Relevant bibliographies by topics / Isotope kinetic effect

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Academic literature on the topic 'Isotope kinetic effect'

Author: Grafiati
Published: 14 March 2023

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Journal articles on the topic "Isotope kinetic effect"

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Musich, О., A. Zubko, and О. Demyanуuk. "Isotopic effect of macro- and microelements in ecosystems." Balanced nature using, no. 4 (August 18, 2020): 132–38. http://dx.doi.org/10.33730/2310-4678.4.2020.226644.

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Isotopic effects occurring in living organisms due to metabolism are analyzed. The phenomenon of metabolism is considered in the classical sense as a combination of biochemical reactions (mainly enzyma­tic) that take place in the cells of living beings and provide the cleavage, synthesis and interconversion of complex compounds. The scope of use of natural isotopes is wide and diverse. Isotopes are carriers of information about the birth and transformation of molecules, and isotope fractionation is a chemical characteristic of a substance. Isotope metabolism consists in the intermolecular fractionation of isotopes at separate stages of biochemical reactions, namely the cleavage, synthesis and interconversion of complex compounds caused by differences in the structure and fundamental properties of isotope nuclei. It is proved that the fractionation of isotopes in chemical and biochemical reactions due to isotopic effects is based on two fundamental properties of atomic nuclei — mass and magnetic moment. The kinetic (mass-depen­ dent) isotopic effect distributes the isotopic nuclei by their masses, and the magnetic one fractionates the nuclei by their magnetic moments. The kinetic isotopic effect depends on the magnitude of the difference in the masses of isotopic molecules, temperature and the difference in the activation energies of isotopic forms. The magnetic isotope effect depends on the reaction rate in a single cell, its projection, magnetic moment and energy of electron-nuclear interaction. It is determined that the fractionation of isotopes in living organisms is that the relative content of one of the isotopes in this compound increases by reducing its content in the other. As a result, there is a fractionation of isotopes within one biological object.
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Xu, Yingkui, Dan Zhu, Xiongyao Li, and Jianzhong Liu. "Why magnesium isotope fractionation is absent from basaltic melts under thermal gradients in natural settings." Geological Magazine 157, no. 7 (November 25, 2019): 1144–48. http://dx.doi.org/10.1017/s0016756819001304.

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AbstractLaboratory experiments have shown that thermal gradients in silicate melts can lead to isotopic fractionation; this is known as the Richter effect. However, it is perplexing that the Richter effect has not been documented in natural samples as thermal gradients commonly exist within natural igneous systems. To resolve this discrepancy, theoretical analysis and calculations were undertaken. We found that the Richter effect, commonly seen in experiments with wholly molten silicates, cannot be applied to natural systems because natural igneous samples are more likely to be formed out of partially molten magma and the presence of minerals adds complexity to the behaviour of the isotope. In this study, we consider two related diffusion-rate kinetic isotope effects that originate from chemical diffusion, which are absent from experiments with wholly molten samples. We performed detailed calculations for magnesium isotopes, and the results indicated that the Richter effect for magnesium isotopes is buffered by kinetic isotope effects and the total value of magnesium isotope fractionation can be zero or even undetectable. Our study provides a new understanding of isotopic behaviour during the processes of cooling and solidification in natural magmatic systems.
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Binder, David A., and Robert Eliason. "Kinetic hydrogen isotope effect." Journal of Chemical Education 63, no. 6 (June 1986): 536. http://dx.doi.org/10.1021/ed063p536.

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Krinkin, David. "Anomalously large kinetic isotope effect." Open Chemistry 5, no. 4 (December 1, 2007): 1019–63. http://dx.doi.org/10.2478/s11532-007-0048-2.

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AbstractActivated diffusion of water between macromolecules in swollen cellulose is accompanied by anomalously high kinetic isotope effects of oxygen. The separation factor of heavy-oxygen water (H218O /H216O) is thousands of permilles instead of tens of permilles according to modern Absolute Rate Theory. This anomalous separation under usual conditions is disguised by the opposing process of very fast equalization to equilibrium through water-filled cellulose pores. This process is quicker by approximately 3 orders of magnitude than diffusion through the cellulose body. As a consequence, this opposition-directed equalization virtually eliminates the results of isotope separation. To reveal this anomaly it is necessary to suppress equalization, which was the primary problem for both discovery of this anomaly and its investigation. The method of investigating the anomalous separation in cellulose was developed with suppression of this negative influence. Discussion of the theoretical nature of the anomalous kinetic isotope effect is presented. This theoretical study would probably permit the discovery and use for isotope separation of the anomalously high isotope effect for other chemical elements, in particular, for those heavier than oxygen.
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Joelsson, L. M. T., J. A. Schmidt, E. J. K. Nilsson, T. Blunier, D. W. T. Griffith, S. Ono, and M. S. Johnson. "Development of a new methane tracer: kinetic isotope effect of <sup>13</sup>CH<sub>3</sub>D + OH from 278 to 313 K." Atmospheric Chemistry and Physics Discussions 15, no. 19 (October 15, 2015): 27853–75. http://dx.doi.org/10.5194/acpd-15-27853-2015.

