Monte Carlo samples since their statistical error does not increase with the number of discrete time slices in the path integral. The calculation treats all 39 degrees of freedom quantum mechanically and uses an empirical valence bond potential based on a molecular mechanics force field.

  16. 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

    OpenAIRE

    2016-01-01

    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. In order to examine the isoto...

  17. Dose enhancement by synchrotron radiation and heavy atoms for the treatment of gliomas; Renforcement de la dose par rayonnement synchrotron et atomes lourds dans le cadre du traitement des gliomes

    Energy Technology Data Exchange (ETDEWEB)

    Bobyk, L.

    2010-11-15

    High grade gliomas are brain tumors of bad prognosis. The standard therapeutic treatment combines surgery, radiotherapy and sometimes use of temozolomide (chemotherapy agent). Healthy tissues radio-sensitivity is a major limitation for radiotherapy treatment. The stereotactic radiotherapy by synchrotron radiation is an innovative technique which combines a low energy radiation (lower 100 keV) with the presence of heavy atoms in the tumoral zone. Such an approach is used to increase the differential of dose deposited in the tumor compared to surrounding healthy tissues. In this study, several compounds containing heavy atoms such as chemotherapy agents: cisplatin/carbo-platin, a DNA base analog: 5-iodo-2'-deoxyuridine (IUdR) and gold nano-particles were considered. The dose enhancement factor induced by the presence of these compounds located for some of them in the extracellular medium or inside the cells for others, was determined using in vitro studies. Thereafter, in vivo studies on rats bearing gliomas, were performed to study the toxicity, the kinetic of distribution and the localization of these compounds together with their potential efficacy of treatment combining intracerebral injection with low energy radiation. (author)

  18. Ion-Isotopic Exchange Reaction Kinetics using Anion Exchange Resins Dowex 550A LC and Indion-930A

    Directory of Open Access Journals (Sweden)

    P.U. Singare

    2014-06-01

    Full Text Available The present paper deals with the characterization of ion exchange resins Dowex 550A LC and Indion-930A based on kinetics of ion-isotopic exchange reactions for which the short lived radioactive isotopes 131I and 82Br were used as a tracers. The study was performed for different concentration of ionic solution varying from 0.001 mol/L to 0.004 mol/L and temperature in the range of 30.0 °C to 45.0 °C. The results indicate that as compared to bromide ion-isotopic exchange reaction, iodide exchange reaction take place at the faster rate. For both the ion-isotopic exchange reactions, under identical experimental conditions, the values of specific reaction rate increases with increase in the ionic concentration and decreases with rise in temperature. It was observed that at 35.00C, 1.000 g of ion exchange resins and 0.002 mol/L labeled iodide ion solution for iodide ion-isotopic exchange reaction, the values of specific reaction rate (min-1, amount of ion exchanged (mmol, initial rate of ion exchange (mmol/min and log Kd were 0.270, 0.342, 0.092 and 11.8 respectively for Dowex 550A LC resin, which was higher than the respective values of 0.156, 0.241, 0.038 and 7.4 as that obtained for Indion-930A resins. From the results, it appears that Dowex 550A LC resins show superior performance over Indion-930A resins under identical experimental conditions.

  19. Isotopic effects in scattering and kinetics of the atomic cascade of excited μ-p and μ-d atoms

    Science.gov (United States)

    Popov, V. P.; Pomerantsev, V. N.

    2017-02-01

    The quantum-mechanical calculations of the differential and integrated cross sections of the elastic scattering, Stark transitions, and Coulomb deexcitation at collisions of excited μ-p and μ-d atoms with hydrogen isotope atoms in the ground state are performed. The scattering processes are treated in a unified manner in the framework of the close-coupling approach. The basis used includes both open and closed channels corresponding to all exotic-atom states with principal quantum numbers from n =1 up to nmax=20 . The energy shifts of n s states due to electron vacuum polarization and finite nuclear size are taken into account. The kinetics of the atomic cascade of μ-p and μ-d atoms are studied in a wide range of relative target densities (φ =10-8-1 ) within the improved version of the extended cascade model, in which the results of the numerical quantum-mechanical calculations of the cross sections for quantum numbers and kinetic energies of muonic atoms that are of interest for the detailed cascade calculations, are used as input data. Initial (n ,l ,E ) distributions of muonic atoms at the instant of their formation and the target motion are taken into account explicitly in present cascade calculations. The comparison of the calculated cross sections, the kinetic-energy distributions of muonic atoms at the instant of their n p →1 s radiative transitions, as well as the absolute and relative x-ray yields for both muonic hydrogen and muonic deuterium reveals the isotopic effects, which, in principal, may be observed experimentally. The present results are mainly in very good agreement with experimental data available in the literature.

  20. New constraints on kinetic isotope effects during CO2(aq) hydration and hydroxylation: Revisiting theoretical and experimental data

    Science.gov (United States)

    Sade, Ziv; Halevy, Itay

    2017-10-01

    CO2 (de)hydration (i.e., CO2 hydration/HCO3- dehydration) and (de)hydroxylation (i.e., CO2 hydroxylation/HCO3- dehydroxylation) are key reactions in the dissolved inorganic carbon (DIC) system. Kinetic isotope effects (KIEs) during these reactions are likely to be expressed in the DIC and recorded in carbonate minerals formed during CO2 degassing or dissolution of gaseous CO2. Thus, a better understanding of KIEs during CO2 (de)hydration and (de)hydroxylation would improve interpretations of disequilibrium compositions in carbonate minerals. To date, the literature lacks direct experimental constraints on most of the oxygen KIEs associated with these reactions. In addition, theoretical estimates describe oxygen KIEs during separate individual reactions. The KIEs of the related reverse reactions were neither derived directly nor calculated from a link to the equilibrium fractionation. Consequently, KIE estimates of experimental and theoretical studies have been difficult to compare. Here we revisit experimental and theoretical data to provide new constraints on oxygen KIEs during CO2 (de)hydration and (de)hydroxylation. For this purpose, we provide a clearer definition of the KIEs and relate them both to isotopic rate constants and equilibrium fractionations. Such relations are well founded in studies of single isotope source/sink reactions, but they have not been established for reactions that involve dual isotopic sources/sinks, such as CO2 (de)hydration and (de)hydroxylation. We apply the new quantitative constraints on the KIEs to investigate fractionations during simultaneous CaCO3 precipitation and HCO3- dehydration far from equilibrium.

  1. Ab initio path-integral calculations of kinetic and equilibrium isotope effects on base-catalyzed RNA transphosphorylation models.

    Science.gov (United States)

    Wong, Kin-Yiu; Xu, Yuqing; York, Darrin M

    2014-06-30

    Detailed understandings of the reaction mechanisms of RNA catalysis in various environments can have profound importance for many applications, ranging from the design of new biotechnologies to the unraveling of the evolutionary origin of life. An integral step in the nucleolytic RNA catalysis is self-cleavage of RNA strands by 2'-O-transphosphorylation. Key to elucidating a reaction mechanism is determining the molecular structure and bonding characteristics of transition state. A direct and powerful probe of transition state is measuring isotope effects on biochemical reactions, particularly if we can reproduce isotope effect values from quantum calculations. This article significantly extends the scope of our previous joint experimental and theoretical work in examining isotope effects on enzymatic and nonenzymatic 2'-O-transphosphorylation reaction models that mimic reactions catalyzed by RNA enzymes (ribozymes), and protein enzymes such as ribonuclease A (RNase A). Native reactions are studied, as well as reactions with thio substitutions representing chemical modifications often used in experiments to probe mechanism. Here, we report and compare results from eight levels of electronic-structure calculations for constructing the potential energy surfaces in kinetic and equilibrium isotope effects (KIE and EIE) computations, including a "gold-standard" coupled-cluster level of theory [CCSD(T)]. In addition to the widely used Bigeleisen equation for estimating KIE and EIE values, internuclear anharmonicity and quantum tunneling effects were also computed using our recently developed ab initio path-integral method, that is, automated integration-free path-integral method. The results of this work establish an important set of benchmarks that serve to guide calculations of KIE and EIE for RNA catalysis. Copyright © 2014 Wiley Periodicals, Inc.

  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. Exogenous surfactant kinetics in infant respiratory distress syndrome : A novel method with stable isotopes

    NARCIS (Netherlands)

    Torresin, M; Zimmermann, LJI; Cogo, PE; Cavicchioli, P; Badon, T; Giordano, G; Zacchello, F; Sauer, PJJ; Carnielli, VP

    Little is known about surfactant metabolism in newborn infants, since radioactive isotopes cannot be used in humans. We describe here a new method for studying exogenous surfactant pharmacokinetics in vivo. We measured surfactant half-life, pool size, and turnover time in eight preterm infants

  4. Isotopic Effect on the Kinetics of the Belousov-Zhabotinsky Reaction

    Directory of Open Access Journals (Sweden)

    Enzo Tiezzi

    2007-09-01

    Full Text Available In this work we present results about the deuterium isotope effect on the globalkinetics of a Belousov-Zhabotinsky reaction in batch conditions. A nonlinear dependenceof the Induction Period upon the percentage of deuterated reactants was found. The isotopiceffect on the bromination reaction of malonic acid was evaluated.

  5. State-specific heavy-atom effect on intersystem crossing processes in 2-thiothymine: a potential photodynamic therapy photosensitizer.

    Science.gov (United States)

    Cui, Ganglong; Fang, Wei-hai

    2013-01-28

    Thiothymidine has a potential application as a photosensitizer in cancer photodynamic therapy (PDT). As the chromophore of thiothymidine, 2-thiothymine exhibits ultrahigh quantum yield of intersystem crossing to the lowest triplet state T(1) (ca. 100%), which contrasts with the excited-state behavior of the natural thymine that dissipates excess electronic energy via ultrafast internal conversion to the ground state. In this work, we employed high-level complete-active space self-consistent field and its second-order perturbation methods to explore the photophysical mechanism of a 2-thiothymine model. We have optimized the minimum energy structures in the low-lying seven electronic states, as well as ten intersection points. On the basis of the computed potential energy profiles and spin-orbit couplings, we proposed three competitive, efficient nonadiabatic pathways to the lowest triplet state T(1) from the initially populated singlet state S(2). The suggested mechanistic scenario explains well the recent experimental phenomena. The origin responsible for the distinct photophysical behaviors between thymine and 2-thiothymine is ascribed to the heavy-atom effect, which is significantly enhanced in the latter. Additionally, this heavy-atom effect is found to be state-specific, which could in principle be used to tune the photophysics of 2-thiothymine. The present high-level electronic structure calculations also contribute to understand the working mechanism of thiothymidine in PDT.

  6. An exceptional kinetic quantum sieving separation effect of hydrogen isotopes on commercially available carbon molecular sieves.

    Science.gov (United States)

    Xing, Yanlong; Cai, Jinjun; Li, Liangjun; Yang, Menglong; Zhao, Xuebo

    2014-08-14

    The quantum sieving effect of H2/D2 at 77 K on commercially available carbon molecular sieves (1.5GN-H and 3KT-172) was studied. An exceptional reverse kinetic quantum effect is observed on 1.5GN-H where D2 diffuses much faster than H2 with a ratio of up to 5.83 at low pressure, and the difference is still very evident even as the pressure increases up to 1 bar. D2 also diffuses faster than H2 on 3KT-172 with a ratio of up to 1.86. However, the reverse kinetic sieving disappears in a polymer-based carbon (PC). The present kinetic quantum sieving effect of H2 and D2 at 77 K on 1.5GN-H is the highest to date.

  7. Kinetic isotope effects for Cl + CH4 ⇌ HCl + CH3 calculated using ab initio semiclassical transition state theory.

    Science.gov (United States)

    Barker, John R; Nguyen, Thanh Lam; Stanton, John F

    2012-06-21

    Calculations were carried out for 25 isotopologues of the title reaction for various combinations of (35)Cl, (37)Cl, (12)C, (13)C, (14)C, H, and D. The computed rate constants are based on harmonic vibrational frequencies calculated at the CCSD(T)/aug-cc-pVTZ level of theory and X(ij) vibrational anharmonicity coefficients calculated at the CCSD(T) /aug-cc-pVDZ level of theory. For some reactions, anharmonicity coefficients were also computed at the CCSD(T)/aug-cc-pVTZ level of theory. The classical reaction barrier was taken from Eskola et al. [J. Phys. Chem. A 2008, 112, 7391-7401], who extrapolated CCSD(T) calculations to the complete basis set limit. Rate constants were calculated for temperatures from ∼100 to ∼2000 K. The computed ab initio rate constant for the normal isotopologue is in good agreement with experiments over the entire temperature range (∼10% lower than the recommended experimental value at 298 K). The ab initio H/D kinetic isotope effects (KIEs) for CH(3)D, CH(2)D(2), CHD(3), and CD(4) are in very good agreement with literature experimental data. The ab initio (12)C/(13)C KIE is in error by ∼2% at 298 K for calculations using X(ij) coefficients computed with the aug-cc-pVDZ basis set, but the error is reduced to ∼1% when X(ij) coefficients computed with the larger aug-cc-pVTZ basis set are used. Systematic improvements appear to be possible. The present SCTST results are found to be more accurate than those from other theoretical calculations. Overall, this is a very promising method for computing ab initio kinetic isotope effects.

  8. DeuteRater: a tool for quantifying peptide isotope precision and kinetic proteomics.

    Science.gov (United States)

    Naylor, Bradley C; Porter, Michael T; Wilson, Elise; Herring, Adam; Lofthouse, Spencer; Hannemann, Austin; Piccolo, Stephen R; Rockwood, Alan L; Price, John C

    2017-05-15

    Using mass spectrometry to measure the concentration and turnover of the individual proteins in a proteome, enables the calculation of individual synthesis and degradation rates for each protein. Software to analyze concentration is readily available, but software to analyze turnover is lacking. Data analysis workflows typically don't access the full breadth of information about instrument precision and accuracy that is present in each peptide isotopic envelope measurement. This method utilizes both isotope distribution and changes in neutromer spacing, which benefits the analysis of both concentration and turnover. We have developed a data analysis tool, DeuteRater, to measure protein turnover from metabolic D 2 O labeling. DeuteRater uses theoretical predictions for label-dependent change in isotope abundance and inter-peak (neutromer) spacing within the isotope envelope to calculate protein turnover rate. We have also used these metrics to evaluate the accuracy and precision of peptide measurements and thereby determined the optimal data acquisition parameters of different instruments, as well as the effect of data processing steps. We show that these combined measurements can be used to remove noise and increase confidence in the protein turnover measurement for each protein. Source code and ReadMe for Python 2 and 3 versions of DeuteRater are available at https://github.com/JC-Price/DeuteRater . Data is at https://chorusproject.org/pages/index.html project number 1147. Critical Intermediate calculation files provided as Tables S3 and S4. Software has only been tested on Windows machines. jcprice@chem.byu.edu. Supplementary data are available at Bioinformatics online.

  9. Kinetic. cap alpha. secondary deuterium isotope effects for O-ethyl S-phenyl benzaldehyde acetal hydrolysis

    Energy Technology Data Exchange (ETDEWEB)

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

    1979-03-14

    The rate of hydrolysis of O-ethyl S-phenyl benzaldehyde acetal at 25/sup 0/C in 20% dioxane--80% water is independent of pH over the range pH6-12; k/sub obsd/ = 1.9 x 10/sup -7/s/sup -1/. Under more acidic conditions, the rate increases linearly with the activity of the hydrated proton; k/sub 2/ = 2.95 x 10/sup -2/M/sup -1/s/sup -1/. The kinetic ..cap alpha.. secondary deuterium isotope effect for acid-catalyzed hydrolysis of O-ethyl S-phenyl benzaldehyde acetal, measured at 25/sup 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/sup 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.

  10. Comparisons of phosphorothioate with phosphate transfer reactions for a monoester, diester, and triester: isotope effect studies.

    Science.gov (United States)

    Catrina, Irina E; Hengge, Alvan C

    2003-06-25

    Phosphorothioate esters are sometimes used as surrogates for phosphate ester substrates in studies of enzymatic phosphoryl transfer reactions. To gain better understanding of the comparative inherent chemistry of the two types of esters, we have measured equilibrium and kinetic isotope effects for several phosphorothioate esters of p-nitrophenol (pNPPT) and compared the results with data from phosphate esters. The primary (18)O isotope effect at the phenolic group ((18)k(bridge)), the secondary nitrogen-15 isotope effect ((15)k) in the nitro group, and (for the monoester and diester) the secondary oxygen-18 isotope effect ((18)k(nonbridge)) in the phosphoryl oxygens were measured. The equilibrium isotope effect (EIE) (18)k(nonbridge) for the deprotonation of the monoanion of pNPPT is 1.015 +/- 0.002, very similar to values previously reported for phosphate monoesters. The EIEs for complexation of Zn(2+) and Cd(2+) with the dianion pNPPT(2-) were both unity. The mechanism of the aqueous hydrolysis of the monoanion and dianion of pNPPT, the diester ethyl pNPPT, and the triester dimethyl pNPPT was probed using heavy atom kinetic isotope effects. The results were compared with the data reported for analogous phosphate monoester, diester, and triester reactions. The results suggest that leaving group bond fission in the transition state of reactions of the monoester pNPPT is more advanced than for its phosphate counterpart pNPP, while alkaline hydrolysis of the phosphorothioate diester and triester exhibits somewhat less advanced bond fission than that of their phosphate ester counterparts.

  11. Internal heavy atom effect of Au(III) and Pt(IV) on hypocrellin A for enhanced in vitro photodynamic therapy of cancer.

    Science.gov (United States)

    Zhou, Lin; Ge, Xuefeng; Liu, Jihua; Zhou, Jiahong; Wei, Shaohua; Li, Fuyou; Shen, Jian

    2013-10-01

    Hypocrellin A (HA), an a natural perylene quinine photosensitizers (PSs), can chelate with heavy metal ions, including Au(III) and Pt(IV), to form a 1:2 complex, which exhibits enhanced (1)O2 generation quantum yield through the increased intersystem crossing efficiency mediated by internal heavy atom effect. Besides, the chelate process greatly improved the water solubility of HA. Comparative studies with HA and complexes have demonstrated that the heavy-atom effect on HA molecules enhances the efficiency of in vitro photodynamic (PDT) efficacy.

  12. Heavy Atom Effect on the First Hyperpolarizabilities of Squaric Acid Homologues Studied by Ab Initio and DFT Methods

    Institute of Scientific and Technical Information of China (English)

    FU Wei-Wei; ZHOU Li-Xin; WAN Hua-Ping

    2004-01-01

    We have calculated the first hyperpolarizabilities of four squaric acid homologue molecules: 3,4-dithiohydroxy-3-cyclobutene-1,2-dione (OSSQ), 3,4-dithiohydroxy-3-cyclobutene-1, 2-dithione (SSSQ), 3,4-dithiohydroxy-3-cyclobutene-1,2-diselenone (SeSSQ) and 3,4-dithiohydroxy- 3-cyclobutene-1,2-ditellurone (TeSSQ). The correlation effect was investigated at the second-order Mφller-Plesset (MP2) perturbation and density functional theory (DFT) levels. The frequency disper- sion and solvent effect were considered to compare the theoretical values with the experimental observations. Based on all of these studies, it is worthy to point out that the heavy atom effect dis- covered for furan homologues is an influence on the first hyperpolarizabilities of squaric acid homologues.

  13. Quantification of biodegradation for o-xylene and naphthalene using first order decay models, Michaelis-Menten kinetics and stable carbon isotopes

    Science.gov (United States)

    Blum, Philipp; Hunkeler, Daniel; Weede, Matthias; Beyer, Christof; Grathwohl, Peter; Morasch, Barbara

    2009-04-01

    At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis-Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d - 1 and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d - 1 . Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of kmax = 0.1 µg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d - 1 . The stable isotope-based biodegradation rate constant of 0.0027 d - 1 was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d - 1 . With MM-kinetics a maximum degradation rate of kmax = 12 µg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor ɛfield of - 1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.

  14. Quantification of biodegradation for o-xylene and naphthalene using first order decay models, Michaelis-Menten kinetics and stable carbon isotopes.

    Science.gov (United States)

    Blum, Philipp; Hunkeler, Daniel; Weede, Matthias; Beyer, Christof; Grathwohl, Peter; Morasch, Barbara

    2009-04-01

    At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis-Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d(-1) and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d(-1). Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of k(max)=0.1 microg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d(-1). The stable isotope-based biodegradation rate constant of 0.0027 d(-1) was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d(-1). With MM-kinetics a maximum degradation rate of k(max)=12 microg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor epsilon(field) of -1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.

  15. {beta}-Secondary and solvent deuterium kinetic isotope effects and the mechanisms of base- and acid-catalyzed hydrolysis of penicillanic acid

    Energy Technology Data Exchange (ETDEWEB)

    Deraniyagala, S.A.; Adediran, S.A.; Pratt, R.F. [Wesleyan Univ., Middletown, CT (United States)

    1995-03-24

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

  16. Non-covalent binding of the heavy atom compound [Au(CN)2]- at the halide binding site of haloalkane dehalogenase from Xanthobacter autotrophicus GJ10

    NARCIS (Netherlands)

    Verschueren, K.H.G.; Rozeboom, H.J.; Kalk, K.H.; Dijkstra, B.W.

    1993-01-01

    The Na[Au(CN)2] heavy atom derivative contributed considerably to the successful elucidation of the crystal structure of haloalkane dehalogenase isolated from Xanthobacter autotrophicus GJ10. The gold cyanide was located in an internal cavity of the enzyme, which also contains the catalytic residues

  17. NONCOVALENT BINDING OF THE HEAVY-ATOM COMPOUND [AU(CN)2]- AT THE HALIDE BINDING-SITE OF HALOALKANE DEHALOGENASE FROM XANTHOBACTER-AUTOTROPHICUS GJ10

    NARCIS (Netherlands)

    VERSCHUEREN, KHG; FRANKEN, SM; ROZEBOOM, HJ; KALK, KH; DIJKSTRA, BW

    1993-01-01

    The Na[Au(CN)2] heavy atom derivative contributed considerably to the successful elucidation of the crystal structure of haloalkane dehalogenase isolated from Xanthobacter autotrophicus GJ10. The gold cyanide was located in an internal cavity of the enzyme, which also contains the catalytic residues

  18. Surfactant disaturated-phosphatidylcholine kinetics in acute respiratory distress syndrome by stable isotopes and a two compartment model

    Directory of Open Access Journals (Sweden)

    Cogo Paola E

    2007-02-01

    Full Text Available Abstract Background In patients with acute respiratory distress syndrome (ARDS, it is well known that only part of the lungs is aerated and surfactant function is impaired, but the extent of lung damage and changes in surfactant turnover remain unclear. The objective of the study was to evaluate surfactant disaturated-phosphatidylcholine turnover in patients with ARDS using stable isotopes. Methods We studied 12 patients with ARDS and 7 subjects with normal lungs. After the tracheal instillation of a trace dose of 13C-dipalmitoyl-phosphatidylcholine, we measured the 13C enrichment over time of palmitate residues of disaturated-phosphatidylcholine isolated from tracheal aspirates. Data were interpreted using a model with two compartments, alveoli and lung tissue, and kinetic parameters were derived assuming that, in controls, alveolar macrophages may degrade between 5 and 50% of disaturated-phosphatidylcholine, the rest being lost from tissue. In ARDS we assumed that 5–100% of disaturated-phosphatidylcholine is degraded in the alveolar space, due to release of hydrolytic enzymes. Some of the kinetic parameters were uniquely determined, while others were identified as lower and upper bounds. Results In ARDS, the alveolar pool of disaturated-phosphatidylcholine was significantly lower than in controls (0.16 ± 0.04 vs. 1.31 ± 0.40 mg/kg, p de novo synthesis of disaturated-phosphatidylcholine were also significantly lower, while mean resident time in lung tissue was significantly higher in ARDS than in controls. Recycling was 16.2 ± 3.5 in ARDS and 31.9 ± 7.3 in controls (p = 0.08. Conclusion In ARDS the alveolar pool of surfactant is reduced and disaturated-phosphatidylcholine turnover is altered.

  19. Kinetic Isotope Effects for Alkaline Phosphatase Reactions: Implications for the Role of Active Site Metal Ions in Catalysis

    Science.gov (United States)

    Zalatan, Jesse G.; Catrina, Irina; Mitchell, Rebecca; Grzyska, Piotr K.; O’Brien, Patrick J.; Herschlag, Daniel; Hengge, Alvan C.

    2011-01-01

    Enzyme-catalyzed phosphoryl transfer reactions have frequently been suggested to proceed through transition states that are altered from their solution counterparts, with the alterations presumably arising from interactions with active site functional groups. In particular, the phosphate monoester hydrolysis reaction catalyzed by Escherichia coli alkaline phosphatase (AP) has been the subject of intensive scrutiny. Recent linear free energy relationship (LFER) studies suggest that AP catalyzes phosphate monoester hydrolysis through a loose transition state, similar to that in solution. To gain further insight into the nature of the transition state and active site interactions, we have determined kinetic isotope effects (KIEs) for AP-catalyzed hydrolysis reactions with several phosphate monoester substrates. The LFER and KIE data together provide a consistent picture for the nature of the transition state for AP-catalyzed phosphate monoester hydrolysis and support previous models suggesting that the enzymatic transition state is similar to that in solution. Moreover, the KIE data provides unique information regarding specific interactions between the transition state and the active site Zn2+ ions. These results provide strong support for a model in which electrostatic interactions between the bimetallo Zn2+ site and a nonbridging phosphate ester oxygen atom make a significant contribution to the large rate enhancement observed for AP-catalyzed phosphate monoester hydrolysis. PMID:17630738

  20. Kinetic isotope effects for alkaline phosphatase reactions: implications for the role of active-site metal ions in catalysis.

    Science.gov (United States)

    Zalatan, Jesse G; Catrina, Irina; Mitchell, Rebecca; Grzyska, Piotr K; O'brien, Patrick J; Herschlag, Daniel; Hengge, Alvan C

    2007-08-08

    Enzyme-catalyzed phosphoryl transfer reactions have frequently been suggested to proceed through transition states that are altered from their solution counterparts, with the alterations presumably arising from interactions with active-site functional groups. In particular, the phosphate monoester hydrolysis reaction catalyzed by Escherichia coli alkaline phosphatase (AP) has been the subject of intensive scrutiny. Recent linear free energy relationship (LFER) studies suggest that AP catalyzes phosphate monoester hydrolysis through a loose transition state, similar to that in solution. To gain further insight into the nature of the transition state and active-site interactions, we have determined kinetic isotope effects (KIEs) for AP-catalyzed hydrolysis reactions with several phosphate monoester substrates. The LFER and KIE data together provide a consistent picture for the nature of the transition state for AP-catalyzed phosphate monoester hydrolysis and support previous models suggesting that the enzymatic transition state is similar to that in solution. Moreover, the KIE data provides unique information regarding specific interactions between the transition state and the active-site Zn2+ ions. These results provide strong support for a model in which electrostatic interactions between the bimetallo Zn2+ site and a nonbridging phosphate ester oxygen atom make a significant contribution to the large rate enhancement observed for AP-catalyzed phosphate monoester hydrolysis.

  1. Theoretical Analysis on the Kinetic Isotope Effects of Bimolecular Nucleophilic Substitution (SN2 Reactions and Their Temperature Dependence

    Directory of Open Access Journals (Sweden)

    Wan-Chen Tsai

    2013-04-01

    Full Text Available Factors affecting the kinetic isotope effects (KIEs of the gas-phase SN2 reactions and their temperature dependence have been analyzed using the ion-molecule collision theory and the transition state theory (TST. The quantum-mechanical tunneling effects were also considered using the canonical variational theory with small curvature tunneling (CVT/SCT. We have benchmarked a few ab initio and density functional theory (DFT methods for their performance in predicting the deuterium KIEs against eleven experimental values. The results showed that the MP2/aug-cc-pVDZ method gave the most accurate prediction overall. The slight inverse deuterium KIEs usually observed for the gas-phase SN2 reactions at room temperature were due to the balance of the normal rotational contribution and the significant inverse vibrational contribution. Since the vibrational contribution is a sensitive function of temperature while the rotation contribution is temperature independent, the KIEs are thus also temperature dependent. For SN2 reactions with appreciable barrier heights, the tunneling effects were predicted to contribute significantly both to the rate constants and to the carbon-13, and carbon-14 KIEs, which suggested important carbon atom tunneling at and below room temperature.

  2. Using heavy atom rare gas matrix to control the reactivity of 4-methoxybenzaldehyde: A comparison with benzaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Kus, Nihal [Department of Chemistry, University of Coimbra, 3004-535 Coimbra (Portugal); Department of Physics, Anadolu University, 26470 Eskisehir (Turkey); Sharma, Archna; Reva, Igor; Fausto, Rui [Department of Chemistry, University of Coimbra, 3004-535 Coimbra (Portugal); Lapinski, Leszek [Institute of Physics, Polish Academy of Sciences, Warsaw (Poland)

    2012-04-14

    Different patterns of photochemical behavior were observed for 4-methoxybenzaldehyde (p-anisaldehyde) isolated in xenon and in argon matrices. Monomers of the compound isolated in solid Xe decarbonylate upon middle ultraviolet irradiation, yielding methoxybenzene (anisole), and CO. On the other hand, p-anisaldehyde isolated in an Ar matrix and subjected to identical irradiation, predominantly isomerizes to the closed-ring isomeric ketene (4-methoxycyclohexa-2,4-dien-1-ylidene) methanone. Experimental detection of a closed-ring ketene photoproduct, generated from an aromatic aldehyde, constitutes a rare observation. The difference between the patterns of photochemical transformations of p-anisaldehyde isolated in argon and xenon environments can be attributed to the external heavy-atom effect, where xenon enhances the rate of intersystem crossing from the singlet to the triplet manifold in which decarbonylation (via p-methoxybenzoyl radical) takes place. The parent compound, benzaldehyde, decarbonylates (to benzene + CO) when subjected to middle ultraviolet irradiation in both argon and xenon matrices. This demonstrates the role of the methoxy p-anisaldehyde substituent in activation of the reaction channel leading to the formation of the ketene photoproduct.

  3. A new way towards high-efficiency thermally activated delayed fluorescence devices via external heavy-atom effect

    Science.gov (United States)

    Zhang, Wenzhi; Jin, Jiangjiang; Huang, Zhi; Zhuang, Shaoqing; Wang, Lei

    2016-07-01

    Thermally activated delayed fluorescence (TADF) mechanism is a significant method that enables the harvesting of both triplet and singlet excitons for emission. However, up to now most efforts have been devoted to dealing with the relation between singlet-triplet splitting (ΔEST) and fluorescence efficiency, while the significance of spin-orbit coupling (SOC) is usually ignored. In this contribution, a new method is developed to realize high-efficiency TADF-based devices through simple device-structure optimizations. By inserting an ultrathin external heavy-atom (EHA) perturber layer in a desired manner, it provides useful means of accelerating the T1 → S1 reverse intersystem crossing (RISC) in TADF molecules without affecting the corresponding S1 → T1 process heavily. Furthermore, this strategy also promotes the utilization of host triplets through Förster mechanism during host → guest energy transfer (ET) processes, which helps to get rid of the solely dependence upon Dexter mechanism. Based on this strategy, we have successfully raised the external quantum efficiency (EQE) in 4CzPN-based devices by nearly 38% in comparison to control devices. These findings provide keen insights into the role of EHA played in TADF-based devices, offering valuable guidelines for utilizing certain TADF dyes which possess high radiative transition rate but relatively inefficient RISC.

  4. Theoretical analysis of kinetic isotope effects on proton transfer reactions between substituted alpha-methoxystyrenes and substituted acetic acids.

    Science.gov (United States)

    Wong, Kin-Yiu; Richard, John P; Gao, Jiali

    2009-10-01

    Primary kinetic isotope effects (KIEs) on a series of carboxylic acid-catalyzed protonation reactions of aryl-substituted alpha-methoxystyrenes (X-1) to form oxocarbenium ions have been computed using the second-order Kleinert variational perturbation theory (KP2) in the framework of Feynman path integrals (PI) along with the potential energy surface obtained at the B3LYP/6-31+G(d,p) level. Good agreement with the experimental data was obtained, demonstrating that this novel computational approach for computing KIEs of organic reactions is a viable alternative to the traditional method employing Bigeleisen equation and harmonic vibrational frequencies. Although tunneling makes relatively small contributions to the lowering of the free energy barriers for the carboxylic acid catalyzed protonation reaction, it is necessary to include tunneling contributions to obtain quantitative estimates of the KIEs. Consideration of anharmonicity can further improve the calculated KIEs for the protonation of substituted alpha-methoxystyrenes by chloroacetic acid, but for the reactions of the parent and 4-NO(2) substituted alpha-methoxystyrene with substituted carboxylic acids, the correction of anharmonicity overestimates the computed KIEs for strong acid catalysts. In agreement with experimental findings, the largest KIEs are found in nearly ergoneutral reactions, DeltaG(o) approximately 0, where the transition structures are nearly symmetric and the reaction barriers are relatively low. Furthermore, the optimized transition structures are strongly dependent on the free energy for the formation of the carbocation intermediate, that is, the driving force DeltaG(o), along with a good correlation of Hammond shift in the transition state structure.

  5. The escape of heavy atoms from the ionosphere of HD209458b. I. A photochemical-dynamical model of the thermosphere

    CERN Document Server

    Koskinen, T T; Yelle, R V; Lavvas, P

    2012-01-01

    The detections of atomic hydrogen, heavy atoms and ions surrounding the extrasolar giant planet (EGP) HD209458b constrain the composition, temperature and density profiles in its upper atmosphere. Thus the observations provide guidance for models that have so far predicted a range of possible conditions. We present the first hydrodynamic escape model for the upper atmosphere that includes all of the detected species in order to explain their presence at high altitudes, and to further constrain the temperature and velocity profiles. This model calculates the stellar heating rates based on recent estimates of photoelectron heating efficiencies, and includes the photochemistry of heavy atoms and ions in addition to hydrogen and helium. The composition at the lower boundary of the escape model is constrained by a full photochemical model of the lower atmosphere. We confirm that molecules dissociate near the 1 microbar level, and find that complex molecular chemistry does not need to be included above this level. ...

  6. Exploring the aryl esterase catalysis of paraoxonase-1 through solvent kinetic isotope effects and phosphonate-based isosteric analogues of the tetrahedral reaction intermediate.

    Science.gov (United States)

    Bavec, Aljoša; Knez, Damijan; Makovec, Tomaž; Stojan, Jure; Gobec, Stanislav; Goličnik, Marko

    2014-11-01

    Although a recent study of Debord et al. in Biochimie (2014; 97:72-77) described the thermodynamics of the catalysed hydrolysis of phenyl acetate by human paraoxonase-1, the mechanistic details along the reaction route of this enzyme remain unclear. Therefore, we briefly present the solvent kinetic isotope effects on the phenyl acetate esterase activity of paraoxonase-1 and its inhibition with the phenyl methylphosphonate anion, which is a stable isosteric analogue that mimics the high-energy tetrahedral intermediate on the hydroxide-promoted hydrolysis pathway. The data show normal isotope effects, while proton inventory analysis indicates that two protons contribute to the kinetic isotope effect. Coherently, moderate competitive inhibition with the phenyl methylphosphonate anion reveals that the rate-limiting transition state suboptimally resembles the tetrahedral intermediate. The implications of these findings can be attributed to two possible reaction mechanisms that might occur during the paraoxonase-1-catalysed hydrolysis of phenyl acetate. Copyright © 2014 Elsevier B.V. and Société française de biochimie et biologie Moléculaire (SFBBM). All rights reserved.

  7. Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

    Science.gov (United States)

    Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

    2016-06-01

    The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental

  8. The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

    Science.gov (United States)

    Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

    2014-04-01

    Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

  9. Late production of hydrocarbon gases in sedimentary basins: kinetic and isotopic study; Genese tardive des gaz hydrocarbures dans les bassins sedimentaires: etude cinetique et isotopique

    Energy Technology Data Exchange (ETDEWEB)

    Lorant, F.

    1999-06-23

    The thermal decomposition of sedimentary organic matter, or kerogen, within the metagenesis zone (T > 170 deg. C) leads to the formation of large amounts of late gas, mainly composed by methane. The work reported in this dissertation aims at understanding and quantifying the mechanisms of late methane generation and isotopic fractionation. With this purpose, natural samples of Type II and Type III mature kerogens (Ro > 1.3%, H/C < 0.65), were artificially heated in both open (T = 350 to 900 deg. C at 25 deg. C/min) and closed (T = 375 to 550 deg. C with t = 1 to 216 h) systems. For each experiment, mass and atomic (C, H, O) balances were obtained by recovering, fractionating and quantifying the entire pyrolysis effluents. Moreover, the isotopic compositions ({sup 13}C/{sup 12}C ratios) of methane and insoluble residue produced in closed system were measured. These experimental simulations have shown that the amounts of methane generated in an open-pyrolysis system (9 to 40 mg/gC) are systematically inferior to that observed in a closed-pyrolysis system (44 to 68 mg/gC), even after correction of the possible C{sub 2}-C{sub 5} and C{sub 6+} hydrocarbons secondary cracking. This shift, which is larger for Type II kerogens compared to coals and Type II-S kerogens, seems to be correlated with the pyrite content of the samples. Based on the closed-pyrolysis system data, a kinetic scheme, suitable for both Type II and Type III kerogens, was established. It includes three consecutive reactions, whose apparent kinetic parameters do not allow accounting for the corresponding rate constants observed in open system: E{sub 1} = 64.7 kcal/mol and A{sub 1} = 2.58 x 10{sup 15} s{sup -1}, E{sub 2} = 52.8 kcal/mol and A{sub 2} = 5.50 x 10{sup 10} s{sup -1}, E{sub 3} = 55-58 kcal/mol and A{sub 3} = 7.52 x 10{sup 9} s{sup -1}. By extrapolation to geological setting, it was thus predicted that kerogens might generate about 15 mg/gC of late methane between 170 and 200 deg. C. In order

  10. Efficient Estimators for Quantum Instanton Evaluation of theKinetic Isotope Effects: Application to the Intramolecular HydrogenTransfer in Pentadiene

    Energy Technology Data Exchange (ETDEWEB)

    Vanicek, Jiri; Miller, William H.

    2007-06-13

    The quantum instanton approximation is used to compute kinetic isotope effects for intramolecular hydrogen transfer in cis-1,3-pentadiene. Due to the importance of skeleton motions, this system with 13 atoms is a simple prototype for hydrogen transfer in enzymatic reactions. The calculation is carried out using thermodynamic integration with respect to the mass of the isotopes and a path integral Monte Carlo evaluation of relevant thermodynamic quantities. Efficient 'virial' estimators are derived for the logarithmic derivatives of the partition function and the delta-delta correlation functions. These estimators require significantly fewer Monte Carlo samples since their statistical error does not increase with the number of discrete time slices in the path integral. The calculation treats all 39 degrees of freedom quantum-mechanically and uses an empirical valence bond potential based on a modified general AMBER force field.

  11. Mechanistic insights into RNA transphosphorylation from kinetic isotope effects and linear free energy relationships of model reactions.

    Science.gov (United States)

    Chen, Haoyuan; Giese, Timothy J; Huang, Ming; Wong, Kin-Yiu; Harris, Michael E; York, Darrin M

    2014-10-27

    Phosphoryl transfer reactions are ubiquitous in biology and the understanding of the mechanisms whereby these reactions are catalyzed by protein and RNA enzymes is central to reveal design principles for new therapeutics. Two of the most powerful experimental probes of chemical mechanism involve the analysis of linear free energy relations (LFERs) and the measurement of kinetic isotope effects (KIEs). These experimental data report directly on differences in bonding between the ground state and the rate-controlling transition state, which is the most critical point along the reaction free energy pathway. However, interpretation of LFER and KIE data in terms of transition-state structure and bonding optimally requires the use of theoretical models. In this work, we apply density-functional calculations to determine KIEs for a series of phosphoryl transfer reactions of direct relevance to the 2'-O-transphosphorylation that leads to cleavage of the phosphodiester backbone of RNA. We first examine a well-studied series of phosphate and phosphorothioate mono-, di- and triesters that are useful as mechanistic probes and for which KIEs have been measured. Close agreement is demonstrated between the calculated and measured KIEs, establishing the reliability of our quantum model calculations. Next, we examine a series of RNA transesterification model reactions with a wide range of leaving groups in order to provide a direct connection between observed Brønsted coefficients and KIEs with the structure and bonding in the transition state. These relations can be used for prediction or to aid in the interpretation of experimental data for similar non-enzymatic and enzymatic reactions. Finally, we apply these relations to RNA phosphoryl transfer catalyzed by ribonuclease A, and demonstrate the reaction coordinate-KIE correlation is reasonably preserved. A prediction of the secondary deuterium KIE in this reaction is also provided. These results demonstrate the utility of

  12. Diffusion-driven kinetic isotope effect of Fe and Ni during formation of the Widmanstätten pattern

    Science.gov (United States)

    Dauphas, Nicolas

    Iron meteorites show resolvable Fe and Ni isotopic fractionation between taenite and kamacite. For Toluca (IAB), the isotopic fractionations between the two phases are around +0.1‰/amu for Fe and -0.4‰/amu for Ni. These variations may be due to i) equilibrium fractionation, ii) differences in the diffusivities of the different isotopes, or iii) a combination of both processes. A computer algorithm was developed in order to follow the growth of kamacite out of taenite during the formation of the Widmanstätten pattern as well as calculate the fractionation of Fe and Ni isotopes for a set of cooling rates ranging from 25 to 500 °C/Myr. Using a relative difference in diffusion coefficients of adjacent isotopes of 4‰/amu for Fe and Ni (β = 0.25), the observations made in Toluca can be reproduced for a cooling rate of 50 °C/Myr. This value agrees with earlier cooling rate estimates based on Ni concentration profiles. This supports the idea that the fractionation measured for Fe and Ni in iron meteorites is driven by differences in diffusivities of isotopes. It also supports the validity of the value of 0.25 adopted for β for diffusion of Fe and Ni in Fe-Ni alloy in the temperature range of 400-700 °C.

  13. Kinetic isotope effects in the gas phase reactions of OH and Cl with CH3Cl, CD3Cl, and 13CH3Cl

    Directory of Open Access Journals (Sweden)

    S. R. Sellevåg

    2005-06-01

    Full Text Available The kinetic isotope effects in the reactions of CH3Cl, 13CH3Cl and CD3Cl with OH radicals and Cl atoms were studied in relative rate experiments at 298±2K and 1013±10mbar. The reactions were carried out in a smog chamber using long path FTIR detection and the spectroscopic data analyzed employing a non-linear least squares spectral fitting method using measured high-resolution infrared spectra as well as absorption cross sections from the HITRAN database. The reaction rates of 13CH3Cl and CD3Cl with OH and Cl were determined relative to CH3Cl as: kOH + CH3Cl/kOH + 13CH3Cl=1.059±0.008, kOH + CH3Cl/kOH + CD3Cl=3.9±0.4, kCl + CH3Cl/kCl + 13CH3Cl=1.070±0.010 and kCl + CH3Cl/kCl + CD3Cl=4.91±0.07. The uncertainties given are 2σ from the statistical analyses and do not include possible systematic errors. The unusually large 13C kinetic isotope effect in the OH reaction of CH3Cl has important implications for the global emission inventory of CH3Cl.

  14. Temperature dependence of stable carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals: Experimental and theoretical studies

    Science.gov (United States)

    Piansawan, T.; Saccon, M.; Vereecken, L.; Gensch, I.; Kiendler-Scharr, A.

    2017-08-01

    The stable carbon kinetic isotope effect (KIE) of ethane photooxidation by OH radicals was deduced by employing both laboratory measurements and theoretical calculations. The investigations were designed to elucidate the temperature dependence of KIE within atmospherically relevant temperature range. The experimental KIE was derived from laboratory compound-specific isotope analyses of ethane with natural isotopic abundance exposed to OH at constant temperature, showing ɛ values of 7.16 ± 0.54‰ (303 K), 7.45 ± 0.48‰ (288 K), 7.36 ± 0.28‰ (273 K), 7.61 ± 0.28‰ (263 K), 8.89 ± 0.90‰ (253 K), and 9.42 ± 2.19‰ (243 K). Compared to previous studies, a significant improvement of the measurement precision was reached at the high end of the investigated temperature range. The KIE was theoretically determined as well, in the temperature range of 150 K to 400 K, by calculating the reaction rate coefficients of 12C and singly 13C substituted ethane isotopologues applying chemical quantum mechanics together with transition state theory. Tunneling effect and internal rotations were also considered. The agreement between experimental and theoretical results for rate coefficients and KIE in an atmospherically relevant temperature range is discussed. However, both laboratory observations and computational predictions show no significant temperature dependence of the KIE for the ethane oxidation by OH radicals.

  15. Understanding the effect of cobalt particle size on Fischer-Tropsch synthesis: surface species and mechanistic studies by SSITKA and kinetic isotope effect.

    Science.gov (United States)

    Yang, Jia; Tveten, Erik Z; Chen, De; Holmen, Anders

    2010-11-02

    Co/γ-Al(2)O(3) catalysts with particle sizes in the range of 4-15 nm were investigated by isothermal hydrogenation (IH), temperature programmed hydrogenation (TPH), and steady-state isotopic transient kinetic analysis (SSITKA). Kinetic isotope effect experiments were used to probe possible mechanisms on Co/γ-Al(2)O(3) with different particle size. It was found that CO dissociated on Co/γ-Al(2)O(3) catalysts at 210 °C. The total amount of CO(2) formed following the dissociation depends on the cobalt crystal size. O-Co binding energy was found to be highly dependent on the Co metal particle size, whereas similar C-Co binding energy was found on catalysts with different Co particle size. Very strongly bonded carbon and oxygen surface species increased with decreasing particle size and acted as site blocking species in the methanation reaction. SSITKA experiments showed that the intrinsic activity (1/τ(CH(x))) remained constant as the particle size increased from 4 to 15 nm. The number of surface intermediates (N(CH(x))) increased with increasing particle size. The apparent activation energies were found similar for these catalysts, about 85 kJ/mol. D(2)-H(2) switches further confirmed that the particle size did not change the kinetically relevant steps in the reaction. The reactivity of the active sites on the 4 nm particles was the same as those on the 8, 11, and 15 nm particles, and only the number of total available surface active sites was less on the 4 nm particles than on the others.

  16. A Local CC2 and TDA-DFT Double Hybrid Study on BODIPY/aza-BODIPY Dimers as Heavy Atom Free Triplet Photosensitizers for Photodynamic Therapy Applications.

    Science.gov (United States)

    Momeni, Mohammad R; Brown, Alex

    2016-04-28

    A series of 11 different boron-dipyrromethene (BODIPY) dimers is carefully examined by means of ab initio and Tamm-Dancoff approximated density functional theory methods. Vertical and 0-0 excitation energies along with the tetraradical character of these dimers are determined. Possible application of a series of linked dimers for photodynamic therapy (PDT) was investigated through computing their excitation energies, spin-orbit coupling matrix elements, and singlet-triplet energy gaps. Finally through a systematic investigation of a series of 36 different BODIPY and aza-BODIPY dimers, a new class of near-IR heavy atom free photosensitizers for PDT action is introduced.

  17. Trapped radioactive isotopes for fundamental symmetry investigations

    Energy Technology Data Exchange (ETDEWEB)

    Willmann, Lorenz, E-mail: willmann@kvi.nl; Jungmann, Klaus; Onderwater, Cornelis J. G.; Timmermans, Rob G. E.; Wilschut, Hans W. [University of Groningen, KVI (Netherlands)

    2012-05-15

    Discrete symmetries tested in high precision atomic physics experiments provide guidance to model building beyond the Standard Model (SM). Here experimental opportunities arise for searches for permanent electric dipole moments (EDMs) and measurements of atomic parity violation (APV). Heavy atoms are favorable for such experiments since symmetry violating effects in atoms increase faster than the third power of the nuclear charge Z. Of special interest are isotopes of the heavy alkaline earth element radium (Z=88) since they offer large enhancement factors for EDMs and provide a new experimental road towards high precision measurements of atomic parity violation. These opportunities are exploited at the TRI{mu}P facility at KVI, Groningen.

  18. Late production of hydrocarbon gases in sedimentary basins: kinetic and isotopic study; Genese tardive des gaz hydrocarbures dans les bassins sedimentaires: etude cinetique et isotopique

    Energy Technology Data Exchange (ETDEWEB)

    Lorant, F.

    1999-06-23

    The thermal decomposition of sedimentary organic matter, or kerogen, within the metagenesis zone (T > 170 deg. C) leads to the formation of large amounts of late gas, mainly composed by methane. The work reported in this dissertation aims at understanding and quantifying the mechanisms of late methane generation and isotopic fractionation. With this purpose, natural samples of Type II and Type III mature kerogens (Ro > 1.3%, H/C < 0.65), were artificially heated in both open (T = 350 to 900 deg. C at 25 deg. C/min) and closed (T = 375 to 550 deg. C with t = 1 to 216 h) systems. For each experiment, mass and atomic (C, H, O) balances were obtained by recovering, fractionating and quantifying the entire pyrolysis effluents. Moreover, the isotopic compositions ({sup 13}C/{sup 12}C ratios) of methane and insoluble residue produced in closed system were measured. These experimental simulations have shown that the amounts of methane generated in an open-pyrolysis system (9 to 40 mg/gC) are systematically inferior to that observed in a closed-pyrolysis system (44 to 68 mg/gC), even after correction of the possible C{sub 2}-C{sub 5} and C{sub 6+} hydrocarbons secondary cracking. This shift, which is larger for Type II kerogens compared to coals and Type II-S kerogens, seems to be correlated with the pyrite content of the samples. Based on the closed-pyrolysis system data, a kinetic scheme, suitable for both Type II and Type III kerogens, was established. It includes three consecutive reactions, whose apparent kinetic parameters do not allow accounting for the corresponding rate constants observed in open system: E{sub 1} = 64.7 kcal/mol and A{sub 1} = 2.58 x 10{sup 15} s{sup -1}, E{sub 2} = 52.8 kcal/mol and A{sub 2} = 5.50 x 10{sup 10} s{sup -1}, E{sub 3} = 55-58 kcal/mol and A{sub 3} = 7.52 x 10{sup 9} s{sup -1}. By extrapolation to geological setting, it was thus predicted that kerogens might generate about 15 mg/gC of late methane between 170 and 200 deg. C. In order

  19. Heavy atom effects in the Paternò–Büchi reaction of pyrimidine derivatives with 4,4’-disubstituted benzophenones

    Directory of Open Access Journals (Sweden)

    Qin-Hua Song

    2011-01-01

    Full Text Available The regioselectivity and the photochemical efficiency were investigated in the Paternò–Büchi reaction of 1,3-dimethylthymine (DMT and 1,3-dimethyluracil (DMU with benzophenone (1b and some 4,4’-disubstituted derivatives (dimethoxy (1a, difluoro (1c, dichloro (1d, dibromo (1e and dicyano benzophenone (1f that gives rise to two regioisomeric oxetanes, 2 and 3. The regioselectivity (the ratio of 2/3 decreased gradually for both DMT/DMU photochemical systems from 1a to 1f. That is, a halogen atom as an electron-withdrawing group (EWG has a pronounced effect on the regioselectivity. However, the photochemical efficiency of the 1e systems did not show the expected increase, but decreased relative to systems with 1b. Temperature effects on the regioselectivity of 1b–e systems showed some interesting features for systems with heavy atoms (including the 1d and 1e systems, such as higher inversion temperatures, and an entropy-controlled regioselectively whereas the regioselectivity for two other systems (1b and 1c is enthalpy–entropy controlled. A heavy atom effect is suggested to be responsible for these unusual phenomena based on the triplet-diradical mechanism of the Paternò–Büchi reaction.