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Abstract. Methane is the second most important long lived greenhouse gas and impacts the oxidative capacity of the Earth's atmosphere. Nontheless there are significant uncertainties in its source budget. Analysis of the isotopic composition of atmospheric methane, including doubly substituted species (e.g. 13CH3D), offers new constraints on the methane source budget as the sources and sinks have distinct isotopic signatures. The most important sink of atmospheric methane is oxidation by OH which accounts for around 90 % of methane removal in the troposphere. Here we present experimentally derived methane + OH kinetic isotope effects and their temperature dependence over the range of 278 to 313 K for CH3D and 13CH3D; the latter is reported here for the first time. We find kCH4/kCH3D=1.31 ± 0.01 and kCH4/k13CH3D = 1.34 ± 0.03 at room temperature, implying that the methane + OH kinetic isotope effect is multiplicative such that (kCH4/k13CH4)(kCH4/kCH3D) = kCH4/k13CH3D to within the experimental uncertainty. In addition the kinetic isotope effect were characterized using transition state theory with tunneling correction. Good agreement between the experimental, quantum chemical and available literature values was obtained. The theoretical calculations show that 13CH3D isotope effects is the product of D- and 13C-isotope effect. Based on the results we conclude that the OH reaction at steady-state can produce an atmospheric clumped isotope signal (Δ(13CH3D) = ln([CH4][13CH3D]/[13CH4][CH3D])) of 0.02 ± 0.02.
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Röckmann, T., S. Walter, B. Bohn, R. Wegener, H. Spahn, T. Brauers, R. Tillmann, E. Schlosser, R. Koppmann, and F. Rohrer. "Isotope effect in the formation of H<sub>2</sub> from H<sub>2</sub>CO studied at the atmospheric simulation chamber SAPHIR." Atmospheric Chemistry and Physics 10, no. 12 (June 16, 2010): 5343–57. http://dx.doi.org/10.5194/acp-10-5343-2010.

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Abstract. 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.
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Away, Kenneth Charles West, and Zhu-Gen Lai. "Solvent effects on SN2 transition state structure. II: The effect of ion pairing on the solvent effect on transition state structure." Canadian Journal of Chemistry 67, no. 2 (February 1, 1989): 345–49. http://dx.doi.org/10.1139/v89-056.

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Identical secondary α-deuterium kinetic isotope effects (transition state structures) in the SN2 reaction between n-butyl chloride and a free thiophenoxide ion in aprotic and protic solvents confirm the validity of the Solvation Rule for SN2 Reactions. These isotope effects also suggest that hydrogen bonding from the solvent to the developing chloride ion in the SN2 transition state does not have a marked effect on the magnitude of the chlorine (leaving group) kinetic isotope effects. Unlike the free ion reactions, the secondary α-deuterium kinetic isotope effect (transition state structure) for the SN2 reaction between n-butyl chloride and the solvent-separated sodium thiophenoxide ion pair complex is strongly solvent dependent. These completely different responses to a change in solvent are rationalized by an extension to the Solvation Rule for SN2 Reactions. Finally, the loosest transition state in the reactions with the solvent-separated ion pair complex is found in the solvent with the smallest dielectric constant. Keywords: ion pairs, transition state, solvent effects, nucleophilic substitution, isotope effects.
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Murata, Yasujiro, Shih-Ching Chuang, Fumiyuki Tanabe, Michihisa Murata, and Koichi Komatsu. "Recognition of hydrogen isotopomers by an open-cage fullerene." Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 371, no. 1998 (September 13, 2013): 20110629. http://dx.doi.org/10.1098/rsta.2011.0629.

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We present our study on the recognition of hydrogen isotopes by an open-cage fullerene through determination of binding affinity of isotopes H 2 /HD/D 2 with the open-cage fullerene and comparison of their relative molecular sizes through kinetic-isotope-release experiments. We took advantage of isotope H 2 /D 2 exchange that generated an equilibrium mixture of H 2 /HD/D 2 in a stainless steel autoclave to conduct high-pressure hydrogen insertion into an open-cage fullerene. The equilibrium constants of three isotopes with the open-cage fullerene were determined at various pressures and temperatures. Our results show a higher equilibrium constant for HD into open-cage fullerene than the other two isotopomers, which is consistent with its dipolar nature. D 2 molecule generally binds stronger than H 2 because of its heavier mass; however, the affinity for H 2 becomes larger than D 2 at lower temperature, when size effect becomes dominant. We further investigated the kinetics of H 2 /HD/D 2 release from open-cage fullerene, proving their relative escaping rates. D 2 was found to be the smallest and H 2 the largest molecule. This notion has not only supported the observed inversion of relative binding affinities between H 2 and D 2 , but also demonstrated that comparison of size difference of single molecules through non-convalent kinetic-isotope effect was applicable.
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Tsai, I.-Chun, Wan-Yu Chen, Jen-Ping Chen, and Mao-Chang Liang. "Kinetic mass-transfer calculation of water isotope fractionation due to cloud microphysics in a regional meteorological model." Atmospheric Chemistry and Physics 19, no. 3 (February 8, 2019): 1753–66. http://dx.doi.org/10.5194/acp-19-1753-2019.