  20. Carbon kinetic isotope effects at natural abundances during iron-catalyzed photolytic cleavage of Csbnd C bonds in aqueous phase α,ω-dicarboxylic acids

    Science.gov (United States)

    Irei, Satoshi

    2016-09-01

    Carbon kinetic isotope effects (KIEs) at natural abundances during photolysis of Fe3+-oxalato, malonato, and succinato complexes in aqueous solution were studied to identify the Csbnd C bond cleaving mechanism of Fe3+-oxalato complexes under sunlight irradiation. Observed overall KIEs were 5.9‰, 11.5‰, and 8.4‰, respectively. This variation is inconsistent with secondary carbon KIEs for the Fesbnd O bond cleavage, but consistent with primary carbon KIEs for sequential cleavage of Fesbnd O and Csbnd C bonds. Position-specific probability of 13C content estimated KIEs of 5.9‰, 17.2‰, and 17‰ for 12Csbnd 13C bond cleavage, respectively, indicating the different KIEs for carboxyl-carboxyl and methyl-carboxyl cleavage.

  1. An Experimental and Theoretical Study on the Kinetic Isotope Effect of C2H6 and C2D6 Reaction with OH

    KAUST Repository

    Khaled, Fathi

    2015-10-30

    We report experimental and theoretical results for the deuterated kinetic isotope effect (DKIE) of the reaction of OH with ethane (C2H6) and deuterated ethane (C2D6). The reactions were investigated behind reflected shock waves over 800–1350 K by monitoring OH radicals near 306.69 nm using laser absorption. In addition, high level CCSD(T)/cc-pV(T,Q)Z//MP2/cc-pVTZ quantum chemical and statistical rate theory calculations were performed which agreed very well with the experimental findings. The results reported herein provide the first experimental evidence that DKIE for alkanes asymptotes to a value of 1.4 at high temperatures.

  2. Quantum rate coefficients and kinetic isotope effect for the reaction Cl + CH4 → HCl + CH3 from ring polymer molecular dynamics.

    Science.gov (United States)

    Li, Yongle; Suleimanov, Yury V; Green, William H; Guo, Hua

    2014-03-20

    Thermal rate coefficients and kinetic isotope effect have been calculated for prototypical heavy-light-heavy polyatomic bimolecular reactions Cl + CH4/CD4 → HCl/DCl + CH3/CD3, using a recently proposed quantum dynamics approach: ring polymer molecular dynamics (RPMD). Agreement with experimental rate coefficients, which are quite scattered, is satisfactory. However, differences up to 50% have been found between the RPMD results and those obtained from the harmonic variational transition-state theory on one of the two full-dimensional potential energy surfaces used in the calculations. Possible reasons for such discrepancy are discussed. The present work is an important step in a series of benchmark studies aimed at assessing accuracy for RPMD for chemical reaction rates, which demonstrates that this novel method is a quite reliable alternative to previously developed techniques based on transition-state theory.

  3. Kinetics of Hg(II) exchange between organic ligands, goethite, and natural organic matter studied with an enriched stable isotope approach.

    Science.gov (United States)

    Jiskra, Martin; Saile, Damian; Wiederhold, Jan G; Bourdon, Bernard; Björn, Erik; Kretzschmar, Ruben

    2014-11-18

    The mobility and bioavailability of toxic Hg(II) in the environment strongly depends on its interactions with natural organic matter (NOM) and mineral surfaces. Using an enriched stable isotope approach, we investigated the exchange of Hg(II) between dissolved species (inorganically complexed or cysteine-, EDTA-, or NOM-bound) and solid-bound Hg(II) (carboxyl-/thiol-resin or goethite) over 30 days under constant conditions (pH, Hg and ligand concentrations). The Hg(II)-exchange was initially fast, followed by a slower phase, and depended on the properties of the dissolved ligands and sorbents. The results were described by a kinetic model allowing the simultaneous determination of adsorption and desorption rate coefficients. The time scales required to reach equilibrium with the carboxyl-resin varied greatly from 1.2 days for Hg(OH)2 to 16 days for Hg(II)-cysteine complexes and approximately 250 days for EDTA-bound Hg(II). Other experiments could not be described by an equilibrium model, suggesting that a significant fraction of total-bound Hg was present in a non-exchangeable form (thiol-resin and NOM: 53-58%; goethite: 22-29%). Based on the slow and incomplete exchange of Hg(II) described in this study, we suggest that kinetic effects must be considered to a greater extent in the assessment of the fate of Hg in the environment and the design of experimental studies, for example, for stability constant determination or metal isotope fractionation during sorption.

  4. Kinetic isotope effects in the gas phase reactions of OH and Cl with CH3Cl, CD3Cl, and 13CH3Cl

    Directory of Open Access Journals (Sweden)

    A. A. Gola

    2005-01-01

    Full Text Available The kinetic isotope effects in the reactions of CH3Cl, 13CH3Cl and CD3Cl with OH radicals and Cl atoms were studied in relative rate experiments at 298±2 K and 1013±10 mbar. The reactions were carried out in a smog chamber using long path FTIR detection and the spectroscopic data analyzed employing a non-linear least squares spectral fitting method using measured high-resolution infrared spectra as well as absorption cross sections from the HITRAN database. The reaction rates of 13CH3Cl and CD3Cl with OH and Cl were determined relative to CH3Cl as: kOH+CH3ClkOH+CH3Cl/kOH+13CH3Cl}kOH+13CH3Cl=1.059±0.008, kOH+CH3ClkOH+CH3Cl/kOH+CD3ClkOH+CD3Cl=3.9±0.4, kCl+CH3ClkCl+CH3Cl/kCl+13CH3ClkCl+13CH3Cl =1.070±0.010 and kCl+CH3ClkCl+CH3Cl/kCl+CD3ClkCl+CD3Cl=4.91±0.07. The uncertainties given are 2σ from the statistical analyses and do not include possible systematic errors. The unexpectedly large 13C kinetic isotope effect in the OH reaction of CH3Cl has important implications for the global emission inventory of CH3Cl.

  5. Rate coefficients and kinetic isotope effects of the X + CH4 → CH3 + HX (X = H, D, Mu) reactions from ring polymer molecular dynamics.

    Science.gov (United States)

    Li, Yongle; Suleimanov, Yury V; Li, Jun; Green, William H; Guo, Hua

    2013-03-07

    The thermal rate coefficients and kinetic isotope effects have been calculated using ring polymer molecular dynamics (RPMD) for the prototypical reactions between methane and several hydrogen isotopes (H, D, and Mu). The excellent agreement with the theoretical rate coefficients of the H + CH4 reaction obtained previously from a multi-configuration time-dependent Hartree calculation on the same potential energy surface provides strong evidence for the accuracy of the RPMD approach. These quantum mechanical rate coefficients are also in good agreement with the results obtained previously using the transition-state theory with semi-classical tunneling corrections for the H∕D + CH4 reactions. However, it is shown that the RPMD rate coefficients for the ultralight Mu reaction with CH4 are significantly smaller than the experimental data, presumably suggesting inaccuracies in the potential energy surface and∕or experimental errors. Significant discrepancies between the RPMD and transition-state theory results have also been found for this challenging system.

  6. Synthesis and radioiodination of di-iodo-Evan's blue via isotopic exchange reaction in the molten state and evaluation of the kinetics

    Energy Technology Data Exchange (ETDEWEB)

    El-Azony, K.M. [Research Center Juelich (Germany). Inst. of Nuclear Chemistry]|[Hot Lab. Center, Cairo (Egypt). Radioactive Isotopes and Generators Dept.; Bier, D.; Coenen, H.H. [Research Center Juelich (Germany). Inst. of Nuclear Chemistry

    2004-07-01

    Many aryl halides were synthesized from aryl amines such as iodo-trypan, iodo-methylene blue and iodo-toluidine. Methylene blue and toludine blue are phenothiazinium dyes and were used to localize parathyroid glands visually during surgery. Radioiodination of these compounds by using iodine-123 analogues for scintgraphic localization of parathyroids was reported. Radiolabelled dyes administered may also localize in tumor tissues. Evan's blue dye was used to study altered sarcolemmal permeability in dystrophic muscle fibers, and in animals to study muscular dystrophy. In this work Diiodo-Evan's blue was synthesized via Sandmeyer reaction and characterized by mass spectrum analysis. A procedure for labelling DIEB with Na{sup 131}I via isotopic exchange in molten medium was developed. The labelling conditions studied for the isotopic exchange of {sup 131}I-for-I in DIEB included the effect of temperature and solvents (melt of acetamide, benzoic and pivalic acid). Kinetic studies were performed to obtain [{sup 131}I] DIEB with more reliable reaction conditions. Quality control for the final product ([{sup 131}I] DIEB) was performed by HPLC. (orig.)

  7. Investigating the Mechanism of Heteroaromatic Decarboxylation Using Solvent Kinetic Isotope Effects and Eyring Transition-State Theory

    Science.gov (United States)

    Mundle, Scott O. C.; Opinska, Liliana Guevara; Kluger, Ronald; Dicks, Andrew P.

    2011-01-01

    An upper-level mechanistic organic experiment is outlined where undergraduates measure kinetic rate constants for decarboxylation of pyrrole-2-carboxylic acid by the initial-rates method. UV spectroscopy is used to monitor reactant disappearance in both hydrochloric acid and deuterium chloride at different temperatures. Individual data are pooled…

  8. pH and solvent H/D isotope effects on the thermodynamics and kinetics of electron transfer for electrode-immobilized native and urea-unfolded stellacyanin.

    Science.gov (United States)

    Ranieri, Antonio; Battistuzzi, Gianantonio; Borsari, Marco; Bortolotti, Carlo Augusto; Di Rocco, Giulia; Sola, Marco

    2012-10-23

    The thermodynamics of Cu(II) to Cu(I) reduction and the kinetics of the electron transfer (ET) process for Rhus vernicifera stellacyanin (STC) immobilized on a decane-1-thiol coated gold electrode have been measured through cyclic voltammetry at varying pH and temperature, in the presence of urea and in D(2)O. Immobilized STC undergoes a limited conformational change that mainly results in an enhanced exposure of one or both copper binding histidines to solvent which slightly stabilizes the cupric state and increases histidine basicity. The large immobilization-induced increase in the pK(a) for the acid transition (from 4.5 to 6.3) makes this electrode-SAM-protein construct an attractive candidate as a biomolecular ET switch operating near neutral pH in molecular electronics. Such a potential interest is increased by the robustness of this interface against chemical unfolding as it undergoes only moderate changes in the reduction thermodynamics and in the ET rate in the presence of up to 8 M urea. The sensitivity of these parameters to solvent H/D isotope effects testifies to the role of protein solvation as effector of the thermodynamics and kinetics of ET.

  9. Insights into the catalytic mechanisms of phenylalanine and tryptophan hydroxylase from kinetic isotope effects on aromatic hydroxylation.

    Science.gov (United States)

    Pavon, Jorge Alex; Fitzpatrick, Paul F

    2006-09-12

    Phenylalanine hydroxylase (PheH) and tryptophan hydroxylase (TrpH) catalyze the aromatic hydroxylation of phenylalanine and tryptophan, forming tyrosine and 5-hydroxytryptophan, respectively. The reactions of PheH and TrpH have been investigated with [4-(2)H]-, [3,5-(2)H(2)]-, and (2)H(5)-phenylalanine as substrates. All (D)k(cat) values are normal with Delta117PheH, the catalytic core of rat phenylalanine hydroxylase, ranging from 1.12-1.41. In contrast, for Delta117PheH V379D, a mutant protein in which the stoichiometry between tetrahydropterin oxidation and amino acid hydroxylation is altered, the (D)k(cat) value with [4-(2)H]-phenylalanine is 0.92 but is normal with [3,5-(2)H(2)]-phenylalanine. The ratio of tetrahydropterin oxidation to amino acid hydroxylation for Delta117PheH V379D shows a similar inverse isotope effect with [4-(2)H]-phenylalanine. Intramolecular isotope effects, determined from the deuterium contents of the tyrosine formed from [4-(2)H]-and [3,5(2)H(2)]-phenylalanine, are identical for Delta117PheH and Delta117PheH V379D, suggesting that steps subsequent to oxygen addition are unaffected in the mutant protein. The inverse effects are consistent with the reaction of an activated ferryl-oxo species at the para position of the side chain of the amino acid to form a cationic intermediate. The normal effects on the (D)k(cat) value for the wild-type enzyme are attributed to an isotope effect of 5.1 on the tautomerization of a dienone intermediate to tyrosine with a rate constant 6- to7-fold that for hydroxylation. In addition, there is a slight ( approximately 34%) preference for the loss of the hydrogen originally at C4 of phenylalanine. With (2)H(5)-indole-tryptophan as a substrate for Delta117PheH, the (D)k(cat) value is 0.89, consistent with hydroxylation being rate-limiting in this case. When deuterated phenylalanines are used as substrates for TrpH, the (D)k(cat) values are within error of those for Delta117PheH V379D. Overall, these results

  10. The δ13C evolution of cave drip water along discreet flow paths in a central Texas cave: Quantifying kinetic isotope fractionation factors

    Science.gov (United States)

    Mickler, P. J.; Carlson, P. E.; Banner, J.; Breecker, D.; Stern, L. A.; Baseman, A.

    2015-12-01

    Gaps remain in our understanding of in-cave processes that influence cave water chemistry during speleothem formation. Quantifying environmental controls on the isotopic and chemical evolution of karst groundwater would improve the accuracy of speleothem-based paleoclimate reconstructions. In this study, drip water chemical evolution along flow paths was sampled monthly at two locations in Inner Space Cavern, Texas, over a period of 8 months. In each of the two locations, cave water drips off a stalactite, flows along a flowstone and subsequently drips off a lower stalactite, allowing cave water to be sampled at two points, 1-2 meters apart, along each flow path. The chemical and isotopic evolution of drip water along its flow path shows seasonality, where 1) summer months (high cave-air pCO2) have small variations in δ13C values along the flow paths, high and relatively invariant DIC and Ca values,; and 2) winter months (low cave-air pCO2) generally have large increases in DIC δ13C values along the flow paths, lower DIC and Ca values. The magnitude of the increase in DIC δ13C values along the flow paths, <~1‰ to ~4‰, is controlled by the extent of DIC loss to CO2 degassing and calcite precipitation which is controlled by the pCO2 gradient between drip water and cave air. If the DIC loss is less than 15%, then the evolution of the δ13C value of the DIC reservoir can be modelled using a Rayleigh distillation model and equilibrium fractionation factors between (CO2(g)-HCO3-(aq)) and (CaCO3-HCO3-(aq)). As the loss of the DIC reservoir increases above 15% the DIC δ13C values become progressively higher such that the ɛ (CO2(g)-HCO3-(aq)) values needed to model the observed results change from equilibrium values of ~8‰ to non-equilibrium values up to ~25‰. The variance in magnitude of carbon isotope fractionation during CO2 degassing cannot be attributed to changes in temperature, and thus we infer significant kinetic isotope effects at higher rates of DIC

  11. O-Alkylated heavy atom carbohydrate probes for protein X-ray crystallography: Studies towards the synthesis of methyl 2-O-methyl-L-selenofucopyranoside

    Directory of Open Access Journals (Sweden)

    Roman Sommer

    2016-12-01

    Full Text Available Selenoglycosides are used as reactive glycosyl donors in the syntheses of oligosaccharides. In addition, such heavy atom analogs of natural glycosides are useful tools for structure determination of their lectin receptors using X-ray crystallography. Some lectins, e.g., members of the tectonin family, only bind to carbohydrate epitopes with O-alkylated ring hydroxy groups. In this context, we report the first synthesis of an O-methylated selenoglycoside, specifically methyl 2-O-methyl-L-selenofucopyranoside, a ligand of the lectin tectonin-2 from the mushroom Laccaria bicolor. The synthetic route required a strategic revision and further optimization due to the intrinsic lability of alkyl selenoglycosides, in particular for the labile fucose. Here, we describe a successful synthetic access to methyl 2-O-methyl-L-selenofucopyranoside in 9 linear steps and 26% overall yield starting from allyl L-fucopyranoside.

  12. Ab initio effective core potentials including relativistic effects and their application to the electronic structure calculations of heavy atoms and molecules

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Y.S.

    1977-11-01

    The effects of the 4f shell of electrons and the relativity of valence electrons are compared. The effect of 4f shell (lanthanide contraction) is estimated from the numerical Hartree-Fock (HF) calculations of pseudo-atoms corresponding to Hf, Re, Au, Hg, Tl, Pb and Bi without 4f electrons and with atomic numbers reduced by 14. The relativistic effect estimated from the numerical Dirac-Hartree-Fock (DHF) calculations of those atoms is comparable in the magnitude with that of the 4f shell of electrons. Both are larger for 6s than for 5d or 6p electrons. The various relativistic effects on valence electrons are discussed in detail to determine the proper level of the approximation for the valence electron calculations of systems with heavy elements. An effective core potential system has been developed for heavy atoms in which relativistic effects are included in the effective potentials.

  13. Quantitative amino acid profiling and stable isotopically labeled amino acid tracer enrichment used for in vivo human systemic and tissue kinetics measurements.

    Science.gov (United States)

    Bornø, Andreas; van Hall, Gerrit

    2014-03-01

    An important area within clinical functional metabolomics is in vivo amino acid metabolism and protein turnover measurements for which accurate amino acid concentrations and stable isotopically labeled amino acid enrichments are mandatory not the least when tissue metabolomics is determined. The present study describes a new sensitive liquid chromatography tandem mass-spectrometry method quantifying 20 amino acids and their tracer(s) ([ring-(13)C6]/D5Phenylalanine) in human plasma and skeletal muscle specimens. Before analysis amino acids were extracted and purified via deprotonization/ion exchange, derivatized using a phenylisothiocyanate reagent and each amino acid was quantitated with its own stable isotopically labeled internal standard (uniformly labeled-(13)C/(15)N). The method was validated according to general recommendations for chromatographic analytical methods. The calibration curve correlations for amino acids were on average; r(2)=0.998. Interday accuracy for amino acids determined in spiked plasma was on average 97.3% and the coefficient of variation (CV) was 2.6%. The ([ring-(13)C6]/D5Phenylalanine) enrichment CV's for machine reproducibility in muscle tissue fluid and plasma were 4.4 and 0.8%, and the interday variability was 3.4% and the recovery was 90.5%, respectively. In conclusion, we have developed and validated a method for quantitative amino acid profiling that meets the requirements for systemic and tissue human in vivo amino acid and protein turnover kinetics measurements. Moreover, citrulline, ornithine, π-methyl-histidine, τ-methyl-l-histidine, hydroxy-proline and carnitine were analysed but when similar precision and accuray are required an additional stable istopically labeled internal standard for these meatablites should be be added.

  14. High-resolution studies of tropolone in the S0 and S1 electronic states: isotope driven dynamics in the zero-point energy levels.

    Science.gov (United States)

    Keske, John C; Lin, Wei; Pringle, Wallace C; Novick, Stewart E; Blake, Thomas A; Plusquellic, David F

    2006-02-21

    Rotationally resolved microwave (MW) and ultraviolet (UV) spectra of jet-cooled tropolone have been obtained in S(0) and S(1) electronic states using Fourier-transform microwave and UV-laser/molecular-beam spectrometers. In the ground electronic state, the MW spectra of all heavy-atom isotopomers including one (18)O and four (13)C isotopomers were observed in natural abundance. The OD isotopomer was obtained from isotopically enriched samples. The two lowest tunneling states of each isotopomer except (18)O have been assigned. The observed inversion splitting for the OD isotopomer is 1523.227(5) MHz. For the asymmetric (13)C structures, the magnitudes of tunneling-rotation interactions are found to diminish with decreasing distance between the heavy atom and the tunneling proton. In the limit of closest approach, the 0(+) state of (18)O was well fitted to an asymmetric rotor Hamiltonian, reflecting significant changes in the tautomerization dynamics. Comparisons of the substituted atom coordinates with theoretical predictions at the MP2/aug-cc-pVTZ level of theory suggest the localized 0(+) and 0(-) wave functions of the heavier isotopes favor the C-OH and C=O forms of tropolone, respectively. The only exception occurs for the (13)C-OH and (13)C[Double Bond]O structures which correlate to the 0(-) and 0(+) states, respectively. These preferences reflect kinetic isotope effects as quantitatively verified by the calculated zero-point energy differences between members of the asymmetric atom pairs. From rotationally resolved data of the 0(+) <--0(+) and 0(-) <--0(-) bands in S(1), line-shape fits have yielded Lorentzian linewidths that differ by 12.2(16) MHz over the 19.88(4) cm(-1) interval in S(1). The fluorescence decay rates together with previously reported quantum yield data give nonradiative decay rates of 7.7(5) x 10(8) and 8.5(5) x 10(8) s(-1) for the 0(+) and 0(-) levels of the S(1) state of tropolone.

  15. Isotopes in heterogeneous catalysis

    CERN Document Server

    Hargreaves, Justin SJ

    2006-01-01

    The purpose of this book is to review the current, state-of-the-art application of isotopic methods to the field of heterogeneous catalysis. Isotopic studies are arguably the ultimate technique in in situ methods for heterogeneous catalysis. In this review volume, chapters have been contributed by experts in the field and the coverage includes both the application of specific isotopes - Deuterium, Tritium, Carbon-14, Sulfur-35 and Oxygen-18 - as well as isotopic techniques - determination of surface mobility, steady state transient isotope kinetic analysis, and positron emission profiling.

  16. Activation Thermodynamics and H/D Kinetic Isotope Effect of the Hox to HredH+ Transition in [FeFe] Hydrogenase

    Energy Technology Data Exchange (ETDEWEB)

    King, Paul W [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Ratzloff, Michael W [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Mulder, David W [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lubner, Carolyn E [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Brown, Katherine A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Wilker, Molly B. [University of Colorado; Hamby, Hayden [University of Colorado; Dukovic, Gordana [University of Colorado

    2017-08-29

    Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here we address the route of electron transfer from CdSe->CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The Hox->HredH+ reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol-1 and a ~2.5-fold kinetic isotope effect. Overall these results support electron injection from CdSe into CaI involving F-clusters, and that the Hox->HredH+ step of catalytic proton reduction in CaI proceeds by a proton-dependent process.

  17. Magnetic isotope effect on kinetic parameters and quantum beats of radical pairs in micellar solution studied by optically detected esr using pulsed microwave.

    Science.gov (United States)

    Kitahama, Yasutaka; Sakaguchi, Yoshio

    2008-01-17

    We investigated the quantum beats, the oscillation between singlet and triplet states of radical pairs induced by the microwave field resonant to one of the component radicals. They were observed as the alternation of the yields of the component radicals by a nanosecond time-resolved optical absorption with the X-band (9.15 GHz) resonant microwave pulse. This technique was applied to the photochemical reaction of benzophenone, benzophenone-d(10), and benzophenone-carbonyl-(13)C in a sodium dodecylsulfate micellar solution with a step-by-step increase of the resonant microwave pulse width. The yields of the component radicals showed alternation with an increase of the microwave pulse width. This indicates that the radical pair retains spin coherence in the micellar solution. The magnetic isotope effect on the amplitude of the quantum beat was observed. The MW effect on the quantum beat of BP-(13)C decreases from 80% to 60% of that of BP by irradiation of the pi-pulse MW due to spin-locking. The kinetic parameters were also determined using the X- or Ku-band (17.44 GHz) region. They are almost similar to each other except for the intersystem recombination rate in the system of BP-(13)C, which may be slightly higher than those in other systems.

  18. Oxygen isotope exchange kinetics of mineral pairs in closed and open systems: Applications to problems of hydrothermal alteration of igneous rocks and Precambrian iron formations

    Science.gov (United States)

    Gregory, R.T.; Criss, R.E.; Taylor, H.P.

    1989-01-01

    The systematics of stable-isotope exchange between minerals and fluids are examined in the context of modal mineralogical variations and mass-balance considerations, both in closed and in open systems. On mineral-pair ??18O plots, samples from terranes that have exchanged with large amounts of fluid typically map out steep positively-sloped non-equilibrium arrays. Analytical models are derived to explain these effects; these models allow for different exchange rates between the various minerals and the external fluids, as well as different fluid fluxes. The steep arrays are adequately modelled by calculated isochron lines that involve the whole family of possible exchange trajectories. These isochrons have initially-steep near-vertical positive slopes that rotate toward a 45?? equilibrium slope as the exchange process proceeds to completion. The actual data-point array is thus analogous to the hand of an "isotopic clock" that measures the duration of the hydrothermal episode. The dimensionless ratio of the volumetric fluid flux to the kinetic rate parameter ( u k) determines the shape of each individual exchange trajectory. In a fluid-buffered system ( u k ??? 1), the solutions to the equations: (1) are independent of the mole fractions of the solid phases; (2) correspond to Taylor's open-system water/rock equation; and (3) yield straight-line isochrons that have slopes that approach 1 f, where f is the fraction reacted of the more sluggishly exchanging mineral. The isochrons for this simple exchange model are closely congruent with the isochrons calculated for all of the more complex models, thereby simplifying the application of theory to actual hydrothermal systems in nature. In all of the models an order of magnitude of time (in units of kt) separates steep non-equilibrium arrays (e.g., slope ??? 10) from arrays approaching an equilibrium slope of unity on a ??-?? diagram. Because we know the approximate lifetimes of many hydrothermal systems from geologic and

  19. Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction: experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass.

    Science.gov (United States)

    Fleming, Donald G; Arseneau, Donald J; Sukhorukov, Oleksandr; Brewer, Jess H; Mielke, Steven L; Truhlar, Donald G; Schatz, George C; Garrett, Bruce C; Peterson, Kirk A

    2011-11-14

    The neutral muonic helium atom (4)Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of (4)Heμ with molecular hydrogen, (4)Heμ + H(2) → (4)HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, k(Heμ), are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for k(Heμ) are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for k(Heμ) on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H(2) and Mu + H(2) reactions in a novel study of kinetic isotope effects for the H + H(2) reactions over a factor of 36.1 in isotopic mass of the atomic reactant. © 2011 American Institute of Physics

  20. A kinetic analysis of leaf uptake of COS and its relation to transpiration, photosynthesis and carbon isotope fractionation

    Directory of Open Access Journals (Sweden)

    U. Seibt

    2009-09-01

    Full Text Available Carbonyl sulfide (COS is an atmospheric trace gas that holds great promise for studies of terrestrial carbon and water exchange. In leaves, COS follows the same pathway as CO2 during photosynthesis. Both gases are taken up in enzyme reactions, making COS and CO2 uptake closely coupled at the leaf scale. The biological background of leaf COS uptake is a hydrolysis reaction catalyzed by the enzyme carbonic anhydrase. Based on this, we derive and test a simple kinetic model of leaf COS uptake, and relate COS to CO2 and water fluxes at the leaf scale. The equation was found to predict realistic COS fluxes compared to observations from field and laboratory chambers. We confirm that COS uptake at the leaf level is directly linked to stomatal conductance. As a consequence, the ratio of deposition velocities (uptake rate divided by ambient mole fraction for leaf COS and CO2 fluxes can provide an estimate of Ci/Ca the ratio of intercellular to atmospheric CO2, an important plant gas exchange parameter that cannot be measured directly. The majority of published deposition velocity ratios for leaf studies on a variety of species fall in the range of 1.5 to 4, corresponding to Ci/Ca ratios of 0.5 to 0.8. In addition, we utilize the coupling of Ci/Ca and photosynthetic ˆ13C discrimination to derive an estimate of 2.8±0.3 for the global mean ratio of deposition velocities. This corresponds to a global vegetation sink of COS in the order of 900±100 Gg S yr−1. COS can now be implemented in the same model framework as CO2 and water vapour. Atmospheric COS measurements can then provide independent constraints on CO2 and water cycles at ecosystem, regional and global scales.

  1. Determining the transition-state structure for different SN2 reactions using experimental nucleophile carbon and secondary alpha-deuterium kinetic isotope effects and theory.

    Science.gov (United States)

    Westaway, Kenneth C; Fang, Yao-ren; MacMillar, Susanna; Matsson, Olle; Poirier, Raymond A; Islam, Shahidul M

    2008-10-16

    Nucleophile (11)C/ (14)C [ k (11)/ k (14)] and secondary alpha-deuterium [( k H/ k D) alpha] kinetic isotope effects (KIEs) were measured for the S N2 reactions between tetrabutylammonium cyanide and ethyl iodide, bromide, chloride, and tosylate in anhydrous DMSO at 20 degrees C to determine whether these isotope effects can be used to determine the structure of S N2 transition states. Interpreting the experimental KIEs in the usual fashion (i.e., that a smaller nucleophile KIE indicates the Nu-C alpha transition state bond is shorter and a smaller ( k H/ k D) alpha is found when the Nu-LG distance in the transition state is shorter) suggests that the transition state is tighter with a slightly shorter NC-C alpha bond and a much shorter C alpha-LG bond when the substrate has a poorer halogen leaving group. Theoretical calculations at the B3LYP/aug-cc-pVDZ level of theory support this conclusion. The results show that the experimental nucleophile (11)C/ (14)C KIEs can be used to determine transition-state structure in different reactions and that the usual method of interpreting these KIEs is correct. The magnitude of the experimental secondary alpha-deuterium KIE is related to the nucleophile-leaving group distance in the S N2 transition state ( R TS) for reactions with a halogen leaving group. Unfortunately, the calculated and experimental ( k H/ k D) alpha's change oppositely with leaving group ability. However, the calculated ( k H/ k D) alpha's duplicate both the trend in the KIE with leaving group ability and the magnitude of the ( k H/ k D) alpha's for the ethyl halide reactions when different scale factors are used for the high and the low energy vibrations. This suggests it is critical that different scaling factors for the low and high energy vibrations be used if one wishes to duplicate experimental ( k H/ k D) alpha's. Finally, neither the experimental nor the theoretical secondary alpha-deuterium KIEs for the ethyl tosylate reaction fit the trend found

  2. Heavy-atom derivatives in lipidic cubic phases: results on hen egg-white lysozyme tetragonal derivative crystals with Gd-HPDO3A complex.

    Science.gov (United States)

    Girard, Eric; Pebay-Peyroula, Eva; Vicat, Jean; Kahn, Richard

    2004-08-01

    Gd-HPDO3A, a neutral gadolinium complex, is a good candidate for obtaining heavy-atom-derivative crystals by the lipidic cubic phase crystallization method known to be effective for membrane proteins. Gadolinium-derivative crystals of hen egg-white lysozyme were obtained by co-crystallizing the protein with 100 mM Gd-HPDO3A in a monoolein cubic phase. Diffraction data were collected to a resolution of 1.7 A using Cu Kalpha radiation from a rotating-anode generator. Two binding sites of the gadolinium complex were located from the strong gadolinium anomalous signal. The Gd-atom positions and their refined occupancies were found to be identical to those found in derivative crystals of hen egg-white lysozyme obtained by co-crystallizing the protein with 100 mM Gd-HPDO3A using the hanging-drop technique. Moreover, the refined structures are isomorphous. The lipidic cubic phase is not disturbed by the high concentration of Gd-HPDO3A. This experiment demonstrates that a gadolinium complex, Gd-HPDO3A, can be used to obtain derivative crystals by the lipidic cubic phase crystallization method. Further studies with membrane proteins that are known to crystallize in lipidic cubic phases will be undertaken with Gd-HPDO3A and other Gd complexes to test whether derivative crystals with high Gd-site occupancies can be obtained.

  3. Kinetic Isotope Effects as a Probe for the Protonolysis Mechanism of Alkylmetal Complexes: VTST/MT Calculations Based on DFT Potential Energy Surfaces.

    Science.gov (United States)

    Mai, Binh Khanh; Kim, Yongho

    2016-10-03

    Protonolysis by platinum or palladium complexes has been extensively studied because it is the microscopic reverse of the C-H bond activation reaction. The protonolysis of (COD)Pt(II)Me2, which exhibits abnormally large kinetic isotope effects (KIEs), is proposed to occur via a concerted pathway (SE2 mechanism) with large tunneling. However, further investigation of KIEs for the protonolysis of ZnMe2 and others led to a conclusion that there is no noticeable correlation between the mechanism and magnitude of KIE. In this study, we demonstrated that variational transition state theory including multidimensional tunneling (VTST/MT) could accurately predict KIEs and Arrhenius parameters of the protonolysis of alkylmetal complexes based on the potential energy surfaces generated by density functional theory. The predicted KIEs, Ea(D) - Ea(H) values, and AH/AD ratios for the protonolysis of (COD)Pt(II)Me2 and Zn(II)Me2 by TFA agreed very well with experimental values. The protonolysis of ZnMe2 with the concerted pathway has a very flat potential energy surface, which produces a very small tunneling effect and therefore a small KIE. The predicted KIE for the stepwise protonolysis (SE(ox) mechanism) of (COD)Pt(II)Me2 was much smaller than that of the concerted pathway, but greater than the KIE of the concerted protonolysis of ZnMe2. A large KIE, which entails a significant tunneling effect, could be used as an experimental probe of the concerted pathway. However, a normal or small KIE should not be used as an indicator of the stepwise mechanism, and the interplay between experiments and reliable theory including tunneling would be essential to uncover the mechanism correctly.

  4. Laboratory studies of carbon kinetic isotope effects on the production mechanism of particulate phenolic compounds formed by toluene photooxidation: a tool to constrain reaction pathways.

    Science.gov (United States)

    Irei, Satoshi; Rudolph, Jochen; Huang, Lin; Auld, Janeen; Collin, Fabrice; Hastie, Donald

    2015-01-08

    In this study, we examined compound-specific stable carbon isotope ratios for phenolic compounds in secondary organic aerosol (SOA) formed by photooxidation of isotope-label-free toluene. SOA generated by photooxidation of toluene using a continuous-flow reactor and an 8 m(3) indoor smog chamber was collected on filters, which were extracted with acetonitrile for compound-specific analysis. Eight phenolic compounds were identified in the extracts using a gas chromatograph coupled with a mass spectrometer, and their compound-specific stable carbon isotope ratios were determined using a gas chromatograph coupled with a combustion furnace followed by an isotope ratio mass spectrometer. The majority of products, including methylnitrophenols and methylnitrocatechols, were isotopically depleted by 5-6‰ compared to the initial isotope ratio of toluene, whereas the isotope ratio for 4-nitrophenol remained identical to that of toluene. On the basis of the reaction mechanisms proposed in previous reports, stable carbon isotope ratios of these products were calculated. By comparing the observed isotope ratios with the predicted isotope ratios, we explored possible production pathways for the particulate phenolic compounds.

  5. Methodology using a portable X-ray fluorescence device for on-site and rapid evaluation of heavy-atom contamination in wounds: a model study for application to plutonium contamination.

    Directory of Open Access Journals (Sweden)

    Hiroshi Yoshii

    Full Text Available Workers decommissioning the Fukushima-Daiichi nuclear power plant damaged from the Great East Japan Earthquake and resulting tsunami are at risk of injury with possible contamination from radioactive heavy atoms including actinides, such as plutonium. We propose a new methodology for on-site and rapid evaluation of heavy-atom contamination in wounds using a portable X-ray fluorescence (XRF device. In the present study, stable lead was used as the model contaminant substitute for radioactive heavy atoms. First, the wound model was developed by placing a liquid blood phantom on an epoxy resin wound phantom contaminated with lead. Next, the correlation between the concentration of contaminant and the XRF peak intensity was formulated considering the thickness of blood exiting the wound. Methods to determine the minimum detection limit (MDL of contaminants at any maximal equivalent dose to the wound by XRF measurement were also established. For example, in this system, at a maximal equivalent dose of 16.5 mSv to the wound and blood thickness of 0.5 mm, the MDL value for lead was 1.2 ppm (3.1 nmol. The radioactivity of 239Pu corresponding to 3.1 nmol is 1.7 kBq, which is lower than the radioactivity of 239Pu contaminating puncture wounds in previous severe accidents. In conclusion, the established methodology could be beneficial for future development of a method to evaluate plutonium contamination in wounds. Highlights: Methodology for evaluation of heavy-atom contamination in a wound was established. A portable X-ray fluorescence device enables on-site, rapid and direct evaluation. This method is expected to be used for evaluation of plutonium contamination in wounds.

  6. Methodology using a portable X-ray fluorescence device for on-site and rapid evaluation of heavy-atom contamination in wounds: a model study for application to plutonium contamination.

    Science.gov (United States)

    Yoshii, Hiroshi; Yanagihara, Kouta; Imaseki, Hitoshi; Hamano, Tsuyoshi; Yamanishi, Hirokuni; Inagaki, Masayo; Sakai, Yasuhiro; Sugiura, Nobuyuki; Kurihara, Osamu; Sakai, Kazuo

    2014-01-01

    Workers decommissioning the Fukushima-Daiichi nuclear power plant damaged from the Great East Japan Earthquake and resulting tsunami are at risk of injury with possible contamination from radioactive heavy atoms including actinides, such as plutonium. We propose a new methodology for on-site and rapid evaluation of heavy-atom contamination in wounds using a portable X-ray fluorescence (XRF) device. In the present study, stable lead was used as the model contaminant substitute for radioactive heavy atoms. First, the wound model was developed by placing a liquid blood phantom on an epoxy resin wound phantom contaminated with lead. Next, the correlation between the concentration of contaminant and the XRF peak intensity was formulated considering the thickness of blood exiting the wound. Methods to determine the minimum detection limit (MDL) of contaminants at any maximal equivalent dose to the wound by XRF measurement were also established. For example, in this system, at a maximal equivalent dose of 16.5 mSv to the wound and blood thickness of 0.5 mm, the MDL value for lead was 1.2 ppm (3.1 nmol). The radioactivity of 239Pu corresponding to 3.1 nmol is 1.7 kBq, which is lower than the radioactivity of 239Pu contaminating puncture wounds in previous severe accidents. In conclusion, the established methodology could be beneficial for future development of a method to evaluate plutonium contamination in wounds. Highlights: Methodology for evaluation of heavy-atom contamination in a wound was established. A portable X-ray fluorescence device enables on-site, rapid and direct evaluation. This method is expected to be used for evaluation of plutonium contamination in wounds.

  7. Effective technique for numerical kinetics calculations in a system of anharmonic oscillators. Application to study of the influence of the isotopic composition of molecules on the properties of a carbon monoxide active medium

    Energy Technology Data Exchange (ETDEWEB)

    Bunkin, S.B.; Islamov, R.S.; Konev, Y.B.; Kochetov, I.V.

    1982-07-01

    A technique is described for numerical analysis of kinetic processes in a system of anharmonic oscillators, based on using implicit numerical integration and replacement of derivatives by means of backward differentiation expressions. A comparison is made with calculations by the Runge--Kutta method, and it is shown that the computer time is reduced by a factor of more than 10 when the backward differentiation method is used. The influence of the natural isotopic composition of carbon monoxide molecules on the gain and lasing properties is investigated and shown to be only slight.

  8. ISOTOPE METHODS IN HOMOGENEOUS CATALYSIS.

    Energy Technology Data Exchange (ETDEWEB)

    BULLOCK,R.M.; BENDER,B.R.

    2000-12-01

    The use of isotope labels has had a fundamentally important role in the determination of mechanisms of homogeneously catalyzed reactions. Mechanistic data is valuable since it can assist in the design and rational improvement of homogeneous catalysts. There are several ways to use isotopes in mechanistic chemistry. Isotopes can be introduced into controlled experiments and followed where they go or don't go; in this way, Libby, Calvin, Taube and others used isotopes to elucidate mechanistic pathways for very different, yet important chemistries. Another important isotope method is the study of kinetic isotope effects (KIEs) and equilibrium isotope effect (EIEs). Here the mere observation of where a label winds up is no longer enough - what matters is how much slower (or faster) a labeled molecule reacts than the unlabeled material. The most careti studies essentially involve the measurement of isotope fractionation between a reference ground state and the transition state. Thus kinetic isotope effects provide unique data unavailable from other methods, since information about the transition state of a reaction is obtained. Because getting an experimental glimpse of transition states is really tantamount to understanding catalysis, kinetic isotope effects are very powerful.

  9. Temperature Dependence of Carbon Kinetic Isotope Effect for the Oxidation Reaction of Ethane by Hydroxyl Radicals Under Atmospherically Relevant Conditions: Experimental and Theoretical Studies

    OpenAIRE

    Piansawan, Tammarat

    2016-01-01

           Ethane is the second most abundant hydrocarbon in the atmosphere, after methane, impacting on air quality, human health and climate. A quantification of its effects requires accurate knowledge of sources, processes along transport, and sinks. Carbon stable isotopic ratio investigations, complementarily to concentration measurements, were demonstrated to give more insight in source apportionment and atmospheric processing of organic compounds.        Yet, apportionment of atmospher...

  10. Evidence for a catalytic six-membered cyclic transition state in aminolysis of 4-nitrophenyl 3,5-dinitrobenzoate in acetonitrile: comparative brønsted-type plot, entropy of activation, and deuterium kinetic isotope effects.

    Science.gov (United States)

    Um, Ik-Hwan; Kim, Min-Young; Bae, Ae-Ri; Dust, Julian M; Buncel, Erwin

    2015-01-02

    A kinetic study for reactions of 4-nitrophenyl 3,5-dinitrobenzoate (1a) with a series of cyclic secondary amines in acetonitrile is reported. Plots of the pseudo-first-order rate constant (kobsd) vs [amine] curve upward, while those of kobsd /[amine] vs [amine] exhibit excellent linear correlations with positive intercepts, indicating that the reaction proceeds through both uncatalyzed and catalyzed routes. Brønsted-type plots for uncatalyzed and catalyzed reactions are linear with βnuc = 1.03 and 0.69, respectively. The ΔH(⧧) and ΔS(⧧) values measured for the catalytic reaction with morpholine are -0.80 kcal/mol and -61.7 cal/(mol K), respectively. The negative ΔH(⧧) with a large negative ΔS(⧧) suggests that the reaction proceeds through a highly ordered transition state (i.e., a six-membered cyclic transition state, which includes a second amine molecule that accepts a proton from the aminium moiety of the zwitterionic tetrahedral intermediate and simultaneously donates a proton to the aryloxyl oxygen of the nucleofuge with concomitant C-OAr bond scission). This proposal is consistent with the smaller βnuc value for the catalyzed reaction as compared to the uncatalyzed reaction. An inverse deuterium kinetic isotope effect (DKIE) value of 0.93 and a contrasting normal primary DKIE value of 3.23 for the uncatalyzed and catalyzed routes, respectively, also support the proposed cyclic transition state.

  11. Quantitative amino acid profiling and stable isotopically labeled amino acid tracer enrichment used for in vivo human systemic and tissue kinetics measurements

    DEFF Research Database (Denmark)

    Bornø, Andreas; van Hall, Gerrit

    2014-01-01

    /ion exchange, derivatized using a phenylisothiocyanate reagent and each amino acid was quantitated with its own stable isotopically labeled internal standard (uniformly labeled-(13)C/(15)N). The method was validated according to general recommendations for chromatographic analytical methods. The calibration...... and plasma were 4.4 and 0.8%, and the interday variability was 3.4% and the recovery was 90.5%, respectively. In conclusion, we have developed and validated a method for quantitative amino acid profiling that meets the requirements for systemic and tissue human in vivo amino acid and protein turnover...

  12. Isotopic yields and kinetic energies of primary residues in 1 A GeV sup 2 sup 0 sup 8 Pb+p reactions

    CERN Document Server

    Enqvist, T; Benlliure, J; Bernas, M; Boudard, A; Czajkowski, S; Legrain, R; Leray, S; Mustapha, B; Pravikoff, M S; Rejmund, F; Schmidt, K H; Stéphan, C; Taieb, J; Tassan-Got, L; Volant, C; Wlazlo, W

    2001-01-01

    The production of primary residual nuclei in the reaction 1 A GeV sup 2 sup 0 sup 8 Pb on proton has been studied by measuring isotopic distributions for all elements from titanium (Z=22) to lead (Z=82). Kinematical properties of the residues were also determined and used to disentangle the relevant reaction mechanisms, spallation (projectile fragmentation) and fission. The fragment separator FRS at GSI, Darmstadt, was used to separate and identify the reaction products. The measured production cross sections are highly relevant for the design of accelerator-driven subcritical reactors and for the planning of future radioactive-beam facilities.

  13. Position-specific and clumped stable isotope studies: comparison of the Urey and path-integral approaches for carbon dioxide, nitrous oxide, methane, and propane.

    Science.gov (United States)

    Webb, Michael A; Miller, Thomas F

    2014-01-16

    We combine path-integral Monte Carlo methods with high-quality potential energy surfaces to compute equilibrium isotope effects in a variety of systems relevant to 'clumped' isotope analysis and isotope geochemistry, including CO2, N2O, methane, and propane. Through a systematic study of heavy-atom isotope-exchange reactions, we quantify and analyze errors that arise in the widely used Urey model for predicting equilibrium constants of isotope-exchange reactions using reduced partition function ratios. These results illustrate that the Urey model relies on a nontrivial cancellation of errors that can shift the apparent equilibrium temperature by as much as 35 K for a given distribution of isotopologues. The calculations reported here provide the same level of precision as the best existing analytical instrumentation, resolving the relative enrichment of certain isotopologues to as little as 0.01‰. These findings demonstrate path-integral methods to be a rigorous and viable alternative to more approximate methods for heavy-atom geochemical applications.

  14. Deuterium kinetic isotope effects in heterotetrameric sarcosine oxidase from Corynebacterium sp. U-96: the anionic form of the substrate in the enzyme-substrate complex is a reactive species.

    Science.gov (United States)

    Saito, Mutsumi; Itoh, Ai; Suzuki, Haruo

    2012-06-01

    Heterotetrameric sarcosine oxidase is a flavoprotein that catalyses the oxidative demethylation of sarcosine. It is thought that the dehydrogenated substrate is the anionic form of sarcosine. To verify this assumption, the rate of flavin-adenine dinucleotide (FAD) reduction (k(red)) was analysed using protiated and deuterated sarcosine (N-methyl-d(3)-Gly) at various pH values using stopped-flow method. By increasing the pH from 6.2 to 9.8, k(red) increased for both substrates and reached a plateau, but the pK(a) value (reflecting the ionization of the enzyme-substrate complex) was 6.8 and 7.1 for protiated and deuterated sarcosine, respectively, and the kinetic isotope effect of k(red) decreased from approximately 19 to 8, indicating deprotonation of the bound sarcosine. The k(red)/K(d) (K(d), sarcosine dissociation constant) increased with increasing pH and reached a plateau. The pK (reflecting the ionization of free enzyme or free sarcosine) was 7.0 for both substrates, suggesting deprotonation of the βLys358 residue, which has a pK(a) of 6.7, as the pK(a) of the free sarcosine amine proton was determined to be approximately 10.1. These results indicate that the amine proton of sarcosine is transferred to the unprotonated Lys residue in the enzyme-substrate complex.

  15. High-level direct-dynamics variational transition state theory calculations including multidimensional tunneling of the thermal rate constants, branching ratios, and kinetic isotope effects of the hydrogen abstraction reactions from methanol by atomic hydrogen.

    Science.gov (United States)

    Meana-Pañeda, Rubén; Truhlar, Donald G; Fernández-Ramos, Antonio

    2011-03-07

    We report a detailed theoretical study of the hydrogen abstraction reaction from methanol by atomic hydrogen. The study includes the analysis of thermal rate constants, branching ratios, and kinetic isotope effects. Specifically, we have performed high-level computations at the MC3BB level together with direct dynamics calculations by canonical variational transition state theory (CVT) with the microcanonically optimized multidimensional tunneling (μOMT) transmission coefficient (CVT/μOMT) to study both the CH(3)OH+H→CH(2)OH+H(2) (R1) reaction and the CH(3)OH+H→CH(3)O+H(2) (R2) reaction. The CVT/μOMT calculations show that reaction R1 dominates in the whole range 298≤T (K)≤2500 and that anharmonic effects on the torsional mode about the C-O bond are important, mainly at high temperatures. The activation energy for the total reaction sum of R1 and R2 reactions changes substantially with temperature and, therefore, the use of straight-line Arrhenius plots is not valid. We recommend the use of new expressions for the total R1 + R2 reaction and for the R1 and R2 individual reactions.

  16. The lowest-lying electronic singlet and triplet potential energy surfaces for the HNO-NOH system: energetics, unimolecular rate constants, tunneling and kinetic isotope effects for the isomerization and dissociation reactions.

    Science.gov (United States)

    Bozkaya, Uğur; Turney, Justin M; Yamaguchi, Yukio; Schaefer, Henry F

    2012-04-28

    The lowest-lying electronic singlet and triplet potential energy surfaces (PES) for the HNO-NOH system have been investigated employing high level ab initio quantum chemical methods. The reaction energies and barriers have been predicted for two isomerization and four dissociation reactions. Total energies are extrapolated to the complete basis set limit applying focal point analyses. Anharmonic zero-point vibrational energies, diagonal Born-Oppenheimer corrections, relativistic effects, and core correlation corrections are also taken into account. On the singlet PES, the (1)HNO → (1)NOH endothermicity including all corrections is predicted to be 42.23 ± 0.2 kcal mol(-1). For the barrierless decomposition of (1)HNO to H + NO, the dissociation energy is estimated to be 47.48 ± 0.2 kcal mol(-1). For (1)NOH → H + NO, the reaction endothermicity and barrier are 5.25 ± 0.2 and 7.88 ± 0.2 kcal mol(-1). On the triplet PES the reaction energy and barrier including all corrections are predicted to be 7.73 ± 0.2 and 39.31 ± 0.2 kcal mol(-1) for the isomerization reaction (3)HNO → (3)NOH. For the triplet dissociation reaction (to H + NO) the corresponding results are 29.03 ± 0.2 and 32.41 ± 0.2 kcal mol(-1). Analogous results are 21.30 ± 0.2 and 33.67 ± 0.2 kcal mol(-1) for the dissociation reaction of (3)NOH (to H + NO). Unimolecular rate constants for the isomerization and dissociation reactions were obtained utilizing kinetic modeling methods. The tunneling and kinetic isotope effects are also investigated for these reactions. The adiabatic singlet-triplet energy splittings are predicted to be 18.45 ± 0.2 and 16.05 ± 0.2 kcal mol(-1) for HNO and NOH, respectively. Kinetic analyses based on solution of simultaneous first-order ordinary-differential rate equations demonstrate that the singlet NOH molecule will be difficult to prepare at room temperature, while the triplet NOH molecule is viable with respect to isomerization and dissociation reactions up to

  17. Pharmacokinetics of lidocaine and bupivacaine following subarachnoid administration in surgical patients: simultaneous investigation of absorption and disposition kinetics using stable isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Burm, A.G.; Van Kleef, J.W.; Vermeulen, N.P.; Olthof, G.; Breimer, D.D.; Spierdijk, J.

    1988-10-01

    The pharmacokinetics of lidocaine and bupivacaine following subarachnoid administration were studied in 12 surgical patients using a stable isotope method. After subarachnoid administration of the agent to be evaluated, a deuterium-labelled analogue was administered intravenously. Blood samples were collected for 24 h. Plasma concentrations of the unlabelled and the deuterium-labelled local anesthetics were determined using a combination of capillary gas chromatography and mass fragmentography. Bi-exponential functions were fitted to the plasma concentration-time data of the deuterium-labelled local anesthetics. The progression of the absorption was evaluated using deconvolution. Mono- and bi-exponential functions were then fitted to the fraction absorbed versus time data. The distribution and elimination half-lives of the deuterium-labelled analogues were 25 +/- 13 min (mean +/- SD) and 121 +/- 31 min for lidocaine and 19 +/- 10 min and 131 +/- 33 min for bupivacaine. The volumes of the central compartment and steady-state volumes of distribution were: lidocaine 57 +/- 10 l and 105 +/- 25 l, bupivacaine 25 +/- 6 l and 63 +/- 22 l. Total plasma clearance values averaged 0.97 +/- 0.21 l/min for lidocaine and 0.56 +/- 0.14 l/min for bupivacaine. The absorption of lidocaine could be described by a single first order absorption process, characterized by a half-life of 71 +/- 17 min in five out of six patients. The absorption of bupivacaine could be described adequately assuming two parallel first order absorption processes in all six patients. The half-lives, characterizing the fast and slow absorption processes of bupivacaine, were 50 +/- 27 min and 408 +/- 275 min, respectively. The fractions of the dose, absorbed in the fast and slow processes, were 0.35 +/- 0.17 and 0.61 +/- 0.16, respectively.

  18. Redefining the utility of the three-isotope method

    Science.gov (United States)

    Cao, Xiaobin; Bao, Huiming

    2017-09-01

    The equilibrium isotope fractionation factor αeq is a fundamental parameter in the study of stable isotope effects. Experimentally, it has been difficult to establish that a system has attained equilibrium. The three-isotope method, using the initial trajectory of changing isotope ratios (e.g. 16O, 17O, and 18O) to deduce the final equilibrium point of isotope exchange, has long been hailed as the most rigorous experimental approach. However, over the years some researchers have cautioned on the limitations of this method, but the foundation of three-isotope method has not been properly examined and the method is still widely used in calibrating αeq for both traditional and increasingly non-traditional isotope systems today. Here, using water-water and dissolved CO2-water oxygen exchange as model systems, we conduct an isotopologues-specific kinetic analysis of the exchange processes and explore the underlying assumptions and validity of the three-isotope method. We demonstrate that without knowing the detailed exchange kinetics a priori the three-isotope method cannot lead to a reliable αeq. For a two-reservoir exchanging system, α determined by this method may be αeq, kinetic isotope effect, or apparent kinetic isotope effect, which can all bear different values. When multiple reservoirs exist during exchange, the evolving trajectory can be complex and hard to predict. Instead of being a tool for αeq determination, three-isotope method should be used as a tool for studying kinetic isotope effect, apparent kinetic isotope effect, and detailed exchange kinetics in diverse systems.

  19. Production of radioactive isotopes from stable isotopes, for nuclear medicine; A partir d`isotopes stables, production d`isotopes radioactifs pour la medecine nucleaire

    Energy Technology Data Exchange (ETDEWEB)

    Bourdoiseau, M. [CEA Centre d`Etudes de Saclay, 91 - Gif-sur-Yvette (France). Office des Rayonnements Ionisants

    1994-12-31

    Around 15 radioactive isotopes only are used for nuclear medicine diagnosis (kinetics or preferential fixation in the body); characteristics of these {gamma} and {beta}-minus emitters are presented: period, energy, production mode (isotopic filiation, fission product separation, cyclotron, reactor); details are given on applications, production mode, properties and consumption of various isotopes: Technetium 99m, Thallium 201, Iodine 123, Indium 111, Gallium 67, Rhenium 186, Erbium 169, Yttrium 90, Iron 59, Chromium 51, Krypton 81m. 1 tab.

  20. Analysis of solvent nucleophile isotope effects: evidence for concerted mechanisms and nucleophilic activation by metal coordination in nonenzymatic and ribozyme-catalyzed phosphodiester hydrolysis.

    Science.gov (United States)

    Cassano, Adam G; Anderson, Vernon E; Harris, Michael E

    2004-08-17

    Heavy atom isotope effects are a valuable tool for probing chemical and enzymatic reaction mechanisms; yet, they are not widely applied to examine mechanisms of nucleophilic activation. We developed approaches for analyzing solvent (18)O nucleophile isotope effects ((18)k(nuc)) that allow, for the first time, their application to hydrolysis reactions of nucleotides and nucleic acids. Here, we report (18)k(nuc) for phosphodiester hydrolysis catalyzed by Mg(2+) and by the Mg(2+)-dependent RNase P ribozyme and deamination by the Zn(2+)-dependent protein enzyme adenosine deaminase (ADA). Because ADA incorporates a single solvent molecule into the product inosine, this reaction can be used to monitor solvent (18)O/(16)O ratios in complex reaction mixtures. This approach, combined with new methods for analysis of isotope ratios of nucleotide phosphates by whole molecule mass spectrometry, permitted determination of (18)k(nuc) for hydrolysis of thymidine 5'-p-nitrophenyl phosphate and RNA cleavage by the RNase P ribozyme. For ADA, an inverse (18)k(nuc) of 0.986 +/- 0.001 is observed, reflecting coordination of the nucleophile by an active site Zn(2+) ion and a stepwise mechanism. In contrast, the observed (18)k(nuc) for phosphodiester reactions were normal: 1.027 +/- 0.013 and 1.030 +/- 0.012 for the Mg(2+)- and ribozyme-catalyzed reactions, respectively. Such normal effects indicate that nucleophilic attack occurs in the rate-limiting step for these reactions, consistent with concerted mechanisms. However, these magnitudes are significantly less than the (18)k(nuc) observed for nucleophilic attack by hydroxide (1.068 +/- 0.007), indicating a "stiffer" bonding environment for the nucleophile in the transition state. Kinetic analysis of the Mg(2+)-catalyzed reaction indicates that a Mg(2+)-hydroxide complex is the catalytic species; thus, the lower (18)k(nuc), in large part, reflects direct metal ion coordination of the nucleophilic oxygen. A similar value for the RNase P

  1. Multiple alternative substrate kinetics.

    Science.gov (United States)

    Anderson, Vernon E

    2015-11-01

    The specificity of enzymes for their respective substrates has been a focal point of enzyme kinetics since the initial characterization of metabolic chemistry. Various processes to quantify an enzyme's specificity using kinetics have been utilized over the decades. Fersht's definition of the ratio kcat/Km for two different substrates as the "specificity constant" (ref [7]), based on the premise that the important specificity existed when the substrates were competing in the same reaction, has become a consensus standard for enzymes obeying Michaelis-Menten kinetics. The expansion of the theory for the determination of the relative specificity constants for a very large number of competing substrates, e.g. those present in a combinatorial library, in a single reaction mixture has been developed in this contribution. The ratio of kcat/Km for isotopologs has also become a standard in mechanistic enzymology where kinetic isotope effects have been measured by the development of internal competition experiments with extreme precision. This contribution extends the theory of kinetic isotope effects to internal competition between three isotopologs present at non-tracer concentrations in the same reaction mix. This article is part of a special issue titled: Enzyme Transition States from Theory and Experiment.

  2. Quantitative Tracking of Isotope Flows in Proteomes of Microbial Communities*

    Science.gov (United States)

    Pan, Chongle; Fischer, Curt R.; Hyatt, Doug; Bowen, Benjamin P.; Hettich, Robert L.; Banfield, Jillian F.

    2011-01-01

    Stable isotope probing (SIP) has been used to track nutrient flows in microbial communities, but existing protein-based SIP methods capable of quantifying the degree of label incorporation into peptides and proteins have been demonstrated only by targeting usually less than 100 proteins per sample. Our method automatically (i) identifies the sequence of and (ii) quantifies the degree of heavy atom enrichment for thousands of proteins from microbial community proteome samples. These features make our method suitable for comparing isotopic differences between closely related protein sequences, and for detecting labeling patterns in low-abundance proteins or proteins derived from rare community members. The proteomic SIP method was validated using proteome samples of known stable isotope incorporation levels at 0.4%, ∼50%, and ∼98%. The method was then used to monitor incorporation of 15N into established and regrowing microbial biofilms. The results indicate organism-specific migration patterns from established communities into regrowing communities and provide insights into metabolism during biofilm formation. The proteomic SIP method can be extended to many systems to track fluxes of 13C or 15N in microbial communities. PMID:21285414

  3. Leatherback Isotopes

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — SWFSC is currently working on a project identifying global marine isotopes using leatherback turtles (Dermochelys coriacea) as the indicator species. We currently...

  4. Isotopic chirality

    Energy Technology Data Exchange (ETDEWEB)

    Floss, H.G. [Univ. of Washington, Seattle, WA (United States)

    1994-12-01

    This paper deals with compounds that are chiral-at least in part, due to isotope substitution-and their use in tracing the steric course of enzyme reaction in vitro and in vivo. There are other applications of isotopically chiral compounds (for example, in analyzing the steric course of nonenzymatic reactions and in probing the conformation of biomolecules) that are important but they will not be discussed in this context.

  5. Isotopic Paleoclimatology

    Science.gov (United States)

    Bowen, R.

    Paleotemperature scales were calculated by H. C. Urey and others in the 1950s to assess past temperatures, and later work using the stable isotopes of oxygen, hydrogen, and carbon employed standards such as Peedee belemnite (PDB) and Standard Mean Ocean Water (SMOW). Subsequently, subjects as diverse as ice volume and paleotemperatures, oceanic ice and sediment cores, Pleistocene/Holocene climatic changes, and isotope chronostratigraphy extending back to the Precambrian were investigated.

  6. Kinetic isotope effect studies on aspartate aminotransferase: Evidence for a concerted 1,3 prototropic shift mechanism for the cytoplasmic isozyme and L-aspartate and dichotomy in mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Julin, D.A.; Kirsch, J.F. (Univ. of California, Berkeley (USA))

    1989-05-02

    The C alpha primary hydrogen kinetic isotope effects (C alpha-KIEs) for the reaction of the cytoplasmic isozyme of aspartate aminotransferase (cAATase) with (alpha-2H)-L-aspartate are small and only slightly affected by deuterium oxide solvent (DV = 1.43 +/- 0.03 and DV/KAsp = 1.36 +/- 0.04 in H{sub 2}O; DV = 1.44 +/- 0.01 and DV/KAsp = 1.61 +/- 0.06 in D{sub 2}O). The D{sub 2}O solvent KIEs (SKIEs) are somewhat larger and are essentially independent of deuterium at C alpha (D{sub 2}OV = 2.21 +/- 0.07 and D{sub 2}OV/KAsp = 1.70 +/- 0.03 with ({alpha}-1H)-L-aspartate; D{sub 2}OV = 2.34 +/- 0.12 and D{sub 2}OV/KAsp = 1.82 +/- 0.06 with ({alpha}-2H)-L- aspartate). The C alpha-KIEs on V and on V/KAsp are independent of pH from pH 5.0 to pH 10.0. These results support a rate-determining concerted 1,3 prototropic shift mechanism by the multiple KIE criteria. The large C alpha-KIEs for the reaction of mitochondrial AATase (mAATase) with L-glutamate (DV = 1.88 +/- 0.13 and DV/KGlu = 3.80 +/- 0.43 in H{sub 2}O; DV = 1.57 +/- 0.05 and DV/KGlu = 4.21 +/- 0.19 in D{sub 2}O) coupled with the relatively small SKIEs (D{sub 2}OV = 1.58 +/- 0.04 and D{sub 2}OV/KGlu = 1.25 +/- 0.05 with ({alpha}-1H)-L-glutamate; D{sub 2}OV = 1.46 +/- 0.06 and D{sub 2}OV/KGlu = 1.16 +/- 0.05 with (alpha-2H)-L-glutamate) are most consistent with a two-step mechanism for the 1,3 prototropic shift for this isozyme-substrate pair.

  7. Kinetic Atom.

    Science.gov (United States)

    Wilson, David B.

    1981-01-01

    Surveys the research of scientists like Joule, Kelvin, Maxwell, Clausius, and Boltzmann as it comments on the basic conceptual issues involved in the development of a more precise kinetic theory and the idea of a kinetic atom. (Author/SK)

  8. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia

    2014-01-01

    After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images.......After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....

  9. Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

    CERN Document Server

    Xie, Xueshu

    2014-01-01

    Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous; instead, at some resonance isotopic compositions, the kinetics increases, while at off resonance compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error plus or minus 0.05%) experiment to measure the bacterial growth parameters in minimal media with varying isotopic compositions. A number of predicted resonance conditions were tested, which kinetic enhancements as strong as plus 3% discovered at these conditions. The combined evidence extremely strongly supports the existence of isotopic resonances. This phenomenon has numerous implications for the origin of life and astrobiology, and possible application...

  10. Combinatorial effects on clumped isotopes and their significance in biogeochemistry

    Science.gov (United States)

    Yeung, Laurence Y.

    2016-01-01

    The arrangement of isotopes within a collection of molecules records their physical and chemical histories. Clumped-isotope analysis interrogates these arrangements, i.e., how often rare isotopes are bound together, which in many cases can be explained by equilibrium and/or kinetic isotope fractionation. However, purely combinatorial effects, rooted in the statistics of pairing atoms in a closed system, are also relevant, and not well understood. Here, I show that combinatorial isotope effects are most important when two identical atoms are neighbors on the same molecule (e.g., O2, N2, and D-D clumping in CH4). When the two halves of an atom pair are either assembled with different isotopic preferences or drawn from different reservoirs, combinatorial effects cause depletions in clumped-isotope abundance that are most likely between zero and -1‰, although they could potentially be -10‰ or larger for D-D pairs. These depletions are of similar magnitude, but of opposite sign, to low-temperature equilibrium clumped-isotope effects for many small molecules. Enzymatic isotope-pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect, although it is not limited to biological reactions. Chemical-kinetic isotope effects, which are related to a bond-forming transition state, arise independently and express second-order combinatorial effects related to the abundance of the rare isotope. Heteronuclear moeties (e.g., Csbnd O and Csbnd H), are insensitive to direct combinatorial influences, but secondary combinatorial influences are evident. In general, both combinatorial and chemical-kinetic factors are important for calculating and interpreting clumped-isotope signatures of kinetically controlled reactions. I apply this analytical framework to isotope-pairing reactions relevant to geochemical oxygen, carbon, and nitrogen cycling that may be influenced by combinatorial

  11. Isotopic mass-dependence of noble gas diffusion coefficients inwater

    Energy Technology Data Exchange (ETDEWEB)

    Bourg, I.C.; Sposito, G.

    2007-06-25

    Noble gas isotopes are used extensively as tracers inhydrologic and paleoclimatic studies. These applications requireknowledge of the isotopic mass (m) dependence of noble gas diffusioncoefficients in water (D), which has not been measured but is estimatedusing experimental D-values for the major isotopes along with an untestedrelationship from kinetic theory, D prop m-0.5. We applied moleculardynamics methods to determine the mass dependence of D for four noblegases at 298 K, finding that D prop m-beta with beta<0.2, whichrefutes the kinetic theory model underlying all currentapplications.

  12. Hydrogen Isotope Exchange Properties of Porous Solids Containing Hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    HEUNG, LEUNGK.

    2004-08-18

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

  13. Kinetic Interface

    DEFF Research Database (Denmark)

    2009-01-01

    A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises.......A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises....

  14. Isotope effects of hydrogen and atom tunnelling

    Science.gov (United States)

    Buchachenko, A. L.; Pliss, E. M.

    2016-06-01

    The abnormally high mass-dependent isotope effects in liquid-phase hydrogen (deuterium) atom transfer reactions, which are customarily regarded as quantum effects, are actually the products of two classical effects, namely, kinetic and thermodynamic ones. The former is determined by the rate constants for atom transfer and the latter is caused by nonbonded (or noncovalent) isotope effects in the solvation of protiated and deuterated reacting molecules. This product can mimic the large isotope effects that are usually attributed to tunnelling. In enzymatic reactions, tunnelling is of particular interest; its existence characterizes an enzyme as a rigid molecular machine in which the residence time of reactants on the reaction coordinate exceeds the waiting time for the tunnelling event. The magnitude of isotope effect becomes a characteristic parameter of the internal dynamics of the enzyme catalytic site. The bibliography includes 61 references.

  15. Stable isotope deltas: Tiny, yet robust signatures in nature

    Science.gov (United States)

    Brand, Willi A.; Coplen, Tyler B.

    2012-01-01

    Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg

  16. Stable isotope deltas: tiny, yet robust signatures in nature.

    Science.gov (United States)

    Brand, Willi A; Coplen, Tyler B

    2012-09-01

    Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including (14)C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. (13)C, (2)H, and (18)O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as-25 per mil can be written as-25 mUr (or-2.5 cUr or-0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg 'units' are easily included (e.g. either+0.015 ‰ or+15 per meg

  17. Utilization of stable isotopes for characterizing an underground gas generator; Utilisation des isotopes stables pour caracteriser un gazogene souterrain

    Energy Technology Data Exchange (ETDEWEB)

    Pirard, J.P.; Antenucci, D.; Renard, X. [Liege Univ. (Belgium); Letolle, R. [Paris-6 Univ., 75 (France)

    1994-12-31

    The principles of isotopic exchange and isotope ratio result interpretation are first reviewed; then, in the framework of an underground coal gasification project in Belgium, experiments and modelling of the underground gas generator have been carried out: isotopic abundances of carbon, hydrogen and oxygen have been measured in the gasifying agent (O{sub 2}, H{sub 2}O) and in the effluent (CO{sub 2}, CO, H{sub 2}, H{sub 2}O, CH{sub 4}, O{sub 2}, heavy oils and various organic and mineral substances). Gasification kinetics and temperatures have been evaluated and isotope application to thermometry is discussed. 1 fig., 9 refs.

  18. Kinetics and

    Directory of Open Access Journals (Sweden)

    Mojtaba Ahmadi

    2016-11-01

    Full Text Available The aqueous degradation of Reactive Yellow 84 (RY84 by potassium peroxydisulfate (K2S2O8 has been studied in laboratory scale experiments. The effect of the initial concentrations of potassium peroxydisulfate and RY84, pH and temperature on RY84 degradation were also examined. Experimental data were analyzed using first and second-order kinetics. The degradation kinetics of RY84 of the potassium peroxydisulfate process followed the second-order reaction kinetics. These rate constants have an extreme values similar to of 9.493 mM−1min−1 at a peroxydisulfate dose of 4 mmol/L. Thermodynamic parameters such as activation (Ea and Gibbs free energy (ΔG° were also evaluated. The negative value of ΔGo and Ea shows the spontaneous reaction natural conditions and exothermic nature.

  19. Stable isotope studies

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. Local hybrid functionals: an assessment for thermochemical kinetics.

    Science.gov (United States)

    Kaupp, Martin; Bahmann, Hilke; Arbuznikov, Alexei V

    2007-11-21

    Local hybrid functionals with position-dependent exact-exchange admixture are a new class of exchange-correlation functionals in density functional theory that promise to advance the available accuracy in many areas of application. Local hybrids with different local mixing functions (LMFs) governing the position dependence are validated for the heats of formation of the extended G3/99 set, and for two sets of barriers of hydrogen-transfer and heavy-atom transfer reactions (HTBH38 and NHTBH38 databases). A simple local hybrid Lh-SVWN with only Slater and exact exchange plus local correlation and a one-parameter LMF, g(r)=b(tau(W)(r)tau(r)), performs best and provides overall mean absolute errors for thermochemistry and kinetics that are a significant improvement over standard state-of-the-art global hybrid functionals. In particular, this local hybrid functional does not suffer from the systematic deterioration that standard functionals exhibit for larger molecules. In contrast, local hybrids based on generalized gradient approximation exchange tend to give rise to nonintuitive LMFs, and no improved functionals have been obtained along this route. The LMF is a real-space function and thus can be analyzed in detail. We use, in particular, graphical analyses to rationalize the performance of different local hybrids for thermochemistry and reaction barriers.

  1. Physisorption kinetics

    CERN Document Server

    Kreuzer, Hans Jürgen

    1986-01-01

    This monograph deals with the kinetics of adsorption and desorption of molecules physisorbed on solid surfaces. Although frequent and detailed reference is made to experiment, it is mainly concerned with the theory of the subject. In this, we have attempted to present a unified picture based on the master equation approach. Physisorption kinetics is by no means a closed and mature subject; rather, in writing this monograph we intended to survey a field very much in flux, to assess its achievements so far, and to give a reasonable basis from which further developments can take off. For this reason we have included many papers in the bibliography that are not referred to in the text but are of relevance to physisorption. To keep this monograph to a reasonable size, and also to allow for some unity in the presentation of the material, we had to omit a number of topics related to physisorption kinetics. We have not covered to any extent the equilibrium properties of physisorbed layers such as structures, phase tr...

  2. Kinetic Biochemistry

    Directory of Open Access Journals (Sweden)

    Lorentz JÄNTSCHI

    2003-03-01

    Full Text Available Mathematics and computer programming have a major contribution to chemistry. Two directions can be identified: one that searches and tries (rich to explain the structural binding and shape of the chemical compounds [1] with major applications in QSPR/QSAR studies [2], and applied sciences such as engineering of materials or agriculture [3]; the second direction is to models the kinetic processes that are involved in chemical reactions [4]. Many such models are available here. The present paper describes three variants of well the known kinetic models and presents the mathematical equations associated with them. The differential equations are numerically solved and fitted with MathCad program. [1] Diudea M., Gutman I., Jäntschi L., Molecular Topology, Nova Science, Huntington, New York, 332 p., 2001, 2002. [2] Diudea M. V., Ed., QSPR / QSAR Studies by Molecular Descriptors, Nova Science, Huntington, New York, 438 p., 2001. [3] Jäntschi L., Microbiology and Toxicology. Phytochemistry Studies (in Romanian, Amici, Cluj-Napoca, 184 p., 2003. [4] Jäntschi L., Unguresan M., Physical Chemistry. Molecular Kinetic and Dynamic (in Romanian, Mediamira, Cluj-Napoca, 159 p., 2001.

  3. The three-isotope method for equilibrium isotope fractionation factor determination: Unfounded optimism

    Science.gov (United States)

    Cao, X.; Hayles, J. A.; Bao, H.

    2015-12-01

    The equilibrium isotope fractionation factor α is a fundamental parameter in stable isotope geochemistry. Although equilibrium α can be determined by theoretical calculation or by measurement of natural samples, direct laboratory experiments are ultimately required to verify those results. The attainment of a true exchange equilibrium in experiments is often difficult, but three methods have been devised and used to ensure that an equilibrium α has been obtained in an isotope exchange experiment. These are the two-directional method, partial-exchange method, and three-isotope method. Of these, the three-isotope method is thought to be the most rigorous. Using water-water exchange as a basic unit, we have developed a set of complex exchange models to study when and why the three-isotope method may work well or not. We found that the method cannot promise to lead to an equilibrium α before the kinetic complexity of the specific exchange experiment is known. An equilibrium point in δ17O-δ18O space can be reached only when all of the isotope exchange pathways are fully reversible, i.e. there is no mass loss at any instant, and the forward and backward reactions share the same pathway. If the exchange pathways are not fully reversible, steady state may be reached, but a steady state α can be very different from the equilibrium α. Our results validated the earlier warning that the trajectory for three-isotope evolution in δ17O-δ18O space may be a distinctly curved line or contain more than one straight line due to the non-fully reversible isotope exchange reactions. The three-isotope method for equilibrium α determination is not as rigorous or as promising as it may seem. Instead, the trajectory of three-isotope evolution provides detailed insights into the kinetics of isotope exchange between compounds. If multiple components exist in the exchange system, the δ17O-δ18O evolving trajectory would be more complex.

  4. Fission properties of einsteinium and fermium. [Half-life, kinetic energy release, mass division, prompt neutron emission

    Energy Technology Data Exchange (ETDEWEB)

    Hoffman, D.C.

    1978-01-01

    The systematics of the low energy fission of the fermium isotopes is studied considering half-lives, masss division, kinetic-energy release, and accompanying prompt neutron emission. It is shown that the low energy fission of the fermium isotopes is a microcosm of the fission process, exhibiting a wide range of half lives, mass and kinetic energy distributions and varying neutron emission. The trends in the fermium isotopes are considered. 23 references. (JFP)

  5. Simulation of cloud microphysical effects on water isotope fractionation in a frontal system

    Science.gov (United States)

    Chen, J. P.; Tsai, I. C.; Chen, W. Y.; Liang, M. C.

    2014-12-01

    The stable water isotopic composition changes due to fractionation during phase changes. This information is useful for understanding the water cycle, such as the water vapor source, transport and cloud microphysical processes. In conventional atmospheric models, the isotope exchange between liquid and gas phase is usually assumed to be in an equilibrium state, which is not sufficient to describe the highly kinetic phase transformation processes in clouds. In this study, a two-moment microphysical scheme incorporated into the NCAR Weather Research and Forecasting (WRF) model is modified to simulate the isotope fractionations. Experimentally determined stable water isotope thermal equilibrium data are converted into isotope saturation vapor pressure, which is then put into the two-stream Maxwellian kinetic equation to calculate the fractionation during vapor condensation/evaporation or deposition/sublimation. Isotope mass transfer between liquid- and ice-phase hydrometeors during freezing/melting are also considered explicitly. The simulation results were compared with rainwater isotope measurements and showed fairly good agreement. Sensitivity tests were also conducted to quantify the contribution of rainwater isotopic due to water vapor source and transport, condensation environment conditions, and cloud microphysical processes. The results show that isotopic water vapor source dominates the stable isotope concentration in rainwater but the cloud microphysical processes including the ice-phase processes are also quite important. The results also showed that the two-stream Maxwellian kinetic method would cause significantly more deuterium to be transported into higher altitudes during convection than the thermal equilibrium method.

  6. Isotopic separation by ion chromatography; La separation isotopique par chromatographie ionique

    Energy Technology Data Exchange (ETDEWEB)

    Albert, M.G.; Barre, Y.; Neige, R. [CEA Centre d`Etudes de la Vallee du Rhone, 26 - Pierrelatte (France). Dept. de Technologie de l`Enrichissement

    1994-12-31

    The isotopic exchange reaction and the isotopic separation factor are first recalled; the principles of ion chromatography applied to lithium isotope separation are then reviewed (displacement chromatography) and the process is modelled in the view of dimensioning and optimizing the industrial process; the various dimensioning parameters are the isotopic separation factor, the isotopic exchange kinetics and the material flow rate. Effects of the resin type and structure are presented. Dimensioning is also affected by physico-chemical and hydraulic parameters. Industrial implementation features are also discussed. 1 fig., 1 tab., 5 refs.

  7. METHOD OF ISOTOPE CONCENTRATION

    Science.gov (United States)

    Spevack, J.S.

    1957-04-01

    An isotope concentration process is described which consists of exchanging, at two or more different temperature stages, two isotopes of an element between substances that are physically separate from each other and each of which is capable of containing either of the isotopes, and withdrawing from a point between at least two of the temperatare stages one of the substances containing an increased concentration of the desired isotope.

  8. Statistical clumped isotope signatures

    NARCIS (Netherlands)

    Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.

    2016-01-01

    High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a m

  9. 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...

  10. Buprenorphine kinetics.

    Science.gov (United States)

    Bullingham, R E; McQuay, H J; Moore, A; Bennett, M R

    1980-11-01

    Buprenorphine kinetics was determined in surgical patients using radioimmunoassay. Buprenorphine was measured in the plasma of 24 patients who had received 0.3 mg buprenorphine intraoperatively. After 3 hr 10 of these patients then received a further 0.3 mg buprenorphine intravenously for postoperative pain relief, and 11 patients were given 0.3 mg intramuscularly; again, plasma levels were measured for 3 hr. The data fitted closely to a triexponential decay curve. There was a very fast initial phase, with a half-life (t1/2) of 2 min. The terminal t1/2 was slow, approximately 3 hr. Comparison of the kinetics of the same patient, awake and anesthetized, showed that the clearance was significantly lower in the anesthetized state. A notable feature of the drug given intramuscularly is rapid systemic availability, so that peaks are obtained in 2 to 5 min, and in 10 min the resulting levels are the same as for the intravenous and intramuscular routes.

  11. Phosphorus kinetics in ovine fed with different phosphorus sources, using the isotopic dilution technique; Cinetica do fosforo em ovinos suplementados com diferentes fontes fosfatadas, atraves da tecnica de diluicao isotopica

    Energy Technology Data Exchange (ETDEWEB)

    Vitti, D.M.S.S.; Abdalla, A.L. [Centro de Energia Nuclear na Agricultura (CENA), Piracicaba, SP (Brazil); Meirelles, C.F. [Sao Paulo Univ., Piracicaba, SP (Brazil). Escola Superior de Agricultura Luiz de Queiroz

    1992-06-01

    Phosphorus kinetics in fluids and tissues of sheep was studied. Sixteen castrated sheep were kept in metabolism cages, receiving a semipuried diet containing as phosphorus sources dicalcium phosphate (BIC), monoammonium phosphate (MAP), superphosphate (SPT) and Tapita phosphate (TAP) 200 {mu}Ci P-32 was intravenously injected in each sheep and blood and feces were collected for eight days. From the specific activities in feces and plasma the endogenous phosphorus and the absorption coefficient were calculated. plasma P-32 half-life was determined. Nine days after injection the animals were killed and liver, kidney and muscle and bone samples were collected. P-32 retention and specific activities in tissues were determined. Endogenous phosphorus and absorption coefficient values were 54.44 {+-} 15.31 mh/kg live weight and 0.60; 47.98 {+-} 12.44 and 0.56; 39.70 {+-} 7.29 and 0.49; 59.11 {+-} 17.12 and 0.58 respectively bor BIC, MAP, TAP and SPT. P-32 retention by tissues was 0.29 {+-} 0.09; 0.27 {+-} 0.06; 0.16 {+-} 0.04 and 0.08 {+-} 0.03 dose/g fresh matter, respectively for bone, liver, kidney and muscle. It was concluded that animals which received TAP showed differences in absorption, distribution and P-32 retention by fluids and tissues. Phosphorus availability was lower for this source. (author) 14 refs., 1 tab.

  12. Generation of Radixenon Isotopes

    Energy Technology Data Exchange (ETDEWEB)

    McIntyre, Justin I.; Bowyer, Ted W.; Hayes, James C.; Heimbigner, Tom R.; Morris, Scott J.; Panisko, Mark E.; Pitts, W. K.; Pratt, Sharon L.; Reeder, Paul L.; Thomas, Charles W.

    2003-06-30

    Pacific Northwest National Laboratory has developed an automated system for separating Xe from air and can detect the following radioxenon isotopes, 131mXe, 133mXe, 133Xe, and 135Xe. This report details the techniques used to generate the various radioxenon isotopes that are used for the calibration of the detector as well as other isotopes that have the potential to interfere with the fission produced radioxenon isotopes. Fission production is covered first using highly enriched uranium followed by a description and results from an experiment to produce radioxenon isotopes from neutron activation of ambient xenon.

  13. 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...

  14. Endogenous surfactant metabolism in critically ill infants measured with stable isotope labeled fatty acids

    NARCIS (Netherlands)

    Cogo, PE; Carnielli, VP; Bunt, JEH; Badon, T; Giordano, G; Zacchello, F; Sauer, PJJ; Zimmermann, LJI

    1999-01-01

    Little is known about endogenous surfactant metabolism in infants, because radioactive isotopes used for this purpose in animals cannot be used in humans. We developed a novel and safe method to measure the endogenous surfactant kinetics in vivo in humans by using stable isotope labeled fatty acids.

  15. Kinetic buffers.

    Science.gov (United States)

    Alibrandi, Giuseppe; Fabbrizzi, Luigi; Licchelli, Maurizio; Puglisi, Antonio

    2015-01-12

    This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH-sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH-t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di-copper(II) bistren complex in a single run, in a completely automatic experiment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Quasi-harmonic calculations of the isotope effect in diffusion

    Energy Technology Data Exchange (ETDEWEB)

    Harding, J.H.

    1986-11-10

    It is shown how the kinetic energy factor for isotope diffusion may be calculated within the quasi-harmonic approximation using methods devised to calculate the vibrational contribution to defect entropies. The results are compared with experiment in the cases of CoO and NiO and good agreement found.

  17. Mass-dependent fractionation of nickel isotopes in meteoritic metal

    Science.gov (United States)

    Cook, David L.; Wadhwa, Meenakshi; Clayton, Robert N.; Dauphas, Nicolas; Janney, Philip E.; Davis, Andrew M.

    We measured nickel isotopes via multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) in the bulk metal from 36 meteorites, including chondrites, pallasites, and irons (magmatic and non-magmatic). The Ni isotopes in these meteorites are mass fractionated; the fractionation spans an overall range of ≈0.4‰ amu-1. The ranges of Ni isotopic compositions (relative to the SRM 986 Ni isotopic standard) in metal from iron meteorites (≈0.0 to ≈0.3‰ amu-1) and chondrites (≈0.0 to ≈0.2‰ amu-1) are similar, whereas the range in pallasite metal (≈-0.1 to 0.0‰ amu-1) appears distinct. The fractionation of Ni isotopes within a suite of fourteen IIIAB irons (≈0.0 to ≈0.3‰ amu-1) spans the entire range measured in all magmatic irons. However, the degree of Ni isotopic fractionation in these samples does not correlate with their Ni content, suggesting that core crystallization did not fractionate Ni isotopes in a systematic way. We also measured the Ni and Fe isotopes in adjacent kamacite and taenite from the Toluca IAB iron meteorite. Nickel isotopes show clearly resolvable fractionation between these two phases; kamacite is heavier relative to taenite by ≈0.4‰ amu-1. In contrast, the Fe isotopes do not show a resolvable fractionation between kamacite and taenite. The observed isotopic compositions of kamacite and taenite can be understood in terms of kinetic fractionation due to diffusion of Ni during cooling of the Fe-Ni alloy and the development of the Widmanstätten pattern.

  18. Coupled extremely light Ca and Fe isotopes in peridotites

    Science.gov (United States)

    Zhao, Xinmiao; Zhang, Zhaofeng; Huang, Shichun; Liu, Yufei; Li, Xin; Zhang, Hongfu

    2017-07-01

    Large metal stable isotopic variations have been observed in both extraterrestrial and terrestrial samples. For example, Ca exhibits large mass-dependent isotopic variation in terrestrial igneous rocks and mantle minerals (on the order of ∼2‰ variation in 44Ca/40Ca). A thorough assessment and understanding of such isotopic variations in peridotites provides important constraints on the evolution and compositon of the Earth's mantle. In order to better understand the Ca and Fe isotopic variations in terrestrial silicate rocks, we report Ca isotopic compositions in a set of peridotitic xenoliths from North China Craton (NCC), which have been studied for Fe isotopes. These NCC peridotites have large Ca and Fe isotopic variations, with δ44/40Ca ranging from -0.08 to 0.92 (delta value relative to SRM915a) and δ57/54Fe (delta value relative to IRMM-014) ranging from -0.61 to 0.16, and these isotopic variations are correlated with large Mg# (100 × Mg/(Mg + Fe) molar ratio) variation, ranging from 80 to 90. Importantly, NCC Fe-rich peridotites have the lowest 44Ca/40Ca and 57Fe/54Fe ratios in all terrestrial silicate rocks. In contrast, although ureilites, mantle rocks from a now broken differentiated asteroid(s), have large Mg# variation, from 70 to 92, they have very limited δ57Fe/54Fe variation (0.03-0.21, delta value relative to IRMM-014). Our model calculations show that the coupled extremely light Ca-Fe isotopic signatures in NCC Fe-rich peridotites most likely reflect kinetic isotopic fractionation during melt-peridotite reaction on a timescale of several to 104 years. In addition, our new data and compiled literature data show a possible compositional effect on the inter-mineral Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene pairs.

  19. 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

  20. Discovery of the Cobalt Isotopes

    OpenAIRE

    Szymanski, T.; Thoennessen, M.

    2009-01-01

    Twenty-six cobalt isotopes have so far been observed; the discovery of these isotopes is discussed. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.

  1. Discovery of the Arsenic Isotopes

    CERN Document Server

    Shore, A; Heim, M; Schuh, A; Thoennessen, M

    2009-01-01

    Twenty-nine arsenic isotopes have so far been observed; the discovery of these isotopes is discussed. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.

  2. Titan's Isotopic Menagerie: The Cassini CIRS Perspective

    Science.gov (United States)

    Nixon, Conor A.; Achterberg, R. K.; Bezard, B.; Bjoraker, G. L.; Coustenis, A.; de Kok, R.; Flasar, F. M.; Hewagama, T.; Irwin, P. G. J.; Jennings, D. E.; Jolly, A.; Romani, P. N.; Teanby, N. A.; Vinatier, S.; CIRS Team

    2008-09-01

    Saturn's long-mysterious moon Titan is gradually yielding up its secrets under the intense scrutiny of the Cassini spacecraft, which has just completed a 4-year prime mission including 45 close flybys of the giant satellite. We here focus on the isotopic composition of the stratosphere, which since Voyager 1 in 1980 has been known to comprise a surprisingly rich mixture of hydrocarbons, nitriles and several oxygen species. These molecules are now understood to originate in the upper atmosphere by chemical processes initiated by the dissociation of the most abundant native species - methane and nitrogen - with some oxygen added from externally-supplied water. Measurements of isotopic ratios in these compounds are important and can provide valuable information on the formation and evolution of Titan's atmosphere. E.g. Chemical processes can cause isotopic fractionation via the 'kinetic isotope effect' (KIE). Cassini's Composite Infrared Spectrometer (CIRS), which is sensitive to thermal infrared radiation from 10-1500 cm-1 (7-1000 micron), is an ideal tool for measuring molecular concentrations and can distinguish between isotopologues due to the shifts in the molecular bands. CIRS has now identified at least eleven isotopologue species in our spectra, with multiple new detections in the past year (13CO2, CO18O, HC13CCCN). CIRS has measured the ratios 12C/13C in a total of seven species, D/H in two species, and 14N/15N and 16O/18O each in one species - the best measurement so far of the important ratio 16O/18O on Titan (346±110). In this presentation we will summarize all our results to date on isotopic ratios, including comparison with Huygens GCMS and other determinations, a discussion of possible isotopic separation in hydrocarbon chains, and formation/evolution implications of these measurements for Titan.

  3. 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

    .1 ± 0.8‰; ε18O, −23.7 ± 1.8‰ to −19.9 ± 0.8‰). The observed isotope effects did not depend on the growth kinetics which were similar for the three types of electron donors. We suggest that different carbon sources change the observed isotope enrichment factors by changing the relative kinetics...... of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification....

  4. Intracellular Cadmium Isotope Fractionation

    Science.gov (United States)

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

    2011-12-01

    Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

  5. Quantifying human vitamin kinetics using AMS

    Energy Technology Data Exchange (ETDEWEB)

    Hillegonds, D; Dueker, S; Ognibene, T; Buchholz, B; Lin, Y; Vogel, J; Clifford, A

    2004-02-19

    Tracing vitamin kinetics at physiologic concentrations has been hampered by a lack of quantitative sensitivity for chemically equivalent tracers that could be used safely in healthy people. Instead, elderly or ill volunteers were sought for studies involving pharmacologic doses with radioisotopic labels. These studies fail to be relevant in two ways: vitamins are inherently micronutrients, whose biochemical paths are saturated and distorted by pharmacological doses; and while vitamins remain important for health in the elderly or ill, their greatest effects may be in preventing slow and cumulative diseases by proper consumption throughout youth and adulthood. Neither the target dose nor the target population are available for nutrient metabolic studies through decay counting of radioisotopes at high levels. Stable isotopic labels are quantified by isotope ratio mass spectrometry at levels that trace physiologic vitamin doses, but the natural background of stable isotopes severely limits the time span over which the tracer is distinguishable. Indeed, study periods seldom ranged over a single biological mean life of the labeled nutrients, failing to provide data on the important final elimination phase of the compound. Kinetic data for the absorption phase is similarly rare in micronutrient research because the phase is rapid, requiring many consecutive plasma samples for accurate representation. However, repeated blood samples of sufficient volume for precise stable or radio-isotope quantitations consume an indefensible amount of the volunteer's blood over a short period. Thus, vitamin pharmacokinetics in humans has often relied on compartmental modeling based upon assumptions and tested only for the short period of maximal blood circulation, a period that poorly reflects absorption or final elimination kinetics except for the most simple models.

  6. 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 vibration frequencies, the mobility of H+/D+ carriers, the kinetics of the electrochemical oxidation of H2/D2, the solubilities of H2O/D2O and, finally, the spontaneous electromotive force that appears across H2/D2 cells with proton conducting electrolytes. Comparable work on tritium-exchanged materials...... is also discussed. The results highlight the usefulness of isotope effects in the study of high temperature proton conductors....

  7. Hydrogen isotope separation by multiple photodissociation of dichlorofluoromethane

    Energy Technology Data Exchange (ETDEWEB)

    Arisawa, T.; Kato, M.; Maruyama, Y.; Shiba, K. (Japan Atomic Energy Research Inst., Tokai, Ibaraki. Tokai Research Establishment)

    1982-06-14

    Multiple photodissociation rates of dichlorofluoromethane were measured from the dissociated products and/or the residual gases which escaped dissociation. It is shown that the relationship between the separation factor for the hydrogen isotopes in the residual gases and that in the products is in good agreement with theory. It is also verified that hydrogen isotope separation is influenced by the chlorine isotopes contained in the molecules. The experimental data obtained are compared with the theoretical dissociation model including two-sets of kinetic equations in which energy exchanges between two kinds of isotopic molecules are considered. This gives a good explanation for the dependence of the dissociation rate on the laser intensity and pressure, and the pressure dependence of the separation factor.

  8. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    Science.gov (United States)

    Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

    1986-01-01

    The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

  9. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    Science.gov (United States)

    Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

    1986-01-01

    The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

  10. Chromium isotope variations

    DEFF Research Database (Denmark)

    D'Arcy, Joan Mary

    is incorporated into carbonates. Hence, ancient carbonates can potentially record the Cr isotopic composition (δ53Cr ‰) of seawater in the geological past. Reliable application and interpretation of this proxy requires a detailed knowledge about processes that fractionate Cr on the Earth’s surface...... deposited during the Early Ordovician — a time of known redox instability in ancient oceans – exhibit a significant positive Cr isotope excursion of +0.5‰. This excursion is interpreted as the reductive drawn down of dissolved Cr in seawater in response to the development of a proximal anoxic sink......, and the quantification the Cr isotope composition of major Cr fluxes into and out of ocean. This thesis adds to the current knowledge of the Cr isotope system and is divided into two studies. The focus of the first study was to determine what processes control the Cr isotopic compositionof river water and to quantify...

  11. Isotopes in Greenland Precipitation

    DEFF Research Database (Denmark)

    Faber, Anne-Katrine

    Greenland ice cores offer a unique opportunity to investigate the climate system behaviour. The objective of this PhD project is to investigate isotope modelling of present- day conditions and conduct model-data comparison using Greenland ice cores. Thus this thesis investigates how the integration...... of model and data can be used to improve the understanding of climate changes. This is done through analysis of isotope modelling, observations and ice core measurements. This dissertation comprises three projects: (1) Modelling the isotopic response to changes in Arctic sea surface conditions, (2......) Constructing a new Greenland database of observations and present-day ice core measurements, and (3) Performance test of isotope-enabled CAM5 for Greenland. The recent decades of rapid Arctic sea ice decline are used as a basis for an observational-based model experiment using the isotope-enabled CAM model 3...

  12. Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

    Science.gov (United States)

    Boshers, D.; Granger, J.; Bohlke, J. K.

    2016-12-01

    Measurements of the naturally occurring nitrogen and oxygen stable isotope ratios of nitrate (NO3-), δ15N and δ18O, can be used to determine the source, dispersal, and fate of natural and contaminant NO3- in aquatic environments. To this end, it is necessary to know the extent to which NO3- isotopologues are modified by biological reactions, as heavy and light isotopes have different reaction rates. The purpose of this study was to determine the influence of the δ18O of ambient water on the isotope composition of NO3- produced during nitrification, the biological oxidation of ammonium (NH4+) to nitrite (NO2-) and then NO3-, which is poorly constrained in freshwater systems. To determine the δ18O of NO3- produced by nitrification in freshwater, we collected water from a stream in New England, which we amended with NH4+ and with increments of 18O-enriched water, to monitor the isotope composition of NO3- produced by a natural consortium of nitrifiers. Added NH4+ was completely oxidized to NO3- over 26 days. The final δ18O of nitrified NO3- revealed sensitivity to the δ18O of water mediated by (a) isotopic equilibration between water and NO2- and (b) kinetic isotope fractionation during O-atom incorporation from water into NO2- and NO3-. Our results concur with nitrifying culture experiments that have demonstrated analogous sensitivity of the δ18O of nitrified NO3- to equilibrium and kinetic O isotope effects (Buchwald et al. 2012), as well as show that these dynamics need to be considered to interpret NO3- isotope distribution in freshwater environments.

  13. 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.

  14. 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.

  15. Silicon Isotopic Fractionation of CAI-like Vacuum Evaporation Residues

    Energy Technology Data Exchange (ETDEWEB)

    Knight, K; Kita, N; Mendybaev, R; Richter, F; Davis, A; Valley, J

    2009-06-18

    Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquids (Richter et al., 2002, 2007a). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, {alpha}{sub Si}, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that {alpha}{sub Si} = 0.98985 {+-} 0.00044 (2{sigma}) for {sup 29}Si/{sup 28}Si with no resolvable variation with temperature over the temperature range of the experiments, 1600-1900 C. This value is different from what has been reported for evaporation of liquid Mg{sub 2}SiO{sub 4} (Davis et al., 1990) and of a melt with CI chondritic proportions of the major elements (Wang et al., 2001). There appears to be some compositional control on {alpha}{sub Si}, whereas no compositional effects have been reported for {alpha}{sub Mg}. We use the values of {alpha}Si and {alpha}Mg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites whose

  16. A Review of Mg Isotope Analytical Methods by MC-ICP-MS

    Institute of Scientific and Technical Information of China (English)

    Yajun An; Fang Huang

    2014-01-01

    Application of multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has led to big breakthrough of analytical methods for metal stable isotopes, resulting in rapid progresses in non-traditional stable isotope geochemistry. As a new geological tracer, Mg isotopes have been widely applied in studies of almost all important disciplines of geochemistry. High precision Mg isotope data measured by MC-ICP-MS are now available with precision about 0.05‰ amu-1 (2SD) or better. Because mass bias caused by chemical procedure and instrument can easily cause significant analytical error, it is still a challenge to obtain accurate Mg isotope data for natural samples. In this paper, we systematically review the development of analytical technique of Mg isotopes, with a detailed description of a series of important techniques used in the measurement process, including calibration of instrumental mass-bias, chemical purification process, matrix effect, and pitfalls for high precision isotope analyses. We compare standard data from different labs and establish a guideline for Mg iso-tope analysis procedure. Additionally, we briefly discuss the behaviors of Mg isotopes during geological processes including equilibrium and kinetic Mg isotope fractionations, such as magma differentiation, chemical and thermal diffusion, and continental weathering. Finally, we propose some future prospects for Mg isotope geochemistry in both high and low temperature geological processes.

  17. Evolution of E. coli on [U-13C] Glucose Reveals a Negligible Isotopic Influence on Metabolism and Physiology

    DEFF Research Database (Denmark)

    Sandberg, Troy E.; Long, Christopher P.; Gonzalez, Jacqueline E.

    2016-01-01

    13C-Metabolic flux analysis (13C-MFA) traditionally assumes that kinetic isotope effects from isotopically labeled compounds do not appreciably alter cellular growth or metabolism, despite indications that some biochemical reactions can be non-negligibly impacted. Here, populations of Escherichia...

  18. Medical applications of Cu, Zn, and S isotope effects.

    Science.gov (United States)

    Albarede, Francis; Télouk, Philippe; Balter, Vincent; Bondanese, Victor P; Albalat, Emmanuelle; Oger, Philippe; Bonaventura, Paola; Miossec, Pierre; Fujii, Toshiyuki

    2016-10-01

    This review examines recent applications of stable copper, zinc and sulfur isotopes to medical cases and notably cancer. The distribution of the natural stable isotopes of a particular element among coexisting molecular species varies as a function of the bond strength, the ionic charge, and the coordination, and it also changes with kinetics. Ab initio calculations show that compounds in which a metal binds to oxygen- (sulfate, phosphate, lactate) and nitrogen-bearing moieties (histidine) favor heavy isotopes, whereas bonds with sulfur (cysteine, methionine) favor light isotopes. Oxidized cations (e.g., Cu(ii)) and low coordination numbers are expected to favor heavy isotopes relative to their reduced counterparts (Cu(i)) and high coordination numbers. Here we discuss the first observations of Cu, Zn, and S isotopic variations, three elements closely related along multiple biological pathways, with emphasis on serum samples of healthy volunteers and of cancer patients. It was found that heavy isotopes of Zn and to an even greater extent Cu are enriched in erythrocytes relative to serum, while the difference is small for sulfur. Isotopic variations related to age and sex are relatively small. The (65)Cu/(63)Cu ratio in the serum of patients with colon, breast, and liver cancer is conspicuously low relative to healthy subjects. The characteristic time over which Cu isotopes may change with disease progression (a few weeks) is consistent with both the turnover time of the element and albumin half-life. A parallel effect on sulfur isotopes is detected in a few un-medicated patients. Copper in liver tumor tissue is isotopically heavy. In contrast, Zn in breast cancer tumors is isotopically lighter than in healthy breast tissue. (66)Zn/(64)Zn is very similar in the serum of cancer patients and in controls. Possible reasons for Cu isotope variations may be related to the cytosolic storage of Cu lactate (Warburg effect), release of intracellular copper from cysteine

  19. Strong Exchange Anisotropy in Heavy Atom Radical Ferromagnets

    Science.gov (United States)

    Winter, Stephen

    2012-02-01

    The discovery twenty years ago of ferromagnetic ordering in ``light atom'' p-block (N, O based) radicals appeared to provide a major conceptual advance, suggesting the possibility of a new era in non-metal molecular magnetism. However, the weak through-space magnetic exchange interactions present in these early radical-based ferromagnets afforded very low Curie temperatures TC (JACS 130, 8414-8425 (2008), JACS 133, 8126-8129 (2011).