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Abstract. In conventional atmospheric models, isotope exchange between liquid, gas, and solid phases is usually assumed to be in equilibrium, and the highly kinetic phase transformation processes inferred in clouds are yet to be fully investigated. In this study, a two-moment microphysical scheme in the National Center for Atmospheric Research (NCAR) Weather Research and Forecasting (WRF) model was modified to allow kinetic calculation of isotope fractionation due to various cloud microphysical phase-change processes. A case of a moving cold front is selected for quantifying the effect of different factors controlling isotopic composition, including water vapor sources, atmospheric transport, phase transition pathways of water in clouds, and kinetic-versus-equilibrium mass transfer. A base-run simulation was able to reproduce the ∼ 50 ‰ decrease in δD that was observed during the frontal passage. Sensitivity tests suggest that all the above factors contributed significantly to the variations in isotope composition. The thermal equilibrium assumption commonly used in earlier studies may cause an overestimate of mean vapor-phase δD by 11 ‰, and the maximum difference can be more than 20 ‰. Using initial vertical distribution and lower boundary conditions of water stable isotopes from satellite data is critical to obtain successful isotope simulations, without which the δD in water vapor can be off by about 34 ‰ and 28 ‰, respectively. Without microphysical fractionation, the δD in water vapor can be off by about 25 ‰.
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Uspenskaya, Elena V., Tatyana V. Pleteneva, Anton V. Syroeshkin, Ilaha V. Kazimova, Tatyana E. Elizarova, and Artem I. Odnovorov. "Role of stable hydrogen isotope variations in water for drug dissolution managing." Current Issues in Pharmacy and Medical Sciences 33, no. 2 (June 1, 2020): 94–101. http://dx.doi.org/10.2478/cipms-2020-0017.

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AbstractIn the present work, we provide the results of defining by utilizing Laser diffraction spectroscopy, the kinetic isotopic effect of solvent and constant of dissolution rate κ, s−1 of аn active pharmaceutical ingredient (API) in water with a different content of a stable _2^1{\rm{H}} isotope on the basis of the laws of first-order kinetics. This approach is based on the analysis of the light scattering profile that occurs when the particles of the dispersion phase in the aquatic environment are covered with a collimated laser beam. For the first time, the dependence of the rate of dissolution is demonstrated not only on the properties of the pharmaceutical substance itself (water solubility mg/ml, octanol–water partition coefficient log P oct/water, topological polar surface area, Abraham solvation parameters, the lattice type), but also on the properties of the solvent, depending on the content of stable hydrogen isotope. We show that the rate constant of dissolution of a sparingly hydrophobic substance moxifloxacin hydrochloride (MF · HCl) in the Mili-Q water is: k=1.20±0.14∙10−2 s−1 at 293.15 K, while in deuterium depleted water, it is k=4.24±0.4∙10−2 s−1. Consequently, we have established the development of the normal kinetic isotopic effect (kH/kD >1) of the solvent. This effect can be explained both by the positions of the difference in the vibrational energy of zero levels in the initial and transition states, and from the position of water clusters giving volumetric effects of salvation, depending on the ratio D/H. The study of kinetic isotopic effects is a method that gives an indication of the mechanism of reactions and the nature of the transition state. The effect of increasing the dissolution of the API, as a function of the D/H ratio, we have discovered, can be used in the chemical and pharmaceutical industries in the study of API properties and in the drug production through improvement in soluble and pharmacokinetic characteristics.
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Dissertations / Theses on the topic "Isotope kinetic effect"

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Lu, Siran. "Single molecule kinetic isotope effect." Thesis, University of Oxford, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.526483.

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Kopec-Harding, Kamilla Rosa. "Computational studies of the kinetic isotope effect inmethylamine dehydrogenase." Thesis, University of Manchester, 2012. https://www.research.manchester.ac.uk/portal/en/theses/computational-studies-of-the-kinetic-isotope-effect-inmethylamine-dehydrogenase(b6883173-40ea-4a35-948b-c966105230cd).html.

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There is currently experimental evidence of hydrogen tunnelling in over 20 different enzymes include yeast alcohol dehydrogenase (YADH), morphinone reductase (MR) and methylamine dehydrogenase (MADH). Various models have been used to describe hydrogen tunnelling in enzymes including the static barrier model, the vibrationally enhanced ground state tunnelling model (VEGST) and the environmentally coupled tunnelling model (ECT). Despite some differences in these models, there is a general consensus that a temperature dependent kinetic isotope effect (KIE) is indicative of tunnelling dominated by a ratepromoting motion. Stopped flow studies of MADH with ethanolamine as substrate (mm-MADH/EA) show that the KIE of the proton transfer decreases with temperature - within the framework of the ECT model, the kinetics of this proton transfer are consistent with ground state tunnelling dominated by active dynamics (a promoting vibration). However, an alternative hypothesis is that this temperature dependence can be attributed to the population of multiple reactive configurations within the active site. If distinct substrate configurations are associated with distinct kinetic behaviour, the temperature dependence of the KIE could be due to temperature dependent fluctuations in the relative populations of these configurations. Long and short time molecular dynamics simulations of mm-MADH/EA were carried out to explore both of these scenarios. Theethanoliminoquinone intermediate was found to adopt a number of different hydrogen bonding configurations in the active site of MADH. Adiabatic scans of the proton transfer event in conjunction with WKB calculations of the KIE showed that these hydrogen bonding patterns are associated with different barrier heights and KIEs. However, simple modelling with the Boltzmann distribution showed that fluctuations in the relative population of these configurations of the magnitude expected in the temperature range 278K-308K leads to negligible changes in the magnitude of the KIE. This suggested thatmultiple reactive configurations are unlikely to account for the temperature dependence of the KIE. Spectral density analysis of the short-time MD simulations was then carried out try to identify any promoting motions in mm-MADH/EA. Since no evidence of promoting motions was found, the origin of the temperature dependence on the KIE remains an open question: the analysis in this study was restricted to one of four possible proton transfers in this substrate (HI3-OD1). Further work might look at the possibility of a promoting motion pertinent to the other transfers.
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Burke, Erin E. "Heavy atom and hydrogen kinetic isotope effect studies on recombinant, mammalian sialyltransferases." [Gainesville, Fla.] : University of Florida, 2005. http://purl.fcla.edu/fcla/etd/UFE0011586.