  20. Collisional Cooling of Light Ions by Cotrapped Heavy Atoms.

    Science.gov (United States)

    Dutta, Sourav; Sawant, Rahul; Rangwala, S A

    2017-03-17

    We experimentally demonstrate cooling of trapped ions by collisions with cotrapped, higher-mass neutral atoms. It is shown that the lighter ^{39}K^{+} ions, created by ionizing ^{39}K atoms in a magneto-optical trap (MOT), when trapped in an ion trap and subsequently allowed to cool by collisions with ultracold, heavier ^{85}Rb atoms in a MOT, exhibit a longer trap lifetime than without the localized ^{85}Rb MOT atoms. A similar cooling of trapped ^{85}Rb^{+} ions by ultracold ^{133}Cs atoms in a MOT is also demonstrated in a different experimental configuration to validate this mechanism of ion cooling by localized and centered ultracold neutral atoms. Our results suggest that the cooling of ions by localized cold atoms holds for any mass ratio, thereby enabling studies on a wider class of atom-ion systems irrespective of their masses.

  1. Isotopes in Greenland Precipitation

    DEFF Research Database (Denmark)

    Faber, Anne-Katrine

    the Arctic Ocean. A comprehensive database is created based on ice core and weather station data from Greenland within the period 1890-2014. Present day annual and seasonal mean values are computed for 326 locations in Greenland. Parameterization of the spatial distribution of temperature and δ18O are used...... of model and data can be used to improve the understanding of climate changes. This is done through analysis of isotope modelling, observations and ice core measurements. This dissertation comprises three projects: (1) Modelling the isotopic response to changes in Arctic sea surface conditions, (2......) Constructing a new Greenland database of observations and present-day ice core measurements, and (3) Performance test of isotope-enabled CAM5 for Greenland. The recent decades of rapid Arctic sea ice decline are used as a basis for an observational-based model experiment using the isotope-enabled CAM model 3...

  2. Perchlorate isotope forensics

    Science.gov (United States)

    Böhlke, J.K.; Sturchio, N.C.; Gu, B.; Horita, J.; Brown, G.M.; Jackson, W.A.; Batista, J.; Hatzinger, P.B.

    2005-01-01

    Perchlorate has been detected recently in a variety of soils, waters, plants, and food products at levels that may be detrimental to human health. These discoveries have generated considerable interest in perchlorate source identification. In this study, comprehensive stable isotope analyses ( 37Cl/35Cl and 18O/17O/ 16O) of perchlorate from known synthetic and natural sources reveal systematic differences in isotopic characteristics that are related to the formation mechanisms. In addition, isotopic analyses of perchlorate extracted from groundwater and surface water demonstrate the feasibility of identifying perchlorate sources in contaminated environments on the basis of this technique. Both natural and synthetic sources of perchlorate have been identified in water samples from some perchlorate occurrences in the United States by the isotopic method. ?? 2005 American Chemical Society.

  3. Isotope Production Facility (IPF)

    Data.gov (United States)

    Federal Laboratory Consortium — The Los Alamos National Laboratory has produced radioactive isotopes for medicine and research since the mid 1970s, when targets were first irradiated using the 800...

  4. Calcium stable isotope geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Gausonne, Nikolaus [Muenster Univ. (Germany). Inst. fuer Mineralogie; Schmitt, Anne-Desiree [Strasbourg Univ. (France). LHyGeS/EOST; Heuser, Alexander [Bonn Univ. (Germany). Steinmann-Inst. fuer Geologie, Mineralogie und Palaeontologie; Wombacher, Frank [Koeln Univ. (Germany). Inst. fuer Geologie und Mineralogie; Dietzel, Martin [Technische Univ. Graz (Austria). Inst. fuer Angewandte Geowissenschaften; Tipper, Edward [Cambridge Univ. (United Kingdom). Dept. of Earth Sciences; Schiller, Martin [Copenhagen Univ. (Denmark). Natural History Museum of Denmark

    2016-08-01

    This book provides an overview of the fundamentals and reference values for Ca stable isotope research, as well as current analytical methodologies including detailed instructions for sample preparation and isotope analysis. As such, it introduces readers to the different fields of application, including low-temperature mineral precipitation and biomineralisation, Earth surface processes and global cycling, high-temperature processes and cosmochemistry, and lastly human studies and biomedical applications. The current state of the art in these major areas is discussed, and open questions and possible future directions are identified. In terms of its depth and coverage, the current work extends and complements the previous reviews of Ca stable isotope geochemistry, addressing the needs of graduate students and advanced researchers who want to familiarize themselves with Ca stable isotope research.

  5. Isotopically controlled semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Haller, E.E.

    2004-11-15

    A review of recent research involving isotopically controlled semiconductors is presented. Studies with isotopically enriched semiconductor structures experienced a dramatic expansion at the end of the Cold War when significant quantities of enriched isotopes of elements forming semiconductors became available for worldwide collaborations. Isotopes of an element differ in nuclear mass, may have different nuclear spins and undergo different nuclear reactions. Among the latter, the capture of thermal neutrons which can lead to neutron transmutation doping, can be considered the most important one for semiconductors. Experimental and theoretical research exploiting the differences in all the properties has been conducted and will be illustrated with selected examples. Manuel Cardona, the longtime editor-in-chief of Solid State Communications has been and continues to be one of the major contributors to this field of solid state physics and it is a great pleasure to dedicate this review to him.

  6. Isotopes through the looking glass

    Science.gov (United States)

    Mårtensson Pendrill, Ann Marie

    2000-08-01

    Nuclear distributions affect many aspects of atomic spectra. As an example, recent experimental results for the hyperfine anomaly in Fr isotopes are considered. These depend on nuclear charge and magnetization distributions. The variations in charge radii for these isotopes were studied earlier by measuring optical isotope shifts. The hyperfine anomalies for the odd-odd isotopes involve the neutron distributions, of interest for studies of parity nonconserving effects along a chain of isotopes.

  7. Non-Isothermal Kinetics.

    Science.gov (United States)

    Brown, M. E.; Phillpotts, C. A. R.

    1978-01-01

    Discusses the principle of nonisothermal kinetics and some of the factors involved in such reactions, especially when considering the reliability of the kinetic parameters, compared to those of isothermal conditions. (GA)

  8. Methods of isotopic geochronology

    Science.gov (United States)

    Gorokhov, I. M.; Levchenkov, O. A.

    Papers are presented on such topics as the age of the chemical elements; the age of meteorites, the moon, and the earth; isotopic ages of the most ancient terrestrial formations; and the Archean evolution of Enderby Land in the Antarctic as evidenced by isotopic dating. Consideration is also given to a uranium-lead geochronology technique for investigating Precambrian ore deposits, a Pb-Pb technique of zircon dating, and the potentials and limitations of Sm-Nd geochronology.

  9. Oxygen Isotopes in Meteorites

    Science.gov (United States)

    Clayton, R. N.

    2003-12-01

    Oxygen isotope abundance variations in meteorites are very useful in elucidating chemical and physical processes that occurred during the formation of the solar system (Clayton, 1993). On Earth, the mean abundances of the three stable isotopes are 16O: 99.76%, 17O: 0.039%, and 18O: 0.202%. It is conventional to express variations in abundances of the isotopes in terms of isotopic ratios, relative to an arbitrary standard, called SMOW (for standard mean ocean water), as follows:The isotopic composition of any sample can then be represented by one point on a "three-isotope plot," a graph of δ17O versus δ18O. It will be seen that such plots are invaluable in interpreting meteoritic data. Figure 1 shows schematically the effect of various processes on an initial composition at the center of the diagram. Almost all terrestrial materials lie along a "fractionation" trend; most meteoritic materials lie near a line of "16O addition" (or subtraction). (4K)Figure 1. Schematic representation of various isotopic processes shown on an oxygen three-isotope plot. Almost all terrestrial materials plot along a line of "fractionation"; most primitive meteoritic materials plot near a line of "16O addition." The three isotopes of oxygen are produced by nucleosynthesis in stars, but by different nuclear processes in different stellar environments. The principal isotope, 16O, is a primary isotope (capable of being produced from hydrogen and helium alone), formed in massive stars (>10 solar masses), and ejected by supernova explosions. The two rare isotopes are secondary nuclei (produced in stars from nuclei formed in an earlier generation of stars), with 17O coming primarily from low- and intermediate-mass stars (shielding in the UV photodissociation of CO (van Dishoeck and Black, 1988). This process results from the large differences in abundance between C16O, on the one hand, and C17O and C18O on the other. Photolysis of CO occurs by absorption of stellar UV radiation in the

  10. Degradation and Isotope Source Tracking of Glyphosate and Aminomethylphosphonic Acid.

    Science.gov (United States)

    Li, Hui; Joshi, Sunendra R; Jaisi, Deb P

    2016-01-27

    Glyphosate [N-(phosphonomethyl) glycine], an active ingredient of the herbicide Roundup, and its main metabolite, aminomethylphosphonic acid (AMPA), have been frequently reported to be present in soils and other environments and thus have heightened public concerns on their potential adverse effects. Understanding the fate of these compounds and differentiating them from other naturally occurring compounds require a toolbox of methods that can go beyond conventional methods. Here, we applied individual isotope labeling technique whereby each compound or mineral involved in the glyphosate and AMPA degradation reaction was either synthesized or chosen to have distinct (18)O/(16)O ratios so that the source of incorporated oxygen in the orthophosphate generated and corresponding isotope effect during C-P bond cleavage could be identified. Furthermore, we measured original isotope signatures of a few commercial glyphosate sources to identify their source-specific isotope signatures. Our degradation kinetics results showed that the rate of glyphosate degradation was higher than that of AMPA in all experimental conditions, and both the rate and extent of degradation were lowest under anoxic conditions. Oxygen isotope ratios (δ(18)OP) of orthophosphate generated from glyphosate and AMPA degradation suggested that one external oxygen atom from ambient water, not from dissolved oxygen or mineral, was incorporated into orthophosphate with the other three oxygen atoms inherited from the parent molecule. Interestingly, δ(18)OP values of all commercial glyphosate products studied were found to be the lightest among all orthophosphates known so far. Furthermore, isotope composition was found to be unaffected due to variable degradation kinetics, light/dark, and oxic/anoxic conditions. These results highlight the importance of phosphate oxygen isotope ratios as a nonconventional tool to potentially distinguish glyphosate sources and products from other organophosphorus compounds

  11. Unbiased isotope equilibrium factors from partial isotope exchange experiments in 3-exchange site systems

    Science.gov (United States)

    Agrinier, Pierre; Javoy, Marc

    2016-09-01

    Two methods are available in order to evaluate the equilibrium isotope fractionation factors between exchange sites or phases from partial isotope exchange experiments. The first one developed by Northrop and Clayton (1966) is designed for isotope exchanges between two exchange sites (hereafter, the N&C method), the second one from Zheng et al. (1994) is a refinement of the first one to account for a third isotope exchanging site (hereafter, the Z method). In this paper, we use a simple model of isotope kinetic exchange for a 3-exchange site system (such as hydroxysilicates where oxygen occurs as OH and non-OH groups like in muscovite, chlorite, serpentine, or water or calcite) to explore the behavior of the N&C and Z methods. We show that these two methods lead to significant biases that cannot be detected with the usual graphical tests proposed by the authors. Our model shows that biases originate because isotopes are fractionated between all these exchanging sites. Actually, we point out that the variable mobility (or exchangeability) of isotopes in and between the exchange sites only controls the amplitude of the bias, but is not essential to the production of this bias as previously suggested. Setting a priori two of the three exchange sites at isotopic equilibrium remove the bias and thus is required for future partial exchange experiments to produce accurate and unbiased extrapolated equilibrium fractionation factors. Our modeling applied to published partial oxygen isotope exchange experiments for 3-exchange site systems (the muscovite-calcite (Chacko et al., 1996), the chlorite-water (Cole and Ripley, 1998) and the serpentine-water (Saccocia et al., 2009)) shows that the extrapolated equilibrium fractionation factors (reported as 1000 ln(α)) using either the N&C or the Z methods lead to bias that may reach several δ per mil in a few cases. These problematic cases, may be because experiments were conducted at low temperature and did not reach high

  12. Methods of nonlinear kinetics

    OpenAIRE

    Gorban, A. N.; Karlin, I.V.

    2003-01-01

    Nonlinear kinetic equations are reviewed for a wide audience of specialists and postgraduate students in physics, mathematical physics, material science, chemical engineering and interdisciplinary research. Contents: The Boltzmann equation, Phenomenology and Quasi-chemical representation of the Boltzmann equation, Kinetic models, Discrete velocity models, Direct simulation, Lattice Gas and Lattice Boltzmann models, Minimal Boltzmann models for flows at low Knudsen number, Other kinetic equati...

  13. Stable isotopes in atmospheric water vapor and applications to the hydrologic cycle

    Science.gov (United States)

    Galewsky, Joseph; Steen-Larsen, Hans Christian; Field, Robert D.; Worden, John; Risi, Camille; Schneider, Matthias

    2016-12-01

    The measurement and simulation of water vapor isotopic composition has matured rapidly over the last decade, with long-term data sets and comprehensive modeling capabilities now available. Theories for water vapor isotopic composition have been developed by extending the theories that have been used for the isotopic composition of precipitation to include a more nuanced understanding of evaporation, large-scale mixing, deep convection, and kinetic fractionation. The technologies for in situ and remote sensing measurements of water vapor isotopic composition have developed especially rapidly over the last decade, with discrete water vapor sampling methods, based on mass spectroscopy, giving way to laser spectroscopic methods and satellite- and ground-based infrared absorption techniques. The simulation of water vapor isotopic composition has evolved from General Circulation Model (GCM) methods for simulating precipitation isotopic composition to sophisticated isotope-enabled microphysics schemes using higher-order moments for water and ice size distributions. The incorporation of isotopes into GCMs has enabled more detailed diagnostics of the water cycle and has led to improvements in its simulation. The combination of improved measurement and modeling of water vapor isotopic composition opens the door to new advances in our understanding of the atmospheric water cycle, in processes ranging from the marine boundary layer, through deep convection and tropospheric mixing, and into the water cycle of the stratosphere. Finally, studies of the processes governing modern water vapor isotopic composition provide an improved framework for the interpretation of paleoclimate proxy records of the hydrological cycle.

  14. Isotopic Fingerprint for Phosphorus in Drinking Water Supplies.

    Science.gov (United States)

    Gooddy, Daren C; Lapworth, Dan J; Ascott, Matthew J; Bennett, Sarah A; Heaton, Timothy H E; Surridge, Ben W J

    2015-08-01

    Phosphate dosing of drinking water supplies, coupled with leakage from distribution networks, represents a significant input of phosphorus to the environment. The oxygen isotope composition of phosphate (δ(18)OPO4), a novel stable isotope tracer for phosphorus, offers new opportunities to understand the importance of phosphorus derived from sources such as drinking water. We report the first assessment of δ(18)OPO4 within drinking water supplies. A total of 40 samples from phosphate-dosed distribution networks were analyzed from across England and Wales. In addition, samples of the source orthophosphoric acid used for dosing were also analyzed. Two distinct isotopic signatures for drinking water were identified (average = +13.2 or +19.7‰), primarily determined by δ(18)OPO4 of the source acid (average = +12.4 or +19.7‰). Dependent upon the source acid used, drinking water δ(18)OPO4 appears isotopically distinct from a number of other phosphorus sources. Isotopic offsets from the source acid ranging from -0.9 to +2.8‰ were observed. There was little evidence that equilibrium isotope fractionation dominated within the networks, with offsets from temperature-dependent equilibrium ranging from -4.8 to +4.2‰. While partial equilibrium fractionation may have occurred, kinetic effects associated with microbial uptake of phosphorus or abiotic sorption and dissolution reactions may also contribute to δ(18)OPO4 within drinking water supplies.

  15. Magnetic field, additive and structural effects on the decay kinetics of micellized triplet radical pairs. Role of diffusion, spin-orbit coupling and paramagnetic relaxation

    Science.gov (United States)

    Levin, P. P.; Kuzmin, V. A.

    1992-05-01

    The geminate recombination kinetics of the radical pairs produced by quenching of the triplet aromatic ketones or quinones by 4-phenylphenol and 4-phenylaniline in aqueous micellar solutions of sodium alkyl sulfates in the presence of additives (ethanol, NaCl, bromo- and iodobenzenes, paramagnetic species) has been examined using the laser flash technique. The recombination rates increase as the micellar size in decreased. Application of an external magnetic field (0.45 T) results in the retardation of geminate recombination up to 25 times. The magnetic field effect is quenched by internal or even external heavy atoms as well as by paramagnetic species, including 3O 2. The magnetic field dependences and attendant regularities are considered in terms of a simple kinetic scheme, in which the singlet-triplet evolution in the separated states of a pair due to hyperfine coupling and relaxation mechanisms, as well as intersystem recombination due to the spin-orbit coupling in the contact states of a pair, are included as first-order processes. The corresponding kinetic parameters of the different pathways involved are also discussed.

  16. New short-lived isotope 223Np and the absence of the Z = 92 subshell closure near N = 126

    Science.gov (United States)

    Sun, M. D.; Liu, Z.; Huang, T. H.; Zhang, W. Q.; Wang, J. G.; Liu, X. Y.; Ding, B.; Gan, Z. G.; Ma, L.; Yang, H. B.; Zhang, Z. Y.; Yu, L.; Jiang, J.; Wang, K. L.; Wang, Y. S.; Liu, M. L.; Li, Z. H.; Li, J.; Wang, X.; Lu, H. Y.; Lin, C. J.; Sun, L. J.; Ma, N. R.; Yuan, C. X.; Zuo, W.; Xu, H. S.; Zhou, X. H.; Xiao, G. Q.; Qi, C.; Zhang, F. S.

    2017-08-01

    The N = 130 short-lived isotope 223Np was produced as evaporation residue (ER) in the fusion reaction 40Ar + 187Re at the gas-filled recoil separator Spectrometer for Heavy Atom and Nuclear Structure (SHANS). It was identified through temporal and spatial correlations with α decays of 215Ac and/or 211Fr, the third and fourth members of the α-decay chain starting from 223Np. The pileup signals of ER(223Np)-α(223Np)-α(219Pa) were resolved by using the digital pulse processing technique. An α decay with half-life of T1/2 = 2.15 (10052) μs and energy of Eα = 9477 (44) keV was attributed to 223Np. Spin and parity of 9 /2- were tentatively proposed for the ground state of 223Np by combining the reduced α-decay width and large-scale shell-model calculations. This assignment together with the proton separation energy disprove the existence of a Z = 92 subshell closure.

  17. Probing the metabolic network in bloodstream-form Trypanosoma brucei using untargeted metabolomics with stable isotope labelled glucose.

    Directory of Open Access Journals (Sweden)

    Darren J Creek

    2015-03-01

    Full Text Available Metabolomics coupled with heavy-atom isotope-labelled glucose has been used to probe the metabolic pathways active in cultured bloodstream form trypomastigotes of Trypanosoma brucei, a parasite responsible for human African trypanosomiasis. Glucose enters many branches of metabolism beyond glycolysis, which has been widely held to be the sole route of glucose metabolism. Whilst pyruvate is the major end-product of glucose catabolism, its transamination product, alanine, is also produced in significant quantities. The oxidative branch of the pentose phosphate pathway is operative, although the non-oxidative branch is not. Ribose 5-phosphate generated through this pathway distributes widely into nucleotide synthesis and other branches of metabolism. Acetate, derived from glucose, is found associated with a range of acetylated amino acids and, to a lesser extent, fatty acids; while labelled glycerol is found in many glycerophospholipids. Glucose also enters inositol and several sugar nucleotides that serve as precursors to macromolecule biosynthesis. Although a Krebs cycle is not operative, malate, fumarate and succinate, primarily labelled in three carbons, were present, indicating an origin from phosphoenolpyruvate via oxaloacetate. Interestingly, the enzyme responsible for conversion of phosphoenolpyruvate to oxaloacetate, phosphoenolpyruvate carboxykinase, was shown to be essential to the bloodstream form trypanosomes, as demonstrated by the lethal phenotype induced by RNAi-mediated downregulation of its expression. In addition, glucose derivatives enter pyrimidine biosynthesis via oxaloacetate as a precursor to aspartate and orotate.

  18. Investigation of Stable C and Cl Isotope Effects of Trichloroethene and Tetrachloroethylene during Evaporation at Different Temperatures

    Institute of Scientific and Technical Information of China (English)

    Tingting Yu; Yiqun Gan; Aiguo Zhou; Kai Yu; Yunde Liu

    2014-01-01

    There are variations of reported isotope enrichment factors of chlorinated organic contaminants in evaporation processes. Trichloroethene (TCE) and tetrachloroethylene (PCE) were chosen to study carbon and chlorine isotope effects during evaporation at different temperatures. Equilibrium vapor-liquid carbon and chlorine isotope effects experiments were also conducted. In the equilibrium liquid-vapor system, the 13C was enriched but 37Cl was depleted in the vapor phase, being consistent with previous results. For evaporation average carbon isotope enrichment factor εC were +0.28‰± 0.01‰ for TCE and +0.56‰±0.09‰ for PCE at temperature from 20 to 26 ºC. Meanwhile, average chlorine isotope enrichment factor εCl were -1.33‰±0.21‰ for TCE and -1.00‰±0.00‰ for PCE. The results indicate that during evaporation the equilibrium isotope effect attenuates the magnitude of carbon isotope fractionation whereas enhances the chlorine isotope effect. Isotope fractionation during evaporation is determined by both equilibrium and kinetic factors. Chlorine isotope fractionation is influenced by the evaporation rate which is linked to temperature. When using stable isotope to investigate the behavior of chlorinated organic contaminants in groundwater with slow biodegradation rate, the isotope fractionation resulted from evaporation should be taken into consideration. Furthermore, the environment conditions such as temperature are also factors to be considered.

  19. Isotope geochemistry. Biological signatures in clumped isotopes of O₂.

    Science.gov (United States)

    Yeung, Laurence Y; Ash, Jeanine L; Young, Edward D

    2015-04-24

    The abundances of molecules containing more than one rare isotope have been applied broadly to determine formation temperatures of natural materials. These applications of "clumped" isotopes rely on the assumption that isotope-exchange equilibrium is reached, or at least approached, during the formation of those materials. In a closed-system terrarium experiment, we demonstrate that biological oxygen (O2) cycling drives the clumped-isotope composition of O2 away from isotopic equilibrium. Our model of the system suggests that unique biological signatures are present in clumped isotopes of O2—and not formation temperatures. Photosynthetic O2 is depleted in (18)O(18)O and (17)O(18)O relative to a stochastic distribution of isotopes, unlike at equilibrium, where heavy-isotope pairs are enriched. Similar signatures may be widespread in nature, offering new tracers of biological and geochemical cycling.

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

    Science.gov (United States)

    Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan A.; Wang, David T.; Johnson, Matthew S.; Ono, Shuhei

    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 produced from the reaction of O(1D) (from O3 photolysis) with H2O, and Cl was from photolysis of Cl2. Samples were taken from the reaction cell and analyzed for methane (12CH4, 12CH3D, 13CH4, 13CH3D) isotopologue ratios using tunable infrared laser direct absorption spectroscopy. Measured kinetic isotope 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). The deviation from this relationship is 0.3‰ ± 1.2‰ and 3.5‰ ± 0.7‰ for OH and Cl oxidation, respectively. This is consistent with model calculations performed using quantum chemistry and transition state theory. The OH and Cl reactions enrich the residual methane in the clumped isotopologue in open system 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, will only have a minor (∼0.3‰) impact on the clumped isotope signature (Δ13CH3D, measured as a deviation from a stochastic distribution of isotopes) of tropospheric methane. This paper shows that Δ13CH3D will provide constraints on methane source strengths, and predicts that Δ12CH2D2 can provide information on methane sink strengths.

  1. Stable isotopes. Applications and production; Les isotopes stables. Applications - production

    Energy Technology Data Exchange (ETDEWEB)

    Goldstein, S.; Louvet, P.; Soulie, E. [eds.

    1994-12-31

    This conference presents 46 communications concerning stable isotope production, utilization and application, grouped in 6 sessions and posters. The various themes are: biological applications (pharmacology, medical diagnosis, metabolism and protein studies, toxicity and response studies, labelled compounds), analysis procedures (NMR analysis for macromolecules, tracer studies), nuclear applications (utilization of stable isotopes in nuclear reactors), biological, physical and chemical applications (mass transfer, mobility, crystallography, isotopic exchange), stable isotope production (ion chromatography, ion cyclotron resonance, cryogenic distillation).

  2. Origin of uranium isotope variations in early solar nebula condensates.

    Science.gov (United States)

    Tissot, François L H; Dauphas, Nicolas; Grossman, Lawrence

    2016-03-01

    High-temperature condensates found in meteorites display uranium isotopic variations ((235)U/(238)U), which complicate dating the solar system's formation and whose origin remains mysterious. It is possible that these variations are due to the decay of the short-lived radionuclide (247)Cm (t 1/2 = 15.6 My) into (235)U, but they could also be due to uranium kinetic isotopic fractionation during condensation. We report uranium isotope measurements of meteoritic refractory inclusions that reveal excesses of (235)U reaching ~+6% relative to average solar system composition, which can only be due to the decay of (247)Cm. This allows us to constrain the (247)Cm/(235)U ratio at solar system formation to (1.1 ± 0.3) × 10(-4). This value provides new clues on the universality of the nucleosynthetic r-process of rapid neutron capture.

  3. Origin of uranium isotope variations in early solar nebula condensates

    CERN Document Server

    Tissot, Francois L H; Grossman, Lawrence

    2016-01-01

    High temperature condensates found in meteorites display uranium isotopic variations (235U/238U) that complicate dating of the formation of the Solar System and whose origin remains mysterious. It is possible that these variations are due to decay of the short-lived radionuclide 247Cm (t1/2=15.6 Myr) into 235U but they could also be due to uranium kinetic isotopic fractionation during condensation. We report uranium isotope measurements of meteoritic refractory inclusions that reveal excesses of 235U reaching ~+6 % relative to average solar system composition, which can only be due to decay of 247Cm. This allows us to constrain the 247Cm/235U ratio at Solar System formation to (1.1 +- 0.3) x 10-4. This value provides new clues on the universality of nucleosynthetic r-process of rapid neutron capture.

  4. Isotope effect in the formation of H2 from H2CO studied at the atmospheric simulation chamber SAPHIR

    Directory of Open Access Journals (Sweden)

    R. Koppmann

    2010-06-01

    Full Text Available Formaldehyde of known, near-natural isotopic composition was photolyzed in the SAPHIR atmosphere simulation chamber under ambient conditions. The isotopic composition of the product H2 was used to determine the isotope effects in formaldehyde photolysis. The experiments are sensitive to the molecular photolysis channel, and the radical channel has only an indirect effect and cannot be effectively constrained. The molecular channel kinetic isotope effect KIEmol, the ratio of photolysis frequencies j(HCHO→CO+H2/j(HCDO→CO+HD at surface pressure, is determined to be KIEmol=1.63−0.046+0.038. This is similar to the kinetic isotope effect for the total removal of HCHO from a recent relative rate experiment (KIEtot=1.58±0.03, which indicates that the KIEs in the molecular and radical photolysis channels at surface pressure (≈100 kPa may not be as different as described previously in the literature.

  5. Deformation of C isotopes

    CERN Document Server

    Kanada-Enyo, Y

    2004-01-01

    Systematic analysis of the deformations of proton and neutron densities in even-even C isotopes was done based on the method of antisymmetrized molecular dynamics. The $E2$ transition strength was discussed in relation to the deformation. We analyze the $B(E2;2^+_1\\to 0^+_1)$ in $^{16}$C, which has been recently measured to be abnormally small. The results suggest the difference of the deformations between proton and neutron densities in the neutron-rich C isotopes. It was found that stable proton structure in C isotopes plays an important role in the enhancement the neutron skin structure as well as in the systematics of $B(E2)$ in the neutron-rich C.

  6. Characterization of calcium isotopes in natural and synthetic barite

    Science.gov (United States)

    Griffith, E.M.; Schauble, E.A.; Bullen, T.D.; Paytan, A.

    2008-01-01

    The mineral barite (BaSO4) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (??44/40Ca = -2.01 ?? 0.15???) but are different from hydrothermal and cold seep barite samples (??44/40Ca = -4.13 to -2.72???). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, ??44/40Ca = -3.42 to -2.40???. Temperature, saturation state, a Ba2 + / a SO42 -, and aCa2+/aBa2+ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower 44Ca/40Ca than calcite, by -9??? at 0 ??C and -8??? at 25 ??C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower ??44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca2+ substitution for Ba2+ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca2+ and other elements in inorganic and biogenic minerals. ?? 2008 Elsevier Ltd.

  7. Explicit Integration with GPU Acceleration for Large Kinetic Networks

    CERN Document Server

    Brock, Benjamin; Billings, Jay Jay; Guidry, Mike

    2014-01-01

    We demonstrate the first implementation of recently-developed fast explicit kinetic integration algorithms on modern graphics processing unit (GPU) accelerators. Taking as a generic test case a Type Ia supernova explosion with an extremely stiff thermonuclear network having 150 isotopic species and 1604 reactions coupled to hydrodynamics using operator splitting, we demonstrate the capability to solve of order 100 realistic kinetic networks in parallel in the same time that standard implicit methods can solve a single such network on a CPU. This orders-of-magnitude decrease in compute time for solving systems of realistic kinetic networks implies that important coupled, multiphysics problems in various scientific and technical fields that were intractible, or could be simulated only with highly schematic kinetic networks, are now computationally feasible.

  8. Mathematical treatment of isotopologue and isotopomer speciation and fractionation in biochemical kinetics

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-11-01

    We present a mathematical treatment of the kinetic equations that describe isotopologue and isotopomer speciation and fractionation during enzyme-catalyzed biochemical reactions. These equations, presented here with the name GEBIK (general equations for biochemical isotope kinetics) and GEBIF (general equations for biochemical isotope fractionation), take into account microbial biomass and enzyme dynamics, reaction stoichiometry, isotope substitution number, and isotope location within each isotopologue and isotopomer. In addition to solving the complete GEBIK and GEBIF, we also present and discuss two approximations to the full solutions under the assumption of biomass-free and enzyme steady-state, and under the quasi-steady-state assumption as applied to the complexation rate. The complete and approximate approaches are applied to observations of biological denitrification in soils. Our analysis highlights that the full GEBIK and GEBIF provide a more accurate description of concentrations and isotopic compositions of substrates and products throughout the reaction than do the approximate forms. We demonstrate that the isotopic effects of a biochemical reaction depend, in the most general case, on substrate and complex concentrations and, therefore, the fractionation factor is a function of time. We also demonstrate that inverse isotopic effects can occur for values of the fractionation factor smaller than 1, and that reactions that do not discriminate isotopes do not necessarily imply a fractionation factor equal to 1.

  9. Isotopes in Condensed Matter

    CERN Document Server

    G Plekhanov, Vladimir

    2013-01-01

    This book provides a concise introduction to the newly created sub-discipline of solid state physics isotopetronics. The role of isotopes in materials and their properties are describe  in this book. The problem of the enigma of the atomic mass in microphysics is briefly discussed.  The range of the applications of isotopes is wide: from biochemical process in living organisms to modern technical applications in quantum information. Isotopetronics promises to improve nanoelectronic and optoelectronic devices. With numerous illustrations this book is useful to researchers, engineers and graduate students.

  10. Atomic Weights and Isotopic Compositions

    Science.gov (United States)

    SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

  11. Kinetics of methane fermentation

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Y. R.; Hashimoto, A. G.

    1978-01-01

    The kinetics on methane fermentation are described using published data for livestock residue, sewage sludge, and municipal refuse. Methods are presented to determine the kinetic constants and the finally attainable methane production using steady-state methane production data. The effects of temperature, loading rate, and influent substrate concentration on methane fermentation kinetics are discussed. These relationships were used to predict the rate of methane production of a pilot-scale fermentor with excellent results.

  12. Discoveries of isotopes by fission

    Indian Academy of Sciences (India)

    M Thoennessen

    2015-09-01

    Of the about 3000 isotopes presently known, about 20% have been discovered in fission. The history of fission as it relates to the discovery of isotopes as well as the various reaction mechanisms leading to isotope discoveries involving fission are presented.

  13. Introduction to chemical kinetics

    CERN Document Server

    Soustelle, Michel

    2013-01-01

    This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area. Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental re

  14. Principles of chemical kinetics

    CERN Document Server

    House, James E

    2007-01-01

    James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications. Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative rela

  15. Stable isotopes of transition and post-transition metals as tracers in environmental studies

    Science.gov (United States)

    Bullen, Tomas D.; Baskaran, Mark

    2011-01-01

    The transition and post-transition metals, which include the elements in Groups 3–12 of the Periodic Table, have a broad range of geological and biological roles as well as industrial applications and thus are widespread in the environment. Interdisciplinary research over the past decade has resulted in a broad understanding of the isotope systematics of this important group of elements and revealed largely unexpected variability in isotope composition for natural materials. Significant kinetic and equilibrium isotope fractionation has been observed for redox sensitive metals such as iron, chromium, copper, molybdenum and mercury, and for metals that are not redox sensitive in nature such as cadmium and zinc. In the environmental sciences, the isotopes are increasingly being used to understand important issues such as tracing of metal contaminant sources and fates, unraveling metal redox cycles, deciphering metal nutrient pathways and cycles, and developing isotope biosignatures that can indicate the role of biological activity in ancient and modern planetary systems.

  16. Modelling and interpreting the isotopic composition of water vapour in convective updrafts

    Directory of Open Access Journals (Sweden)

    M. Bolot

    2013-08-01

    Full Text Available The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed-phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters, including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener–Bergeron–Findeisen process. As all of these processes are related to updraft strength, particle size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

  17. GEOCHRONOMETRY ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    <正>20040631 Chen Jiangfeng (School of Earth and Space Sciences, University of Science and Technology of China, Hefei, Anhui) ; Xie Zhi Relationships Between Rb-Sr, Ar - Ar Geochronometers and Oxygen Isotopic Equilibrium of Intrusions from Eastern Anhui Province, China (Geological Journal of China Universities, ISSN 1006 - 7493, CN 32 -

  18. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    <正>20090432 Zhou Shuqing (School of Energy Resources, China University of Geosciences Beijing 100083, China); Huang Haiping Stable Isotopic Records vs. Important Events in Life Evolution and the Concurrent Environment (Geological Review, ISSN0371-5736, CN11-1952, 54(2), 2008, p.225-231, 3 illus., 1 table, 77 refs.)

  19. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20141014Wang Hairan(State Key Laboratory of Continental Dynamics,Department of Geology,Northwest University,Xi’an710069,China);Zhao Hongge Theory and Application of Zircon U-Pb Isotope Dating Technique(Geology and Resources,ISSN1671-1947,CN21-1458/P,22(3),2013,p.229

  20. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20072750 Huang Sijing(State Key Laboratory of Oil/Gas Reservoir Geology and Exploitation,Chengdu University of Technology,Chengdu 610059,China);Pei Changrong Age Calibration for the Boundary between Lower and Middle Triassic by Strontium Isotope Stratigraphy in Eastern Sichuan Province

  1. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20070454 Bao Zengkuan (Institute of High Energy Physics, CAS, Beijing 100049, China); Yuan Wanming Apatite (U-Th)/He Dating and Its Application (Acta Petrologica et Mineralogica, ISSN1000-6524, CN11-1966/P, 24(2), 2005, p.126-132, 2 illus., 25 refs.) Key words: isotopic geochronology

  2. Isotopic Implicit Surface Meshing

    NARCIS (Netherlands)

    Boissonnat, Jean-Daniel; Cohen-Steiner, David; Vegter, Gert

    2004-01-01

    This paper addresses the problem of piecewise linear approximation of implicit surfaces. We first give a criterion ensuring that the zero-set of a smooth function and the one of a piecewise linear approximation of it are isotopic. Then, we deduce from this criterion an implicit surface meshing algor

  3. Isotope hydrograph separation

    Energy Technology Data Exchange (ETDEWEB)

    Fritz, P. [UFZ-Umweltforschungszentrum, Centre of Environmental Research Leipzig-Halle, Leipzig (Germany)

    2000-07-01

    Storm-runoff thus reflects the complex hydraulic behaviour of drainage basins and water-links of such systems. Water of different origin may participate in the events and in this lecture, the application of isotope techniques to separate storm hydrographs into different components will be presented.

  4. Forensic Stable Isotope Biogeochemistry

    Science.gov (United States)

    Cerling, Thure E.; Barnette, Janet E.; Bowen, Gabriel J.; Chesson, Lesley A.; Ehleringer, James R.; Remien, Christopher H.; Shea, Patrick; Tipple, Brett J.; West, Jason B.

    2016-06-01

    Stable isotopes are being used for forensic science studies, with applications to both natural and manufactured products. In this review we discuss how scientific evidence can be used in the legal context and where the scientific progress of hypothesis revisions can be in tension with the legal expectations of widely used methods for measurements. Although this review is written in the context of US law, many of the considerations of scientific reproducibility and acceptance of relevant scientific data span other legal systems that might apply different legal principles and therefore reach different conclusions. Stable isotopes are used in legal situations for comparing samples for authenticity or evidentiary considerations, in understanding trade patterns of illegal materials, and in understanding the origins of unknown decedents. Isotope evidence is particularly useful when considered in the broad framework of physiochemical processes and in recognizing regional to global patterns found in many materials, including foods and food products, drugs, and humans. Stable isotopes considered in the larger spatial context add an important dimension to forensic science.

  5. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide.

    Science.gov (United States)

    Wiegel, Aaron A; Cole, Amanda S; Hoag, Katherine J; Atlas, Elliot L; Schauffler, Sue M; Boering, Kristie A

    2013-10-29

    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in (17)O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the (17)O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O((1)D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of (17)O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

  6. Isotopic modeling of the sub-cloud evaporation effect in precipitation.

    Science.gov (United States)

    Salamalikis, V; Argiriou, A A; Dotsika, E

    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(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 isotopic

  7. An Archean Terrestrial Fractionation Line for Oxygen Isotopes

    Science.gov (United States)

    Rumble, D.; Blake, R. E.; Bao, H.; Bowring, S.; Komiya, T.; Rosing, M.; Ueno, Y.

    2008-12-01

    The Terrestrial Fractionation Line (TFL) for oxygen isotopes is defined by 17O/16O and 18O/16O analyses of meteoric waters, seawater, sedimentary, metamorphic, and igneous rocks and constituent minerals. Interlaboratory measurements of the slope of the TFL on a plot of d18O vs. d17O revealed eclogitic garnets with a slope of 0.526 and hydrothermal quartz of 0.524 from rocks younger than 0.8 Ga (Giga years before present). New measurements show Archean metamorphic rocks and minerals from Barberton, (3.2 Ga, S. Africa), Isua (3.8 Ga, Greenland), and Acasta (4.0 Ga, Canada) have a slope of 0.524 +/- 0.002 (95% confidence, MSWD = 0.66). Analysis of Ag3PO4 prepared from apatite mineral separates from Isua meta-sediments gives a slope of 0.509 +/- 0.022 (95% confidence, MSWD = 0.59). Taken at face value, steeper slopes on a d17O vs. d18O diagram indicate an approach towards isotope exchange equilibrium. Lower slopes are expected when isotope fractionation is kinetically controlled. The lower slope of 0.509 for Isua apatite suggests that the formation of orthophosphate was kinetically controlled. Kinetic fractionations are known to occur during catalysis of reactions by enzymes secreted by microbes. Enzymatic catalysis confers an advantage on organisms because energy-producing reactions may be induced to occur at lower temperature conditions more accessible to the organism. May it be definitively concluded that enzymatic catalysis was responsible for the measured 0.509 slope? No, abiotic kinetic fractionation cannot be disproven with existing data. The preparation of Ag3PO4 from apatite may have introduced kinetic fractionation as an analytical artifact. Conclusions fully supported by the data suggest: (1) Mixing accompanying the violent birth of the Earth- Moon system had already succeeded in establishing Earth's current oxygen isotope composition by 4.0 Ga; and (2) No trace of an episode of late heavy meteorite bombardment remains in the oxygen isotope compositions of

  8. Binding isotope effects as a tool for distinguishing hydrophobic and hydrophilic binding sites of HIV-1 RT.

    Science.gov (United States)

    Krzemińska, Agnieszka; Paneth, Piotr; Moliner, Vicent; Świderek, Katarzyna

    2015-01-22

    The current treatment for HIV-1 infected patients consists of a cocktail of inhibitors, in an attempt to improve the potency of the drugs by adding the possible effects of each supplied compound. In this contribution, nine different inhibitors of HIV-1 RT, one of the three key proteins responsible for the virus replication, have been selected to develop and test a computational protocol that allows getting a deep insight into the inhibitors' binding mechanism. The interaction between the inhibitors and the protein have been quantified by computing binding free energies through FEP calculations, while a more detailed characterization of the kind of inhibitor-protein interactions is based on frequency analysis of the ligands in the initial and final state, i.e. in solution and binding the protein. QM/MM calculation of heavy atoms ((13)C, (15)N, and (18)O) binding isotope effects (BIE) have been used to identify the binding sites of the different inhibitors. Specific interactions between the isotopically labeled atoms of the inhibitors and polar residues and magnesium cations on the hydrophilic pocket of the protein are responsible for the frequencies shifting that can be detected when comparing the IR spectra of the compounds in solution and in the protein. On the contrary, it seems that changes in vdW interactions from solution to the final state when the ligand is interacting with residues of the hydrophobic cavity, does not influence frequency modes and then no BIE are observed. Our results suggest that a proper computational protocol can be a valuable tool which in turn can be used to increase the efficiency of anti AIDS drugs.

  9. Water isotopes in desiccating lichens

    Science.gov (United States)

    Cuntz, Matthias; Máguas, Cristina; Lakatos, Michael

    2009-01-01

    The stable isotopic composition of water is routinely used as a tracer to study water exchange processes in vascular plants and ecosystems. To date, no study has focussed on isotope processes in non-vascular, poikilohydric organisms such as lichens and bryophytes. To understand basic isotope exchange processes of non-vascular plants, thallus water isotopic composition was studied in various green-algal lichens exposed to desiccation. The study indicates that lichens equilibrate with the isotopic composition of surrounding water vapour. A model was developed as a proof of concept that accounts for the specific water relations of these poikilohydric organisms. The approach incorporates first their variable thallus water potential and second a compartmentation of the thallus water into two isotopically distinct but connected water pools. Moreover, the results represent first steps towards the development of poikilohydric organisms as a recorder of ambient vapour isotopic composition. PMID:19888598

  10. Impact of hydrogen isotope species on microinstabilities in helical plasmas

    Science.gov (United States)

    Nakata, Motoki; Nunami, Masanori; Sugama, Hideo; Watanabe, Tomo-Hiko

    2016-07-01

    The impact of isotope ion mass on ion-scale and electron-scale microinstabilities such as ion temperature gradient (ITG) mode, trapped electron mode (TEM), and electron temperature gradient (ETG) mode in helical plasmas are investigated by using gyrokinetic Vlasov simulations with a hydrogen isotope and real-mass kinetic electrons. Comprehensive scans for the equilibrium parameters and magnetic configurations clarify the transition from ITG mode to TEM instability, where a significant TEM enhancement is revealed in the case of inward-shifted plasma compared to that in the standard configuration. It is elucidated that the ion-mass dependence on the ratio of the electron-ion collision frequency to the ion transit one, i.e. {ν\\text{ei}}/{ω\\text{ti}}\\propto {{≤ft({{m}\\text{i}}/{{m}\\text{e}}\\right)}1/2} , leads to a stabilization of the TEM for heavier isotope ions. The ITG growth rate indicates a gyro-Bohm-like ion-mass dependence, where the mixing-length estimate of diffusivity yields γ /k\\bot2\\propto m\\text{i}1/2 . On the other hand, a weak isotope dependence of the ETG growth rate is identified. A collisionality scan also reveals that the TEM stabilization by the isotope ions becomes more significant for relatively higher collisionality in a banana regime.

  11. Bringing organic carbon isotopes and phytoliths to the table as additional constraints on paleoelevation

    Science.gov (United States)

    Sheldon, N. D.; Cotton, J. M.; Hren, M. T.; Hyland, E. G.; Smith, S. Y.; Strömberg, C. A. E.

    2015-12-01

    A commonly used tool in paleotectonic and paleoaltimetry studies is the oxygen isotopic composition of authigenic carbonates formed that formed in lakes or soils, with both spatial (e.g., shoreline to mountain top) or temporally resolved records potentially providing constraints. However, in many cases there is a substantial spread in the oxygen isotope data for a given time period, often to the point of allowing for essentially any interpretation of the data depending upon how they have been used by the investigator. One potential way of distinguishing between different potential paleotectonic or paleoaltimetric interpretations is to use carbon isotope and plant microfossil (phytolith) analyses from the same paleosols to screen the oxygen isotope data by looking for evidence of evaporative enrichment. For example, if both inorganic (carbonate) and organic carbon isotopes are measured from the same paleosol, then in it possible to determine if the two isotope record equilibrium conditions or if they record disequilibrium driven by kinetic effects. In the former case, the oxygen isotope results can be considered reliable whereas in the latter case, the oxygen isotope results can be considered unreliable and could be culled from the interpretation. Similarly, because the distribution of C4 plants varies as a function of temperature and elevation, the presence/absence or abundance of C4 plant phytoliths, or of carbon isotope compositions that require a component of C4 vegetation can also be used to constrain paleoelevation by providing a maximum elevation constraint. Worked examples will include the late Miocene-Pliocene of Catamarca, Argentina, where phytoliths and organic carbon isotopes provide a maximum elevation constraint and can be used to demonstrate that oxygen isotopes do not provide a locally useful constraint on paleoelevation, and Eocene-Miocene of southwestern Montana where organic matter and phytoliths can be used to select between different potential

  12. Bicarbonate kinetics in Indian males

    Indian Academy of Sciences (India)

    T Raj; R Kuriyan; A V Kurpad

    2006-06-01

    Measurement of rates of in vivo substrate oxidation such as that of glucose, fatty acids and amino acids, are based on tracer (14C or 13C) data, and often depend on the isotopic content of expired CO2. The recovery of tracer-labelled CO2 generated from the oxidation of 13C labelled substrates may not be 100% over short term. This can lead to underestimation of oxidation rate of substrates, and consequently a correction for the incomplete recovery of tracer has to be applied by the determination of the recovery of 13CO2 in the breath during tracer bicarbonate infusions. We have studied the recovery of tracer-labelled bicarbonate using a bolus administration model, and further characterized kinetics of bicarbonate using a three-compartment model, to assess which compartmental fluxes changed during the change from a fasted state to fed state. Recovery of bicarbonate was lower at 69% and 67% (fasted and fed state) than the value of 71% and 74% found during earlier longer term of continuous infusions. During feeding, there was a 20-fold increase in the flux of bicarbonate between the central compartment and the compartment that was equivalent to the viscera. This study shows that the difference between the fasted and fed state recovery of tracer bicarbonate similar to that obtained with continuous infusions, and that bicarbonate fluxes show large changes between different compartments in the body depending on metabolic state.

  13. Stable carbon isotope ratios of ambient aromatic volatile organic compounds

    Science.gov (United States)

    Kornilova, Anna; Huang, Lin; Saccon, Marina; Rudolph, Jochen

    2016-09-01

    Measurements of mixing ratios and stable carbon isotope ratios of aromatic volatile organic compounds (VOC) in the atmosphere were made in Toronto (Canada) in 2009 and 2010. Consistent with the kinetic isotope effect for reactions of aromatic VOC with the OH radical the observed stable carbon isotope ratios are on average significantly heavier than the isotope ratios of their emissions. The change of carbon isotope ratio between emission and observation is used to determine the extent of photochemical processing (photochemical age, ∫ [OH]dt) of the different VOC. It is found that ∫ [OH]dt of different VOC depends strongly on the VOC reactivity. This demonstrates that for this set of observations the assumption of a uniform ∫ [OH]dt for VOC with different reactivity is not justified and that the observed values for ∫ [OH]dt are the result of mixing of VOC from air masses with different values for ∫ [OH]dt. Based on comparison between carbon isotope ratios and VOC concentration ratios it is also found that the varying influence of sources with different VOC emission ratios has a larger impact on VOC concentration ratios than photochemical processing. It is concluded that for this data set the use of VOC concentration ratios to determine ∫ [OH]dt would result in values for ∫ [OH]dt inconsistent with carbon isotope ratios and that the concept of a uniform ∫ [OH]dt for an air mass has to be replaced by the concept of individual values of an average ∫ [OH]dt for VOC with different reactivity.

  14. Kinetics and mechanism of the oxidation of formic and oxalic acids by quinolinium fluorochromate

    Indian Academy of Sciences (India)

    Madhu Khurana; Pradeep K Sharma; Kalyan K Banerji

    2000-04-01

    Kinetics and mechanism of oxidation of formic and oxalic acids by quinolinium fluorochromate (QFC) have been studied in dimethylsulphoxide. The main product of oxidation is carbon dioxide. The reaction is first-order with respect to QFC. Michaelis-Menten type of kinetics were observed with respect to the reductants. The reaction is acid-catalysed and the acid dependence has the form: obs = + [H+]. The oxidation of -deuterioformic acid exhibits a substantial primary kinetic isotope effect (H/D = 6.01 at 303 K). The reaction has been studied in nineteen different organic solvents and the solvent effect has been analysed using Taft’s and Swain’s multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical cyclic transition state in the rate-determining step. Suitable mechanisms have been proposed

  15. Secondary. beta. -deuterium isotope effects in decarboxylation and elimination reactions of. cap alpha. -lactylthiamin: intrinsic isotope effects of pyruvate decarboxylase

    Energy Technology Data Exchange (ETDEWEB)

    Kluger, R.; Brandl, M.

    1986-11-26

    The reactions of the adduct of pyruvate and thiamine, lactylthiamin (2-(lact-2-yl)thiamine), are accurate nonenzymic models for reactions of intermediates formed during catalysis by pyruvate decarboxylase. The enzymatic reaction generates lactylthiamin diphosphate from pyruvate and thiamine diphosphate. ..beta..-Deuterium isotope effects were determined for the nonenzymic reactions, and the results were related to isotope effects on the enzymic reaction. 2-(Lact-2-yl-..beta..-d/sub 3/) thiamine was prepared by condensation of methyl pyruvate-d/sub 3/ with thiamine followed by hydrolysis. The isotope effect for decarboxylation of lactylthiamin in acidic solution at 25/sup 0/C (k/sub H3//k/sub D3/) is 1.09 (standard deviation (SD) 0.015) in pH 3.8, 0.5 M sodium acetate: isotope effect = 1.095 (SD 0.014) in 0.001 M HCl. The reaction was also studied using 38% ethanolic aqueous sodium acetate (pH 3.8 before mixing with ethanol) since the enzymic sites are less polar than water and the reaction is significantly accelerated by the cosolvent. The isotope effect is within statistical range of that for the reaction in water, 1.105 (SD 0.016), indicating that acceleration by the solvent does not change the extent of hyperconjugative stabilization of the transition state relative to the ground state. The isotope effect for the base-catalyzed elimination of pyruvate from lactylthiamin was determined from kinetic studies by using multiwavelength analysis for reactions in pH 11 sodium carbonate solution. The isotope effect (k/sub H3//k/sub D3/) is 1.12 (SD 0.01), which is slightly higher than the effect on decarboxylation.