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Ingle, Shakti Singh. "RNA structure investigation: a deuterium kinetic isotope effect/hydroxyl radical cleavage experiment." Thesis, Boston University, 2013. https://hdl.handle.net/2144/12787.

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Thesis (Ph.D.)--Boston University PLEASE NOTE: Boston University Libraries did not receive an Authorization To Manage form for this thesis or dissertation. It is therefore not openly accessible, though it may be available by request. If you are the author or principal advisor of this work and would like to request open access for it, please contact us at open-help@bu.edu. Thank you.
The hydroxyl radical is widely used as a high-resolution footprinting agent for DNA and RNA. The hydroxyl radical abstracts a hydrogen atom from the sugar- phosphate backbone of a nucleic acid molecule, creating a sugar-based radical that eventually results in a strand break. It was shown previously that replacement of deoxyribose hydrogen atoms with deuterium results in a kinetic isotope effect (KIE) on hydroxyl radical cleavage of DNA. The KIE correlates well with the solvent accessible surface area of a deoxyribose hydrogen atom in DNA. We chose the structurally well-defmed sarcin-ricin loop (SRL) RNA molecule as a model system to extend the deuterium KIE/hydroxyl radical cleavage experiment to RNA. We observed a substantial KIE upon deuteration of the 5'-carbon of the ribose. Values ranged from 1.20 to 1.96, and depended on the position of the residue within the SRL. We found a smaller KIE upon 4'-deuteration. Values ranged from 1.05 to 1.23. Values of 5' and 4' KIEs correlate with the extent of cleavage and with the solvent accessible surface areas of ribose hydrogen atoms ofthe SRL. Gel electrophoresis of cleavage products reveals that the strand break is terminated at the 5' end by multiple chemical species. Upon 3'-radiolabeling a specifically 5'-deuterated SRL RNA molecule, we observed a KIE on the production of a cleavage product having a gel mobility different from that of a phosphate-terminated RNA strand. Reduction with sodium borohydride gave rise to an RNA fragment terminated by a 5'-hydroxyl group. These experiments are consistent with 5' hydrogen abstraction by the hydroxyl radical producing a 5'-aldehyde-terminated RNA strand that retains the nucleotide from which the hydrogen atom was abstracted. This is the first report of such a species. This chemistry has important implications for the interpretation of structural analysis experiments on RNA that rely on primer extension to synthesize eDNA copies of hydroxyl radical cleavage products. The different 5'-terminated products resulting from hydroxyl radical cleavage at a given nucleotide would yield cDNAs of two different lengths, thereby distributing the cleavage intensity over two nucleotides instead ofone and lowering the resolution ofthe experiment.
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Yousefi-Shivyari, Niloofar. "Isotope ratios in source determination of formaldehyde emissions." Thesis, Virginia Tech, 2020. http://hdl.handle.net/10919/99308.

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Formaldehyde emissions from non-structural wood composites are regulated and the regulation target is urea-formaldehyde (UF) resin. UF resins are hydrolytically unstable and constantly emit formaldehyde as a function of temperature and relative humidity. When heated, wood also generates formaldehyde, but this was of little concern until 2010 when formaldehyde regulations became much more demanding. This regulation motivated the industry to account for all formaldehyde sources, synthetic as from resin, and biogenic as from wood. This effort represents first steps towards quantifying biogenic and synthetic contributions to formaldehyde emissions in non-structural wood composites. It is possible to distinguish the 13C/12C isotope ratio of UF resins from the isotope ratio of plant biomass. Conditions during and after composite hot-pressing promote reactions that generate formaldehyde from wood and UF resin, and the kinetic isotope effect continuously lowers the product isotope ratios as a function of yield. If such isotope fractionation did not occur, it would be a simple matter to quantify contributions of wood and UF resin to formaldehyde emissions using static isotope ratios. Isotope fractionation, therefore, complicates the requirements for distinguishing biogenic and synthetic formaldehyde in wood composite emissions. Those requirements are 1) establish the reference carbon isotope ratios in wood and in UF resin (just the formaldehyde portion of UF), and 2) estimate the kinetic isotope effects in formaldehyde generation by wood and cured UF resin. The latter requirement fixes a range for the respective isotope ratios; the numerical ranges enable a simple model of the average isotope ratio for a mixture of biogenic and synthetic formaldehyde in wood composite emissions. Finally, the measured isotope ratio of captured emissions would be compared to the model. This work did not achieve all aspects of the requirements mentioned, but a solid foundation was established for future completion of the ultimate goals. In reference to requirement 1, the carbon isotope ratio of experimental Pinus taeda wood was accurately measured (including some isolated fractions) using isotope ratio mass spectroscopy (IRMS). IRMS of UF resin first requires removal of urea carbons- UF resin was subjected to acid hydrolysis and capture of the resin formaldehyde into aqueous ammonium hydroxide. This provided a nearly quantitative conversion (negligible isotope fractionation) of resin formaldehyde into hexamine for IRMS. Using this hexamine method, the formaldehyde carbon isotope ratios of two industrial UF resins were accurately measured, demonstrating basic feasibility for the project goal. Estimating the kinetic isotope effect (Requirement 2) required creation of a thermochemical reactor, where wood or cured UF resin was heated under N2 flow such that the emitted formaldehyde was easily captured. In this case, conversion of captured formaldehyde into hexamine was abandoned in favor of silica gel cartridges loaded with sodium bisulfite. Isolation and IRMS of the formaldehyde-bisulfite adduct were effective and considered easily transferable to industrial settings. This system was employed to measure fractionation in cured resin as a function of relative humidity, and in Pinus taeda wood as a function of relative humidity, temperature, and time. More information about isotope fractionation is required; but most notable was the fractionation behavior in wood where evidence was found for multiple formaldehyde generating reactions. Overall, this work established feasibility for the goals and laid the foundation for future efforts.
Master of Science
Home-interior products like cabinetry are often produced with wood composites adhesively bonded with urea-formaldehyde (UF) resin. UF resins are low cost and highly effective, but their chemical nature results in formaldehyde emission from the composite. High emissions are avoided, and the federal government has regulated and steadily reduced allowable emissions since 1985. The industry continuously improved UF technologies to meet regulations, as in 2010 when the most demanding regulations were implemented. At that time, many people were unaware that wood also generates formaldehyde; this occurs at very low levels but heating during composite manufacture causes a temporary burst of natural formaldehyde. Some wood types produce unusually high formaldehyde levels, making regulation compliance more difficult. This situation, and the desire to raise public awareness, created a major industrial goal: determine how much formaldehyde emission originates from the resin and how much originates from the wood. These formaldehyde sources can be distinguished by measuring the carbon isotope ratio, 13C/12C. This ratio changes and varies due to the kinetic isotope effect. Slight differences in 13C and 12C reactivity reveal the source as either petrochemical (synthetic formaldehyde) or plant-based (biogenic formaldehyde). This work demonstrates that achieving the industry goal is entirely feasible, and it provides the analytical foundation. The technical strategy is: 1) establish reference isotope ratios in wood and in UF resin, and 2) from the corresponding wood composite, capture formaldehyde emissions, measure the isotope ratio, and simply calculate the percentage contributions from the reference sources. However, a complication exists. When the reference sources generate formaldehyde, the respective isotope ratios change systematically in a process called isotope fractionation (another term for the kinetic isotope effect). Consequently, this effort developed methods to measure fractionation when cured UF resin and wood separately generate formaldehyde, with greater emphasis on wood. Isotope fractionation in wood revealed multiple fractionation mechanisms. This complexity presents intriguing possibilities for new perspectives on formaldehyde emission from wood and cured UF resin. In summary, this work demonstrated how source contributions to formaldehyde emissions can be determined; it established effective methods required to refine and perfect the approach, and it revealed that isotope fractionation could serve as an entirely novel tool in the materials science of wood composites.
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MacMillar, Susanna. "Isotopes as Mechanism Spies : Nucleophilic Bimolecular Substitution and Monoamine Oxidase B Catalysed Amine Oxidation Probed with Heavy Atom Kinetic Isotope Effects." Doctoral thesis, Uppsala : Acta Universitatis Upsaliensis (AUU), 2006. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-7441.