  16. Chromium isotope variations

    DEFF Research Database (Denmark)

    D'Arcy, Joan Mary

    is incorporated into carbonates. Hence, ancient carbonates can potentially record the Cr isotopic composition (δ53Cr ‰) of seawater in the geological past. Reliable application and interpretation of this proxy requires a detailed knowledge about processes that fractionate Cr on the Earth’s surface...... deposited during the Early Ordovician — a time of known redox instability in ancient oceans – exhibit a significant positive Cr isotope excursion of +0.5‰. This excursion is interpreted as the reductive drawn down of dissolved Cr in seawater in response to the development of a proximal anoxic sink...... of ancient marine sediments can be a useful tool for understanding the cycling of redox sensitive elements on a local scale....

  17. Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles

    Science.gov (United States)

    Kuga, Maïa; Carrasco, Nathalie; Marty, Bernard; Marrocchi, Yves; Bernard, Sylvain; Rigaudier, Thomas; Fleury, Benjamin; Tissandier, Laurent

    2014-05-01

    The formation of organic compounds is generally assumed to result from abiotic processes in the Solar System, with the exception of biogenic organics on Earth. Nitrogen-bearing organics are of particular interest, notably for prebiotic perspectives but also for overall comprehension of organic formation in the young Solar System and in planetary atmospheres. We have investigated abiotic synthesis of organics upon plasma discharge, with special attention to N isotope fractionation. Organic aerosols were synthesized from N2-CH4 and N2-CO gaseous mixtures using low-pressure plasma discharge experiments, aimed at simulating chemistry occurring in Titan's atmosphere and in the protosolar nebula, respectively. The nitrogen content, the N speciation and the N isotopic composition were analyzed in the resulting organic aerosols. Nitrogen is efficiently incorporated into the synthesized solids, independently of the oxidation degree, of the N2 content of the starting gas mixture, and of the nitrogen speciation in the aerosols. The aerosols are depleted in 15N by 15-25‰ relative to the initial N2 gas, whatever the experimental setup is. Such an isotopic fractionation is attributed to mass-dependent kinetic effect(s). Nitrogen isotope fractionation upon electric discharge cannot account for the large N isotope variations observed among Solar System objects and reservoirs. Extreme N isotope signatures in the Solar System are more likely the result of self-shielding during N2 photodissociation, exotic effect during photodissociation of N2 and/or low temperature ion-molecule isotope exchange. Kinetic N isotope fractionation may play a significant role in the Titan's atmosphere. On the Titan's night side, 15N-depletion resulting from electron driven reactions may counterbalance photo-induced 15N enrichments occurring on the day's side. We also suggest that the low δ15N values of Archaean organic matter (Beaumont and Robert, 1999) are partly the result of abiotic synthesis of

  18. Quantum and isotope effects in lithium metal

    Science.gov (United States)

    Ackland, Graeme J.; Dunuwille, Mihindra; Martinez-Canales, Miguel; Loa, Ingo; Zhang, Rong; Sinogeikin, Stanislav; Cai, Weizhao; Deemyad, Shanti

    2017-06-01

    The crystal structure of elements at zero pressure and temperature is the most fundamental information in condensed matter physics. For decades it has been believed that lithium, the simplest metallic element, has a complicated ground-state crystal structure. Using synchrotron x-ray diffraction in diamond anvil cells and multiscale simulations with density functional theory and molecular dynamics, we show that the previously accepted martensitic ground state is metastable. The actual ground state is face-centered cubic (fcc). We find that isotopes of lithium, under similar thermal paths, exhibit a considerable difference in martensitic transition temperature. Lithium exhibits nuclear quantum mechanical effects, serving as a metallic intermediate between helium, with its quantum effect-dominated structures, and the higher-mass elements. By disentangling the quantum kinetic complexities, we prove that fcc lithium is the ground state, and we synthesize it by decompression.

  19. Nonequilibrium clumped isotope signals in microbial methane

    Science.gov (United States)

    Wang, David T.; Gruen, Danielle S.; Lollar, Barbara Sherwood; Hinrichs, Kai-Uwe; Stewart, Lucy C.; Holden, James F.; Hristov, Alexander N.; Pohlman, John W.; Morrill, Penny L.; Könneke, Martin; Delwiche, Kyle B.; Reeves, Eoghan P.; Sutcliffe, Chelsea N.; Ritter, Daniel J.; Seewald, Jeffrey S.; McIntosh, Jennifer C.; Hemond, Harold F.; Kubo, Michael D.; Cardace, Dawn; Hoehler, Tori M.; Ono, Shuhei

    2015-01-01

    Methane is a key component in the global carbon cycle with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply-substituted “clumped” isotopologues, e.g., 13CH3D, has recently emerged as a proxy for determining methane-formation temperatures; however, the impact of biological processes on methane’s clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on 13CH3D abundances and results in anomalously elevated formation temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters.

  20. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    <正>20050934 Chen Zhihong (Chinese Academy of Geological Sciences, Beijing 100037, China); Lu Songnian Age of the Fushui Intermediate-Mafic Intrusive Complex in the Qinling Orogen, New Zircon U - Pb and Whole -Rock Sm and Nd Isotope Chronological Evidence (Geological Bulletin of China, ISSN 1671-2552, CN11-4648/P, 23(4), 2004, p. 322-328, 3 illus. , 3 tables, 10 refs. )

  1. GEOCHRONOMETRY &ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20131727 Huang Xiaowen(State Key Laboratory of Ore Deposit Geochemistry,Institute of Geochemistry,Chinese Academy of Sciences,Guiyang 550002,China);Qi Liang Preliminary Study on Sample-Preparation for Re-Os Isotopic Dating of Pyrite(Geochimica,ISSN0379-1726,CN44-1398/P,41(4),2012,p.380-386,3illus.,2tables,25refs)Key words:pyrite,Re-Os dating

  2. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20132601 Cui Yurong(Tianjin Institute of Geology and Mineral Resources,China Geological Survey,Tianjin 300170,China);Zhou Hongying In Situ LA-MC-ICP-MS U-Pb Isotopic Dating of Monazite(Acta Geoscientica Sinica,ISSN0375-5444,CN11-1856/P,33(6),2012,p.865-876,6illus.,4tables,41refs.)Key words:monazite,U-Pb dating

  3. Cadmium Isotope Fractionation in Seawater - A Signature of Nutrient Utilization

    Science.gov (United States)

    Wichtlhuber, S.; Rehkaemper, M.; Halliday, A. N.

    2005-12-01

    Cadmium displays a nutrient-like distribution akin to phosphorous in the oceans. This has been attributed to the assimilation of Cd by phytoplankton in surface waters and re-mineralization at depth. If biological uptake is associated with kinetic isotopic fractionation, as recently suggested by Lacan et al. (2005), then the Cd-depleted surface waters of the oceans (with Cd contents of Lacan et al., 2005). In this study, we have extended the search for Cd isotope variations in the oceans with analyses of two depth profiles and various additional seawater samples from the North Pacific, the Arctic, and the Southern Ocean. The Cd isotope measurements utilized a double spike technique in conjunction with multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS), to achieve a precision and accuracy of about ± 0.8 to 1.5 ɛ114/110Cd. This precision is about a factor of 3 to 4 better than that of previous studies, which did not utilize a double spike. The data collected for the samples display a clear co-variation of Cd isotope compositions with Cd concentrations. The most Cd-rich water samples (with ~1 nmol/kg Cd) display the "lightest" Cd isotope compositions with ɛ114/110Cd ~ +3, akin to results previously obtained for crustal and mantle rocks (Wombacher et. al, 2003). In contrast, samples from the upper water column of the North Pacific (with Lacan et al. (2005), because inorganic geological processes (other than evaporation/condensation) do not appear to generate isotope effects as large as those observed in the present study (Wombacher et. al, 2003). These preliminary results suggest that Cd isotopes have the potential to become a useful proxy of nutrient utilization, which could supplement the Cd/Ca and δ13C records of previous studies, if suitable sedimentary archives can be identified that preserve the Cd isotope signatures of past seawater. References: Lacan F., Francois R., Ji Y. and Sherrell R., 2005. Does oceanic productivity production

  4. Developments in bile acid kinetic measurements using C-13 and H-2 : 10(5) times improved sensitivity during the last 40 years

    NARCIS (Netherlands)

    Stellaard, Frans; Brufau, Gemma; Boverhof, Renze; Jonkers, Elles Zwanet; Boer, Theo; Kuipers, Folkert

    2009-01-01

    Bile acid kinetics involve the measurement of pool sizes and turnover rates of individual bile acids. The technique is based on isotope dilution and was first described in the 1950s using radioactive C-14-labelled cholic acid (CA). It took until the 1970s before stable isotopes were introduced for t

  5. Kinetics and magnetic field effect in geminate recombination of triplet radical pairs adsorbed onto porous glass studied by laser flash technique

    Science.gov (United States)

    Levin, P. P.; Katalnikov, I. V.; Kuzmin, V. A.

    1991-07-01

    Geminate recombination kinetics of radical pairs (RP) formed by electron or hydrogen atom transfer from triphenylamine, tri(4-bromophenyl)amine, 4-phenylaniline or 4-phenylphenol to triplet 9,10-anthraquinone, benzophenone or 4-bromobenzophenone both adsorbed onto an optically transparent SiO 2 porous glass have been studied, using the laser flash technique with spectrophotometric registration. The kinetics are adequately described by the sum of two exponentials, ascribed to the existence of different kinds of "supercages" on the surface. At the same time, the simplest approximation by only one exponential is fair in many cases, because the contribution of a "slow" exponential is comparatively low and is masked by the slow component because of the decay of the escaped radicals. Introduction of a heavy Br atom leads to the acceleration of the geminate recombination; application of an external magnetic field results in retardation. The heavy-atom effect displays the contribution of the intersystem backwards electron transfer or intersystem recombination in the contact states of a triplet RP owing to the spin-orbit coupling. The magnetic field effect is the result of the significant contribution of the recombination route through the separated RP, where the hyperfine coupling and relaxation mechanisms of the RP spin evolution are active.

  6. Nuclear physics and stable isotopes; Physique nucleaire et isotopes stables

    Energy Technology Data Exchange (ETDEWEB)

    Goutte, D. [CEA Centre d`Etudes de Saclay, 91 - Gif-sur-Yvette (France). Dept. d`Astrophysique, de la Physique des Particules, de la Physique Nucleaire et de l`Instrumentation Associee

    1994-12-31

    The aim of this paper is to show that fundamental research in nuclear physics requires utilization of stable isotopes; stable isotopes are essential as target material since a large quantity of nucleus have to be studied in order to appreciate all the complexity of the nuclear structure, but also as a tool, such as beams, for the same purpose. Examples are given with samarium, tin and germanium isotopes. 7 figs.

  7. Irreversible processes kinetic theory

    CERN Document Server

    Brush, Stephen G

    2013-01-01

    Kinetic Theory, Volume 2: Irreversible Processes deals with the kinetic theory of gases and the irreversible processes they undergo. It includes the two papers by James Clerk Maxwell and Ludwig Boltzmann in which the basic equations for transport processes in gases are formulated, together with the first derivation of Boltzmann's ""H-theorem"" and a discussion of this theorem, along with the problem of irreversibility.Comprised of 10 chapters, this volume begins with an introduction to the fundamental nature of heat and of gases, along with Boltzmann's work on the kinetic theory of gases and s

  8. Nickel isotopes and methanogens

    Science.gov (United States)

    Neubeck, A.; Ivarsson, M.

    2013-12-01

    Methanogens require Ni for their growth and as a consequence the microbial fractionation of Ni isotopes can be used as a biomarker for activity of methanogenic communities1. Anaerobic laboratory experiments was performed using methanogens to investigate methanogenic growth in a modified nutrient media2 with olivine Fo91 (5g/l) added as an additional mineral nutrient source and as the only H2 provider. One of the investigated methanogens showed an increased growth in the experiments with added olivine. There were also a close relationship between the mobilized Ni and the growth of the methanogen. Ni is an element that previously has been neglected in the study of fossilized microorganisms and their interaction with mineral substrates and, thus, there are no records or published data of Ni in association with microfossils. However, we have detected enrichments of Ni in fossilized microorganisms and ichno-fossils, respectively, from three separate locations. Ni is not present in the host rock in any of the samples. Thus, Ni is present in association with fossilized microorganisms from environments and more extensive analysis is required to understand the magnitude, uptake, preservation and fractionation of Ni in microfossils. In order to analyze Ni isotope fractionation from microbe-mineral interaction, we plan to use a high-resolution Laser-Ablation Time-of-Flight Mass Spectrometer (LMS)3. In situ profile ablation will provide detailed and localized data on fractionation patterns between microfossils and their host rock. Also, this technique will allow us to identify the change in Ni isotopic fractionation in rock samples caused by abiotic and biogenic processes in a faster and easier way and with less risk for contamination compared to the wet chemistry analyses of Ni isotopes. 1. Cameron, V., Vance, D., Archer, C. & House, C. H. A biomarker based on the stable isotopes of nickel. Proceedings of the National Academy of Sciences 106, 10944-10948 (2009). 2. Schn

  9. Controls on the stable isotope compositions of travertine from hyperalkaline springs in Oman: Insights from clumped isotope measurements

    Science.gov (United States)

    Falk, E. S.; Guo, W.; Paukert, A. N.; Matter, J. M.; Mervine, E. M.; Kelemen, P. B.

    2016-11-01

    -members. Our results suggest that carbonate clumped isotope analysis can be a valuable tool for identifying and distinguishing processes not readily apparent from the carbonate bulk stable isotope compositions alone, e.g., kinetic effects or mixing of different carbonate end-members, which can significantly alter both the apparent formation temperatures and apparent radiocarbon ages. The isotope trends observed in these travertine samples could be applied more broadly to identify extinct hyperalkaline springs in terrestrial and extraterrestrial environments, to better constrain the formation conditions and post-depositional alteration of hyperalkaline spring carbonates, and to extract potential paleoclimate information.

  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

    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. Iron and nickel isotope fractionation by diffusion, with applications to iron meteorites

    Science.gov (United States)

    Watson, Heather C.; Richter, Frank; Liu, Ankun; Huss, Gary R.

    2016-10-01

    Mass-dependent, kinetic fractionation of isotopes through processes such as diffusion can result in measurable isotopic signatures. When these signatures are retained in geologic materials, they can be used to help interpret their thermal histories. The mass dependence of the diffusion coefficient of isotopes 1 and 2 can be written as (D1 /D2) =(m2 /m1) β, where D1 and D2 are the diffusion coefficients of m1 and m2 respectively, and β is an empirical coefficient that relates the two ratios. Experiments have been performed to measure β in the Fe-Ni alloy system. Diffusion couple experiments between pure Fe and Ni metals were run in a piston cylinder at 1300-1400 °C and 1 GPa. Concentration and isotopic profiles were measured by electron microprobe and ion microprobe respectively. We find that a single β coefficient of β = 0.32 ± 0.04 can describe the isotopic effect in all experiments. This result is comparable to the isotope effect determined in many other similar alloy systems. The new β coefficient is used in a model of the isotopic profiles to be expected during the Widmanstätten pattern formation in iron meteorites. The results are consistent with previous estimates of the cooling rate of the iron meteorite Toluca. The application of isotopic constraints based on these results in addition to conventional cooling rate models could provide a more robust picture of the thermal history of these early planetary bodies.

  12. Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

    Science.gov (United States)

    Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.

    2004-01-01

    Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

  13. Therapeutic use of radioactive isotopes

    CERN Multimedia

    Caroline Duc

    2013-01-01

    In December, researchers from ISOLDE-CERN, the Paul Scherrer Institute (PSI) and the Institut Laue-Langevin (ILL) published the results of an in vivo study which successfully proved the effectiveness of four terbium isotopes for diagnosing and treating cancerous tumours.   Four terbium isotopes suitable for clinical purposes. “ISOLDE is the only installation capable of supplying terbium isotopes of such purity and intensity in the case of three out of the four types used in this study,” explains Karl Johnson, a physicist at ISOLDE.  “Producing over a thousand different isotopes, our equipment offers the widest choice of isotopes in the world!” Initially intended for fundamental physics research, ISOLDE has diversified its activities over time to invest in various projects in the materials science, biochemistry and nuclear medicine fields. The proof-of-concept study has confirmed that the four terbium isotopes 149Tb, 152Tb, 155Tb produ...

  14. Passage of stable isotope-labeled grass silage fiber and fiber-bound protein through the gastroinstestinal tract of dairy cows

    NARCIS (Netherlands)

    Warner, D.; Dijkstra, J.; Hendriks, W.H.; Pellikaan, W.F.

    2013-01-01

    Fractional passage rates are required to predict nutrient absorption in ruminants but data on nutrient-specific passage kinetics are largely lacking. With the use of the stable isotope ratio (d) as an internal marker, we assessed passage kinetics of fiber and fiber-bound nitrogen (N) of intrinsicall

  15. Kinetic equations: computation

    CERN Document Server

    Pareschi, Lorenzo

    2013-01-01

    Kinetic equations bridge the gap between a microscopic description and a macroscopic description of the physical reality. Due to the high dimensionality the construction of numerical methods represents a challenge and requires a careful balance between accuracy and computational complexity.

  16. Thermal kinetic inductance detector

    Energy Technology Data Exchange (ETDEWEB)

    Cecil, Thomas; Gades, Lisa; Miceli, Antonio; Quaranta, Orlando

    2016-12-20

    A microcalorimeter for radiation detection that uses superconducting kinetic inductance resonators as the thermometers. The detector is frequency-multiplexed which enables detector systems with a large number of pixels.

  17. Chemical Kinetics Database

    Science.gov (United States)

    SRD 17 NIST Chemical Kinetics Database (Web, free access)   The NIST Chemical Kinetics Database includes essentially all reported kinetics results for thermal gas-phase chemical reactions. The database is designed to be searched for kinetics data based on the specific reactants involved, for reactions resulting in specified products, for all the reactions of a particular species, or for various combinations of these. In addition, the bibliography can be searched by author name or combination of names. The database contains in excess of 38,000 separate reaction records for over 11,700 distinct reactant pairs. These data have been abstracted from over 12,000 papers with literature coverage through early 2000.

  18. Lithium isotope separation by laser

    Energy Technology Data Exchange (ETDEWEB)

    Arisawa, T.; Maruyama, Y.; Suzuki, Y.; Shiba, K.

    1982-01-01

    A lithium isotope separation was performed using a laser isotope separation method. It was found that the lithium atoms with a natural isotopic abundance enhanced its /sup 6/Li concentration up to over 90% by tuning the laser wavelength to the /sup 2/Psub(1/2) of /sup 6/Li. Too high power, however, leads to a loss of enrichment due to the power broadening effect which was analysed by the equation of motion of density matrices.

  19. Electrochemical kinetics theoretical aspects

    CERN Document Server

    Vetter, Klaus J

    1967-01-01

    Electrochemical Kinetics: Theoretical Aspects focuses on the processes, methodologies, reactions, and transformations in electrochemical kinetics. The book first offers information on electrochemical thermodynamics and the theory of overvoltage. Topics include equilibrium potentials, concepts and definitions, electrical double layer and electrocapillarity, and charge-transfer, diffusion, and reaction overvoltage. Crystallization overvoltage, total overvoltage, and resistance polarization are also discussed. The text then examines the methods of determining electrochemical reaction mechanisms

  20. Modelling the budget of middle atmospheric water vapour isotopes

    Directory of Open Access Journals (Sweden)

    A. Zahn

    2006-01-01

    Full Text Available A one-dimensional chemistry model is applied to study the stable hydrogen (D and stable oxygen isotope (17O, 18O composition of water vapour in stratosphere and mesosphere. In the troposphere, this isotope composition is determined by 'physical'' fractionation effects, that are phase changes (e.g. during cloud formation, diffusion processes (e.g. during evaporation from the ocean, and mixing of air masses. Due to these processes water vapour entering the stratosphere first shows isotope depletions in D/H relative to ocean water, which are ~5 times of those in 18O/16O, and secondly is mass-dependently fractionated (MDF, i.e. changes in the isotope ratio 17O/16O are ~0.52 times of those of 18O/16O. In contrast, in the stratosphere and mesosphere 'chemical'' fractionation mechanisms, that are the production of HO due to the oxidation of methane, re-cycling of H2O via the HOx family, and isotope exchange reactions considerably enhance the isotope ratios in the water vapour imported from the troposphere. The model reasonably predicts overall enhancements of the stable isotope ratios in H2O by up to ~25% for D/H, ~8.5% for 17O/16O, and ~14% for 18O/16O in the mesosphere relative to the tropopause values. The 17O/16O and 18O/16O ratios in H2O are shown to be a measure of the relative fractions of HOx that receive the O atom either from the reservoirs O2 or O3. Throughout the middle atmosphere, MDF O2 is the major donator of oxygen atoms incorporated in OH and HO2 and thus in H2O. In the stratosphere the known mass-independent fractionation (MIF signal in O3 is in a first step transferred to the NOx family and only in a second step to HOx and H2O. In contrast to CO2, O(1D only plays a minor role in this MIF transfer. The major uncertainty in our calculation arises from poorly quantified isotope exchange reaction rate coefficients and kinetic isotope fractionation factors.

  1. Cold regions isotope applications

    Energy Technology Data Exchange (ETDEWEB)

    Perrigo, L.D.; Divine, T.E.

    1976-04-01

    Pacific Northwest Laboratories (PNL) started the Cold Regions Isotope Applications Program in FY-1975 to identify special conditions in the Arctic and similar geographic areas (Cold Regions) where radioisotope power, heater, or sterilization systems would be desirable and economically viable. Significant progress was made in the first year of this program and all objectives for this initial 12-month period were achieved. The major conclusions and recommendations resulting for this effort are described below. The areas of interest covered include: radiosterilization of sewage; heating of septic tanks; and radioisotope thermoelectric generators as power sources for meteorological instruments and navigational aids. (TFD)

  2. Tracking transformation processes of organic micropollutants in aquatic environments using multi-element isotope fractionation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Hofstetter, Thomas B., E-mail: thomas.hofstetter@eawag.ch [Eawag, Swiss Federal Institute of Aquatic Science and Technology, CH-8600 Duebendorf (Switzerland)] [Institute of Biogeochemistry and Pollutant Dynamics (IBP), ETH Zurich, CH-8092 Zurich (Switzerland); Bolotin, Jakov [Eawag, Swiss Federal Institute of Aquatic Science and Technology, CH-8600 Duebendorf (Switzerland); Skarpeli-Liati, Marita; Wijker, Reto [Eawag, Swiss Federal Institute of Aquatic Science and Technology, CH-8600 Duebendorf (Switzerland)] [Institute of Biogeochemistry and Pollutant Dynamics (IBP), ETH Zurich, CH-8092 Zurich (Switzerland); Kurt, Zohre; Nishino, Shirley F.; Spain, Jim C. [School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States)

    2011-06-15

    The quantitative description of enzymatic or abiotic transformations of man-made organic micropollutants in rivers, lakes, and groundwaters is one of the major challenges associated with the risk assessment of water resource contamination. Compound-specific isotope analysis enables one to identify (bio)degradation pathways based on changes in the contaminants' stable isotope ratios even if multiple reactive and non-reactive processes cause concentrations to decrease. Here, we investigated how the magnitude and variability of isotope fractionation in some priority pollutants is determined by the kinetics and mechanisms of important enzymatic and abiotic redox reactions. For nitroaromatic compounds and substituted anilines, we illustrate that competing transformation pathways can be assessed via trends of N and C isotope signatures.

  3. Sulfur isotope effects associated with protonation of HS- and volatilization of H2S

    Science.gov (United States)

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

    1986-01-01

    The isotope effects associated with: (1) formation of H2S from HS- by protonation in aqueous solution; and (2) volatilization of H2S have been experimentally determined. Both isotopic distributions in closed systems at equilibrium and differential rates of volatilization of isotopic species in open systems were measured at 22 +/- 1 degrees C. It was found that, at equilibrium aqueous H2S is enriched in 34S by 2.0 - 2.7% relative to HS- and that H2S volatilized from solution is depleted in 34S by 0.5% relative to dissolved H2S. A small kinetic isotope effect accompanying volatilization of H2S was observed in the open-system experiments.

  4. Carbon isotopes in biological carbonates: Respiration and photosynthesis

    Science.gov (United States)

    McConnaughey, Ted A.; Burdett, Jim; Whelan, Joseph F.; Paull, Charles K.

    1997-02-01

    Respired carbon dioxide is an important constituent in the carbonates of most air breathing animals but is much less important in the carbonates of most aquatic animals. This difference is illustrated using carbon isotope data from freshwater and terrestrial snails, ahermatypic corals, and chemoautotrophic and methanotrophic pelecypods. Literature data from fish otoliths and bird and mammal shell and bone carbonates are also considered. Environmental CO 2/O 2 ratios appear to be the major controlling variable. Atmospheric CO 2/O 2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO 2 in the course of obtaining 0 2. Tissue CO 2 therefore, does not isotopically equilibrate with environmental CO 2 as thoroughly in air breathers as in aquatic animals, and this is reflected in skeletal carbonates. Animals having efficient oxygen transport systems, such as vertebrates, also accumulate more respired CO 2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO 2 uptake is several times faster than respiratory CO 2 release. Photosynthesis, therefore, affects skeletal δ13C more strongly than does respiration. Corals also illustrate how "metabolic" effects on skeletal isotopic composition can be estimated, despite the presence of much larger "kinetic" isotope effects.

  5. Rate of radiocarbon retention onto calcite by isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Lempinen, Janne; Lehto, Jukka [Helsinki Univ. (Finland). Lab. of Radiochemistry

    2016-11-01

    Radiocarbon ({sup 14}C) is a top priority class radionuclide associated with the long-term safety of spent nuclear fuel disposal. Dissolved inorganic radiocarbon can be retained in bedrock via isotope exchange with calcite (CaCO{sub 3}) at solubility equilibrium with groundwater. In the present study, the rate of the isotope exchange process was investigated on synthetic calcite using batch experiments. Experiments were performed in solutions with a calcium concentration of 0.0002-0.1 M, including two synthetic reference groundwaters. The radiocarbon activity in the solutions decreased exponentially as a function of time, thus following first-order kinetics. The rate of isotope exchange was quantified from an exponential fit to the activity data over time. The rate of radiocarbon retention increased as a function of the calcium activity. The isotope exchange half-life was only 4.3 days at calcium ion activities over 0.01. This half-life is very much shorter than the half-life of {sup 14}C or the time scale of groundwater movements; consequently calcite can effectively retain radiocarbon from brackish and saline groundwaters.

  6. Si Isotopes of Brownleeite

    Science.gov (United States)

    Nakamura-Messenger, K.; Messenger, Scott R.; Ito, M.; Keller, L. P.; Clemett, S. J.; Jones, J. H.; Tatsuoka, H.; Zolensky, M. E.; Tatsuoka, H.

    2010-01-01

    Brownleeite is a manganese silicide, ideally stoichiometric MnSi, not previously observed in nature until its discovery within an interplanetary dust particle (IDP) that likely originated from a comet [1]. Three discrete brownleeite grains in the IDP L2055 I3 (4 microns in size, hereafter IDP I3) were identified with maximum dimensions of 100, 250 and 600 nm and fully analyzed using scanning-transmission electron microscopy (STEM) [1]. One of the grains (100 nm in size) was poikilitically enclosed by low-Fe, Mn-enriched (LIME) olivine. LIME olivine is epitaxial to the brownleeite with the brownleeite (200) parallel to the olivine c* [1]. LIME olivine is an enigmatic phase first reported from chondritic porous IDPs and some unequilibrated ordinary chondrites [ 2], that is commonly observed in chondritic-porous IDPs. Recently, LIME olivine has been also found in comet Wild-2 (Stardust) samples [3], indicating that LIME olivine is a common mineral component of comets. LIME olivine has been proposed to form as a high temperature condensate in the protosolar nebula [2]. Brownleeite grains also likely formed as high-temperature condensates either in the early Solar System or in the outflow of an evolved star or supernova explosion [1]. The isotopic composition of the brownleeite grains may strongly constrain their ultimate source. To test this hypothesis, we performed isotopic analyses of the brownleeite and the associated LIME olivine, using the NASA/JSC NanoSIMS 50L ion microprobe.

  7. Onsager reciprocity principle for kinetic models and kinetic schemes

    CERN Document Server

    Mahendra, Ajit Kumar

    2013-01-01

    Boltzmann equation requires some alternative simpler kinetic model like BGK to replace the collision term. Such a kinetic model which replaces the Boltzmann collision integral should preserve the basic properties and characteristics of the Boltzmann equation and comply with the requirements of non equilibrium thermodynamics. Most of the research in development of kinetic theory based methods have focused more on entropy conditions, stability and ignored the crucial aspect of non equilibrium thermodynamics. The paper presents a new kinetic model formulated based on the principles of non equilibrium thermodynamics. The new kinetic model yields correct transport coefficients and satisfies Onsager's reciprocity relationship. The present work also describes a novel kinetic particle method and gas kinetic scheme based on this linkage of non-equilibrium thermodynamics and kinetic theory. The work also presents derivation of kinetic theory based wall boundary condition which complies with the principles of non-equili...

  8. Calcium isotopes in wine

    Science.gov (United States)

    Holmden, C. E.

    2011-12-01

    The δ 44/40Ca values of bottled wine vary between -0.76% to -1.55% on the seawater scale and correlate weakly with inverse Ca concentration and Mg/Ca ratio, such that the lowest δ 44/40Ca values have the highest Ca concentrations and lowest Mg/Ca ratios. The correlation is notable in the sense that the measured wines include both whites and reds sampled from different wine growing regions of the world, and cover a wide range of quality. Trends among the data yield clues regarding the cause of the observed isotopic fractionation. White wines, and wines generally perceived to be of lower quality, have lower δ 44/40Ca values compared to red wines and wines of generally perceived higher quality. Quality was assessed qualitatively through sensory evaluation, price, and scores assigned by critics. The relationship between δ 44/40Ca and wine quality was most apparent when comparing wines of one varietal from one producer from the same growing region. In the vineyard, wine quality is related to factors such as the tonnage of the crop and the ripeness of the grapes at the time of harvesting, the thickness of the skins for reds, the age of the vines, as well as the place where the grapes were grown (terroir). Quality is also influenced by winemaking practices such as fermentation temperature, duration of skin contact, and barrel ageing. Accordingly, the relationship between δ 44/40Ca and wine quality may originate during grape ripening in the vineyard or during winemaking in the cellar. We tested the grape ripening hypothesis using Merlot grapes sampled from a vineyard in the Okanagan, British Columbia, using sugar content (degrees Brix) as an indicator of ripeness. The grapes were separated into pulp, skin, and pip fractions and were analyzed separately. Thus far, there is no clear evidence for a systematic change in δ 44/40Ca values associated with progressive ripening of grapes in the vineyard. On the day of harvesting, the δ 44/40Ca value of juice squeezed from

  9. Bond energies in polyunsaturated acids and kinetics of co-oxidation of protiated and deuterated acids

    Science.gov (United States)

    Andrianova, Z. S.; Breslavskaya, N. N.; Pliss, E. M.; Buchachenko, A. L.

    2016-10-01

    A computational program specially designed to analyze co-oxidation of substances in mixtures is suggested. The rigorous kinetic scheme of 32 reactions describing co-oxidation of isotope differing polyunsaturated fatty acids was computed to enlighten experimentally detected enormously large H/D isotope effects. The latter were shown to depend on the kinetic chain length and exhibit two extreme regimes of short and long chains which characterize isotope effects on the initiation and propagation chain reactions of hydrogen (deuterium) atom abstraction. No protective effect of deuterated polyunsaturated acids on the oxidation of protiated acids was detected. Protective effect of the deuterated compounds on the biologically important processes seems to be induced by the low yield of products formed in the chain termination reactions due to the low rate of initiation by deuterated compounds.

  10. Isotope Fractionation by Diffusion in Liquids (Final Technical Report)

    Energy Technology Data Exchange (ETDEWEB)

    Richter, Frank [Univ. of Chicago, IL (United States)

    2016-11-09

    The overall objective of the DOE-funded research by grant DE-FG02-01ER15254 was document and quantify kinetic isotope fractionations during chemical and thermal (i.e., Soret) diffusion in liquids (silicate melts and water) and in the later years to include alloys and major minerals such as olivine and pyroxene. The research involved both laboratory experiments and applications to natural settings. The key idea is that major element zoning on natural geologic materials is common and can arise for either changes in melt composition during cooling and crystallization or from diffusion. The isotope effects associated with diffusion that we have documented are the key for determining whether or not the zoning observed in a natural system was the result of diffusion. Only in those cases were the zoning is demonstrably due to diffusion can use independently measured rates of diffusion to constrain the thermal evolution of the system.

  11. The isotopic composition of methane in the stratosphere: high-altitude balloon sample measurements

    Directory of Open Access Journals (Sweden)

    T. Röckmann

    2011-12-01

    Full Text Available The isotopic composition of stratospheric methane has been determined on a large suite of air samples from stratospheric balloon flights covering subtropical to polar latitudes and a time period of 16 yr. 154 samples were analyzed for δ13C and 119 samples for δD, increasing the previously published dataset for balloon borne samples by an order of magnitude, and more than doubling the total available stratospheric data (including aircraft samples published to date. The samples also cover a large range in mixing ratio from tropospheric values near 1800 ppb down to only 250 ppb, and the strong isotope fractionation processes accordingly increase the isotopic composition up to δ13C = −14‰ and δD = +190‰, the largest enrichments observed for atmospheric CH4 so far. When analyzing and comparing kinetic isotope effects (KIEs derived from single balloon profiles, it is necessary to take into account the residence time in the stratosphere in combination with the observed mixing ratio and isotope trends in the troposphere, and the range of isotope values covered by the individual profile. The isotopic composition of CH4 in the stratosphere is affected by both chemical and dynamical processes. This severely hampers interpretation of the data in terms of the relative fractions of the three important sink mechanisms (reaction with OH, O(1D and Cl. It is shown that a formal sink partitioning using the measured data severely underestimates the fraction removed by OH, which is likely due to the insensitivity of the measurements to the kinetic fractionation in the lower stratosphere. Full quantitative interpretation of the CH4 isotope data in terms of the three sink reactions requires a global model.

  12. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  13. Copper isotope fractionation between aqueous compounds relevant to low temperature geochemistry and biology

    Science.gov (United States)

    Fujii, Toshiyuki; Moynier, Frédéric; Abe, Minori; Nemoto, Keisuke; Albarède, Francis

    2013-06-01

    Isotope fractionation between the common Cu species present in solution (Cu+, Cu2+, hydroxide, chloride, sulfide, carbonate, oxalate, and ascorbate) has been investigated using both ab initio methods and experimental solvent extraction techniques. In order to establish unambiguously the existence of equilibrium isotope fractionation (as opposed to kinetic isotope fractionation), we first performed laboratory-scale liquid-liquid distribution experiments. Upon exchange between HCl medium and a macrocyclic complex, the 65Cu/63Cu ratio fractionated by -1.06‰ to -0.39‰. The acidity dependence of the fractionation was appropriately explained by ligand exchange reactions between hydrated H2O and Cl- via intramolecular vibrations. The magnitude of the Cu isotope fractionation among important Cu ligands was also estimated by ab initio methods. The magnitude of the nuclear field shift effect to the Cu isotope fractionation represents only ˜3% of the mass-dependent fractionation. The theoretical estimation was expanded to chlorides, hydroxides, sulfides, sulfates, and carbonates under different conditions of pH. Copper isotope fractionation of up to 2‰ is expected for different forms of Cu present in seawater and for different sediments (carbonates, hydroxides, and sulfides). We found that Cu in dissolved carbonates and sulfates is isotopically much heavier (+0.6‰) than free Cu. Isotope fractionation of Cu in hydroxide is minimal. The relevance of these new results to the understanding of metabolic processes was also discussed. Copper is an essential element used by a large number of proteins for electron transfer. Further theoretical estimates of δ65Cu in hydrated Cu(I) and Cu(II) ions, Cu(II) ascorbates, and Cu(II) oxalate predict Cu isotope fractionation during the breakdown of ascorbate into oxalate and account for the isotopically heavy Cu found in animal kidneys.

  14. Technical Note: Silica stable isotopes and silicification in a carnivorous sponge \\textit{Asbestopluma} sp.

    Directory of Open Access Journals (Sweden)

    K. R. Hendry

    2014-12-01

    Full Text Available The stable isotope composition of benthic sponge spicule silica is a potential source of palaeoceanographic information about past deep seawater chemistry. The silicon isotopic composition of spicules has been shown to relate to the silicic acid concentration of ambient water, although existing calibrations do exhibit a degree of scatter in the relationship. Less is known about how the oxygen isotope composition of sponge spicule silica relates to environmental conditions during growth. Here, we investigate the biological vital effects on silica silicon and oxygen isotope composition in a carnivorous sponge, Asbestopluma sp., from the Southern Ocean. We find significant variations in silicon and oxygen isotopic composition within the specimen that appear related to unusual spicule silicification. The largest variation in both isotope systems was associated to the differential distribution of an unconventional, hypersilicified spicule type (desma along the sponge body. The absence of an internal canal in the desmas suggests an unconventional silicification pattern leading to an unusually heavy isotopic signature. Additional internal variability derives from a systematic offset between the peripheral skeleton of the body having systematically a higher isotopic composition than the internal skeleton. A simplified silicon isotope fractionation model, in which desmas were excluded, suggests that the lack of a system for seawater pumping in carnivorous sponges favours a low replenishment of dissolved silicon within the internal tissues, causing kinetic fractionation during silicification that impacts the isotopic signature of the internal skeleton. Analysis of multiple spicules should be carried out to "average out" any artefacts in order to produce more robust downcore measurements.

  15. Quantum kinetic theory

    CERN Document Server

    Bonitz, Michael

    2016-01-01

    This book presents quantum kinetic theory in a comprehensive way. The focus is on density operator methods and on non-equilibrium Green functions. The theory allows to rigorously treat nonequilibrium dynamics in quantum many-body systems. Of particular interest are ultrafast processes in plasmas, condensed matter and trapped atoms that are stimulated by rapidly developing experiments with short pulse lasers and free electron lasers. To describe these experiments theoretically, the most powerful approach is given by non-Markovian quantum kinetic equations that are discussed in detail, including computational aspects.

  16. Oxygen Isotope Fractionation in TiO2 Polymorphs and Application to Geothermometry of Eclogites

    Institute of Scientific and Technical Information of China (English)

    郑永飞

    1995-01-01

    Oxygen isotope fractionation in TiO2 polymorphs has been calculated by the modi-fied increment method .The results that rutile is enriched in 18O relative to brookite but depleted in 18O relative to anatase.Due to the same crystal structure ,oxygen isotope partitioning in the TiO2 polymorphs is determined by the cation-oxygen inter-atomic distances.The theoretical calibrations involving rutile are in fair agreement with known experimental measurements and empirical estimates.Application of the theoretic-cal quartz-rutile calibration to geothermometry of natural eclogite assemblages indicates the preservation of isotopic equilibrium at high temperatures.The isotopic temperatures calculated are only slightly lower than the non-isotopic temperatures,indicating the slow rates of exchange for oxygen diffusion in rutile.The kinetics of exchange for oxygen diffu-sion in rutile is accordingly estimated by reconciling the differences between the isotopic and the non-isotopic temperatures.The rates of exchange for oxygen diffusion in rutile should be smaller than those for hornblende,but may be equal to or greater than those for diopside.

  17. Tracking the weathering of basalts on Mars using lithium isotope fractionation models

    Science.gov (United States)

    Fairén, Alberto G.; Losa-Adams, Elisabeth; Gil-Lozano, Carolina; Gago-Duport, Luis; Uceda, Esther R.; Squyres, Steven W.; Rodríguez, J. Alexis P.; Davila, Alfonso F.; McKay, Christopher P.

    2015-04-01

    Lithium (Li), the lightest of the alkali elements, has geochemical properties that include high aqueous solubility (Li is the most fluid mobile element) and high relative abundance in basalt-forming minerals (values ranking between 0.2 and 12 ppm). Li isotopes are particularly subject to fractionation because the two stable isotopes of lithium—7Li and 6Li—have a large relative mass difference (˜15%) that results in significant fractionation between water and solid phases. The extent of Li isotope fractionation during aqueous alteration of basalt depends on the dissolution rate of primary minerals—the source of Li—and on the precipitation kinetics, leading to formation of secondary phases. Consequently, a detailed analysis of Li isotopic ratios in both solution and secondary mineral lattices could provide clues about past Martian weathering conditions, including weathering extent, temperature, pH, supersaturation, and evaporation rate of the initial solutions in contact with basalt rocks. In this paper, we discuss ways in which Martian aqueous processes could have lead to Li isotope fractionation. We show that Li isotopic data obtained by future exploration of Mars could be relevant to highlighting different processes of Li isotopic fractionation in the past, and therefore to understanding basalt weathering and environmental conditions early in the planet's history.

  18. Kinetic study on the H + SiH4 abstraction reaction using an ab initio potential energy surface.

    Science.gov (United States)

    Cao, Jianwei; Zhang, Zhijun; Zhang, Chunfang; Bian, Wensheng; Guo, Yin

    2011-01-14

    Variational transition state theory calculations with the correction of multidimensional tunneling are performed on a 12-dimensional ab initio potential energy surface for the H + SiH(4) abstraction reaction. The surface is constructed using a dual-level strategy. For the temperature range 200-1600 K, thermal rate constants are calculated and kinetic isotope effects for various isotopic species of the title reaction are investigated. The results are in very good agreement with available experimental data.

  19. Sensitivity Analysis for Reactor Period Induced by Positive Reactivity Using One-point Adjoint Kinetic Equation

    Science.gov (United States)

    Chiba, G.; Tsuji, M.; Narabayashi, T.

    2014-04-01

    In order to better predict a kinetic behavior of a nuclear fission reactor, an improvement of the delayed neutron parameters is essential. The present paper specifies important nuclear data for a reactor kinetics: Fission yield and decay constant data of 86Ge, some bromine isotopes, 94Rb, 98mY and some iodine isotopes. Their importance is quantified as sensitivities with a help of the adjoint kinetic equation, and it is found that they are dependent on an inserted reactivity (or a reactor period). Moreover, dependence of sensitivities on nuclear data files is also quantified using the latest files. Even though the currently evaluated data are used, there are large differences among different data files from a view point of the delayed neutrons.

  20. Kinetics and mechanism of the oxidation of some diols by benzyltrimethylammonium tribromide

    Indian Academy of Sciences (India)

    Garima Goswami; Seema Kothari; Kalyan K Banerji

    2001-02-01

    The kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers by benzyltrimethylammonium tribromide (BTMAB) have been studied in 3:7 (/) acetic acid-water mixture. The vicinal diols yield the carbonyl compounds arising out of the glycol bond fission while the other diols give the hydroxycarbonyl compounds. The reaction is first-order with respect to BTMAB. Michaelis-Menten type kinetics is observed with respect to diol. Addition of benzyltrimethylammonium chloride does not affect the rate. Tribromide ion is postulated to be the reactive oxidizing species. Oxidation of [1,1,2,2-2H4] ethanediol shows the absence of a kinetic isotope effect. The reaction exhibits substantial solvent isotope effect. A mechanism involving a glycol-bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidized by a hydride ion transfer to the oxidant, as are the monohydric alcohols.

  1. Competition from Isotopic Modelling

    Directory of Open Access Journals (Sweden)

    Virginie Fabre

    2011-01-01

    Full Text Available During later MOIS3, in Europe two populations were present, autochthonous Neanderthals and modern humans. Ecological competition between these two populations has often been evoked but never demonstrated. Our aim is to establish whether resource competition occurred. In this paper, in order to examine the possibility of ecological competition between these two populations, 599 isotopic data were subjected to rigorous statistical treatment and analysis through mixing models. The aim of this paper was to compare dietary strategies of Neanderthals and modern humans over time. Our conclusions suggest that Neanderthals and modern humans shared dietary habits in the particular environmental context of MOIS3 characterised in Europe by climatic deterioration. In this environmental context, the resource competition between Neanderthals and modern humans may have accelerated the disappearance of the Neanderthal population.

  2. Precise measurement of chromium isotopes by MC-ICPMS.

    Science.gov (United States)

    Schiller, Martin; Van Kooten, Elishevah; Holst, Jesper C; Olsen, Mia B; Bizzarro, Martin

    2014-08-01

    We report novel analytical procedures allowing for the concurrent determination of the stable and mass-independent Cr isotopic composition of silicate materials by multiple collector inductively coupled mass spectrometry (MC-ICPMS). In particular, we focus on improved precision of the measurement of the neutron-rich isotope (54)Cr. Because nitride and oxide interferences are a major obstacle to precise and accurate (54)Cr measurements by MC-ICPMS, our approach is designed to minimize these interferences. Based on repeat measurements of standards, we show that the mass-independent (53)Cr and (54)Cr compositions can be routinely determined with an external reproducibility better than 2.5 and 5.8 ppm (2 sd), respectively. This represents at least a two-fold improvement compared to previous studies. Although this approach uses significantly more Cr (30-60 μg) than analysis by thermal ionization mass spectrometry (TIMS), our result indicate that it is possible to obtain an external reproducibility of 19 ppm for the μ(54)Cr when consuming amounts similar to that typically analyzed by TIMS (1 μg). In addition, the amount of time required for analysis by MC-ICPMS is much shorter thereby enabling a higher sample throughput. As a result of the improved analytical precision, we identified small apparent mass-independent differences between different synthetic Cr standards and bulk silicate Earth (BSE) when using the kinetic law for the mass bias correction. These differences are attributed to the Cr loss by equilibrium processes during production of the synthetic standards. The stable isotope data concurrently obtained have a precision of 0.05‰ Da (-1), which is comparable to earlier studies. Comparison of the measured isotopic composition of four meteorites with published data indicates that Cr isotope data measured by the technique described here are accurate to stated uncertainties. The stable Cr composition of the Bilanga and NWA 2999 achondrites suggests that the

  3. Kinetic and Related Determinants of Plasma Triglyceride Concentration in Abdominal Obesity: Multicenter Tracer Kinetic Study.

    Science.gov (United States)

    Borén, Jan; Watts, Gerald F; Adiels, Martin; Söderlund, Sanni; Chan, Dick C; Hakkarainen, Antti; Lundbom, Nina; Matikainen, Niina; Kahri, Juhani; Vergès, Bruno; Barrett, P Hugh R; Taskinen, Marja-Riitta

    2015-10-01

    Patients with obesity and diabetes mellitus have increased risk of cardiovascular disease. A major cause is an atherogenic dyslipidemia related primarily to elevated plasma concentrations of triglyceride-rich lipoproteins. The aim of this study was to clarify determinants of plasma triglyceride concentration. We focused on factors that predict the kinetics of very-low density lipoprotein 1 (VLDL1) triglycerides. A multicenter study using dual stable isotopes (deuterated leucine and glycerol) and multicompartmental modeling was performed to elucidate the kinetics of triglycerides and apoB in VLDL1 in 46 subjects with abdominal obesity and additional cardiometabolic risk factors. Results showed that plasma triglyceride concentrations were dependent on both the secretion rate (r=0.44, Ptriglycerides and VLDL1-apoB. Liver fat mass was independently and directly associated with secretion rates of VLDL1-triglycerides (r=0.56, Ptriglycerides (r=0.48, Ptriglyceride concentrations in abdominal obesity are determined by the kinetics of VLDL1 subspecies, catabolism being mainly dependent on apoC-III concentration and secretion on liver fat content. Reduction in liver fat and targeting apoC-III may be an effective approach for correcting triglyceride metabolism atherogenic dyslipidemia in obesity. © 2015 American Heart Association, Inc.

  4. Isotope Effects in ESR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Werner Herrmann

    2013-06-01

    Full Text Available In order to present the relationship between ESR spectroscopy and isotope effects three levels are considered: (i ESR spectroscopy is described on a general level up to the models for interpretation of the experimental spectra, which go beyond the usually used time and mass independent spin-Hamilton operator, (ii the main characteristics of the generalized isotope effects are worked out, and finally (iii the basic, mainly quantum mechanical effects are used to describe the coupling of electron spins with the degrees of freedom, which are accessible under the selected conditions, of the respective paramagnetic object under investigation. The ESR parameters and the respective models are formalized so far, that they include the time and mass depending influences and reflect the specific isotope effects. Relations will be established between the effects in ESR spectra to spin relaxation, to spin exchange, to the magnetic isotope effect, to the Jahn-Teller effects, as well as to the influence of zero-point vibrations. Examples will be presented which demonstrate the influence of isotopes as well as the kind of accessible information. It will be differentiated with respect to isotope effects in paramagnetic centres itself and in the respective matrices up to the technique of ESR imaging. It is shown that the use of isotope effects is indispensable in ESR spectroscopy.

  5. CANCELLED Molecular dynamics simulations of noble gases in liquidwater: Solvati on structure, self-diffusion, and kinetic isotopeeffect

    Energy Technology Data Exchange (ETDEWEB)

    Bourg, I.C.; Sposito, G.

    2007-05-25

    Despite their great importance in low-temperaturegeochemistry, self-diffusion coefficients of noble gas isotopes in liquidwater (D) have been measured only for the major isotopes of helium, neon,krypton and xenon. Data on the self-diffusion coefficients of minor noblegas isotopes are essentially non-existent and so typically are estimatedby a kinetic theory model in which D varies as the inverse square root ofthe isotopic mass (m): D proportional to m-0.5. To examine the validityof the kinetic theory model, we performed molecular dynamics (MD)simulations of the diffusion of noble gases in ambient liquid water withan accurate set of noble gas-water interaction potentials. Our simulationresults agree with available experimental data on the solvation structureand self-diffusion coefficients of the major noble gas isotopes in liquidwater and reveal for the first time that the isotopic mass-dependence ofall noble gas self-diffusion coefficients has the power-law form Dproportional to m-beta with 0kinetic fractionation of noble gasisotopes caused by diffusion in ambient liquid water.

  6. Oxidative desulfurization: kinetic modelling.

    Science.gov (United States)

    Dhir, S; Uppaluri, R; Purkait, M K

    2009-01-30

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

  7. Kinetics and Catalysis Demonstrations.

    Science.gov (United States)

    Falconer, John L.; Britten, Jerald A.

    1984-01-01

    Eleven videotaped kinetics and catalysis demonstrations are described. Demonstrations include the clock reaction, oscillating reaction, hydrogen oxidation in air, hydrogen-oxygen explosion, acid-base properties of solids, high- and low-temperature zeolite reactivity, copper catalysis of ammonia oxidation and sodium peroxide decomposition, ammonia…

  8. Kinetic Gravity Separation

    NARCIS (Netherlands)

    Van Kooy, L.; Mooij, M.; Rem, P.