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Pagano, Philip Lee Jr. "Investigating fast dynamics at the tunneling ready state in formate dehydrogenase." Diss., University of Iowa, 2017. https://ir.uiowa.edu/etd/5592.

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Enzyme dynamics occur on a wide range of length and timescales. This work is focused on understanding enzyme dynamic at the fs-ps timescale as this is the dynamic range at which bonds are typically made and broken during chemical reactions. Our work focuses on enzymes that catalyze hydride transfer between two carbon atoms - a fundamental reaction in biology. Primary kinetic isotope effects and their temperature dependence have implied that fast dynamics of the enzyme are important in facilitating hydride transfer, however these experiments do not measure any such motions directly. We make use of two-dimensional infrared spectroscopy (2D IR), a technique that interrogates the vibrations of molecules to extract dynamic information from the surrounding environment with 100 fs resolution. A model system, formate dehydrogenase (FDH), is an excellent probe of dynamics at the fs-ps timescale. Azide bound to the ternary complex of FDH offers the ability to measure dynamics of an analog structure of the reactive complex using 2D IR, while also studying the reaction directly with and KIE’s and their temperature dependence. By altering various parts of the structure of FDH via mutagenesis and other techniques, we investigate the role of structure and dynamics to determine how fast dynamics of the active site influence the the kinetics of hydride transfer. These experiments are the first means of providing a dynamic interpretation of KIEs and their temperature dependence.
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Indurugalla, Deepani. "A kinetic isotope effect study on the acid-catalyzed hydrolysis of methyl xylopyranosides and methyl 5-thioxylopyranosides." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape10/PQDD_0021/NQ37716.pdf.

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Lorenzini, Leonardo. "Effects of T3 and 3-iodothyronamine (T1AM) on cellular metabolism, and influence of serum proteins on T1AM assay." Doctoral thesis, Università di Siena, 2018. http://hdl.handle.net/11365/1046523.