    2004-01-01

    Separations by density, such as the separation of non-ferrous scrap into light and heavy alloys, are often realized by means of heavy media. In principle, kinetic gravity separations in water can be faster and cheaper, because they do not rely on suspensions or salt solutions of which the density

  9. Kinetic modelling of molecular hydrogen transport in microporous carbon materials.

    Science.gov (United States)

    Hankel, Marlies; Zhang, Hong; Nguyen, Thanh X; Bhatia, Suresh K; Gray, Stephen K; Smith, Sean C

    2011-05-07

    The proposal of kinetic molecular sieving of hydrogen isotopes is explored by employing statistical rate theory methods to describe the kinetics of molecular hydrogen transport in model microporous carbon structures. A Lennard-Jones atom-atom interaction potential is utilized for the description of the interactions between H(2)/D(2) and the carbon framework, while the requisite partition functions describing the thermal flux of molecules through the transition state are calculated quantum mechanically in view of the low temperatures involved in the proposed kinetic molecular sieving application. Predicted kinetic isotope effects for initial passage from the gas phase into the first pore mouth are consistent with expectations from previous modeling studies, namely, that at sufficiently low temperatures and for sufficiently narrow pore mouths D(2) transport is dramatically favored over H(2). However, in contrast to expectations from previous modeling, the absence of any potential barrier along the minimum energy pathway from the gas phase into the first pore mouth yields a negative temperature dependence in the predicted absolute rate coefficients-implying a negative activation energy. In pursuit of the effective activation barrier, we find that the minimum potential in the cavity is significantly higher than in the pore mouth for nanotube-shaped models, throwing into question the common assumption that passage through the pore mouths should be the rate-determining step. Our results suggest a new mechanism that, depending on the size and shape of the cavity, the thermal activation barrier may lie in the cavity rather than at the pore mouth. As a consequence, design strategies for achieving quantum-mediated kinetic molecular sieving of H(2)/D(2) in a microporous membrane will need, at the very least, to take careful account of cavity shape and size in addition to pore-mouth size in order to ensure that the selective step, namely passage through the pore mouth, is also

  10. Isotope-edited infrared spectroscopy.

    Science.gov (United States)

    Buchner, Ginka S; Kubelka, Jan

    2012-01-01

    Isotope-edited infrared (IR) spectroscopy is a powerful tool for studying structural and dynamical properties of peptides and proteins with site-specific resolution. Labeling of selected amide carbonyls with (13)C results in detectable sidebands of amide I' vibrations, which provide information about local conformation and/or solvent exposure without structural perturbation to the protein. Incorporation of isotopically labeled amino acids at specific positions is achieved by the chemical synthesis of the studied proteins. We describe the basic procedures for synthesis of (13)C isotopically edited protein samples, experimental IR spectroscopic measurements, and analysis of the site-specific structural changes from the thermal unfolding IR data.

  11. Compelling Research Opportunities using Isotopes

    Energy Technology Data Exchange (ETDEWEB)

    None

    2009-04-23

    Isotopes are vital to the science and technology base of the US economy. Isotopes, both stable and radioactive, are essential tools in the growing science, technology, engineering, and health enterprises of the 21st century. The scientific discoveries and associated advances made as a result of the availability of isotopes today span widely from medicine to biology, physics, chemistry, and a broad range of applications in environmental and material sciences. Isotope issues have become crucial aspects of homeland security. Isotopes are utilized in new resource development, in energy from bio-fuels, petrochemical and nuclear fuels, in drug discovery, health care therapies and diagnostics, in nutrition, in agriculture, and in many other areas. The development and production of isotope products unavailable or difficult to get commercially have been most recently the responsibility of the Department of Energy's Nuclear Energy program. The President's FY09 Budget request proposed the transfer of the Isotope Production program to the Department of Energy's Office of Science in Nuclear Physics and to rename it the National Isotope Production and Application program (NIPA). The transfer has now taken place with the signing of the 2009 appropriations bill. In preparation for this, the Nuclear Science Advisory Committee (NSAC) was requested to establish a standing subcommittee, the NSAC Isotope Subcommittee (NSACI), to advise the DOE Office of Nuclear Physics. The request came in the form of two charges: one, on setting research priorities in the short term for the most compelling opportunities from the vast array of disciplines that develop and use isotopes and two, on making a long term strategic plan for the NIPA program. This is the final report to address charge 1. NSACI membership is comprised of experts from the diverse research communities, industry, production, and homeland security. NSACI discussed research opportunities divided into three areas: (1

  12. Carbon isotope geochemistry and geobiology

    Science.gov (United States)

    Desmarais, D.

    1985-01-01

    Carbon isotope fractionation values were used to understand the history of the biosphere. For example, plankton analyses confirmed that marine extinctions at the end of the Cretaceous period were indeed severe (see Hsu's article in Sundquist and Broeker, 1984). Variations in the isotopic compositions of carbonates and evaporitic sulfates during the Paleozoic reflect the relative abundances of euxinic (anoxic) marine environments and organic deposits from terrestrial flora. The carbon isotopic composition of Precambrian sediments suggest that the enzyme ribulose bisphosphate carboxylase has existed for perhaps 3.5 billion years.

  13. Apparatus and process for separating hydrogen isotopes

    Science.gov (United States)

    Heung, Leung K; Sessions, Henry T; Xiao, Xin

    2013-06-25

    The apparatus and process for separating hydrogen isotopes is provided using dual columns, each column having an opposite hydrogen isotopic effect such that when a hydrogen isotope mixture feedstock is cycled between the two respective columns, two different hydrogen isotopes are separated from the feedstock.

  14. Clumped-Isotope Thermometry and Oxygen Isotope Systematics in Speleothem Calcite From a Near Cave-Entrance Environment

    Science.gov (United States)

    Carlson, P. E.; Banner, J.; Breecker, D.; Affek, H. P.

    2015-12-01

    Speleothems that grow in well-ventilated zones of caves have not been widely used in paleoclimate studies, yet may provide paleotemperature records. These zones are characterized by low CO2 concentrations year-round and, in temperate climates, large seasonal temperature fluctuations. They are typically avoided for paleoclimate reconstruction due to concerns about kinetic isotope effects (KIE). However, speleothems in general seem to be sensitive to KIE, even in non-ventilated areas and can nonetheless provide useful paleoclimate records. At Westcave Preserve (Westcave), a shallow, well-ventilated cave in central Texas, we have found seasonal temperature differences recorded in both the oxygen isotope and clumped isotope compositions of speleothem calcite grown on glass-plate substrates harvested from active drips. Although growth rates in this cave are relatively rapid, speleothem analogs in Westcave are growing near oxygen-isotopic equilibrium with their drip waters (between the calibrations of Kim and O'Neil, 1997 and Coplen, 2007). We have tested the compatibility of the Zaarur et al. (2013) clumped isotope bulk solution thermometer calibration to glass-substrate calcite in the cave collected during various months. This technique can provide absolute temperatures, but is sensitive to kinetic isotope effects, often significantly overestimating growth temperatures of speleothems. When this thermometer was applied to calcite collected from near where the plates were impacted by drip water, it overestimated measured temperatures by 7.7 ± 4.3°C, showing moderate KIE. When applied to calcite away from the drip impact, it overestimated temperatures by 18.7 ± 4.2°C, showing KIE increasing away from the drip. Measured monthly average temperatures in the cave ranged seasonally between 8 and 28°C, and daily temperatures vary significantly. At Westcave, calcite growth rates increase with temperature, and the calcite may therefore preferentially record warmer daily or

  15. Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

    Energy Technology Data Exchange (ETDEWEB)

    Frierdich, Andrew J. [Univ. of Wisconsin, Madison, WI (United States); Univ. of Iowa, Iowa City, IA (United States); Beard, Brian L. [Univ. of Wisconsin, Madison, WI (United States); Rosso, Kevin M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Scherer, Michelle M. [Univ. of Iowa, Iowa City, IA (United States); Spicuzza, Michael J. [Univ. of Wisconsin, Madison, WI (United States); Valley, John W. [Univ. of Wisconsin, Madison, WI (United States); Johnson, Clark M. [Univ. of Wisconsin, Madison, WI (United States)

    2015-07-01

    The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Fe isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II)aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II)aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II)aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous

  16. Utilization of stable isotopes in pharmacology and living matter sciences; Emploi des isotopes stables en pharmacologie et dans les sciences de la matiere vivante

    Energy Technology Data Exchange (ETDEWEB)

    Brazier, J.L. [Institut des Sciences Pharmaceutiques et Biologiques, 69 -Lyon (France)

    1994-12-31

    A survey of the various application fields of stable isotopes in the pharmacological and biomedical domains is presented: utilization of labelled molecules as real tracers (metabolism studies with chromatography and mass spectrometry, studies in bio-pharmacy, bio-availability and bio-equivalence for comparison of medicaments forms, use of stable isotope pulsed doses for medicament kinetics study); methods using voluntary induced isotopic effects in a biologic system; utilization of the carbon {sup 13}C/{sup 12}C ratio and its evolution with time in a living system for in vitro, ex vivo, in vivo studies on man and animals: metabolic tests, dysabsorption tests, bacterial proliferation and infection tests, enzymatic induction and inhibition determination tests.

  17. Alignments in the nobelium isotopes

    Institute of Scientific and Technical Information of China (English)

    ZHENG Shi-Zie; XU Fu-Rong; YUAN Cen-Xi; QI Chong

    2009-01-01

    Total-Routhian-Surface calculations have been performed to investigate the deformation and align-ment properties of the No isotopes. It is found that normal deformed and superdeformed states in these nuclei can coexist at low excitation energies. In neutron-deficient No isotopes, the superdeformed shapes can even become the ground states. Moreover, we plotted the kinematic moments of inertia of the No isotopes, which follow very nicely available experimental data. It is noted that, as the rotational frequency increases, align-ments develop at hω=0.2-0.3 MeV. Our calculations show that the occupation of the vj orbital plays an important role in the alignments of the No isotopes.

  18. Isotope-based quantum information

    CERN Document Server

    G Plekhanov, Vladimir

    2012-01-01

    The present book provides to the main ideas and techniques of the rapid progressing field of quantum information and quantum computation using isotope - mixed materials. It starts with an introduction to the isotope physics and then describes of the isotope - based quantum information and quantum computation. The ability to manipulate and control electron and/or nucleus spin in semiconductor devices provides a new route to expand the capabilities of inorganic semiconductor-based electronics and to design innovative devices with potential application in quantum computing. One of the major challenges towards these objectives is to develop semiconductor-based systems and architectures in which the spatial distribution of spins and their properties can be controlled. For instance, to eliminate electron spin decoherence resulting from hyperfine interaction due to nuclear spin background, isotopically controlled devices are needed (i.e., nuclear spin-depleted). In other emerging concepts, the control of the spatial...

  19. Isotopic Changes During Digestion: Protein

    Science.gov (United States)

    Tuross, N.

    2013-12-01

    Nutrient and hydrological inputs traverse a complicated route of pH, enzymatic and cellular processes in digestion in higher animals. The end products of digestion are the starting products for biosynthesis that are often used to interpret past life-ways. Using an artificial gut system, the isotopic changes (dD, d18O, d13C and d15N) of protein are documented. Three separate protein sources are subjected to the conditions, chemical and enzymatic, found in the stomach and upper small intestine with only a small shift in the oxygen isotopic composition of the proteins observed. Middle to lower small intestine parameters produced both greater isotopic effects and significantly lower molecular weight products. The role of the gastric enterocyte and the likely involvement of the internal milieu of this cell in the isotopic composition of amino acids that are transported to the liver are reported.

  20. Isotopic Composition of Light Nuclei in Cosmic Rays: Results from AMS-01

    Science.gov (United States)

    Aguilar, M.; Alcaraz, J.; Allaby, J.; Alpat, B.; Ambrosi, G.; Anderhub, H.; Ao, L.; Arefiev, A.; Arruda, L.; Azzarello, P.; Basile, M.; Barao, F.; Barreira, G.; Bartoloni, A.; Battiston, R.; Becker, R.; Becker, U.; Bellagamba, L.; Berdugo, J.; Berges, P.; Bertucci, B.; Biland, A.; Bindi, V.; Boella, G.; Boschini, M.; Bourquin, M.; Bruni, G.; Buénerd, M.; Burger, J. D.; Burger, W. J.; Cai, X. D.; Cannarsa, P.; Capell, M.; Casadei, D.; Casaus, J.; Castellini, G.; Cernuda, I.; Chang, Y. H.; Chen, H. F.; Chen, H. S.; Chen, Z. G.; Chernoplekov, N. A.; Chiueh, T. H.; Choi, Y. Y.; Cindolo, F.; Commichau, V.; Contin, A.; Cortina-Gil, E.; Crespo, D.; Cristinziani, M.; Dai, T. S.; dela Guia, C.; Delgado, C.; Di Falco, S.; Djambazov, L.; D'Antone, I.; Dong, Z. R.; Duranti, M.; Engelberg, J.; Eppling, F. J.; Eronen, T.; Extermann, P.; Favier, J.; Fiandrini, E.; Fisher, P. H.; Flügge, G.; Fouque, N.; Galaktionov, Y.; Gervasi, M.; Giovacchini, F.; Giusti, P.; Grandi, D.; Grimm, O.; Gu, W. Q.; Haino, S.; Hangarter, K.; Hasan, A.; Hermel, V.; Hofer, H.; Hungerford, W.; Ionica, M.; Jongmanns, M.; Karlamaa, K.; Karpinski, W.; Kenney, G.; Kim, D. H.; Kim, G. N.; Kim, K. S.; Kirn, T.; Klimentov, A.; Kossakowski, R.; Kounine, A.; Koutsenko, V.; Kraeber, M.; Laborie, G.; Laitinen, T.; Lamanna, G.; Laurenti, G.; Lebedev, A.; Lechanoine-Leluc, C.; Lee, M. W.; Lee, S. C.; Levi, G.; Lin, C. H.; Liu, H. T.; Lu, G.; Lu, Y. S.; Lübelsmeyer, K.; Luckey, D.; Lustermann, W.; Maña, C.; Margotti, A.; Mayet, F.; McNeil, R. R.; Menichelli, M.; Mihul, A.; Mujunen, A.; Natale, S.; Oliva, A.; Palmonari, F.; Paniccia, M.; Park, H. B.; Park, W. H.; Pauluzzi, M.; Pauss, F.; Pereira, R.; Perrin, E.; Pevsner, A.; Pilo, F.; Pimenta, M.; Plyaskin, V.; Pojidaev, V.; Pohl, M.; Produit, N.; Quadrani, L.; Rancoita, P. G.; Rapin, D.; Ren, D.; Ren, Z.; Ribordy, M.; Riihonen, E.; Ritakari, J.; Ro, S.; Roeser, U.; Sagdeev, R.; Santos, D.; Sartorelli, G.; Saouter, P.; Sbarra, C.; Schael, S.; Schultz von Dratzig, A.; Schwering, G.; Seo, E. S.; Shin, J. W.; Shoumilov, E.; Shoutko, V.; Siedenburg, T.; Siedling, R.; Son, D.; Song, T.; Spada, F. R.; Spinella, F.; Steuer, M.; Sun, G. S.; Suter, H.; Tang, X. W.; Ting, Samuel C. C.; Ting, S. M.; Tomassetti, N.; Tornikoski, M.; Torsti, J.; Trümper, J.; Ulbricht, J.; Urpo, S.; Valtonen, E.; Vandenhirtz, J.; Velikhov, E.; Verlaat, B.; Vetlitsky, I.; Vezzu, F.; Vialle, J. P.; Viertel, G.; Vité, D.; Von Gunten, H.; Waldmeier Wicki, S.; Wallraff, W.; Wang, J. Z.; Wiik, K.; Williams, C.; Wu, S. X.; Xia, P. C.; Xu, S.; Xu, Z. Z.; Yan, J. L.; Yan, L. G.; Yang, C. G.; Yang, J.; Yang, M.; Ye, S. W.; Zhang, H. Y.; Zhang, Z. P.; Zhao, D. X.; Zhou, F.; Zhou, Y.; Zhu, G. Y.; Zhu, W. Z.; Zhuang, H. L.; Zichichi, A.; Zimmermann, B.; Zuccon, P.

    2011-08-01

    The variety of isotopes in cosmic rays allows us to study different aspects of the processes that cosmic rays undergo between the time they are produced and the time of their arrival in the heliosphere. In this paper, we present measurements of the isotopic ratios 2H/4He, 3He/4He, 6Li/7Li, 7Be/(9Be+10Be), and 10B/11B in the range 0.2-1.4 GeV of kinetic energy per nucleon. The measurements are based on the data collected by the Alpha Magnetic Spectrometer, AMS-01, during the STS-91 flight in 1998 June.

  1. Isotopic Composition of Light Nuclei in Cosmic Rays: Results from AMS-01

    CERN Document Server

    Aguilar, M; Wiik, K; Grimm, O; Sartorelli, G; Zhou, Y; Pauss, F; Alpat, B; Capell, M; Djambazov, L; Yang, M; Yang, J; Extermann, P; Arefiev, A; Zhuang, H L; Hermel, V; Mihul, A; Galaktionov, Y; Park, H B; Von Gunten, H; Vetlitsky, I; Zhou, F; Vandenhirtz, J; Ambrosi, G; Suter, H; Becker, U; Zhang, H Y; Alcaraz, J; Casaus, J; Ren, Z; Fiandrini, E; Hungerford, W; Ren, D; Wicki, S W; Eppling, F J; Flugge, G; Karlamaa, K; Boella, G; Levi, G; Choi, Y Y; Laborie, G; Lubelsmeyer, K; Gervasi, M; Kirn, T; Azzarello, P; Kounine, A; Barreira, G; Yan, L G; Burger, W J; Koutsenko, V; Grandi, D; Ribordy, M; Gu, W Q; Bindi, V; Favier, J; Haino, S; Shin, J W; Mana, C; Seo, E S; Plyaskin, V; Shoumilov, E; Cannarsa, P; Xia, P C; Ionica, M; Jongmanns, M; Shoutko, V; Wallraff, W; Margotti, A; Lee, S C; Giovacchini, F; Schael, S; Bourquin, M; Roeser, U; Lu, Y S; Torsti, J; Kossakowski, R; Chang, Y H; Menichelli, M; Verlaat, B; Paniccia, M; Steuer, M; Fouque, N; Boschini, M; Zimmermann, B; Song, T; Zuccon, P; Contin, A; Produit, N; Laitinen, T; Kim, K S; Viertel, G; Lin, C H; Lechanoine-Leluc, C; Delgado, C; Lu, G; Pohl, M; Yang, C G; Tornikoski, M; Duranti, M; Cindolo, F; Xu, S; Lebedev, A; Xu, Z Z; Crespo, D; Cristinziani, M; Tomassetti, N; Kim, D H; Biland, A; Bertucci, B; Trumper, J; Buenerd, M; Hangarter, K; Kenney, G; Quadrani, L; Hofer, H; Berdugo, J; Siedenburg, T; Chen, Z G; Ting, S M; Vezzu, F; Cortina-Gil, E; Dai, T S; Barao, F; Commichau, V; Zhang, Z P; Sun, G S; Zhu, W Z; Laurenti, G; Chen, H S; Kim, G N; Sagdeev, R; Wu, S X; Urpo, S; Lee, M W; Rapin, D; Kraeber, M; Chen, H F; Engelberg, J; Ritakari, J; Di Falco, S; Zhu, G Y; Vite, D; Ulbricht, J; Bruni, G; Bellagamba, L; Williams, C; Fisher, P H; D'Antone, I; Pevsner, A; Castellini, G; Chernoplekov, N A; Ao, L; Giusti, P; McNeil, R R; Allaby, J; Yan, J L; Son, D; Santos, D; Cai, X D; Rancoita, P G; Becker, R; Wang, J Z; Oliva, A; Karpinski, W; Cernuda, I; Saouter, P; Ro, S; Anderhub, H; Dela Guia, C; Schwering, G; Ting, S C C; Lamanna, G; Pauluzzi, M; Berges, P; Riihonen, E; Pojidaev, V; Chiueh, T H; Valtonen, E; Pereira, R; Spinella, F; Perrin, E; Park, W H; Dong, Z R; Zichichi, A; Battiston, R; von Dratzig, A S; Vialle, J P; Klimentov, A; Liu, H T; Bartoloni, A; Arruda, L; Tang, X W; Mujunen, A; Pimenta, M; Casadei, D; Spada, F R; Eronen, T; Mayet, F; Palmonari, F; Lustermann, W; Velikhov, E; Pilo, F; Zhao, D X; Luckey, D; Basile, M; Sbarra, C; Natale, S; Siedling, R; Ye, S W; Burger, J D

    2011-01-01

    The variety of isotopes in cosmic rays allows us to study different aspects of the processes that cosmic rays undergo between the time they are produced and the time of their arrival in the heliosphere. In this paper, we present measurements of the isotopic ratios (2)H/(4)He, (3)He/(4)He, (6)Li/(7)Li, (7)Be/((9)Be+(10)Be), and (10)B/(11)B in the range 0.2-1.4 GeV of kinetic energy per nucleon. The measurements are based on the data collected by the Alpha Magnetic Spectrometer, AMS-01, during the STS-91 flight in 1998 June.

  2. Isotopic Composition of Light Nuclei in Cosmic Rays: Results from AMS-01

    OpenAIRE

    Aguilar, M.; Alcaraz, J.; Allaby, J.; Alpat, B.; Ambrosi, G.; Anderhub, H.; Ao, L.; Arefiev, A.; Arruda, L.; P. Azzarello(c); Basile, M.; Barao, F.; G. Barreira(LIP Lisboa); Bartoloni, A; Battiston, R.

    2011-01-01

    The variety of isotopes in cosmic rays allows us to study different aspects of the processes that cosmic rays undergo between the time they are produced and the time of their arrival in the heliosphere. In this paper, we present measurements of the isotopic ratios 2H/4He, 3He/4He, 6Li/7Li, 7Be/(9Be+10Be), and 10B/11B in the range 0.2–1.4 GeV of kinetic energy per nucleon. The measurements are based on the data collected by the Alpha Magnetic Spectrometer, AMS-01, during the STS-91...

  3. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

    OpenAIRE

    Wiegel, Aaron A.; Cole, Amanda S.; Hoag, Katherine J.; Atlas, Elliot L.; Schauffler, Sue M.; Boering, Kristie A.

    2013-01-01

    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone–CO2 isotope exchange demonst...

  4. Experimental Evidence for Hydrogen Tunneling when the Isotopic Arrhenius Prefactor (AH/AD) is Unity

    Science.gov (United States)

    Sharma, Sudhir C.; Klinman, Judith P.

    2009-01-01

    The temperature dependence of the kinetic isotope effect (KIE) is one of the major tools used for the investigation of hydrogen tunneling in condensed phase. Hydrogen transfer reactions displaying isotopic Arrhenius prefactor ratios (AH/AD) of unity are generally ascribed to a semi-classical mechanism. Here, we have identified a double mutant of soybean lipoxygenase (SLO-1, an enzyme previously shown to follow quantum mechanical hydrogen tunneling), that displays an AH/AD of unity and highly elevated (non-classical) KIEs. This observation highlights the shortcoming of assigning a hydrogen transfer reaction to a semi-classical model based solely on an Arrhenius prefactor ratio. PMID:19061319

  5. Applying clumped isotopes of O2 to atmospheric and biogeochemical problems

    Science.gov (United States)

    Yeung, Laurence

    2016-04-01

    I will describe recent measurements of isotopic "clumps" in diatomic molecules, e.g., 18O18O in O2, which are being utilized to constrain atmospheric circulation on glacial-interglacial timescales and biogeochemical cycling in the oceans. While our understanding of these tracers is still evolving, several features of their geochemistry are apparent: (1) the proportional abundance of these isotopic "clumps" is governed by traditional chemical effects as well as combinatorial effects unique to clumped isotopes, and (2) when isotopic exchange reactions are disfavoured, chemical-kinetic and/or reservoir effects, rather than thermodynamic equilibrium, determine their clumped-isotope composition. Combinatorial clumped-isotope signatures imparted during photosynthesis are being developed as endmember signatures of gross primary productivity in the oceans. In addition, clumped-isotope measurements of O2 in the atmosphere (i.e., Δ36 values) suggest that isotopic clumping in O2 is continuously being altered by ozone photochemistry in the troposphere and stratosphere. Yet, the contrast in isotope-exchange rates between the stratosphere (where exchange is fast) and the troposphere (where exchange is slow) results in a gradient in Δ36 values with altitude, wherein stratospheric intrusions are detectable as elevated Δ36 values. Moreover, global chemical-transport model simulations suggest that ozone photochemistry in the troposphere re-orders the O2 reservoir in the troposphere on annual timescales. The Δ36 value at the surface is therefore sensitive to the tropospheric residence time of O2 with respect to stratosphere-troposphere exchange. Consequently, Δ36 values at the surface likely respond to changes in the strength of the global overturning circulation.

  6. Stable carbon and oxygen isotope study on benthic foraminifera: Implication for microhabitat preferences and interspecies correlation

    Indian Academy of Sciences (India)

    Ajoy K Bhaumik; Shiv Kumar; Shilpi Ray; G K Vishwakarma; Anil K Gupta; Pushpendra Kumar; Kalachand Sain

    2017-07-01

    Stable isotopes of benthic foraminifera have widely been applied in micropalaeontological research to understand vital effects in foraminifera. Isotopic fractionations are mainly controlled by ontogeny, bottom/pore water chemistry, habitat preference, kinetic effect and respiration. Discontinuous abundance of a species for isotopic analysis has forced us to select multiple species from down-core samples. Thus standardisation factors are required to convert isotopic values of one species with respect to other species. The present study is pursued on isotopic values of different pairs of benthic foraminifera from the Krishna–Godavari basin and Peru offshore to understand habitat-wise isotopic variation and estimation of isotopic correction factors for the paired species (Cibicides wuellerstorfi–Bulimina marginata, Ammonia spp.–Loxostomum amygdalaeformis and Bolivina seminuda–Nonionella auris). Infaunal species (B. marginata, Ammonia spp. and N. auris) show a lighter carbon isotopic excursion with respect to the epifaunal to shallow infaunal forms (C. wuellerstorfi, L. amygdalaeformis and B. seminuda). These lighter δ13C values are related to utilisation of CO2 produced by anaerobic remineralisation of organic matter. However, enrichment of δ18O for the deeper microhabitat (bearing lower pH and decreased CO32−) is only recorded in case of B. marginata. It is reverse in case of N. auris and related to utilisation of respiratory CO2 and internal dissolve inorganic carbon pool. Estimation of interspecies isotopic correction factors for the species pairs (δ13C of C. wuellerstorfi–B. marginata, L. amygdalaeformis–Ammonia spp., N. auris–B. seminuda) and δ18O of C. wuellerstorfi–B. marginata are statistically reliable and may be used in palaeoecological studies.

  7. W. W. "Mo" Cleland: a catalytic life.

    Science.gov (United States)

    Dunaway-Mariano, Debra; Holden, Hazel M; Raushel, Frank M

    2013-12-23

    Professor W. Wallace Cleland, the architect of modern steady-state enzyme kinetics, died on March 6, 2013, from injuries sustained in a fall outside of his home. He will be most remembered for giving the enzyme community Ping-Pong kinetics and the invention of dithiothreitol (DTT). He pioneered the utilization of heavy atom isotope effects for the elucidation of the chemical mechanisms of enzyme-catalyzed reactions. His favorite research journal was Biochemistry, in which he published more than 135 papers beginning in 1964 with the disclosure of DTT.

  8. A new method for studying iodine metabolism; the isotopic equilibrium method - kinetic and quantitative aspects of measurements made on rats; Une nouvelle methode d'etude du metabolisme de l'iode: la methode d'equilibre isotopique - aspects cinetiques et quantitatifs obtenus chez le rat

    Energy Technology Data Exchange (ETDEWEB)

    Simon, C. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-05-15

    The isotopic equilibrium method which has been developed in the case of the rat has made it possible to measure the absolute values of the principal parameters of iodine metabolism in this animal. The quantities and concentrations of iodine have been measured in the thyroid gland and in the plasma with a sensitivity of 0.001 {mu}g of {sup 127}I. This sensitivity has made it possible to measure pools as small as the iodide and the free iodotyrosines of the thyroid and to demonstrate the absence of free iodotyrosines in the plasma of the normal rat. In vivo, the isotopic equilibrium method has made it possible to measure the iodine content of the thyroid gland and to calculate the intensity of this gland's secretion without removing it. By double labelling with {sup 125}I and {sup 131}I the isotopic equilibrium method has made it possible to measure the flux, intensity of the intrathyroidal recycling as well as the turnover rates of all the iodine containing compounds of the thyroid gland. For this gland no precursor-product relationship has been found between The iodotyrosines (MIT and DIT) and the iodothyronines (T{sub 4} and T{sub 3}). The absence of this relationship is due to the heterogeneity of the thyroglobulin turnover. It has been shown furthermore that there exists in the plasma an organic fraction of the iodine which is different to thyroglobulin and which is renewed more rapidly than the circulating hormones T{sub 3} and T{sub 4}. The isotopic equilibrium method is very useful for series measurements of iodine. It makes it possible furthermore to improve the biochemical fractionations by adding carriers without affecting the subsequent {sup 127}I measurements. (author) [French] La methode d'equilibre isotopique, mise au point chez le rat, a permis de mesurer en valeur absolue les principaux parametres du metabolisme de l'iode chez cet animal. Les quantites ou les concentrations d'iode ont ete mesurees pour la thyroide et pour le

  9. Kinetic Damage from Meteorites

    Science.gov (United States)

    Cooke, W.; Brown, P.; Matney, M.

    2017-01-01

    Comparing the natural meteorite flux at the Earth's surface to that of space debris, re-entering debris is 2 orders of magnitude less of a kinetic hazard at all but the very largest (and therefore rarest) sizes compared to natural impactors. Debris re-entries over several metric tonnes are roughly as frequent as natural impactors, but the survival fraction is expected to be much higher. Kinetic hazards from meteorites are very small, with only one recorded (indirect) injury reported. We expect fatalities to be even more rare, on the order of one person killed per several millennia. That several reports exist of small fragments/sand hitting people during meteorite falls is consistent with our prediction that this should occur every decade or so.

  10. Kinetic Actviation Relaxation Technique

    CERN Document Server

    Béland, Laurent Karim; El-Mellouhi, Fedwa; Joly, Jean-François; Mousseau, Normand

    2011-01-01

    We present a detailed description of the kinetic Activation-Relaxation Technique (k-ART), an off-lattice, self-learning kinetic Monte Carlo algorithm with on-the-fly event search. Combining a topological classification for local environments and event generation with ART nouveau, an efficient unbiased sampling method for finding transition states, k-ART can be applied to complex materials with atoms in off-lattice positions or with elastic deformations that cannot be handled with standard KMC approaches. In addition to presenting the various elements of the algorithm, we demonstrate the general character of k-ART by applying the algorithm to three challenging systems: self-defect annihilation in c-Si, self-interstitial diffusion in Fe and structural relaxation in amorphous silicon.

  11. Photon kinetics in plasmas

    Directory of Open Access Journals (Sweden)

    V.G. Morozov

    2009-01-01

    Full Text Available We present a kinetic theory of radiative processes in many-component plasmas with relativistic electrons and nonrelativistic heavy particles. Using the non-equilibrium Green's function technique in many-particle QED, we show that the transverse field correlation functions can be naturally decomposed into sharply peaked (non-Lorentzian parts that describe resonant (propagating photons and off-shell parts corresponding to virtual photons in the medium. Analogous decompositions are obtained for the longitudinal field correlation functions and the correlation functions of relativistic electrons. We derive a kinetic equation for the resonant photons with a finite spectral width and show that the off-shell parts of the particle and field correlation functions are essential to calculate the local radiating power in plasmas and recover the results of vacuum QED. The plasma effects on radiative processes are discussed.

  12. Kinetic Tetrazolium Microtiter Assay

    Science.gov (United States)

    Pierson, Duane L.; Stowe, Raymond; Koenig, David

    1993-01-01

    Kinetic tetrazolium microtiter assay (KTMA) involves use of tetrazolium salts and Triton X-100 (or equivalent), nontoxic, in vitro color developer solubilizing colored metabolite formazan without injuring or killing metabolizing cells. Provides for continuous measurement of metabolism and makes possible to determine rate of action of antimicrobial agent in real time as well as determines effective inhibitory concentrations. Used to monitor growth after addition of stimulatory compounds. Provides for kinetic determination of efficacy of biocide, greatly increasing reliability and precision of results. Also used to determine relative effectiveness of antimicrobial agent as function of time. Capability of generating results on day of test extremely important in treatment of water and waste, disinfection of hospital rooms, and in pharmaceutical, agricultural, and food-processing industries. Assay also used in many aspects of cell biology.

  13. Paleoproxies: Heavy Stable Isotope Perspectives

    Science.gov (United States)

    Nagler, T. F.; Hippler, D.; Siebert, C.; Kramers, J. D.

    2002-12-01

    Recent advances in isotope ratio mass spectrometry, namely multiple collector ICP-MS and refined TIMS techniques, will significantly enhance the ability to measure heavy stable isotope fractionation, which will lead to the development of a wide array of process-identifying (bio)-geochemical tools. Thus far research in this area is not easily assessable to scientists outside the isotope field. This is due to the fact that analyzing heavy stable isotopes does not provide routine numbers which are per se true (the preciser the truer) but is still a highly experimental field. On the other hand resolving earth science problems requires specialists familiar with the environment being studied. So what is in there for paleoceanographers? In a first order approach, relating isotope variations to physical processes is straightforward. A prominent example are oxygen isotope variations with temperature. The total geological signal is of course far more complicated. At low temperatures, heavy stable isotopes variations have been reported for e.g. Ca, Cr, Fe, Cu, Zn, Mo and Tl. Fractionation mechanisms and physical parameters responsible for the observed variations are not yet resolved for most elements. Significant equilibrium isotope fractionation is expected from redox reactions of transition metals. However a difference in coordination number between two coexisting speciations of an element in the same oxidation state can also cause fractionation. Protonation of dissolved Mo is one case currently discussed. For paleoceanography studies, a principal distinction between transition metals essential for life (V to Zn plus Mo) or not will be helpful. In case of the former group, distinction between biogenic and abiogenic isotope fractionation will remain an important issue. For example, abiotic Fe redox reactions result in isotope fractionations indistinguishable in direction and magnitude from microbial effects. Only a combination of different stable isotope systems bears the

  14. Magnesium isotope fractionation by chemical diffusion in natural settings and in laboratory analogues

    Science.gov (United States)

    Chopra, Rahul; Richter, Frank M.; Bruce Watson, E.; Scullard, Christian R.

    2012-07-01

    between the mafic and felsic rocks. The different degrees of magnesium isotopic fractionation associated with otherwise similar composition gradients in natural settings show that kinetic isotope fractionations provide a key discriminator for establishing whether or not molecular diffusion was the process responsible for an observed elemental gradient. In the one case of a contact at Vinal Cove where we are confident that the magnesium elemental and isotopic gradients were produced by diffusion, we deduced a cooling rate of about 1.5 °C per day.

  15. Flocculation Kinetics of Chitosan

    Institute of Scientific and Technical Information of China (English)

    陈亮; 林志艳; 陈东辉

    2003-01-01

    Under the various conditions, the experiments of flocculation of bentonite solution with chitosan were carried out. And the flocculation kinetics was studied by the changes of floc size along with time. The results show that hydraulic gradient G (s-1) plays a key role in growing up of floc size and both of molecular weight and initial turbidity of bentonite solution influence the floc size in steady state and the time needed for steady floc size.

  16. 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

  17. What is the Role of the Transition State in Soret and Chemical Diffusion Induced Isotopic Fractionation?

    Science.gov (United States)

    Dominguez, G.

    2013-12-01

    For over six decades, Urey's (1) statistical mechanical model of isotopic fractionation based on partition functions with quantized energy levels have enjoyed enormous success in quantitatively explaining equilibrium isotopic fractionation in a wide variety of geochemical systems For example, the interpretation of oxygen isotopic variations in carbonate systems (e.g. foraminiferas), in terms of partition functions with quantized energy levels, forms the basis for paleothermometry (2). Recent observations of isotopic fractionation from chemical and thermal (Soret) diffusion (3-7) appear to challenge our theoretical understanding of mass-transport and isotopic fractionation (8, 9). For example, a recently proposed quantum mechanical model of Soret diffusion, which correctly predicts the isotopic fractionation in thermal gradients for isotopes of Mg, Ca, Fe, Si, and possibly oxygen, was critiqued as being unphysical. First, it was argued that the zero point energies needed to explain the magnitude of isotopic fractionation in basalt melts were unrealistically high based on infrared spectra of these melts. Second, it was argued that the chemical diffusion isotopic fractionation (beta) factors expected from these zero-point energies were also unphysical (10). A recently proposed collision-momentum transfer model partially explains observed fractionation factors, although it fails miserably (by a factor of 3) to account for the isotopic fractionation of Mg isotopes (11). In this presentation, I will review recent observations and models of isotopic fractionation in geochemical melts with thermal gradients and expand upon previous work (8, 12) to show how transition state theory can simultaneously explain mass-transport induced isotopic fractionation, including kinetic, equilibrium, and Soret isotopic fractionation. I show this by providing a few example calculations of the kinetic fractionation factors (a.k.a. beta factors) expected in chemical diffusion as well as

  18. Lactate kinetics in human tissues at rest and during exercise

    DEFF Research Database (Denmark)

    van Hall, Gerrit

    2010-01-01

    of lactate in skeletal muscle. With the introduction of lactate isotopes muscle lactate kinetics and oxidation could be studied and a simultaneous lactate uptake and release was observed, not only in muscle but also in other tissues. Therefore, this review will discuss in vivo human: (1) skeletal muscle...... lactate metabolism at rest and during exercise and suggestions are put forward to explain the simultaneous lactate uptake and release; and (2) lactate metabolism in the heart, liver, kidneys, brain, adipose tissue and lungs will be discussed and its potential importance in these tissues....

  19. 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 ...

  20. Trapped radioactive isotopes for fundamental symmetry investigations : The TRIμP Facility

    NARCIS (Netherlands)

    Willmann, Lorenz; Jungmann, Klaus-Peter; Onderwater, C. J G; Timmermans, Robertus; Wilschut, Henricus

    2012-01-01

    Discrete symmetries tested in high precision atomic physics experiments provide guidance to model building beyond the Standard Model (SM). Here experimental opportunities arise for searches for permanent electric dipole moments (EDMs) and measurements of atomic parity violation (APV). Heavy atoms ar

  1. Trapped radioactive isotopes for fundamental symmetry investigations : The TRIμP Facility

    NARCIS (Netherlands)

    Willmann, Lorenz; Jungmann, Klaus; Onderwater, Cornelis J.G.; Wilschut, Hans W.; Timmermans, Rob G.E.

    2011-01-01

    Discrete symmetries tested in high precision atomic physics experiments provide guidance to model building beyond the Standard Model (SM). Here experimental opportunities arise for searches for permanent electric dipole moments (EDMs) and measurements of atomic parity violation (APV). Heavy atoms ar

  2. Calcium Isotope Analysis by Mass Spectrometry

    Science.gov (United States)

    Boulyga, S.; Richter, S.

    2010-12-01

    The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. This presentation discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. Additionally, the availability of Ca isotope reference materials will be discussed.

  3. Stable iron isotope fractionation between aqueous Fe(II) and model Archean ocean Fe-Si coprecipitates and implications for iron isotope variations in the ancient rock record

    Science.gov (United States)

    Wu, Lingling; Percak-Dennett, Elizabeth M.; Beard, Brian L.; Roden, Eric E.; Johnson, Clark M.

    2012-05-01

    Iron isotope fractionation between aqueous Fe(II) (Fe(II)aq) and two amorphous Fe(III) oxide-Si coprecipitates was investigated in an aqueous medium that simulated Archean marine conditions, including saturated amorphous silica, low sulfate, and zero dissolved oxygen. The equilibrium isotope fractionation (in 56Fe/54Fe) between Fe(II)aq and Fe(III)-Si coprecipitates at circum-neutral pH, as inferred by the three-isotope method, was -3.51 ± 0.20 (2σ)‰ and -3.99 ± 0.17 (2σ)‰ for coprecipitates that had Fe:Si molar ratios of 1:2 and 1:3, respectively. These results, when combined with earlier work, indicate that the equilibrium isotope fractionation factor between Fe(II)aq and Fe(III)-Si coprecipitates changes as a function of Fe:Si ratio of the solid. Isotopic fractionation was least negative when Fe:Si = 1:1 and most negative when Fe:Si = 1:3. This change corresponds with changes in the local structure of iron, as revealed by prior spectroscopic studies. The kinetics of isotopic exchange was controlled by movement of Fe(II) and Si, where sorption of Fe(II) from aqueous to solid phase facilitated atom exchange, but sorption of Si hindered isotopic exchange through blockage of reactive surface sites. Although Fe(II)-Fe(III) isotopic exchange rates were a function of solid and solution compositions in the current study, in all cases they were much higher than that determined in previous studies of aqueous Fe(III) and ferrihydrite interaction, highlighting the importance of electron exchange in promoting Fe atom exchange. When compared to analogous microbial reduction experiments of overlapping Fe(II) to Fe(III) ratios, isotopic exchange rates were faster in the biological experiments, likely due to promotion of atom exchange by the solid-phase Fe(II) produced in the biological experiments. These results provide constraints for interpreting the relatively large range of Fe isotope compositions in Precambrian marine sedimentary rocks, and highlight important

  4. 41Ca ultratrace determination with isotopic selectivity > 10(12) by diode-laser-based RIMS.

    Science.gov (United States)

    Müller, P; Bushaw, B A; Blaum, K; Diel, S; Geppert, C; Nähler, A; Trautmann, N; Nörtershäuser, W; Wendt, K

    2001-07-01

    41Ca ultratrace determination by diode-laser-based resonance ionization mass spectrometry with extremely high isotopic selectivity is presented. Application to environmental dosimetry of nuclear reactor components, to cosmochemical investigations of production cross sections, and biomedical isotope-tracer studies of human calcium kinetics are discussed. Future investigations are possible use in 41Ca-radiodating. Depending on the application, 41Ca isotopic abundances in the range of 10(-9) to 10(-15) relative to the dominant stable isotope 40Ca must be determined. Either double- or triple-resonance optical excitation with narrow-band extended cavity diode lasers and subsequent non-resonant photoionization of calcium in a collimated atomic beam were used. The resulting photoions are detected with a quadrupole mass spectrometer optimized for background reduction and neighboring mass suppression. Applying the full triple-resonance scheme provides a selectivity of approximately 5 x 10(12) in the suppression of neighboring isotopes and > 10(8) for isobars, together with an overall detection efficiency of approximately 5 x 10(-5). Measurements on a variety of sample types are discussed; the accuracy and reproducibility of the resulting 41Ca/40Ca isotope ratios was better than 5%.

  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.

  6. Isotope fractionation during the anaerobic consumption of acetate by methanogenic and sulfate-reducing microorganisms

    Science.gov (United States)

    Gövert, D.; Conrad, R.

    2009-04-01

    During the anaerobic degradation of organic matter in anoxic sediments and soils acetate is the most important substrate for the final step in production of CO2 and/or CH4. Sulfate-reducing bacteria (SRB) and methane-producing archaea both compete for the available acetate. Knowledge about the fractionation of 13C/12C of acetate carbon by these microbial groups is still limited. Therefore, we determined carbon isotope fractionation in different cultures of acetate-utilizing SRB (Desulfobacter postgatei, D. hydrogenophilus, Desulfobacca acetoxidans) and methanogens (Methanosarcina barkeri, M. acetivorans). Including literature values (e.g., Methanosaeta concilii), isotopic enrichment factors (epsilon) ranged between -35 and +2 permil, possibly involving equilibrium isotope effects besides kinetic isotope effects. The values of epsilon were dependent on the acetate-catabolic pathway of the particular microorganism, the methyl or carboxyl position of acetate, and the relative availability or limitation of the substrate acetate. Patterns of isotope fractionation in anoxic lake sediments and rice field soil seem to reflect the characteristics of the microorganisms actively involved in acetate catabolism. Hence, it might be possible using environmental isotopic information to determine the type of microbial metabolism converting acetate to CO2 and/or CH4.

  7. Mechanistic studies of sesquiterpene cyclases based on their carbon isotope ratios at natural abundance.

    Science.gov (United States)

    Tan, Wenhua; Bartram, Stefan; Boland, Wilhelm

    2017-01-03

    During the process of terpene biosynthesis, C-C bond breaking and forming steps are subjected to kinetic carbon isotope effects, leading to distinct carbon isotopic signatures of the products. Accordingly, carbon isotopic signatures could be used to reveal the 'biosynthetic history' of the produced terpenoids. Five known sesquiterpene cyclases, regulating three different pathways, representing simple to complex biosynthetic sequences, were heterologously expressed and used for in vitro assays with farnesyl diphosphate as substrate. Compound specific isotope ratio mass spectrometry measurements of the enzyme substrate farnesyl diphosphate (FDP) and the products of all the five cyclases were performed. The calculated δ(13) C value for FDP, based on δ(13) C values and relative amounts of the products, was identical with its measured δ(13) C value, confirming the reliability of the approach and the precision of measurements. The different carbon isotope ratios of the products reflect the complexity of their structure and are correlated with the frequency of carbon-carbon bond forming and breaking steps on their individual biosynthetic pathways. Thus, the analysis of carbon isotopic signatures of terpenes at natural abundance can be used as a powerful tool in elucidation of associated biosynthetic mechanisms of terpene synthases and in future in vivo studies even without 'touching' the plant. © 2017 John Wiley & Sons Ltd.

  8. Identification of methanogenic pathways in anaerobic digesters using stable carbon isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Laukenmann, Stephan; Polag, Daniela; Greule, Markus; Lelieveld, Jos; Keppler, Frank [Max-Planck-Institut fuer Chemie, Mainz (Germany); Heuwinkel, Hauke; Gronauer, Andreas [Landesanstalt fuer Landwirtschaft, Freising (Germany)

    2010-12-15

    In a series of anaerobic batch experiments, the stable carbon isotopes, {delta}{sup 13}C{sub CH4} and {delta}{sup 13}C{sub CO2}, were measured in biogas produced from various sources (maize, cellulose, inoculum) to identify the degradation kinetics and specific methanogenic pathways. Isotopic analysis was performed using a new absorption laser spectrometer in addition to conventional MS. A comparison of the isotopic evolution shows large isotope dynamics for maize and cellulose, indicating a temporal change in degradation pathways and/or a change in the relative contribution from different carbon fractions within the substrate. Further batch experiments with isotopically labelled acetate (either {sup 13}CH{sub 3}CO{sub 2}Na or CH{sup 13}{sub 3}CO{sub 2}Na) were carried out to study the degradation of acetate in inoculum systematically. The results suggest that the acetate is completely oxidized into CO{sub 2} which in turn is partly reduced to CH{sub 4}. Furthermore, the distinct isotopic signature CH{sub 4} and CO{sub 2} (for acetate-methyl labelling as well as for acetate-carboxy labelling) indicate that only a minor part of the produced methane derives from acetate. A substantial fraction of methane may have been produced at an earlier stage of the reaction chain or by other potential methane precursors such as formate or methanol. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Water transport in protoplanetary disks and the hydrogen isotopic composition of chondrites

    CERN Document Server

    Jacquet, Emmanuel

    2013-01-01

    The D/H ratios of carbonaceous chondrites, believed to reflect that of water in the inner early solar system, are intermediate between the protosolar value and that of most comets. The isotopic composition of cometary water has been accounted for by several models where the isotopic composition of water vapor evolved by isotopic exchange with hydrogen gas in the protoplanetary disk. However, the position and the wide variations of the distribution of D/H ratios in carbonaceous chondrites have yet to be explained. In this paper, we assume that the D/H composition of cometary ice was achieved in the disk building phase and model the further isotopic evolution of water in the inner disk in the classical T Tauri stage. Reaction kinetics compel isotopic exchange between water and hydrogen gas to stop at $\\sim$500 K, but equilibrated water can be transported to the snow line (and beyond) via turbulent diffusion and consequently mix with isotopically comet-like water. Under certain simplifying assumptions, we calcul...

  10. Substrate and Transition State Binding in Alkaline Phosphatase Analyzed by Computation of Oxygen Isotope Effects.

    Science.gov (United States)

    Roston, Daniel; Cui, Qiang

    2016-09-14

    Enzymes are powerful catalysts, and a thorough understanding of the sources of their catalytic power will facilitate many medical and industrial applications. Here we have studied the catalytic mechanism of alkaline phosphatase (AP), which is one of the most catalytically proficient enzymes known. We have used quantum mechanics calculations and hybrid quantum mechanics/molecular mechanics (QM/MM) simulations to model a variety of isotope effects relevant to the reaction of AP. We have calculated equilibrium isotope effects (EIEs), binding isotope effects (BIEs), and kinetic isotope effects (KIEs) for a range of phosphate mono- and diester substrates. The results agree well with experimental values, but the model for the reaction's transition state (TS) differs from the original interpretation of those experiments. Our model indicates that isotope effects on binding make important contributions to measured KIEs on V/K, which complicated interpretation of the measured values. Our results provide a detailed interpretation of the measured isotope effects and make predictions that can test the proposed model. The model indicates that the substrate is deformed in the ground state (GS) of the reaction and partially resembles the TS. The highly preorganized active site preferentially binds conformations that resemble the TS and not the GS, which induces the substrate to adapt to the enzyme, rather than the other way around-as with classic "induced fit" models. The preferential stabilization of the TS over the GS is what lowers the barrier to the chemical step.

  11. Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary

    Science.gov (United States)

    Chen, Mengli; Boyle, Edward A.; Lee, Jong-Mi; Nurhati, Intan; Zurbrick, Cheryl; Switzer, Adam D.; Carrasco, Gonzalo

    2016-11-01

    Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

  12. Charge radii of neon isotopes across the sd neutron shell

    CERN Document Server

    Marinova, K; Kowalska, M; Kotrotsios, G; Kloos, S; Neugart, R; Blaum, K; Simon, H; Keim, M; Lievens, P; Wilbert, S; Kappertz, S

    2011-01-01

    We report on the changes in mean square charge radii of unstable neon nuclei relative to the stable (20)Ne, based on the measurement of optical isotope shifts. The studies were carried out using collinear laser spectroscopy on a fast beam of neutral neon atoms. High sensitivity on short-lived isotopes was achieved thanks to nonoptical detection based on optical pumping and state-selective collisional ionization, which was complemented by an accurate determination of the beam kinetic energy. The new results provide information on the structural changes in the sequence of neon isotopes all across the neutron sd shell, ranging from the proton drip line nucleus and halo candidate (17)Ne up to the neutron-rich (28)Ne in the vicinity of the ``island of inversion.{''} Within this range the charge radius is smallest for (24)Ne with N = 14 corresponding to the closure of the neutron d(5/2) shell, while it increases toward both neutron shell closures, N = 8 and N = 20. The general trend of the charge radii correlates w...

  13. Compound-Specific Isotope Analysis of Nitroaromatic Contaminant Transformations by Nitroarene Dioxygenases

    Science.gov (United States)

    Pati, Sarah G.; Kohler, Hans-Peter E.; Hofstetter, Thomas B.

    2014-05-01

    Dioxygenation is an important biochemical reaction that often initiates the mineralization of recalcitrant organic contaminants such as nitroaromatic explosives, chlorinated benzenes, and polycyclic aromatic hydrocarbons. However, to assess the extent of dioxygenation in contaminated environments is difficult because of competing transformation processes and further reactions of the dioxygenation products. Compound-specific isotope analysis (CSIA) offers a new approach to reliably quantify biodegradation initiated by dioxygenation based on changes in stable isotope ratios of the pollutant. For CSIA it is essential to know the kinetic isotope effects (KIEs) pertinent to the dioxygenation mechanism of organic contaminants. Unfortunately, the range of KIEs of such reactions is poorly constrained although many dioxygenase enzymes with a broad substrate specificity have been reported. Dioxygenase enzymes usually exhibit complex reaction kinetics involving multiple substrates and substrate-specific binding modes which makes the determination of KIEs challenging. The goal of this study was to explore the magnitude and variability of 13C-, 2H-, and 15N-KIEs for the dioxygenation of one contaminant class, that is nitroaromatic contaminants (NACs). To this end, we investigated the C, H, and N isotope fractionation during the dioxygenation of nitrobenzene (NB), 2-nitrotoluene (2-NT), and 3-nitrotoluene (3-NT) by pure cultures, E. coli clones, cell extracts, and purified enzymes. From isotope fractionations measured in the substrates and reaction products, we determined dioxygenation KIEs for different combinations of the three substrates with nitrobenzene dioxygenase (NBDO) and 2-nitrotoluene dioxygenase (2NTDO). The 13C-, 2H-, and 15N-KIEs for the dioxygenation of NB by NBDO were consistent for all experimental systems considered (i.e., Comamonas sp. Strain JS765, E. coli clones, cell extracts of E. coli clones, and purified NBDO). This observation suggests that the isotope

  14. Kinetic distance and kinetic maps from molecular dynamics simulation

    CERN Document Server

    Noe, Frank

    2015-01-01

    Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly-interconverting states. Here we build upon diffusion map theory and define a kinetic distance for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine...

  15. Isotopes a very short introduction

    CERN Document Server

    Ellam, Rob

    2016-01-01

    An isotope is a variant form of a chemical element, containing a different number of neutrons in its nucleus. Most elements exist as several isotopes. Many are stable while others are radioactive, and some may only exist fleetingly before decaying into other elements. In this Very Short Introduction, Rob Ellam explains how isotopes have proved enormously important across all the sciences and in archaeology. Radioactive isotopes may be familiar from their use in nuclear weapons, nuclear power, and in medicine, as well as in carbon dating. They have been central to establishing the age of the Earth and the origins of the solar system. Combining previous and new research, Ellam provides an overview of the nature of stable and radioactive isotopes, and considers their wide range of modern applications. ABOUT THE SERIES: The Very Short Introductions series from Oxford University Press contains hundreds of titles in almost every subject area. These pocket-sized books are the perfect way to get ahead in a new subjec...

  16. Exotic Structure of Carbon Isotopes

    CERN Document Server

    Suzuki, T; Hagino, K; Suzuki, Toshio; Sagawa, Hiroyuki; Hagino, Kouichi

    2002-01-01

    We studied firstly the ground state properties of C-isotopes using a deformed Hartree-Fock (HF)+ BCS model with Skyrme interactions. Shallow deformation minima are found in several neutron$-$rich C-isotopes. It is shown also that the deformation minima appear in both the oblate and the prolate sides in $^{17}$C and $^{19}$C having almost the same binding energies. Secondly, we carried out shell model calculations to study electromagnetic moments and electric dipole transitions of the C-isotopes. We point out the clear configuration dependence of the quadrupole and magnetic moments in the odd C-isotopes, which will be useful to find out the deformations and the spin-parities of the ground states of these nuclei. We studied electric dipole states of C-isotopes focusing on the interplay between low energy Pigmy strength and giant dipole resonances. Reasonable agreement is obtained with available experimental data for the photoreaction cross sections both in the low energy region below $\\hbar \\omega $=14 MeV and ...

  17. Handbook of environmental isotope geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Baskaran, Mark (ed.) [Wayne State Univ., Detroit, MI (United States). Dept. Geology

    2011-07-01

    Applications of radioactive and stable isotopes have revolutionized our understanding of the Earth and near-earth surface processes. The utility of the isotopes are ever-increasing and our sole focus is to bring out the applications of these isotopes as tracers and chronometers to a wider audience so that they can be used as powerful tools to solve environmental problems. New developments in this field remain mostly in peer-reviewed journal articles and hence our goal is to synthesize these findings for easy reference for students, faculty, regulators in governmental and non-governmental agencies, and environmental companies. While this volume maintains its rigor in terms of its depth of knowledge and quantitative information, it contains the breadth needed for wide variety problems and applications in the environmental sciences. This volume presents all of the newer and older applications of isotopes pertaining to the environmental problems in one place that is readily accessible to readers. This book not only has the depth and rigor that is needed for academia, but it has the breadth and case studies to illustrate the utility of the isotopes in a wide variety of environments (atmosphere, oceans, lakes, rivers and streams, terrestrial environments, and sub-surface environments) and serves a large audience, from students and researchers, regulators in federal, state and local governments, and environmental companies. (orig.)

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

    DEFF Research Database (Denmark)

    Farver, O; Zhang, J; Chi, Q;

    2001-01-01

    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...... dependence of E(0') is also different, yielding entropy changes of -57 J K(-1) mol(-1) in water and -84 J K(-1) mol(-1) in deuterium oxide. The driving force difference of 10 mV is in keeping with the kinetic isotope effect, but the contribution to DeltaS from the temperature dependence of E(0') is positive...

  19. Differential Isotope Labeling Strategy for Determining the Structure of Myristoylated Recoverin by NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Toshiyuki [University of Tsukuba, Center for Tsukuba Advanced Research Alliance and Institute of Applied Biochemistry (Japan); Ames, James B. [Stanford University School of Medicine, Department of Neurobiology (United States); Kainosho, Masatsune [Tokyo Metropolitan University, Department of Chemistry (Japan); Stryer, Lubert [Stanford University School of Medicine, Department of Neurobiology (United States); Ikura, Mitsuhiko [University of Tsukuba, Center for Tsukuba Advanced Research Alliance and Institute of Applied Biochemistry (Japan)

    1998-02-15

    The three-dimensional solution structure of recombinant bovine myristoylated recoverin in the Ca2+-free state has been refined using an array of isotope-assisted multidimensional heteronuclear NMR techniques. In some experiments, the myristoyl group covalently attached to the protein N-terminus was labeled with 13C and the protein was unlabeled or vice versa; in others, both were 13C-labeled. This differential labeling strategy was essential for structural refinement and can be applied to other acylated proteins. Stereospecific assignments of 41 pairs of {beta}-methylene protons and 48 methyl groups of valine and leucine were included in the structure refinement. The refined structure was constructed using a total of 3679 experimental NMR restraints, comprising 3242 approximate interproton distance restraints (including 153 between the myristoyl group and the polypeptide), 140 distance restraints for 70 backbone hydrogen bonds, and 297 torsion angle restraints. The atomic rms deviations about the averaged minimized coordinate positions for the secondary structure region of the N-terminal and C-terminal domains are 0.44 {+-} 0.07 and 0.55 {+-} 0.18 A for backbone atoms, and 1.09 {+-} 0.07 and 1.10 {+-} 0.15 A for all heavy atoms, respectively. The refined structure allows for a detailed analysis of the myristoyl binding pocket. The myristoyl group is in a slightly bent conformation: the average distance between C1 and C14 atoms of the myristoyl group is 14.6 A. Hydrophobic residues Leu28, Trp31, and Tyr32 form a cluster that interacts with the front end of the myristoyl group (C1-C8), whereas residues Phe49, Phe56, Tyr86, Val87, and Leu90 interact with the tail end (C9-C14). The relatively deep hydrophobic pocket that binds the myristoyl group (C14:0) could also accommodate other naturally occurring acyl groups such as C12:0, C14:1, and C14:2 chains.

  20. Kinetics of tetrataenite disordering

    Energy Technology Data Exchange (ETDEWEB)

    Dos Santos, E., E-mail: edisanfi@cbpf.br [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro (Brazil); Gattacceca, J.; Rochette, P. [Centre Européen de Recherche et d’Enseignement des Géosciences de l’Environnement, UM34, CNRS/Aix-Marseille University, Aix-en-Provence (France); Fillion, G. [Laboratoire National des Champs Magnétiques Intenses (LNCMI), CNRS, UJF, 38042 Grenoble (France); Scorzelli, R.B. [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro (Brazil)

    2015-02-01

    Tetrataenite is a chemically ordered L1{sub 0}-type Fe{sub 50}Ni{sub 50} alloy detected for the first time in 1977 by {sup 57}Fe Mössbauer spectroscopy studies in iron meteorites. The thermal history of meteorites, in particular short thermal events like those associated to hypervelocity impacts, can be constrained by tracing the presence of tetrataenite or its disordering into taenite. The knowledge of the disordering kinetics of tetrataenite, that is associated with changes in its magnetic properties, is still very fragmentary so that the time–temperature history of these meteorites cannot be constrained in details. Furthermore, knowledge of disordering kinetics is important due to potential technological application of tetrataenite as a rare-earth free strong magnet. Thus, this work provides the first time–temperature data for disordering reaction of tetrataenite. We have shown that disordering is not an instantaneous process but is a kinetic limited reaction. It was shown that disordering may take place at any temperature above the order–disorder transition for L{sub 10} superstructure phase (∼320 °C) when the appropriate time-scale is considered. This result means that the apparent Curie point for tetrataenite is not an absolute property in the sense that any estimate of this parameter should be referred to a given time-scale. - Highlights: • The first time–temperature data for tetrataenite disordering reaction is provided. • Previous works does not give a complete picture of tetrataenite disordering. • Apparent Curie temperature of tetrataenite should be referred to a time-scale. • Tetrataenite can be used as a probe to detect thermal/shock events recorded in meteorites.

  1. Chemical kinetics modeling

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Pitz, W.J. [Lawrence Livermore National Laboratory, CA (United States)

    1993-12-01

    This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.

  2. Stochastic Electrochemical Kinetics

    CERN Document Server

    Beruski, O

    2016-01-01

    A model enabling the extension of the Stochastic Simulation Algorithm to electrochemical systems is proposed. The physical justifications and constraints for the derivation of a chemical master equation are provided and discussed. The electrochemical driving forces are included in the mathematical framework, and equations are provided for the associated electric responses. The implementation for potentiostatic and galvanostatic systems is presented, with results pointing out the stochastic nature of the algorithm. The electric responses presented are in line with the expected results from the theory, providing a new tool for the modeling of electrochemical kinetics.

  3. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

    Science.gov (United States)

    Saccon, M.; Kornilova, A.; Huang, L.; Moukhtar, S.; Rudolph, J.

    2015-09-01

    A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all with substantial secondary formation from the photooxidation of aromatic volatile organic compounds (VOCs), was conducted in the gas phase and particulate matter (PM) together and in PM alone. Their concentrations in the atmosphere are in the low ng m-3 range and, consequently, a large volume of air (> 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between -34 and -33 ‰, which is well within the range predicted by mass balance. However, the observed carbon isotope ratios cover a range of nearly 9 ‰ and approximately 20 % of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban center with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in summer, a substantial difference is observed. This

  4. Transient kinetic analysis of the catalytic mechanism of haloalkane dehalogenase : Identification of the rate-determining step

    NARCIS (Netherlands)

    Schanstra, JP; Kingma, Jacob; Janssen, DB; Ornstein, RL

    1997-01-01

    We have studied the rate-determining step(s) in the conversion (k(cat)) of 1,2-dibromoethane by haloalkane dehalogenase, a bacterial enzyme involved in degradation of halogenated aliphatic compounds. Analysis of solvent kinetic isotope effects and stopped-flow fluorescence experiments with enzyme

  5. Laws of the oxidation of carbon isotopes in plasma processes under magnetic field

    Science.gov (United States)

    Myshkin, V. F.; Bespala, E. V.; Khan, V. A.; Makarevich, S. V.

    2016-06-01

    From law of quantum mechanics it follows that spin precession phase of unpaired electron in external magnetic field cannot be determined. It uncertainty necessary take into account in different physical and chemical processes. The expression of the rate constant of a chemical reaction based on the number of discrete spin states was obtained. The equations of chemical kinetics of plasma oxidation of carbon isotopes in the magnetic field were given.

  6. 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

    2017-02-22

    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.

  7. Isotope Fractionation of Toluene: A Perspective to Characterise Microbial In Situ Degradation

    Directory of Open Access Journals (Sweden)

    H.H. Richnow

    2002-01-01

    Full Text Available A concept to assess in situ biodegradation of organic contaminants in aquifers is presented. The alteration of the carbon isotope composition of contaminants along the groundwater flow path indicates microbial degradation processes and can be used as an indicator for in situ biodegradation. The Rayleigh equation was applied to calculate the percentage of the in situ biodegradation (B[%] using the change in the isotopic composition of contaminants (Rt/R0 along the ground water flow path and a kinetic carbon isotope fractionation factor (αC derived from defined biodegradation experiments in the laboratory. When the groundwater hydrology is known and a representative source concentration (C0 for a groundwater flow path can be determined, the extent of in situ biodegradation can be quantified.

  8. Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

    Science.gov (United States)

    Yuen, G.; Blair, N.; Des Marais, D. J.; Chang, S.

    1984-01-01

    Carbon isotopic compositions have been measured for individual hydrocarbons and monocarboxylic acids from the Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of C-13 to C-12 decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar, and impose constraints on the identity of the reactant species.

  9. Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR)

    Energy Technology Data Exchange (ETDEWEB)

    Roth, Justine P. [Johns Hopkins Univ., Baltimore, MD (United States)

    2015-03-03

    Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR) Research during the project period focused primarily on mechanisms of water oxidation by structurally defined transition metal complexes. Competitive oxygen isotope fractionation of water, mediated by oxidized precursors or reduced catalysts together with ceric, Ce(IV), ammonium nitrate in aqueous media, afforded oxygen-18 kinetic isotope effects (O-18 KIEs). Measurement, calculation, and interpretation of O-18 KIEs, described in the accompanying report has important ramifications for the production of electricity and solar hydrogen (as fuel). The catalysis division of BES has acknowledged that understanding mechanisms of transition metal catalyzed water oxidation has major ramifications, potentially leading to transformation of the global economy and natural environment in years to come. Yet, because of program restructuring and decreased availability of funds, it was recommended that the Solar Photochemistry sub-division of BES would be a more appropriate parent program for support of continued research.

  10. Photonuclear reactions on titanium isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Belyshev, S. S. [Moscow State University (Russian Federation); Dzhilavyan, L. Z. [Russian Academy of Sciences, Institute for Nuclear Research (Russian Federation); Ishkhanov, B. S.; Kapitonov, I. M. [Moscow State University (Russian Federation); Kuznetsov, A. A., E-mail: kuznets@depni.sinp.msu.ru; Orlin, V. N.; Stopani, K. A. [Moscow State University, Skobeltsyn Institute of Nuclear Physics (Russian Federation)

    2015-03-15

    The photodisintegration of titanium isotopes in the giant-dipole-resonance energy region is studied by the photon-activation method. Bremsstrahlung photons whose spectrum has the endpoint energy of 55 MeV is used. The yields and integrated cross sections are determined for photoproton reactions on the titanium isotopes {sup 47,48,49,50}Ti. The respective experimental results are compared with their counterparts calculated on the basis of the TALYS code and a combined photonucleon-reaction model. The TALYS code disregards the isospin structure of the giant dipole resonance and is therefore unable to describe the yield of photoproton reactions on the heavy titanium isotopes {sup 49,50}Ti.

  11. Quantification and isotopic analysis of intracellular sulfur metabolites in the dissimilatory sulfate reduction pathway

    Science.gov (United States)

    Sim, Min Sub; Paris, Guillaume; Adkins, Jess F.; Orphan, Victoria J.; Sessions, Alex L.

    2017-06-01

    Microbial sulfate reduction exhibits a normal isotope effect, leaving unreacted sulfate enriched in 34S and producing sulfide that is depleted in 34S. However, the magnitude of sulfur isotope fractionation is quite variable. The resulting changes in sulfur isotope abundance have been used to trace microbial sulfate reduction in modern and ancient ecosystems, but the intracellular mechanism(s) underlying the wide range of fractionations remains unclear. Here we report the concentrations and isotopic ratios of sulfur metabolites in the dissimilatory sulfate reduction pathway of Desulfovibrio alaskensis. Intracellular sulfate and APS levels change depending on the growth phase, peaking at the end of exponential phase, while sulfite accumulates in the cell during stationary phase. During exponential growth, intracellular sulfate and APS are strongly enriched in 34S. The fractionation between internal and external sulfate is up to 49‰, while at the same time that between external sulfate and sulfide is just a few permil. We interpret this pattern to indicate that enzymatic fractionations remain large but the net fractionation between sulfate and sulfide is muted by the closed-system limitation of intracellular sulfate. This 'reservoir effect' diminishes upon cessation of exponential phase growth, allowing the expression of larger net sulfur isotope fractionations. Thus, the relative rates of sulfate exchange across the membrane versus intracellular sulfate reduction should govern the overall (net) fractionation that is expressed. A strong reservoir effect due to vigorous sulfate reduction might be responsible for the well-established inverse correlation between sulfur isotope fractionation and the cell-specific rate of sulfate reduction, while at the same time intraspecies differences in sulfate uptake and/or exchange rates could account for the significant scatter in this relationship. Our approach, together with ongoing investigations of the kinetic isotope

  12. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    Science.gov (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  13. 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

  14. The terrestrial uranium isotope cycle.

    Science.gov (United States)

    Andersen, Morten B; Elliott, Tim; Freymuth, Heye; Sims, Kenneth W W; Niu, Yaoling; Kelley, Katherine A

    2015-01-15

    Changing conditions on the Earth's surface can have a remarkable influence on the composition of its overwhelmingly more massive interior. The global distribution of uranium is a notable example. In early Earth history, the continental crust was enriched in uranium. Yet after the initial rise in atmospheric oxygen, about 2.4 billion years ago, the aqueous mobility of oxidized uranium resulted in its significant transport to the oceans and, ultimately, by means of subduction, back to the mantle. Here we explore the isotopic characteristics of this global uranium cycle. We show that the subducted flux of uranium is isotopically distinct, with high (238)U/(235)U ratios, as a result of alteration processes at the bottom of an oxic ocean. We also find that mid-ocean-ridge basalts (MORBs) have (238)U/(235)U ratios higher than does the bulk Earth, confirming the widespread pollution of the upper mantle with this recycled uranium. Although many ocean island basalts (OIBs) are argued to contain a recycled component, their uranium isotopic compositions do not differ from those of the bulk Earth. Because subducted uranium was probably isotopically unfractionated before full oceanic oxidation, about 600 million years ago, this observation reflects the greater antiquity of OIB sources. Elemental and isotope systematics of uranium in OIBs are strikingly consistent with previous OIB lead model ages, indicating that these mantle reservoirs formed between 2.4 and 1.8 billion years ago. In contrast, the uranium isotopic composition of MORB requires the convective stirring of recycled uranium throughout the upper mantle within the past 600 million years.

  15. Kinetics of coal pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Seery, D.J.; Freihaut, J.D.; Proscia, W.M. (United Technologies Research Center, East Hartford, CT (USA)); Howard, J.B.; Peters, W.; Hsu, J.; Hajaligol, M.; Sarofim, A. (Massachusetts Inst. of Tech., Cambridge, MA (USA)); Jenkins, R.; Mallin, J.; Espindola-Merin, B. (Pennsylvania State Univ., University Park, PA (USA)); Essenhigh, R.; Misra, M.K. (Ohio State Univ., Columbus, OH (USA))

    1989-07-01

    This report contains results of a coordinated, multi-laboratory investigation of coal devolatilization. Data is reported pertaining to the devolatilization for bituminous coals over three orders of magnitude in apparent heating rate (100 to 100,000 + {degree}C/sec), over two orders of magnitude in particle size (20 to 700 microns), final particle temperatures from 400 to 1600{degree}C, heat transfer modes ranging from convection to radiative, ambient pressure ranging from near vacuum to one atmosphere pressure. The heat transfer characteristics of the reactors are reported in detail. It is assumed the experimental results are to form the basis of a devolatilization data base. Empirical rate expressions are developed for each phase of devolatilization which, when coupled to an awareness of the heat transfer rate potential of a particular devolatilization reactor, indicate the kinetics emphasized by a particular system reactor plus coal sample. The analysis indicates the particular phase of devolatilization that will be emphasized by a particular reactor type and, thereby, the kinetic expressions appropriate to that devolatilization system. Engineering rate expressions are developed from the empirical rate expressions in the context of a fundamental understanding of coal devolatilization developed in the course of the investigation. 164 refs., 223 figs., 44 tabs.

  16. Isotopic fractionation during soil uptake of atmospheric hydrogen

    Directory of Open Access Journals (Sweden)

    A. Rice

    2011-03-01

    Full Text Available Soil uptake of atmospheric hydrogen (H2 and the associated hydrogen isotope effect were studied using soil chambers in a Western Washington second-growth coniferous forest. Chamber studies were conducted during both winter and summer seasons to account for large natural variability in soil moisture content (4–50% and temperature (6–22 °C. H2 deposition velocities were found to range from 0.01–0.06 cm s−1 with an average of 0.033 ± 0.008 cm s−1 (95% confidence interval. Consistent with prior studies, deposition velocities were correlated with soil moisture below 20% soil moisture content during the summer season. During winter, there was considerable variability observed in deposition velocity that was not closely related to soil moisture. The hydrogen kinetic isotope effect with H2 uptake was found to range from −24‰ to −109‰. Aggregate analysis of experimental data results in an average KIE of −57 ± 5‰ (95% CI. Some of the variability in KIE can be explained by larger isotope effects at lower (<10% and higher (>30% soil moisture contents. The measured KIE was also found to be correlated with deposition velocity, with smaller isotope effects occurring at higher deposition velocities. If correct, these findings will have an impact on the interpretation of atmospheric measurements and modeling of δD of H2.

  17. Non-linear Isotope Effects

    DEFF Research Database (Denmark)

    Schmidt, Johan Albrecht

    The isotopic fractionation associated with photodissociation of N2O, OCS and CO2, at different altitudes in Earth’s atmosphere, is investigated theoretically using constructed quantum mechanical models of the dissociation processes (i.e. potential energy surfaces and relevant coupling elements...... or moderate, and overall sulfur fractionation in the stratosphere is very weak which does not exclude OCS from being an acceptable background the Stratospheric Sulfate Aerosol layer. (iii) CO2 photolysis in the upper stratosphere and lower mesosphere is highly fractionating in both isotopes, enriching...

  18. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  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. Adsorption analysis equilibria and kinetics

    CERN Document Server

    Do, Duong D

    1998-01-01

    This book covers topics of equilibria and kinetics of adsorption in porous media. Fundamental equilibria and kinetics are dealt with for homogeneous as well as heterogeneous particles. Five chapters of the book deal with equilibria and eight chapters deal with kinetics. Single component as well as multicomponent systems are discussed. In kinetics analysis, we deal with the various mass transport processes and their interactions inside a porous particle. Conventional approaches as well as the new approach using Maxwell-Stefan equations are presented. Various methods to measure diffusivity, such

  1. Stochastic Kinetics of Nascent RNA

    Science.gov (United States)

    Xu, Heng; Skinner, Samuel O.; Sokac, Anna Marie; Golding, Ido

    2016-09-01

    The stochastic kinetics of transcription is typically inferred from the distribution of RNA numbers in individual cells. However, cellular RNA reflects additional processes downstream of transcription, hampering this analysis. In contrast, nascent (actively transcribed) RNA closely reflects the kinetics of transcription. We present a theoretical model for the stochastic kinetics of nascent RNA, which we solve to obtain the probability distribution of nascent RNA per gene. The model allows us to evaluate the kinetic parameters of transcription from single-cell measurements of nascent RNA. The model also predicts surprising discontinuities in the distribution of nascent RNA, a feature which we verify experimentally.

  2. The separation of stable isotopes of carbon

    Science.gov (United States)

    Oziashvili, E. D.; Egiazarov, A. S.

    1989-04-01

    The present state of work on the separation of carbon isotopes by diffusion, fractional distillation, chemical isotopic exchange, and the selective excitation and dissociation of molecules in electrical discharges or in the field of laser radiation has been examined. The characteristics of new laboratory and industrial assemblies for separating carbon isotopes have been described. Promising directions of study aimed at developing effective technological processes for separating carbon isotopes have been noted. The bibliography contains 148 references.

  3. Abiologic silicon isotope fractionation between aqueous Si and Fe(III)-Si gel in simulated Archean seawater: Implications for Si isotope records in Precambrian sedimentary rocks

    Science.gov (United States)

    Zheng, Xin-Yuan; Beard, Brian L.; Reddy, Thiruchelvi R.; Roden, Eric E.; Johnson, Clark M.

    2016-08-01

    Precambrian Si-rich sedimentary rocks, including cherts and banded iron formations (BIFs), record a >7‰ spread in 30Si/28Si ratios (δ30Si values), yet interpretation of this large variability has been hindered by the paucity of data on Si isotope exchange kinetics and equilibrium fractionation factors in systems that are pertinent to Precambrian marine conditions. Using the three-isotope method and an enriched 29Si tracer, a series of experiments were conducted to constrain Si isotope exchange kinetics and fractionation factors between amorphous Fe(III)-Si gel, a likely precursor to Precambrian jaspers and BIFs, and aqueous Si in artificial Archean seawater under anoxic conditions. Experiments were conducted at room temperature, and in the presence and absence of aqueous Fe(II) (Fe(II)aq). Results of this study demonstrate that Si solubility is significantly lower for Fe-Si gel than that of amorphous Si, indicating that seawater Si concentrations in the Precambrian may have been lower than previous estimates. The experiments reached ˜70-90% Si isotope exchange after a period of 53-126 days, and the highest extents of exchange were obtained where Fe(II)aq was present, suggesting that Fe(II)-Fe(III) electron-transfer and atom-exchange reactions catalyze Si isotope exchange through breakage of Fe-Si bonds. All experiments except one showed little change in the instantaneous solid-aqueous Si isotope fractionation factor with time, allowing extraction of equilibrium Si isotope fractionation factors through extrapolation to 100% isotope exchange. The equilibrium 30Si/28Si fractionation between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -2.30 ± 0.25‰ (2σ) in the absence of Fe(II)aq. In the case where Fe(II)aq was present, which resulted in addition of ˜10% Fe(II) in the final solid, creating a mixed Fe(II)-Fe(III) Si gel, the equilibrium fractionation between Fe(II)-Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -3.23 ± 0.37‰ (2σ). Equilibrium

  4. Brief review on the development of isotope hydrology in China

    Institute of Scientific and Technical Information of China (English)

    汪集旸; 孙占学

    2001-01-01

    The development of isotope hydrology in China is briefly reviewed. It includes oxygen and hydrogen isotopes of precipitation, application of isotope hydrological methodologies in solving water resources problems, isotope hydrological studies on brines and salt lake waters, as well as isotope hydrological investigations of thermal waters. The review focuses on isotope hydrology in China during the last two decades.

  5. Dry phase reactor for generating medical isotopes

    Science.gov (United States)

    Mackie, Thomas Rockwell; Heltemes, Thad Alexander

    2016-05-03

    An apparatus for generating medical isotopes provides for the irradiation of dry-phase, granular uranium compounds which are then dissolved in a solvent for separation of the medical isotope from the irradiated compound. Once the medical isotope is removed, the dissolved compound may be reconstituted in dry granular form for repeated irradiation.

  6. Substitution of stable isotopes in Chlorella

    Science.gov (United States)

    Flaumenhaft, E.; Katz, J. J.; Uphaus, R. A.

    1969-01-01

    Replacement of biologically important isotopes in the alga Chlorella by corresponding heavier stable isotopes produces increasingly greater deviations from the normal cell size and changes the quality and distribution of certain cellular components. The usefulness of isotopically altered organisms increases interest in the study of such permuted organisms.

  7. Stable isotope composition of mercury forms in flue gases from a typical coal-fired power plant, Inner Mongolia, northern China.

    Science.gov (United States)

    Tang, Shunlin; Feng, Chaohui; Feng, Xinbin; Zhu, Jianming; Sun, Ruoyu; Fan, Huipeng; Wang, Lina; Li, Ruiyang; Mao, Tonghua; Zhou, Ting

    2017-04-15

    Mercury forms emitted from coal combustion via air pollution control devices are speculated to carry different Hg isotope signatures. Yet, their Hg isotope composition is still not reported. Here, we present the first onsite Hg isotope data for gaseous elemental Hg (GEM) and gaseous oxidized Hg (GOM) of flue gases from a typical lignite-fired power plant (CFPP). Significant mass dependent fractionation (MDF) and insignificant mass independent fractionation (MIF) are observed between feed coal and coal combustion products. As compared to feed coal (δ(202)Hg=-2.04±0.25‰), bottom ash, GEM and GOM in flue gases before and after wet flue gas desulfurization system significantly enrich heavy Hg isotopes by 0.7-2.6‰ in δ(202)Hg, while fly ash, desulfurization gypsum and waste water show slight but insignificant enrichment of light Hg isotopes. GEM is significantly enriched heavy Hg isotopes compared to GOM and Hg in fly ash. Our observations verify the previous speculation on Hg isotope fractionation mechanism in CFPPs, and suggest a kinetically-controlled mass dependent Hg isotope fractionation during transformation of Hg forms in flue gases. Finally, our data are compared to Hg isotope compositions of atmospheric Hg pools, suggesting that coal combustion Hg emission is likely an important atmospheric Hg contributor.

  8. Deformation effects in the alpha accompanied cold ternary fission of even-even 244-260Cf isotopes

    Science.gov (United States)

    Santhosh, K. P.; Krishnan, Sreejith

    2016-04-01

    Within the unified ternary fission model (UTFM), the alpha accompanied ternary fission of even-even 244-260Cf isotopes has been studied by taking the interacting barrier as the sum of Coulomb and proximity potential. For the alpha accompanied ternary fission of the 244Cf isotope, the highest yield is obtained for the fragment combination 108Ru + 4He + 132Te, which contains the near doubly magic nucleus 132Te ( N = 80, Z = 52). In the case of 246Cf and 248Cf isotopes, the highest yield is obtained for the fragment combinations with the near doubly magic nucleus 134Te ( N = 82, Z = 52) as the heaviest fragment. The highest yield obtained for 250Cf, 252Cf, 254Cf, 256Cf, 258Cf and 260Cf isotopes is for the fragment combination with the doubly magic nucleus 132Sn ( N = 82), Z = 50 as the heaviest fragment. We have included the effect of deformation and orientation of fragments and this has revealed that in addition to the closed shell effect, ground-state deformation also plays an important role in the calculation of the relative yield of favorable fragment combinations. The computed isotopic yields for the alpha accompanied ternary fission of the 252Cf isotope are found to be in agreement with the experimental data. The emission probability and kinetic energy of the long-range alpha particle is calculated for the various isotopes of Cf and are found to be in good agreement with the experimental data.

  9. Stable carbon isotope fractionation of six strongly fractionating microorganisms is not affected by growth temperature under laboratory conditions

    Science.gov (United States)

    Penger, Jörn; Conrad, Ralf; Blaser, Martin

    2014-09-01

    Temperature is the major driving force for many biological as well as chemical reactions and may impact the fractionation of stable carbon isotopes. Thus, a good correlation between temperature and fractionation is observed in many chemical systems that are controlled by an equilibrium isotope effect. In contrast, biological systems that are usually controlled by a kinetic isotope effect are less well studied with respect to temperature effects and have shown contrasting results. We studied three different biological pathways (methylotrophic methanogenesis, hydrogenotrophic methanogenesis, acetogenesis by the acetyl-CoA pathway) which are characterized by very strong carbon isotope enrichment factors (-50‰ to -83‰). The microorganisms (Methanosarcina barkeri, Methanosarcina acetivorans, Methanolobus zinderi, Methanothermobacter marburgensis, Methanothermobacter thermoautotrophicus, Thermoanaerobacter kivui) exhibiting these pathways were grown at different temperatures ranging between 25 and 68 °C, and the fractionation factors were determined from 13C/12C isotope discrimination during substrate depletion and product formation. Our experiments showed that the fractionation factors were different for the different metabolic pathways but were not much affected by the different growth temperatures. Slight variations were well within the standard errors of replication and regression analysis. Our results showed that temperature had no significant effect on the fractionation of stable carbon isotopes during anaerobic microbial metabolism with relatively strong isotope fractionation.

  10. Isotope Harvesting Opportunities at FRIB

    Science.gov (United States)

    Morrissey, David

    2017-01-01

    The fragmentation of fast heavy ion beams now at the National Superconducting Cyclotron Laboratory (NSCL) and in the future at the Facility for Rare Isotope Beams (FRIB) under construction produce an unprecedentedly broad spectrum of radionuclides but only a small fraction are used in the on-line rare-isotope program. Projectile fragmentation facilities provide an electromagnetically purified beam of a single projectile fragment for nuclear physics experiments ranging from low energy astrophysics, through nuclear structure studies, to probing fundamental symmetries. By augmenting the NSCL and FRIB production facilities with complimentary collection and purification of discarded ions, called isotope harvesting with chemical purification, many other nuclides will become available for off-line experiments in parallel with the primary experiment. A growing user community has established a list of key target isotopes and is working with the FRIB design team to allow inclusion of necessary equipment in the future. An overview of the possibilities and the techniques will be presented in this talk. Supported by Office of Science, US DOE and Michigan State University.

  11. Operation of Electromagnetic Isotope Separator

    Institute of Scientific and Technical Information of China (English)

    MI; Ya-jing

    2015-01-01

    In 2015,we mainly completed the installation of the electromagnetic isotope separator comprehensive technical transformation projects,including the work of installation,debugging,commissioning and acceptance.In June 30,2015,according to the schedule requirements,the project

  12. Research Progress of Isotope Technology

    Institute of Scientific and Technical Information of China (English)

    Department; of; Isotope

    2015-01-01

    Radioactive isotope is one of the origins of nonnuclear power technology.In the 12th Five Year Plan period,CIAE made breakthrough progresses on several important fields such as research and development of preparation of radioactive nuclides,preparation of radioactive source and study of radiopharmaceuticals relied on different financial support,successfully

  13. Bayesian stable isotope mixing models

    Science.gov (United States)

    In this paper we review recent advances in Stable Isotope Mixing Models (SIMMs) and place them into an over-arching Bayesian statistical framework which allows for several useful extensions. SIMMs are used to quantify the proportional contributions of various sources to a mixtur...

  14. Kinetic transport in crystals

    CERN Document Server

    Marklof, Jens

    2009-01-01

    One of the central challenges in kinetic theory is the derivation of macroscopic evolution equations--describing, for example, the dynamics of an electron gas--from the underlying fundamental microscopic laws of classical or quantum mechanics. An iconic mathematical model in this research area is the Lorentz gas, which describes an ensemble of non-interacting point particles in an infinite array of spherical scatterers. In the case of a disordered scatterer configuration, the classical results by Gallavotti, Spohn and Boldrighini-Bunimovich-Sinai show that the time evolution of a macroscopic particle cloud is governed, in the limit of small scatterer density (Boltzmann-Grad limit), by the linear Boltzmann equation. In this lecture I will discuss the recent discovery that for a periodic configuration of scatterers the linear Boltzmann equation fails, and the random flight process that emerges in the Boltzmann-Grad limit is substantially more complicated. The key ingredient in the description of the limiting st...

  15. Kinetic inductance magnetometer.

    Science.gov (United States)

    Luomahaara, Juho; Vesterinen, Visa; Grönberg, Leif; Hassel, Juha

    2014-09-10

    Sensing ultra-low magnetic fields has various applications in the fields of science, medicine and industry. There is a growing need for a sensor that can be operated in ambient environments where magnetic shielding is limited or magnetic field manipulation is involved. To this end, here we demonstrate a new magnetometer with high sensitivity and wide dynamic range. The device is based on the current nonlinearity of superconducting material stemming from kinetic inductance. A further benefit of our approach is of extreme simplicity: the device is fabricated from a single layer of niobium nitride. Moreover, radio frequency multiplexing techniques can be applied, enabling the simultaneous readout of multiple sensors, for example, in biomagnetic measurements requiring data from large sensor arrays.

  16. Kinetics of Social Contagion

    Science.gov (United States)

    Ruan, Zhongyuan; Iñiguez, Gerardo; Karsai, Márton; Kertész, János

    2015-11-01

    Diffusion of information, behavioral patterns or innovations follows diverse pathways depending on a number of conditions, including the structure of the underlying social network, the sensitivity to peer pressure and the influence of media. Here we study analytically and by simulations a general model that incorporates threshold mechanism capturing sensitivity to peer pressure, the effect of "immune" nodes who never adopt, and a perpetual flow of external information. While any constant, nonzero rate of dynamically introduced spontaneous adopters leads to global spreading, the kinetics by which the asymptotic state is approached shows rich behavior. In particular, we find that, as a function of the immune node density, there is a transition from fast to slow spreading governed by entirely different mechanisms. This transition happens below the percolation threshold of network fragmentation, and has its origin in the competition between cascading behavior induced by adopters and blocking due to immune nodes. This change is accompanied by a percolation transition of the induced clusters.

  17. Kinetics of Social Contagion

    CERN Document Server

    Ruan, Zhongyuan; Karsai, Marton; Kertesz, Janos

    2015-01-01

    Diffusion of information, behavioural patterns or innovations follows diverse pathways depending on a number of conditions, including the structure of the underlying social network, the sensitivity to peer pressure and the influence of media. Here we study analytically and by simulations a general model that incorporates threshold mechanism capturing sensitivity to peer pressure, the effect of `immune' nodes who never adopt, and a perpetual flow of external information. While any constant, non-zero rate of dynamically-introduced innovators leads to global spreading, the kinetics by which the asymptotic state is approached show rich behaviour. In particular we find that, as a function of the density of immune nodes, there is a transition from fast to slow spreading governed by entirely different mechanisms. This transition happens below the percolation threshold of fragmentation of the network, and has its origin in the competition between cascading behaviour induced by innovators and blocking of adoption due ...

  18. In Vivo Mass-independent Fractionation of Mercury Isotopes in Fish

    Science.gov (United States)

    Das, R.; Odom, L. A.

    2008-12-01

    hyperfine coupling influence radical recombination and thus reaction kinetics. There is experimental evidence that this can occur during the inhibiting activity of methylmercury on creatine kinase. Here the enzyme provides the free radicals. Previously, reports of chemical mass- independent fractionation of isotopes in nature have involved gas phase reactions and largely explained by photolysis. It now seems that isotopic MIF can occur during metabolic processes as well.

  19. Temperature effects on the fractionation of multiple sulfur isotopes by Thermodesulfobacterium and Desulfovibrio strains

    Science.gov (United States)

    Wang, P.; Sun, C.; Ono, S.; Lin, L.

    2012-12-01

    the Δ33S and 34ɛ values assuming equilibrium fractionation among internal steps. Either larger isotope effects or kinetic fractionation has to be considered in the metabolic flux model to explain the multiple sulfur isotope effect produced by these two strains. Overall, the metabolic flux model warrants further revision and further studies regarding physiological responses to growth conditions may probably offer a linkage between multiple sulfur isotope effects and environmental factors for microbial dissimilatory sulfate reduction.

  20. Calcium isotope analysis by mass spectrometry.

    Science.gov (United States)

    Boulyga, Sergei F

    2010-01-01

    The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use

  1. A global Ge isotope budget

    Science.gov (United States)

    Baronas, J. Jotautas; Hammond, Douglas E.; McManus, James; Wheat, C. Geoffrey; Siebert, Christopher

    2017-04-01

    We present measurements of Ge isotope composition and ancillary data for samples of river water, low- and high-temperature hydrothermal fluids, and seawater. The dissolved δ74Ge composition of analyzed rivers ranges from 2.0 to 5.6‰, which is significantly heavier than previously determined values for silicate rocks (δ74Ge = 0.4-0.7‰, Escoube et al., Geostand. Geoanal. Res., 36(2), 2012) from which dissolved Ge is primarily derived. An observed negative correlation between riverine Ge/Si and δ74Ge signatures suggests that the primary δ74Ge fractionation mechanism during rock weathering is the preferential incorporation of light isotopes into secondary weathering products. High temperature (>150 °C) hydrothermal fluids analyzed in this study have δ74Ge of 0.7-1.6‰, most likely fractionated during fluid equilibration with quartz in the reaction zone. Low temperature (25-63 °C) hydrothermal fluids are heavier (δ74Ge between 2.9‰ and 4.1‰) and most likely fractionated during Ge precipitation with hydrothermal clays. Seawater from the open ocean has a δ74Gesw value of 3.2 ± 0.4‰, and is indistinguishable among the different ocean basins at the current level of precision. This value should be regulated over time by the isotopic balance of Ge sources and sinks, and a new compilation of these fluxes is presented, along with their estimated isotopic compositions. Assuming steady-state, non-opal Ge sequestration during sediment authigenesis likely involves isotopic fractionation Δ74Gesolid-solution that is -0.6 ± 1.8‰.

  2. Dimensional enhancement of kinetic energies

    DEFF Research Database (Denmark)

    Schleich, W.P.; Dahl, Jens Peder

    2002-01-01

    Simple thermodynamics considers kinetic energy to be an extensive variable which is proportional to the number N of particles. We present a quantum state of N noninteracting particles for which the kinetic energy increases quadratically with N. This enhancement effect is tied to the quantum centr...

  3. Kinetic competition during glass formation

    Energy Technology Data Exchange (ETDEWEB)

    Perepezko, J.H., E-mail: perepezk@engr.wisc.edu [University of Wisconsin-Madison, Department of Materials Science and Engineering, 1509 University Ave., Madison, WI 53706 (United States); Santhaweesuk, C.; Wang, J.Q. [University of Wisconsin-Madison, Department of Materials Science and Engineering, 1509 University Ave., Madison, WI 53706 (United States); Imhoff, S.D. [Los Alamos National Laboratory, Materials Science and Technology Div., Los Alamos, NM 87545 (United States)

    2014-12-05

    Highlights: • The kinetics of glass formation has been elucidated in an Fe and Au-base alloy. • A critical cooling rate range should be considered for glass formation. • Wedge casting, calorimetry and upquenching data are used to model TTT curves. - Abstract: For vitrification of an alloy melt during cooling there is a kinetic competition with the nucleation and growth of metastable and stable crystalline phases. Many of the measures of glass forming ability (GFA) attempt to capture some of the features of the kinetic competition, but the GFA metrics are static measures and the kinetic processes are dynamic in nature. In fact, the critical cooling rate for glass formation should be viewed in terms of a critical cooling rate range to acknowledge the stochastic nature of crystal nucleation behavior. Direct measurements of the critical cooling rate range confirm this behavior and also provide useful input for kinetics analysis. Usually kinetics analyses are based upon crystallization behavior that is measured either isothermally or upon heating to temperatures near the crystallization onset, T{sub x} and the results are extrapolated to much higher temperatures. This practice is based upon a number of assumptions about transport behavior in the undercooled liquid. With rapid up-quenching of amorphous samples, the high temperature crystallization behavior can be measured and used to refine the kinetics analysis and provide useful insight on the kinetic competition and glass forming ability.

  4. Constraints on the vital effect in coccolithophore and dinoflagellate calcite by oxygen isotopic modification of seawater

    Science.gov (United States)

    Hermoso, Michaël; Horner, Tristan J.; Minoletti, Fabrice; Rickaby, Rosalind E. M.

    2014-09-01

    In this study, we show that there are independent controls of 18O/16O and 13C/12C fractionation in coccolithophore and dinoflagellate calcite due to the contrasting kinetics of each isotope system. We demonstrate that the direction and magnitude of the oxygen isotope fractionation with respect to equilibrium is related to the balance between calcification rate and the replenishment of the internal pool of dissolved inorganic carbon (DIC). As such, in fast growing cells, such as those of Emiliania huxleyi and Gephyrocapsa oceanica (forming the so-called “heavy group”), calcification of the internal carbon pool occurs faster than complete isotopic re-adjustment of the internal DIC pool with H2O molecules. Hence, coccoliths reflect the heavy oxygen isotope signature of the CO2 overprinting the whole DIC pool. Conversely, in large and slow growing cells, such as Coccolithus pelagicus ssp. braarudii, complete re-equilibration is achieved due to limited influx of CO2 leading to coccoliths that are precipitated in conditions close to isotopic equilibrium (“equilibrium group”). Species exhibiting the most negative oxygen isotope composition, such as Calcidiscus leptoporus (“light group”), precipitate coccolith under increased pH in the coccolith vesicle, as previously documented by the “carbonate ion effect”. We suggest that, for the carbon isotope system, any observed deviation from isotopic equilibrium is only “apparent”, as the carbon isotopic composition in coccolith calcite is controlled by a Rayleigh fractionation originating from preferential incorporation of 12C into organic matter. Therefore, species with low PIC/POC ratios as E. huxleyi and G. oceanica are shifted towards positive carbon isotope values as a result of predominant carbon fixation into the organic matter. By contrast, cells with higher PIC/POC as C. braarudii and C. leptoporus maintain, to some extent, the original negative isotopic composition of the CO2. The calcareous

  5. Modelling stable water isotopes: Status and perspectives

    Directory of Open Access Journals (Sweden)

    Werner M.

    2010-12-01

    Full Text Available Modelling of stable water isotopes H2 18O and HDO within various parts of the Earth’s hydrological cycle has clearly improved our understanding of the interplay between climatic variations and related isotope fractionation processes. In this article key principles and major research results of stable water isotope modelling studies are described. Emphasis is put on research work using explicit isotope diagnostics within general circulation models as this highly complex model setup bears many resemblances with studies using simpler isotope modelling approaches.

  6. Toward a Kinetic Model of Silicon Carbide Condensation in Type II Supernovae

    Science.gov (United States)

    Deneault, Ethan A. N.

    2017-01-01

    One of the most interesting types of dust grain extracted from terrestrial meteorites is the silicon carbide X-grain (SiC-X). These grains bear distinct isotopic signatures which classify them as supernova condensates, but their formation within the ejecta has not been well-studied. Using a kinetic chemistry network, we investigate possible pathways that lead to the formation of silicon carbide grains in the cooling outflows of type II supernovae.

  7. Kinetics and mechanism of the oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate

    Indian Academy of Sciences (India)

    Poonam Gupta; Seema Kothari

    2001-04-01

    The oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate (BTMACI), in the presence of zinc chloride, leads to the formation of carbon dioxide. The reaction is first order with respect to BTMACI, zinc chloride and organic acid. Oxidation of deuteriated formic acid indicates the presence of a kinetic isotope effect. Addition of benzyltrimethylammonium chloride enhances the rate. It is proposed that the reactive oxidizing species is [(PhCH2Me3N)+ (IZn2Cl6)−]. Suitablemechanisms have been proposed.

  8. Kinetics of Bio-Reactions

    DEFF Research Database (Denmark)

    2015-01-01

    his chapter predicts the specific rates of reaction by means of a mathematical expression, the kinetics of the reaction. This expression can be derived through a mechanistic interpretation of an enzymatically catalyzed reaction, but it is essentially of empirical nature for cell reactions....... The models can be used in mass balances for design of processes under process conditions not yet studied experimentally. The value of the predictive kinetic model depends on the quality of the experimental data on which the model is based, and well-founded kinetic models for enzyme reactions have...... a considerable predictive power. This is also true for cell reaction models, when the model is used in its proper context. The chapter first discusses the kinetics for enzymatically catalyzed reactions (“enzyme reactions”). The kinetics can be derived from a mechanistic model. Then, the chapter derives empirical...

  9. Kinetic distance and kinetic maps from molecular dynamics simulation.

    Science.gov (United States)

    Noé, Frank; Clementi, Cecilia

    2015-10-13

    Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly interconverting states. Here, we build upon diffusion map theory and define a kinetic distance metric for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here, we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine pancreatic trypsin inhibitor and protein-inhibitor association in trypsin and benzamidine. We find that the total kinetic variance (TKV) is an excellent indicator of model quality and can be used to rank different input feature sets.

  10. Zinc isotopic compositions of breast cancer tissue.

    Science.gov (United States)

    Larner, Fiona; Woodley, Laura N; Shousha, Sami; Moyes, Ashley; Humphreys-Williams, Emma; Strekopytov, Stanislav; Halliday, Alex N; Rehkämper, Mark; Coombes, R Charles

    2015-01-01

    An early diagnostic biomarker for breast cancer is essential to improve outcome. High precision isotopic analysis, originating in Earth sciences, can detect very small shifts in metal pathways. For the first time, the natural intrinsic Zn isotopic compositions of various tissues in breast cancer patients and controls were determined. Breast cancer tumours were found to have a significantly lighter Zn isotopic composition than the blood, serum and healthy breast tissue in both groups. The Zn isotopic lightness in tumours suggests that sulphur rich metallothionein dominates the isotopic selectivity of a breast tissue cell, rather than Zn-specific proteins. This reveals a possible mechanism of Zn delivery to Zn-sequestering vesicles by metallothionein, and is supported by a similar signature observed in the copper isotopic compositions of one breast cancer patient. This change in intrinsic isotopic compositions due to cancer has the potential to provide a novel early biomarker for breast cancer.

  11. Measuring SNM Isotopic Distributions using FRAM

    Energy Technology Data Exchange (ETDEWEB)

    Geist, William H. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-12-02

    The first group of slides provides background information on the isotopic composition of plutonium. It is shown that 240Pu is the critical isotope in neutron coincidence/multiplicity counting. Next, response function analysis to determine isotopic composition is discussed. The isotopic composition can be determined by measuring the net peak counts from each isotope and then taking the ratio of the counts for each isotope relative to the total counts for the element. Then FRAM (Fixed energy Response function Analysis with Multiple efficiencies) is explained. FRAM can control data acquisition, automatically analyze newly acquired data, analyze previously acquired data, provide information on the quality of the analysis, and facilitate analysis in unusual situations (non-standard energy calibrations, gamma rays from non-SNM isotopes, poor spectra (within limits)).

  12. Isotope hydrology of catchment basins: lithogenic and cosmogenic isotopic systems

    Energy Technology Data Exchange (ETDEWEB)

    Nimz, G. J., LLNL

    1998-06-01

    A variety of physical processes affect solute concentrations within catchment waters. The isotopic compositions of the solutes can indicate which processes have determined the observed concentrations. These processes together constitute the physical history of the water. Many solutes in natural waters are derived from the interaction between the water and the rock and/or soil within the system - these are termed `lithogenic` solutes. The isotopic compositions of these solutes provide information regarding rock-water interactions. Many other solutes have their isotopic compositions determined both within and outside of the catchment - i.e., in addition to being derived from catchment rock and soil, they are solutes that are also transported into the catchment. Important members of this group include solutes that have isotopic compositions produced by atomic particle interactions with other nuclides. The source of the atomic particles can be cosmic radiation (producing `cosmogenic` nuclides in the atmosphere and land surface), anthropogenic nuclear reactions (producing `thermonuclear` nuclides), or radioactive and fission decay of naturally-occurring elements, principally {sup 238}U (producing `in-situ` lithogenic nuclides in the deep subsurface). Current language usage often combines all of the atomic particle-produced nuclides under the heading `cosmogenic nuclides`, and for simplicity we will often follow that usage here, although always indicating which variety is being discussed. This paper addresses the processes that affect the lithogenic and cosmogenic solute concentrations in catchment waters, and how the isotopic compositions of the solutes can be used in integrative ways to identify these processes, thereby revealing the physical history of the water within a catchment system. The concept of a `system` is important in catchment hydrology. A catchment is the smallest landscape unit that can both participate in all of the aspects of the hydrologic cycle and

  13. Excited state kinetics of anthracene-bridge-aniline intramolecular exciplexes

    DEFF Research Database (Denmark)

    Thyrhaug, Erling; Hammershøj, Peter; Kjær, Kasper Skov

    2014-01-01

    We report on the synthesis and characterization of fluorescent halogen substituted anthracene-bridge-aniline (ABA) supermolecules that undergo structural reorganization on photoexcitation to form transient complexes. The syntheses were achieved in high yields on a large scale and the molecular...... structures were confirmed by single crystal X-ray diffraction. The photophysics of the ABA supermolecules were investigated using steady state and time resolved optical spectroscopy. Despite the presence of heavy atoms the series of ABA molecules have high quantum yields of fluorescence from both a locally...