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Thyroxine (T4) is the predominant form of thyroid hormone (TH). In target tissues, T4 is enzymatically deiodinated to 3,5,3′-triiodothyronine (T3), a high-affinity ligand for the nuclear TH receptors TRα and Trβ. T3 modulates genes transcription via activation of TRα and TRβ. Non-genomic effects have also been described. In 2004 the research groups of professors Scanlan Grandy and Zucchi discovered an endogenous thyroid hormone derivative called 3-iodothyronamine (T1AM). They proved that at nanomolar concentrations it can activate trace amine associated receptors 1 (TAARs)[1] and it may also interact with other targets, such as plasma membrane transporters, mitochondrial proteins and vesicular biogenic amine transporters [2]–[4]. Endogenous T1AM has been detected in human and rodent blood and tissues samples by liquid chromatography coupled mass spectrometry (LC/MS/MS) [5]. Its endogenous levels are a matter of argument due to the challenges that its accurate quantification poses. For this reason, so far a worldwide adopted extraction method has not been established. Circulating T1AM has so far been considered to be largely bound to apolipoprotein apoB100 [6]. The first T1AM functional effect to be discovered was severe hypothermia [7]. This effect is associated to a decrease in oxygen consumption and a reduction of the respiratory quotient (CO2/O2), which reflects the relationship between glucose and fatty acid oxidation, resulting in a shift from carbohydrate to lipid as energy source [8]. The molecular mechanisms underlying T1AM effects are still unknown, however Mariotti and colleagues [9] analyzed gene expression profiles in adipose tissue and liver of T1AM chronically treated rats and found significant transcriptional effects involving sirtuin genes, which regulate important metabolic pathways. Therefore, the first aim of this work was to compare the effect of T1AM and T3 chronic treatment on mammalian sirtuin expression in hepatoma cells (HepG2) and isolated hepatocytes. Isolated rat hepatocytes were obtained by liver in-situ collagenase perfusion. Sirtuin expression was determined by Western Blot analysis in cells treated for 24 h with 1-20 µM T1AM or T3. In addition, cell viability was evaluated by MTT test upon 24 h treatment with 100 nM to 20 µM T1AM or T3. In HepG2, T1AM significantly reduced SIRT1 and SIRT4 protein expression at 20 µM while T3 strongly decreased the expression of SIRT1 (20 µM) and SIRT2 (any tested concentration). In primary rat hepatocytes T1AM, did not affect protein expression whereas T3 decreased SIRT2 at 10 µM. The extent of MTT-staining was moderately but significantly reduced by T1AM, particularly in HepG2 cells, in which the effect occurred at concentration starting from 100 nM. T3 reduced MTT staining in HepG2 but not in isolated hepatocytes. T1AM and T3 differently affected sirtuin expression in hepatocytes. Since SIRT4 is an important regulator of lipid and glucose metabolism, whereas SIRT1 and SIRT2 have a key role in regulating cell cycle and tumorigenesis, our observations are consistent with the shift from carbohydrates to lipids induced by T1AM and indicate a potential new role of T1AM in modulating tumor proliferation. The second part of this project was aimed at clarifying the issue that, so far, every research group working on this molecule has encountered when trying to accurately quantifying T1AM endogenous levels. These difficulties were usually attributed to problems in extraction or other pre‐analytical steps. Most researchers have developed various workaround for this issue. For example, on cell culture experiments, to avoid the presence of serum proteins in the culturing media, experiments have often be performed with unphysiological protein‐free media. The second goal of this project was therefore to evaluate the effect of serum protein on the recovery of exogenous T1AM. Cell culture media (Krebs buffer, DMEM, FBS, DMEM+FBS, used either in the absence or in the presence of NG108‐15 cells) and other biological matrices (rat brain and liver homogenates, human plasma and blood) were spiked with T1AM and/or deuterated T1AM (d4‐T1AM) and incubated for times ranging from 0 to 240 min. Samples were extracted using a liquid/liquid method and analysed using liquid chromatography coupled to mass spectrometry (LC-MS/MS), to assay T1AM and some of its metabolites. For the first time in the history of this molecule, in FBS‐containing buffers, an exponential decrease in T1AM levels was observed over time. T1AM metabolites were not detected, except for minimum amounts of TA1. Notably, d4‐T1AM decreased over time at a much lower rate, reaching 50‐70% of the baseline at 60 min. These effects were completely abolished by protein denaturation and partly reduced by semicarbazide, however, the process could not be reverted. In the presence of cells, T1AM concentration decreased virtually to 0 within 60 min, but TA1 accumulated in the incubation medium, with quantitative recovery. Spontaneous decrease in T1AM concentration with isotopic difference was confirmed in rat organ homogenates and human whole blood. Conclusions. On the whole, these results suggest binding and sequestration of T1AM by blood and tissue proteins, with significant isotope effects. These issues might account for the technical problems complicating the analytical assays of endogenousT1AM.
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Richan, Teisha. "Conservative Tryptophan Mutations in Protein Tyrosine Phosphatase PTP1B and its Effect on Catalytic Rate and Chemical Reaction." DigitalCommons@USU, 2017. https://digitalcommons.usu.edu/etd/5584.

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Protein-tyrosine phosphatases (PTPs) catalyze the hydrolysis of phosphorylated tyrosines by a 2-step mechanism involving nucleophilic attack by cysteine and general acid catalysis by aspartic acid. In most PTPs the aspartic acid resides on a flexible protein loop, consisting of about a dozen residues, called the WPD loop. PTP catalysis rates span several orders of magnitude, and differences in WPD loop dynamics have recently been show to correlate with the rate of enzymatic catalysis. The rate of WPD loop motion could possibly be related to a widely conserved tryptophan residue on the WPD loop. Therefore, point mutants were made in PTP1B (a human PTP) to the conserved tryptophan residue and their effects on catalytic rate and chemical reaction were studied. The results of these studies are presented in this thesis.
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Books on the topic "Isotope kinetic effect"

1

Wilson, Mathew John. Investigating the possibility of measuring a primary leaving group iodine kinetic isotope effect. Sudbury, Ont: Laurentian University, 1999.

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Jiang, Wenyi. Using kinetic isotope effects to determine the effect of ion pairing, substituents and the solvent on the structure of the Sn2 transition state. Sudbury, Ont: Laurentian University Press, 1995.

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Osborne, Craig. Measuring the rate constant and secondary a-deuterium kinetic isotope effect for the SN2 reaction between para-nitrobenzyl choride and cyanide ion in 15% aqueous DMSO. Sudbury, Ont: Laurentian University, 1996.

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F, Cook Paul, ed. Enzyme mechanism from isotope effects. Boca Raton: CRC Press, 1991.