  14. Differential Permeability of Proton Isotopes through Graphene and Graphene Analogue Monolayer.

    Science.gov (United States)

    Zhang, Qiuju; Ju, Minggang; Chen, Liang; Zeng, Xiao Cheng

    2016-09-01

    Two-dimensional (2D) monolayer nanomaterials can be exploited as the thinnest membrane with distinct differential sieving properties for proton isotopes. Motivated from the experimental evidence of differential sieving proton isotopes through graphene and hexagonal boron nitrate (h-BN) monolayer, we compute the kinetic barrier of isotope H(+) and D(+) permeation through model graphene and h-BN fragments at the MP2/6-31++G(d,p) level of theory. On the basis of the ratio of tunneling reaction rate constant, the isotope separation ratio of H(+)/D(+) and H(+)/T(+) is predicted to be ∼12 and 37, respectively. The tunneling reaction rate constant can be estimated from the zero-point-energy computed at the transition state for the proton isotope permeation though the 2D model systems. We show that the presence of Stone-Wales (55-77) defect in the model graphene fragment can significantly lower the proton permeation barrier by 0.55 eV. With the defect, the ratio of tunneling reaction rate constant of H(+)/D(+) is increased to ∼25. In addition to model graphene and h-BN, we have examined proton permeation capability of α-boron monolayer. We compute the tunneling reaction pathway for H(+) through α-boron monolayer using both the climbing nudged elastic band (c-NEB) method and the scanning-path method. Both methods suggest that α-boron monolayer entails a relatively low barrier of ∼0.20 eV for H(+) permeation, much lower than that of the model graphene and h-BN fragments. Our studies provide molecular-level insights into the differential permeation of proton isotopes through 2D materials. The methods can be extended to examine isotope separation capability of other 2D materials as well.

  15. Stable Ni Isotope Fractionation In Systems Relevant To Banded Iron-Formations

    Science.gov (United States)

    Howe, H.; Spivak-Birndorf, L.; Newkirk, D.; Wasylenki, L. E.

    2013-12-01

    An important event in the evolution of life was the rise of atmospheric oxygen during the Proterozoic. Preceding the rise in O2 was a decline in atmospheric methane concentrations, likely due to decreased productivity of methanogenic Archaea. Based on Ni concentrations in banded iron formations (BIF), Konhauser et al. (2009) hypothesized that mantle cooling during the Archaean reduced the amount of Ni present in igneous rocks and in oceans, causing a Ni shortage for methanogens. Methanogens use Ni for cofactor F430, a catalyst during methanogenesis. To confirm Konhauser's hypothesis, a proxy for methanogen productivity in the rock record is necessary, in order to determine whether a decline in methanogen populations correlated with the observed decrease in maximum Ni contents in rocks from the Archaean. Ni isotope ratios recorded in BIF (oceanic sediments consisting of layered iron oxides and cherts) may provide evidence of a decline in methane production. Cameron et al. (2009) have shown that methanogens preferentially assimilate light Ni isotopes. Thus Ni isotopes in BIF have potential use as biomarkers for methanogenesis. Ferrihydrite was almost certainly the dominant Fe-oxide phase precipitating during BIF deposition. Ferrihydrite nanoparticles have large surface areas and are able to remove aqueous metals from solution through multiple sorption mechanisms. Thus we investigated experimentally the relationship between Ni isotopes in solution and Ni associated with ferrihydrite. We experimented with two different sorption mechanisms: adsorption of aqueous Ni onto surfaces of synthetic ferrihydrite and coprecipitation of aqueous Ni with ferrihydrite. Preliminary results indicate that light isotopes are preferentially associated with ferrihydrite in both adsorption and coprecipitation experiments, with an average fractionation of 0.3‰ in terms of δ60/58 Ni. Future experiments will investigate whether the observed isotope fractionations reflect kinetics or

  16. The Kinetics of Enzyme Mixtures

    Directory of Open Access Journals (Sweden)

    Simon Brown

    2014-03-01

    Full Text Available Even purified enzyme preparations are often heterogeneous. For example, preparations of aspartate aminotransferase or cytochrome oxidase can consist of several different forms of the enzyme. For this reason we consider how different the kinetics of the reactions catalysed by a mixture of forms of an enzyme must be to provide some indication of the characteristics of the species present. Based on the standard Michaelis-Menten model, we show that if the Michaelis constants (Km of two isoforms differ by a factor of at least 20 the steady-state kinetics can be used to characterise the mixture. However, even if heterogeneity is reflected in the kinetic data, the proportions of the different forms of the enzyme cannot be estimated from the kinetic data alone. Consequently, the heterogeneity of enzyme preparations is rarely reflected in measurements of their steady-state kinetics unless the species present have significantly different kinetic properties. This has two implications: (1 it is difficult, but not impossible, to detect molecular heterogeneity using kinetic data and (2 even when it is possible, a considerable quantity of high quality data is required.

  17. Experimental evidence for hydrogen tunneling when the isotopic arrhenius prefactor (A(H)/A(D)) is unity.

    Science.gov (United States)

    Sharma, Sudhir C; Klinman, Judith P

    2008-12-31

    The temperature dependence of the kinetic isotope effect (KIE) is one of the major tools used for the investigation of hydrogen tunneling in condensed phase. Hydrogen transfer reactions displaying isotopic Arrhenius prefactor ratios (A(H)/A(D)) of unity are generally ascribed to a semiclassical mechanism. Here, we have identified a double mutant of soybean lipoxygenase (SLO-1, an enzyme previously shown to follow quantum mechanical hydrogen tunneling), that displays an A(H)/A(D) of unity and highly elevated (nonclassical) KIEs. This observation highlights the shortcoming of assigning a hydrogen transfer reaction to a semiclassical model based solely on an Arrhenius prefactor ratio.

  18. Kinetic properties of cyanase.

    Science.gov (United States)

    Anderson, P M; Little, R M

    1986-04-01

    Cyanase is an inducible enzyme in Escherichia coli that catalyzes the hydrolysis of cyanate. Bicarbonate is required for activity, perhaps as a substrate, and the initial product of the reaction is carbamate, which spontaneously breaks down to ammonia and bicarbonate [Anderson, P. M. (1980) Biochemistry 19, 2882]. The purpose of this study was to characterize the kinetic properties of cyanase. Initial velocity studies showed that both cyanate and bicarbonate act as competitive substrate inhibitors. A number of monovalent anions act as inhibitors. Azide and acetate appear to act as competitive inhibitors with respect to cyanate and bicarbonate, respectively. Chloride, bromide, nitrate, nitrite, and formate also inhibit, apparently as the result of binding at either substrate site. Malonate and several other dicarboxylic dianions at very low concentrations display "slow-binding", reversible inhibition which can be prevented by saturating concentrations of either substrate. The results are consistent with a rapid equilibrium random mechanism in which bicarbonate acts as a substrate, bicarbonate and cyanate bind at adjacent anion-binding sites, and both substrates can bind at the other substrate anion binding site to give a dead-end complex.

  19. Measuring Kinetic Plasma Eigenmodes

    Science.gov (United States)

    Mattingly, Sean; Berumen, Jorge; Chu, Feng; Hood, Ryan; Skiff, Fred

    2015-11-01

    We present a method for measuring kinetic plasma eigenmodes of a cylindrical axially magnetized (1 kG) laboratory plasma (n ~109cm-3 , Te ~ 5eV , Ti ~ 0 . 06eV) by measuring velocity space correlation functions. This method simultaneously observes two separate laser induced fluorescence schemes. Each scheme has its own indepedently tunable laser and its own set of collection optics. With this setup, we are able to measure the time - averaged correlation function as a function of position on the cylindrical axis parallel to the magnetic field (z) and velocity on the deconvolved ion velocity distribution function (v) : C (z , v ,z' ,v' , τ) = t. The freedom of two lasers allows us to measure a two dimensional velocity correlation matrix. This matrix is investigated with the Vlasov equation in the collisionless and weakly collisional regime. The former case, which is continuous, is diagonalized with an integral transform defined by P. J. Morrison while the latter case, which is discrete, is diagonalized through the use of Hermite polynomials.

  20. Kinetic Transport in Crystals

    Science.gov (United States)

    Marklof, Jens

    2010-03-01

    One of the central challenges in kinetic theory is the derivation of macroscopic evolution equations--describing, for example, the dynamics of an electron gas--from the underlying fundamental microscopic laws of classical or quantum mechanics. An iconic mathematical model in this research area is the Lorentz gas, which describes an ensemble of non-interacting point particles in an infinite array of spherical scatterers. In the case of a disordered scatterer configuration, the classical results by Gallavotti, Spohn and Boldrighini-Bunimovich-Sinai show that the time evolution of a macroscopic particle cloud is governed, in the limit of small scatterer density (Boltzmann-Grad limit), by the linear Boltzmann equation. In this lecture I will discuss the recent discovery that for a periodic configuration of scatterers the linear Boltzmann equation fails, and the random flight process that emerges in the Boltzmann-Grad limit is substantially more complicated. The key ingredient in the description of the limiting stochastic process is the renormalization dynamics on the space of lattices, a powerful technique that has recently been successfully applied also to other open problems in mathematical physics, including KAM theory and quantum chaos. This lecture is based on joint work with Andreas Strömbergsson, Uppsala.

  1. An efficient climate model with water isotope physics: NEEMY

    Science.gov (United States)

    Hu, J.; Emile-Geay, J.

    2015-12-01

    This work describes the development of an isotope-enabled atmosphere-ocean global climate model, NEEMY. This is a model of intermediate complexity, which can run 100 model years in 30 hours using 33 CPUs. The atmospheric component is the SPEEDY-IER (Molteni et al. 2003; Dee et al. 2015a), which is a water isotope-enabled (with equilibrium and kinetic fractionation schemes in precipitation, evaporation and soil moisture) simplified atmospheric general circulation model, with T30 horizontal resolution and 8 vertical layers. The oceanic component is NEMO 3.4 (Madec 2008), a state-of-the-art oceanic model (~2° horizontal resolution and 31 vertical layers) with an oceanic isotope module (a passive tracer scheme). A 1000-year control run shows that NEEMY is stable and its energy is conserved. The mean state is comparable to that of CMIP3-era CGCMs, though much cheaper to run. Atmospheric teleconnections such as the NAO and PNA are simulated very well. NEEMY also simulates the oceanic meridional overturning circulation well. The tropical climate variability is weaker than observations, and the climatology exhibits a double ITCZ problem despite bias corrections. The standard deviation of the monthly mean Nino3.4 index is 0.61K, compared to 0.91K in observations (Reynolds et al. 2002). We document similarities and differences with a close cousin, SPEEDY-NEMO (Kucharski et al. 2015). With its fast speed and relatively complete physical processes, NEEMY is suitable for paleoclimate studies ; we will present some forced simulations of the past millennium and their use in forward-modeling climate proxies, via proxy system models (PSMs, Dee et al 2015b). References Dee, S., D. Noone, N. Buenning, J. Emile-Geay, and Y. Zhou, 2015a: SPEEDY-IER: A fast atmospheric GCM with water isotope physics. J. Geophys. Res. Atmos., 120: 73-91. doi:10.1002/2014JD022194. Dee, S. G., J. Emile-Geay, M. N. Evans, Allam, A., D. M. Thompson, and E. J. Steig, 2015b: PRYSM: an open-source framework

  2. Natural fractionation of uranium isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Noordmann, Janine

    2015-01-24

    The topic of this thesis was the investigation of U (n({sup 238}U) / n({sup 235}U)) isotope variations in nature with a focus on samples (1) that represent the continental crust and its weathering products (i.e. granites, shales and river water) (2) that represent products of hydrothermal alteration on mid-ocean ridges (i.e. altered basalts, carbonate veins and hydrothermal water) and (3) from restricted euxinic basins (i.e. from the water column and respective sediments). The overall goal was to explore the environmental conditions and unravel the mechanisms that fractionate the two most abundant U isotopes, n({sup 238}U) and n({sup 235}U), on Earth.

  3. Lasers utilizing CO2 isotopes

    Science.gov (United States)

    Pechenin, Iu. V.; Domanov, M. S.

    1980-08-01

    The emission spectra and power characteristics of CW (C-12)(O-16)2, (C-13)(O-16)2, (C-12)(O-16)(O-18)2 and (C-12)(O-18) lasers are investigated. Laser output power is found to depend equally on the proportion of carbon and oxygen isotopes in the active medium for all isotopes except the asymmetrical (C-12)(O-16)(O-18), in which maximum output power is four to five times less due to the doubling of emission lines and limited enrichment caused by recombination into (C-12)(O-16)2 and (C-12)(O-18)2 molecules during discharge. The unsaturated gain is observed to increase linearly with enrichment, with that of nonsymmetrical molecules half that of the symmetrical molecules, while the maximum power output is independent of enrichment.

  4. Interstellar Isotopes: Prospects with ALMA

    Science.gov (United States)

    Charnley Steven B.

    2010-01-01

    Cold molecular clouds are natural environments for the enrichment of interstellar molecules in the heavy isotopes of H, C, N and O. Anomalously fractionated isotopic material is found in many primitive Solar System objects, such as meteorites and comets, that may trace interstellar matter that was incorporated into the Solar Nebula without undergoing significant processing. Models of the fractionation chemistry of H, C, N and O in dense molecular clouds, particularly in cores where substantial freeze-out of molecules on to dust has occurred, make several predictions that can be tested in the near future by molecular line observations. The range of fractionation ratios expected in different interstellar molecules will be discussed and the capabilities of ALMA for testing these models (e.g. in observing doubly-substituted isotopologues) will be outlined.

  5. Isotope exchange reactions involving HCO+ with CO: A theoretical approach

    Science.gov (United States)

    Mladenović, M.; Roueff, E.

    2017-09-01

    Aims: We aim to investigate fractionation reactions involved in the 12C/13C, 16O/18O, and 17O balance. Methods: Full-dimensional rovibrational calculations were used to compute numerically exact rovibrational energies and thermal equilibrium conditions to derive the reaction rate coefficients. A nonlinear least-squares method was employed to represent the rate coefficients by analytic functions. Results: New exothermicities are derived for 30 isotopic exchange reactions of HCO+ with CO. For each of the reactions, we provide the analytic three-parameter Arrhenius-Kooij formula for both the forward reaction and backward reaction rate coefficients, that can further be used in astrochemical kinetic models. Rotational constants derived here for the 17O containing forms of HCO+ may assist detection of these cations in outer space.

  6. Copper isotope signatures in modern marine sediments

    Science.gov (United States)

    Little, Susan H.; Vance, Derek; McManus, James; Severmann, Silke; Lyons, Timothy W.

    2017-09-01

    The development of metal stable isotopes as tools in paleoceanography requires a thorough understanding of their modern marine cycling. To date, no Cu isotope data has been published for modern sediments deposited under low oxygen conditions. We present data encompassing a broad spectrum of hydrographic and redox regimes, including continental margin and euxinic (sulphide-containing) settings. Taken together with previously published data from oxic settings, these data indicate that the modern oceanic sink for Cu has a surprisingly homogeneous isotopic composition of about +0.3‰ (δ65Cu, relative to NIST SRM976). We suggest that this signature reflects one of two specific water-column processes: (1) an equilibrium isotope fractionation between soluble, isotopically heavy, Cu complexed to strong organic ligands and an isotopically light pool sorbed to particles that deliver Cu to the sediment, or (2) an equilibrium isotope fractionation between the same isotopically heavy ligand-bound pool and the particle reactive free Cu2+ species, with the latter being scavenged by particulates and thereby delivered to the sediment. An output flux of about +0.3‰ into sediments is isotopically light relative to the known inputs to the ocean (at around +0.6‰) and the seawater value of +0.6 to +0.9‰, suggesting the presence of an as yet unidentified isotopically light source of Cu to the oceans. We hypothesize that this source may be hydrothermal, or may result from the partial dissolution of continentally derived particles.

  7. Comparative isotope ecology of African great apes.

    Science.gov (United States)

    Oelze, Vicky M; Fahy, Geraldine; Hohmann, Gottfried; Robbins, Martha M; Leinert, Vera; Lee, Kevin; Eshuis, Henk; Seiler, Nicole; Wessling, Erin G; Head, Josephine; Boesch, Christophe; Kühl, Hjalmar S

    2016-12-01

    The isotope ecology of great apes is a useful reference for palaeodietary reconstructions in fossil hominins. As extant apes live in C3-dominated habitats, variation in isotope signatures is assumed to be low compared to hominoids exploiting C4-plant resources. However, isotopic differences between sites and between and within individuals are poorly understood due to the lack of vegetation baseline data. In this comparative study, we included all species of free-ranging African great apes (Pan troglodytes, Pan paniscus, Gorilla sp.). First, we explore differences in isotope baselines across different habitats and whether isotopic signatures in apes can be related to feeding niches (faunivory and folivory). Secondly, we illustrate how stable isotopic variations within African ape populations compare to other extant and extinct primates and discuss possible implications for dietary flexibility. Using 701 carbon and nitrogen isotope data points resulting from 148 sectioned hair samples and an additional collection of 189 fruit samples, we compare six different great ape sites. We investigate the relationship between vegetation baselines and climatic variables, and subsequently correct great ape isotope data to a standardized plant baseline from the respective sites. We obtained temporal isotopic profiles of individual animals by sectioning hair along its growth trajectory. Isotopic signatures of great apes differed between sites, mainly as vegetation isotope baselines were correlated with site-specific climatic conditions. We show that controlling for plant isotopic characteristics at a given site is essential for faunal data interpretation. While accounting for plant baseline effects, we found distinct isotopic profiles for each great ape population. Based on evidence from habituated groups and sympatric great ape species, these differences could possibly be related to faunivory and folivory. Dietary flexibility in apes varied, but temporal variation was overall

  8. {Stable isotope probing of the physical and biological controls that influence the fate and isotopic composition of carbon derived from the terrestrial methane sink }

    Science.gov (United States)

    Maxfield, P. J.; Hornibrook, E. R. C.; Dildar, N.; Evershed, R. P.

    2009-04-01

    Methane oxidizing bacteria (Methanotrophs) occur in every soil order, and are an important sink for atmospheric CH4 in well aerated soils. The quantity of C cycled via methanotrophic bacteria in soils is globally significant (Le Mer et al., 2001) yet the fate of methane derived carbon remains largely unknown and unquantified. There is generally good agreement regarding the magnitude of the soil CH4 sink determined by methane flux measurements and process modeling. More poorly characterised aspects of the soil CH4 sink include: (i) the physical and biological controls that influence the mechanism of CH4 oxidation in soils; (ii) the fate of oxidized CH4 carbon; (iii) the proportion of C from CH4 oxidation that is sequestered as organic C or released as CO2 (iv) the magnitude of kinetic isotope effects (KIEs) associated with high affinity methanotrophy in soils and the potential influence on the stable carbon isotope composition of atmospheric CH4. This research combines multiple stable isotope analytical approaches to investigate the magnitude, mechanism and pathways of the terrestrial methane sink. Principally 13CH4 stable isotope labeling techniques (Stable isotope probing; SIP) have been used to characterize and quantify methanotrophic populations in a range of different soils (Maxfield et al., 2006). Following 13CH4-incubations soil cores were removed for compound-specific C isotope analyses. Identification and quantification of methanotrophs was effectively achieved via the analysis of 13C-labelled phospholipid fatty acids (PLFAs) to link bacterial structure and function. It was also possible to identify the predominant controls influencing the active methanotrophic populations in both grassland and woodland soils (Maxfield et al., 2008). SIP can be combined with further isotopic analyses to facilitate a broader study of methanotroph C uptake and CH4 derived C sequestration. As SIP facilitates taxonomic assignments of the soil microorganisms involved in CH4 C

  9. Arrhenius curves of hydrogen transfers: tunnel effects, isotope effects and effects of pre-equilibria

    Science.gov (United States)

    Limbach, Hans-Heinrich; Miguel Lopez, Juan; Kohen, Amnon

    2006-01-01

    In this paper, the Arrhenius curves of selected hydrogen-transfer reactions for which kinetic data are available in a large temperature range are reviewed. The curves are discussed in terms of the one-dimensional Bell–Limbach tunnelling model. The main parameters of this model are the barrier heights of the isotopic reactions, barrier width of the H-reaction, tunnelling masses, pre-exponential factor and minimum energy for tunnelling to occur. The model allows one to compare different reactions in a simple way and prepare the kinetic data for more-dimensional treatments. The first type of reactions is concerned with reactions where the geometries of the reacting molecules are well established and the kinetic data of the isotopic reactions are available in a large temperature range. Here, it is possible to study the relation between kinetic isotope effects (KIEs) and chemical structure. Examples are the tautomerism of porphyrin, the porphyrin anion and related compounds exhibiting intramolecular hydrogen bonds of medium strength. We observe pre-exponential factors of the order of kT/h≅1013 s−1 corresponding to vanishing activation entropies in terms of transition state theory. This result is important for the second type of reactions discussed in this paper, referring mostly to liquid solutions. Here, the reacting molecular configurations may be involved in equilibria with non- or less-reactive forms. Several cases are discussed, where the less-reactive forms dominate at low or at high temperature, leading to unusual Arrhenius curves. These cases include examples from small molecule solution chemistry like the base-catalysed intramolecular H-transfer in diaryltriazene, 2-(2′-hydroxyphenyl)-benzoxazole, 2-hydroxy-phenoxyl radicals, as well as in the case of an enzymatic system, thermophilic alcohol dehydrogenase. In the latter case, temperature-dependent KIEs are interpreted in terms of a transition between two regimes with different temperature

  10. Modelling heart rate kinetics.

    Science.gov (United States)

    Zakynthinaki, Maria S

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women).

  11. Modelling heart rate kinetics.

    Directory of Open Access Journals (Sweden)

    Maria S Zakynthinaki

    Full Text Available The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise. Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women.

  12. Modelling Heart Rate Kinetics

    Science.gov (United States)

    Zakynthinaki, Maria S.

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual’s cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women). PMID:25876164

  13. The kinetics and mechanism of the organo-iridium catalysed racemisation of amines.

    Science.gov (United States)

    Stirling, Matthew J; Mwansa, Joseph M; Sweeney, Gemma; Blacker, A John; Page, Michael I

    2016-08-07

    The dimeric iodo-iridium complex [IrCp*I2]2 (Cp* = pentamethylcyclopentadiene) is an efficient catalyst for the racemisation of secondary and tertiary amines at ambient and higher temperatures with a low catalyst loading. The racemisation occurs with pseudo-first-order kinetics and the corresponding four rate constants were obtained by monitoring the time dependence of the concentrations of the (R) and (S) enantiomers starting with either pure (R) or (S) and show a first-order dependence on catalyst concentration. Low temperature (1)H NMR data is consistent with the formation of a 1 : 1 complex with the amine coordinated to the iridium and with both iodide anions still bound to the metal-ion, but at the higher temperatures used for kinetic studies binding is weak and so no saturation zero-order kinetics are observed. A cross-over experiment with isotopically labelled amines demonstrates the intermediate formation of an imine which can dissociate from the iridium complex. Replacing the iodides in the catalyst by other ligands or having an amide substituent in Cp* results in a much less effective catalysts for the racemisation of amines. The rate constants for a deuterated amine yield a significant primary kinetic isotope effect kH/kD = 3.24 indicating that hydride transfer is involved in the rate-limiting step.

  14. Kinetic Magnetorotational Turbulence and Dynamo

    Science.gov (United States)

    Kunz, Matthew; Stone, James; Quataert, Eliot

    2016-10-01

    Low-luminosity black-hole accretion flows, such as that at the Galactic center, are collisionless. A kinetic approach is thus necessary to understand the transport of heat and angular momentum, the acceleration of particles, and the growth and structure of the magnetic field in these systems. We present results from the first 6D kinetic numerical simulation of magnetorotational turbulence and dynamo, using the local shearing-box model. Special attention will be paid to the enhanced transport of angular momentum by field-aligned pressure anisotropies, as well as to the ion-Larmor-scale kinetic instabilities (firehose, mirror, ion-cyclotron) which regulate those anisotropies. Energy spectra and phase-space evolution will be discussed. Time permitting, dedicated nonlinear studies of firehose and mirror instabilities in a shearing plasma will also be presented as a complement to the study of the magnetorotational instability. The profits, perils, and price of using a kinetic approach will be briefly mentioned.

  15. Kinetic properties of fractal media

    CERN Document Server

    Chumak, Oleg V

    2016-01-01

    Kinetic processes in fractal stellar media are analyzed in terms of the approach developed in our earlier paper (Chumak, Rastorguev, 2016) involving a generalization of the nearest neighbor and random force distributions to fractal media. Diffusion is investigated in the approximation of scale-dependent conditional density based on an analysis of the solutions of the corresponding Langevin equations. It is shown that kinetic parameters (time scales, coefficients of dynamic friction, diffusion, etc.) for fractal stellar media can differ significantly both qualitatively and quantitatively from the corresponding parameters for a quasi-uniform random media with limited fluctuations. The most important difference is that in the fractal case kinetic parameters depend on spatial scale length and fractal dimension of the medium studied. A generalized kinetic equation for stellar media (fundamental equation of stellar dynamics) is derived in the Fokker-Planck approximation with the allowance for the fractal properties...

  16. 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

  17. The role of extracellular carbonic anhydrase activity in inorganic carbon utilization of Phaeocystis globosa (Prymnesiophyceae) : A comparison with other marine algae using the isotopic disequilibrium technique

    NARCIS (Netherlands)

    Elzenga, JTM; Prins, HBA; Stefels, J

    2000-01-01

    The utilization of inorganic carbon species by the marine microalga Phaeocystis globasa (Prymnesiophyceae) and several other algal species from different taxa, was investigated by determining the time course of C-14 incorporation in isotopic disequilibrium experiments. From these kinetic data, concl

  18. Retrievals of boundary layer methane and isotope fractionation on Titan

    Science.gov (United States)

    Adamkovics, Mate; Lora, Juan M.; Mitchell, Jonathan L.

    2016-10-01

    The amount of methane in the boundary layer on Titan is an interesting diagnostic of whether or not it might be seeping out of the regolith. We know that kinetic fractionation of methane isotopes can be diagnostic of evaporation at the surface and condensation in the atmosphere. If a parcel is constrained to follow a moist adiabat while condensation occurs, we can predict the amount of fractionation that is expected (Ádámkovics & Mitchell, 2016). We will present our most recent efforts to measure boundary layer methane abundance and isotopic composition, which include our recently published Keck NIRSPAO observations from 17 July 2014 (Ádámkovics et al., 2016), as well as preliminary results from follow-up measurements made on 15 May 2016. Our measurements are tantalizingly close to being able to distinguish between different hydrological parameterizations of the polar regions in the Titan Atmospheric Model (Lora & Ádámkovics, 2016). We will discuss the systematic uncertainties that can be evaluated with the combination of these two datasets and the prospects for exceptionally high S/N observations via particularly deep integrations over multiple nights.

  19. Clinical validation of simultaneous dual-isotope myocardial scintigraphy

    Energy Technology Data Exchange (ETDEWEB)

    Weinmann, Pierre; Moretti, Jean Luc [Department of Nuclear Medicine, Avicenne Hospital, Paris XIII University, 125, Rue de Stalingrad, 93 009 Bobigny Cedex (France); Faraggi, Marc [Department of Nuclear Medicine, Bichat Hospital, Paris VII University (France); Hannequin, Pascal [Centre d' Imagerie Nucleaire, Annecy (France)

    2003-01-01

    Simultaneous dual-isotope (rest thallium-201/stress technetium-99m sestamibi) myocardial single-photon emission tomography (SPET) would be an ideal procedure; however, {sup 99m}Tc cross-talk on the {sup 201}Tl window hampers its routine use. Photon energy recovery (PER) is a spectral deconvolution technique validated for scatter and cross-talk removal in phantom studies and a limited series of patients. In this study we aimed to validate the technique in 295 patients within a context of clinical routine practice. Conventional separate rest {sup 201}Tl myocardial SPET data sets were visually compared with simultaneous dual-isotope data sets corrected by PER. Conventional separate rest {sup 201}Tl data sets were identical to dual PER-corrected {sup 201}Tl data sets in 173 (58.6%) patients. As dual PER {sup 201}Tl data sets are corrected for {sup 99m}Tc cross-talk but also for {sup 201}Tl scatter, they were compared with separate rest {sup 201}Tl data sets corrected by PER in the 122 discordant patients. No difference was found in 77 (26.1%) patients. In 26 (8.8%) patients, the difference consisted in the presence of a defect on dual PER {sup 201}Tl data sets only, mirroring an ischaemic defect on {sup 99m}Tc-sestamibi data sets. This difference can be attributed to the influence of stress on the kinetics of {sup 201}Tl injected at rest. In the remaining 19 (6.4%) patients, the difference between separate and simultaneous PER-corrected data sets was scored as mild in 11 and moderate in eight patients and seemed to be related to multiple methodological factors. It is concluded that PER correctly removes {sup 99m}Tc cross-talk. With the addition of an appropriate attenuation correction, the PER technique may allow the routine use of simultaneous dual-isotope myocardial scintigraphy in the near future. (orig.)

  20. Kinetics Modeling of Cancer Immunology.

    Science.gov (United States)

    1986-05-09

    CANCER IMMUNOLOGY -1 DTICS ELECTED SEP 9 8 UNITED STATES NAVAL ACADEMY ANNAPOLIS, MARYLAND V ,1986 %,e docment ha le approved for public A." I and sale...1986 4. TITLE (and Subtitle) S. TYPE OF REPORT & PERIOD COVERED KINETICS MODELING OF CANCER IMMUNOLOGY Final: 1985/1986 6. PERFORMING ORG. REPORT...137 (1986) "Kinetics Modeling of Cancer Immunology " A Trident Scholar Project Report by Midn I/C Scott Helmers, Class of 1986 United States Naval

  1. Morphogenesis of Kinetic Reciprocal Frames

    DEFF Research Database (Denmark)

    Parigi, Dario; Sassone, Mario

    2011-01-01

    Kinetic structures in civil engineering and architecture gained considerable more attention in the very recent years as a practical solution to face time dependant performances. Realized projects are mostly bridges, retractable roofs, while in architecture the trend follows the category of intera......Kinetic structures in civil engineering and architecture gained considerable more attention in the very recent years as a practical solution to face time dependant performances. Realized projects are mostly bridges, retractable roofs, while in architecture the trend follows the category...

  2. Pb isotopes during mingling and melting

    DEFF Research Database (Denmark)

    Waight, Tod Earle; Lesher, Charles E.

    2010-01-01

    Pb isotopic data are presented for hybrid rocks formed by mingling between mantle-derived tholeiitic magma of the Eocene Miki Fjord macrodike (East Greenland) and melt derived from the adjacent Precambrian basement. Bulk mixing and AFC processes between end-members readily identified in the field...... fail to model the Pb isotope systematics. Selective contamination during diffusional exchange, which can explain the complex Sr and Nd isotope compositions of the hybrid rocks (Blichert-Toft et al., 1992), cannot fully account for the variability of the Pb isotopic data using the identified crustal end......-members. The crustal anatectic end-member, although similar in Sr and Nd isotope composition, has a markedly different Pb isotopic composition than its source gneiss. The differences are consistent with preferential incorporation of radiogenic Pb from accessory phases such as metamict zircon or loosely-bound Pb from...

  3. Measuring In Vivo Ureagenesis With Stable Isotopes

    Science.gov (United States)

    Yudkoff, Marc; Mew, Nicholas Ah; Daikhin, Yevgeny; Horyn, Oksana; Nissim, Ilana; Nissim, Itzhak; Payan, Irma; Tuchman, Mendel

    2010-01-01

    Stable isotopes have been an invaluable adjunct to biomedical research for more than 70 years. Indeed, the isotopic approach has revolutionized our understanding of metabolism, revealing it to be an intensely dynamic process characterized by an unending cycle of synthesis and degradation. Isotopic studies have taught us that the urea cycle is intrinsic to such dynamism, since it affords a capacious mechanism by which to eliminate waste nitrogen when rates of protein degradation (or dietary protein intake) are especially high. Isotopes have enabled an appreciation of the degree to which ureagenesis is compromised in patients with urea cycle defects. Indeed, isotopic studies of urea cycle flux correlate well with the severity of cognitive impairment in these patients. Finally, the use of isotopes affords an ideal tool with which to gauge the efficacy of therapeutic interventions to augment residual flux through the cycle. PMID:20338795

  4. Isotope Geochemistry for Comparative Planetology of Exoplanets

    Science.gov (United States)

    Mandt, K. E.; Atreya, S.; Luspay-Kuti, A.; Mousis, O.; Simon, A.; Hofstadter, M. D.

    2017-01-01

    Isotope geochemistry has played a critical role in understanding processes at work in and the history of solar system bodies. Application of these techniques to exoplanets would be revolutionary and would allow comparative planetology with the formation and evolution of exoplanet systems. The roadmap for comparative planetology of the origins and workings of exoplanets involves isotopic geochemistry efforts in three areas: (1) technology development to expand observations of the isotopic composition of solar system bodies and expand observations to isotopic composition of exoplanet atmospheres; (2) theoretical modeling of how isotopes fractionate and the role they play in evolution of exoplanetary systems, atmospheres, surfaces and interiors; and (3) laboratory studies to constrain isotopic fractionation due to processes at work throughout the solar system.

  5. Stable Oxygen-18 and Deuterium Isotopes

    DEFF Research Database (Denmark)

    Müller, Sascha

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

  6. Determination of the Fe(II)aq-magnetite equilibrium iron isotope fractionation factor using the three-isotope method and a multi-direction approach to equilibrium

    Science.gov (United States)

    Frierdich, Andrew J.; Beard, Brian L.; Scherer, Michelle M.; Johnson, Clark M.

    2014-04-01

    Magnetite is ubiquitous in the Earth's crust and its presence in modern marine sediments has been taken as an indicator of biogeochemical Fe cycling. Magnetite is also the most abundant Fe oxide in banded iron formations (BIFs) that have not been subjected to ore-forming alteration. Magnetite is therefore an important target of stable Fe isotope studies, and yet interpretations are currently difficult because of large uncertainties in the equilibrium stable Fe isotope fractionation factors for magnetite relative to fluids and other minerals. In this study, we utilized the three-isotope method (57Fe-56Fe-54Fe) to explore isotopic exchange via an enriched-57Fe tracer, and natural mass-dependent fractionation using 56Fe/54Fe variations, during reaction of aqueous Fe(II) (Fe(II)aq) with magnetite. Importantly, we employed a multi-direction approach to equilibrium by reacting four 57Fe-enriched Fe(II) solutions that had distinct 56Fe/54Fe ratios, which identifies changes in the instantaneous Fe isotope fractionation factor and hence identifies kinetic isotope effects. We find that isotopic exchange can be described by two 56Fe/54Fe fractionations, where an initial rapid exchange (∼66% isotopic mixing within 1 day) involved a relatively small Fe(II)aq-magnetite 56Fe/54Fe fractionation, followed by slower exchange (∼25% isotopic mixing over 50 days) that was associated with a larger Fe(II)aq-magnetite 56Fe/54Fe fractionation; this later fractionation is interpreted to approach isotopic equilibrium between Fe(II)aq and the total magnetite. All four Fe(II) solutions extrapolate to the same final equilibrium 56Fe/54Fe fractionation for Fe(II)aq-magnetite of -1.56±0.20‰ (2σ) at 22 °C. Additional experiments that synthesized magnetite via conversion of ferrihydrite by reaction with aqueous Fe(II) yield final 56Fe/54Fe fractionations that are identical to those of the exchange experiments. Our experimental results agree well with calculated fractionation factors using

  7. Kinetic Parameters of Methane Generated from Source Rocks in the Kuqa Depression of Tarim Basin and Their Application

    Institute of Scientific and Technical Information of China (English)

    LI Xianqing; DONG Peng; XIAO Xianming; MI Jingkui; TANG Yongchun; XIAO Zhongyao; LIU Dehan; SHEN Jiagui; YANG Yunfeng; WANG Yan

    2008-01-01

    In a thermal simulation experiment of gold tubes of closed-system, calculating with the KINETICS and GOR-ISOTOPE KINETICS software, kinetic parameters of gas generation and methane carbon isotopic fractionation from Triassic-Jurassic hydrocarbon source rocks in the Kuqa depression of Tarim Basin are obtained. The activation energies of methane generated from Jurassic coal, Jurassic mudstone and Triassic mudstone in the Kuqa Depression are 197-268 kJ/mol, 180-260 kJ/mol and 214-289 kJ/mol, respectively, and their frequency factors are 5.265×1013s-1, 9.761×1011 s-1 and 2.270×1014 s-1. This reflects their differences of hydrocarbon generation behaviors. The kinetic parameters of methane carbon isotopic fractionation are also different in Jurassic coal, Jurassic mudstone and Triassic mudstone, whose average activation energies are 228 kJ/mol, 205 kJ/mol and 231 kJ/mol, respectively. Combined with the geological background, the origin of natural gas in the Yinan-2 gas pool is discussed, and an accumulation model of natural gas is thus established. The Yinan-2 gas is primarily derived from Jurassic coal-bearing source rocks in the Yangxia Sag. Main gas accumulation time is 5-0 Ma and the corresponding Ro is in the range from 1.25%-1.95%. The loss rate of natural gas is 25%-30%.

  8. Fractionated Mercury Isotopes in Fish: The Effects of Nuclear Mass, Spin, and Volume

    Science.gov (United States)

    Das, R.; Odom, A. L.

    2007-12-01

    .3, and thus more than one mass-independent isotope effect is inferred. MIF of mercury can be caused by the nuclear volume effect. Schauble, 2007 has calculated nuclear volume fractionation scaling factors for a number of common mercury chemical species in equilibrium with Hg° vapor. From his calculations the nuclear field shift effect is larger in Δ199Hg than in Δ201Hg by approximately a factor of two. The predominant mercury chemical species in fish is methylmercury cysteine. From the experimental studies of Buchachenko and others (2004) on the reaction of methylmercury chloride with creatine kinase it seems reasonable to predicted that the thiol functional groups of cysteine gets enriched in 199Hg and 201Hg. Here the magnetic isotope effect (MIE) produces a kinetic partial separation of isotopes with non-zero nuclear spin quantum numbers from the even-N isotopes. The ratio of enrichment of Δ201Hg /Δ199Hg is predicted from theory to be 1.11, which is the ratio of the magnetic moments of 199Hg and 201Hg. Because mercury possesses two odd-N isotopes, it is possible to detect and evaluate the effects of two distinct, mass-independent isotope fractionating processes. From the data obtained on fish samples, we can deconvolute the contributions of the isotope effects of nuclear mass, spin and volume. For these samples the role of spin or the magnetic isotope effect is the most dominant.

  9. Kinetics and mechanism of oxidation of chloramphenicol by 1-chlorobenzotriazole in acidic medium

    Indian Academy of Sciences (India)

    R C Hiremath; R V Jagadeesh; Puttaswamy; S M Mayanna

    2005-07-01

    Chloramphenicol (CAP) is an antibiotic drug having a wide spectrum of activity. The kinetics of oxidation of chloramphenicol by 1-chlorobenzotriazole (CBT) in HClO4 medium over the temperature range 293-323 K has been investigated. The reaction exhibits first-order kinetics with respect to [CBT]o and zero-order with respect to [CAP]o. The fractional-order dependence of rate on [H+] suggests complex formation between CBT and H+. It fails to induce polymerization of acrylonitrile under the experimental conditions employed. Activation parameters are evaluated. The observed solvent isotope effect indicates the absence of hydride transfer during oxidation. Effects of dielectric constant and ionic strength of the medium on the reaction rate have been studied. Oxidation products are identified. A suitable reaction scheme is proposed and an appropriate rate law is deduced to account for the observed kinetic data.

  10. 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.

  11. Silicon isotopes: from cosmos to benthos

    OpenAIRE

    Chakrabarti, Ramananda

    2015-01-01

    Silicon is the second most abundant element on the Earth and one of the more abundant elements in our Solar System. Variations in the relative abundance of the stable isotopes of Si (Si isotope fractionation) in different natural reservoirs, both terrestrial (surface and deep Earth) as well as extra-terrestrial (e.g. meteorites, lunar samples), are a powerful tracer of present and past processes involving abiotic as well as biotic systems. The versatility of the Si isotope tracer is reflected...

  12. Quantitative microbial ecology through stable isotope probing.

    Science.gov (United States)

    Hungate, Bruce A; Mau, Rebecca L; Schwartz, Egbert; Caporaso, J Gregory; Dijkstra, Paul; van Gestel, Natasja; Koch, Benjamin J; Liu, Cindy M; McHugh, Theresa A; Marks, Jane C; Morrissey, Ember M; Price, Lance B

    2015-11-01

    Bacteria grow and transform elements at different rates, and as yet, quantifying this variation in the environment is difficult. Determining isotope enrichment with fine taxonomic resolution after exposure to isotope tracers could help, but there are few suitable techniques. We propose a modification to stable isotope probing (SIP) that enables the isotopic composition of DNA from individual bacterial taxa after exposure to isotope tracers to be determined. In our modification, after isopycnic centrifugation, DNA is collected in multiple density fractions, and each fraction is sequenced separately. Taxon-specific density curves are produced for labeled and nonlabeled treatments, from which the shift in density for each individual taxon in response to isotope labeling is calculated. Expressing each taxon's density shift relative to that taxon's density measured without isotope enrichment accounts for the influence of nucleic acid composition on density and isolates the influence of isotope tracer assimilation. The shift in density translates quantitatively to isotopic enrichment. Because this revision to SIP allows quantitative measurements of isotope enrichment, we propose to call it quantitative stable isotope probing (qSIP). We demonstrated qSIP using soil incubations, in which soil bacteria exhibited strong taxonomic variations in (18)O and (13)C composition after exposure to [(18)O]water or [(13)C]glucose. The addition of glucose increased the assimilation of (18)O into DNA from [(18)O]water. However, the increase in (18)O assimilation was greater than expected based on utilization of glucose-derived carbon alone, because the addition of glucose indirectly stimulated bacteria to utilize other substrates for growth. This example illustrates the benefit of a quantitative approach to stable isotope probing.

  13. Modeling study of vibrational photochemical isotope enrichment. [HBr + Cl/sub 2/; HCl + Br/sub 2/

    Energy Technology Data Exchange (ETDEWEB)

    Badcock, C.C.; Hwang, W.C.; Kalsch, J.F.

    1978-09-29

    Chemical kinetic modeling studies of vibrational-photochemical isotope enrichment have been performed on two systems: Model (I), H/sup 79/Br(H/sup 81/Br) + Cl/sub 2/ and, Model (II), H/sup 37/Cl(H/sup 35/Cl) + Br. Pulsed laser excitation was modeled to the first excited vibrational level of H/sup 79/Br in Model I and the first and second excited vibrational levels of both HCl isotopes in Model II. These are prototype systems of exoergic (Model I) and endoergic (Model II) reactions. The effects on enrichment of varying the external parameters (pressure, laser intensity) and the internal parameters (rate constants for V-V exchange and excited-state reactions) were examined. Studies of these prototype systems indicate that a favorable reaction for enrichment, with isotopically-specific excitation and a significantly accelerated vibrationally-excited-state reaction should have the following properties: the reaction from v = 0 should be only moderately exoergic, and the most favorable coreactant should be a polyatomic species, such as alkyl radical. Direct excitation of the reacting vibrational level is at least an order of magnitude more favorable for enrichment than is population by energy transfer. Enrichment of the minor isotope by these processes is more effective than is major isotope enrichment. Within limits, increased laser intensity is beneficial. However, for sequential excitation of a second vibrational level, major isotope enrichment can be diminished by high populations of the first vibrational level.

  14. Modeling and Classification of Kinetic Patterns of Dynamic Metabolic Biomarkers in Physical Activity.

    Science.gov (United States)

    Breit, Marc; Netzer, Michael; Weinberger, Klaus M; Baumgartner, Christian

    2015-08-01

    The objectives of this work were the classification of dynamic metabolic biomarker candidates and the modeling and characterization of kinetic regulatory mechanisms in human metabolism with response to external perturbations by physical activity. Longitudinal metabolic concentration data of 47 individuals from 4 different groups were examined, obtained from a cycle ergometry cohort study. In total, 110 metabolites (within the classes of acylcarnitines, amino acids, and sugars) were measured through a targeted metabolomics approach, combining tandem mass spectrometry (MS/MS) with the concept of stable isotope dilution (SID) for metabolite quantitation. Biomarker candidates were selected by combined analysis of maximum fold changes (MFCs) in concentrations and P-values resulting from statistical hypothesis testing. Characteristic kinetic signatures were identified through a mathematical modeling approach utilizing polynomial fitting. Modeled kinetic signatures were analyzed for groups with similar behavior by applying hierarchical cluster analysis. Kinetic shape templates were characterized, defining different forms of basic kinetic response patterns, such as sustained, early, late, and other forms, that can be used for metabolite classification. Acetylcarnitine (C2), showing a late response pattern and having the highest values in MFC and statistical significance, was classified as late marker and ranked as strong predictor (MFC = 1.97, P modeling approach demonstrates high potential for dynamic biomarker identification and the investigation of kinetic mechanisms in disease or pharmacodynamics studies using MS data from longitudinal cohort studies.

  15. Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis.

    Science.gov (United States)

    Larsen, K K; Wielandt, D; Schiller, M; Bizzarro, M

    2016-04-22

    chromatographic elution strategy that takes advantage of the slow reaction kinetics of de-chlorination of Cr in dilute HCl at room temperature. These procedures significantly improve cation chromatographic purification of Cr over previous methods and allow for high-purity Cr isotope analysis with a total recovery of >95%.

  16. Scattering lengths of calcium and barium isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Dammalapati, U.; Willmann, L.; Knoop, S. [Kernfysisch Versneller Instituut (KVI), University of Groningen, Zernikelaan 25, 9747 AA Groningen (Netherlands); LaserLaB Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam (Netherlands)

    2011-11-15

    We have calculated the s-wave scattering length of all the even isotopes of calcium (Ca) and barium (Ba) in order to investigate the prospect of Bose-Einstein condensation (BEC). For Ca we have used an accurate molecular potential based on detailed spectroscopic data. Our calculations show that Ca does not provide other isotopes alternative to the recently Bose condensed {sup 40}Ca that suffers strong losses because of a very large scattering length. For Ba we show by using a model potential that the even isotopes cover a broad range of scattering lengths, opening the possibility of BEC for at least one of the isotopes.

  17. The trend of stable isotope separation

    Energy Technology Data Exchange (ETDEWEB)

    Yonekawa, Shigeru [Power Reactor and Nuclear Fuel Development Corp., Kamisaibara, Okayama (Japan). Ningyo Toge Works; Aoki, Eiji; Yato, Yumio

    1994-12-01

    Recently, stable isotopes are used in the field of medical science, nuclear physics, environmental science and agriculture. This report reviews the present status of stable isotope enrichment in ORNL, Urenco, Russia and PNC. Further the utilization method of the stable isotopes in the field of medical science, nuclear power and material science are described, and the application possibility of Laser separation method and Gas Centrifuge method are estimated. There are many overseas actual results of stable isotope separation with Gas Centrifuge method, therefore this method is possible enough in principle. (author).

  18. Copper isotope fractionation by desert shrubs

    Energy Technology Data Exchange (ETDEWEB)

    Navarrete, Jesica U., E-mail: jnavarrete2@miners.utep.edu [University of Texas at El Paso, Department of Geological Sciences, 500 W. University Ave, El Paso, TX 79968 (United States); Viveros, Marian; Ellzey, Joanne T. [University of Texas at El Paso, Department of Biological Sciences, El Paso, TX 79968 (United States); Borrok, David M. [University of Texas at El Paso, Department of Geological Sciences, 500 W. University Ave, El Paso, TX 79968 (United States)

    2011-06-15

    Copper has two naturally occurring stable isotopes of masses 63 and 65 which can undergo mass dependent fractionation during various biotic and abiotic chemical reactions. These interactions and their resulting Cu isotope fractionations can be used to determine the mechanisms involved in the cycling of Cu in natural systems. In this study, Cu isotope changes were investigated at the organismal level in the metal-accumulating desert plant, Prosopis pubescens. Initial results suggest that the lighter Cu isotope was preferentially incorporated into the leaves of the plant, which may suggest that Cu was actively transported via intracellular proteins. The roots and stems show a smaller degree of Cu isotope fractionation and the direction and magnitude of the fractionations was dependent upon the levels of Cu exposure. Based on this and previous work with bacteria and yeast, a trend is emerging that suggests the lighter Cu isotope is preferentially incorporated into biological components, while the heavier Cu isotope tends to become enriched in aqueous solutions. In bacteria, plants and animals, intracellular Cu concentrations are strictly regulated via dozens of enzymes that can bind, transport, and store Cu. Many of these enzymes reduce Cu(II) to Cu(I). These initial results seem to fit into a broader picture of Cu isotope cycling in natural systems where oxidation/reduction reactions are fundamental in controlling the distributions of Cu isotopes.

  19. Rate constants and isotope effects for the reaction of H-atom abstraction from RH substrates by PINO radicals

    Science.gov (United States)

    Opeida, I. A.; Litvinov, Yu. E.; Kushch, O. V.; Kompanets, M. A.; Shendrik, A. N.; Matvienko, A. G.; Novokhatko, A. A.

    2016-11-01

    The kinetics of the reactions of hydrogen atom abstraction from the C-H bonds of substrates of different structures by phthalimide- N-oxyl radicals is studied. The rate constants of this reaction are measured and the kinetic isotope effects are determined. It is shown that in addition to the thermodynamic factor, Coulomb forces and donor-acceptor interactions affect the reaction between phthalimide- N-oxyl radicals and substrate molecules, altering the shape of the transition state. This favors the tunneling of hydrogen atoms and leads to a substantial reduction in the activation energy of the process.

  20. Crystallization Kinetics within a Generic Modelling Framework

    DEFF Research Database (Denmark)

    Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist

    2013-01-01

    An existing generic modelling framework has been expanded with tools for kinetic model analysis. The analysis of kinetics is carried out within the framework where kinetic constitutive models are collected, analysed and utilized for the simulation of crystallization operations. A modelling...... procedure is proposed to gain the information of crystallization operation kinetic model analysis and utilize this for faster evaluation of crystallization operations....