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E, Buncel, and Saunders William Hundley 1926-, eds. Heavy atom isotope effects. Amsterdam: Elsevier, 1992.

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Bruce, Cook. The Feasibility of measuring the rate constant and secondary [alpha]-deuterium kinetic isotope effect for the Sn2 reaction between sodium phenoxide and benzyl chloride at low concentrations of phenoxide ion. Sudbury, Ont: Laurentian University, 1995.

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E, Buncel, and Lee C. C. 1924-, eds. Secondary and solvent isotope effects. Amsterdam: Elsevier, 1987.

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Buchachenko, A. L. Magnetic isotope effect in chemistry and biochemistry. Hauppauge, NY: Nova Science Publishers, 2009.

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Amnon, Kohen, and Limbach Hans-Heinrich, eds. Isotope effects in chemistry and biology. Boca Raton: Taylor & Francis, 2006.

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Ikeda, Glenn Kazuo. Kinetic isotope effects in the fragmentation of N1'-methyl-2-(1-hydroxybenzyl)thiamin. Ottawa: National Library of Canada, 2003.

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Book chapters on the topic "Isotope kinetic effect"

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Kobayashi, Kensei. "Kinetic Isotope Effect." In Encyclopedia of Astrobiology, 1337. Berlin, Heidelberg: Springer Berlin Heidelberg, 2015. http://dx.doi.org/10.1007/978-3-662-44185-5_5240.

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Kobayashi, Kensei. "Kinetic Isotope Effect." In Encyclopedia of Astrobiology, 1. Berlin, Heidelberg: Springer Berlin Heidelberg, 2014. http://dx.doi.org/10.1007/978-3-642-27833-4_5240-1.

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Werner, Roland A., and Marc-André Cormier. "Isotopes—Terminology, Definitions and Properties." In Stable Isotopes in Tree Rings, 253–89. Cham: Springer International Publishing, 2022. http://dx.doi.org/10.1007/978-3-030-92698-4_8.

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AbstractThe intention of this chapter is to give insight into the properties and peculiarities of the stable isotopes of the bioelements. Following an overview about the terminology and ʻtechnical jargonʼ used in stable isotope sciences, methods to calculate and express isotopic abundances are presented. Subsequently, a short description of the physicochemical basis of equilibrium and kinetic (mass-dependent) isotope effects (EIEs and KIEs) as origin of isotope fractionation in chemical and biological systems is given. Further, measures for calculation and presentation of isotope fractionation are introduced and the corresponding properties of these quantities are critically discussed. Finally, examples for equilibrium and kinetic isotope fractionation in biochemical reactions are presented in more details and subsequent effects and consequences including the relationship between EIEs and KIEs are reviewed.
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Scheer, Milton D. "A Kinetic Isotope Effect in the Thermal Dehydration of Cellobiose." In Fundamentals of Thermochemical Biomass Conversion, 89–94. Dordrecht: Springer Netherlands, 1985. http://dx.doi.org/10.1007/978-94-009-4932-4_5.

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Vanoni, M. A., K. K. Wong, and J. S. Blanchard. "Kinetic isotope effect studies on yeast, spinach and human erythrocyte glutathione reductases." In Flavins and Flavoproteins 1987, edited by D. E. Edmondson and D. B. McCormick, 55–58. Berlin, Boston: De Gruyter, 1987. http://dx.doi.org/10.1515/9783110884715-010.

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Shackelford, Scott A. "Mechanistic Investigations of Condensed Phase Energetic Material Decomposition Processes Using the Kinetic Deuterium Isotope Effect." In Chemistry and Physics of Energetic Materials, 413–32. Dordrecht: Springer Netherlands, 1990. http://dx.doi.org/10.1007/978-94-009-2035-4_18.

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Wolfsberg, Max, W. Alexander Van Hook, and Piotr Paneth. "Kinetic Isotope Effects on Chemical Reactions." In Isotope Effects, 313–42. Dordrecht: Springer Netherlands, 2009. http://dx.doi.org/10.1007/978-90-481-2265-3_10.

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Bagshaw, Clive R. "Kinetic Isotope Effects." In Encyclopedia of Biophysics, 1–3. Berlin, Heidelberg: Springer Berlin Heidelberg, 2018. http://dx.doi.org/10.1007/978-3-642-35943-9_58-1.

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Bagshaw, Clive R. "Kinetic Isotope Effects." In Encyclopedia of Biophysics, 1200–1201. Berlin, Heidelberg: Springer Berlin Heidelberg, 2013. http://dx.doi.org/10.1007/978-3-642-16712-6_58.

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Wolfsberg, Max, W. Alexander Van Hook, and Piotr Paneth. "Kinetic Isotope Effects Continued: Variational Transition State Theory and Tunneling." In Isotope Effects, 181–202. Dordrecht: Springer Netherlands, 2009. http://dx.doi.org/10.1007/978-90-481-2265-3_6.

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Conference papers on the topic "Isotope kinetic effect"

1

Jiang, Clancy Zhijian, Itay Halevy, and Nicholas Tosca. "Kinetic Isotope Effect of C in Siderite Growth at 298.15 K." In Goldschmidt2020. Geochemical Society, 2020. http://dx.doi.org/10.46427/gold2020.1191.

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Ober, Douglas, Mitchio Okumura, and TzuLing Chen. "SINGLE SUBSTITUTION KINETIC ISOTOPE EFFECT MEASUREMENTS FOR CH4 + O(1D) USING CAVITY RING-DOWN SPECTROSCOPY." In 2020 International Symposium on Molecular Spectroscopy. Urbana, Illinois: University of Illinois at Urbana-Champaign, 2020. http://dx.doi.org/10.15278/isms.2020.fb09.

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Jiang, Clancy Zhijian, Itay Halevy, and Nicholas Tosca. "Kinetic isotope effect in siderite growth; an abiotic origin for depleted δ13C-siderite in banded iron formations." In Goldschmidt2021. France: European Association of Geochemistry, 2021. http://dx.doi.org/10.7185/gold2021.4155.

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Ober, Douglas, Mitchio Okumura, THINH Bui, LINHAN SHEN, and TzuLing Chen. "SINGLE SUBSTITUTION KINETIC ISOTOPE EFFECT MEASUREMENTS FOR CH<sub>4</sub> + O(<sup>1</sup>D) USING CAVITY RING-DOWN SPECTROSCOPY." In 2021 International Symposium on Molecular Spectroscopy. Urbana, Illinois: University of Illinois at Urbana-Champaign, 2021. http://dx.doi.org/10.15278/isms.2021.wc03.

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Lee, Jin-Ha, Mamoru Nishimoto, Masayuki Okuyama, Haruhide Mori, Atsuo Kimura, Doman Kim, Masao Ohguchi, and Seiya Chiba. "ALPHA-SECONDARY DEUTERIUM KINETIC ISOTOPE EFFECTS FOR HYDROLYSIS OF TREHALOSE BY TREHALASE." In XXIst International Carbohydrate Symposium 2002. TheScientificWorld Ltd, 2002. http://dx.doi.org/10.1100/tsw.2002.731.

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Mehboob, Khurram, and Mohammad S. Aljohani. "Effect of Spray System on in Containment Fission Product Washout During In-Vessel Release Phase." In 2017 25th International Conference on Nuclear Engineering. American Society of Mechanical Engineers, 2017. http://dx.doi.org/10.1115/icone25-66056.

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The response of containment sprinkles during the in-vessel release phase of low-pressure loss of coolant accident (LOCA) has for two-loop PWR been simulated. Cleaning and wash out of radioactive isotopes is essential to limit the risk of radioactive exposure. An uncontrolled LOCA has been selected for this study. In this work, numerical simulation of spray system with its parameter has been carried out to study the sensitivity analysis of airborne radioactive isotopes on spray system parameters. Therefore, we have developed a kinetic model and implemented in MATLAB which used the ORIGEN 2.2 as a subroutine code. The sensitivity analysis and airborne isotopes and removal rate has been carried out for spray activation time, droplet size. It has been seen that the droplets mean size plays an important role in containment washout. The droplet absorption ratio indicates that the smaller droplet size has higher absorption efficiency.
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Chew, Kathryn, Patrick Vaccaro, and Zachary Vealey. "VIBRATIONALLY-RESOLVED KINETIC ISOTOPE EFFECTS IN THE PROTON-TRANSFER DYNAMICS OF GROUND-STATE TROPOLONE." In 70th International Symposium on Molecular Spectroscopy. Urbana, Illinois: University of Illinois at Urbana-Champaign, 2015. http://dx.doi.org/10.15278/isms.2015.ti11.

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Lobyshev, V. I. "PROSPECTS FOR THE USE OF ISOTOPE-MODIFIED WATER IN BIOLOGY AND MEDICINE." In NOVEL TECHNOLOGIES IN MEDICINE, BIOLOGY, PHARMACOLOGY AND ECOLOGY. Institute of information technology, 2022. http://dx.doi.org/10.47501/978-5-6044060-2-1.87-91.

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The review gives a brief history of the study of biological isotopic effects associated with the replacement of H2O by D2O, explains the quantum nature of kinetic and thermodynamic iso-topic effects of deuterium, as well as isotopic effects of heavy water as a solvent. Some possible medical applications are considered.
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Ulrich, Robert, Rachel Han, Jamie Lucarelli, Julia Campbell, Abbas Hakim, Shayleen Singh, Justin Ries, Aradhna Tripati, and Robert Eagle. "Coupled Δ47–Δ48 clumped isotope analysis indicates origins of kinetic isotope effects in cultured biogenic marine carbonates." In Goldschmidt2021. France: European Association of Geochemistry, 2021. http://dx.doi.org/10.7185/gold2021.7851.

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Schwab, Lorenz, Niklas Gallati, David McLagan, Harald Biester, Stephan Kraemer, and Jan Wiederhold. "Kinetic versus Equilibrium Mercury Isotope Effects During Homogenous and Surface Catalyzed Mercury(II) Reduction by Iron(II)." In Goldschmidt2022. France: European Association of Geochemistry, 2022. http://dx.doi.org/10.46427/gold2022.11919.

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Reports on the topic "Isotope kinetic effect"

1

Chang, Paul. Theoretical calculations of kinetic isotope effects. Portland State University Library, January 2000. http://dx.doi.org/10.15760/etd.785.

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Brown, Gilbert M., Thomas J. Meyer, and Bruce A. Moyer. Utilization of Kinetic Isotope Effects for the Concentration of Tritium. Office of Scientific and Technical Information (OSTI), June 2000. http://dx.doi.org/10.2172/827388.

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Brown, Gilbert M., Thomas j. Meyer, and Bruce A. Moyer. Utilization of Kinetic Isotope Effects for the Concentration of Tritium. Office of Scientific and Technical Information (OSTI), June 1999. http://dx.doi.org/10.2172/827393.

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Brown, Gilbert M., and Thomas J. Meyer. UTILIZATION OF KINETIC ISOTOPE EFFECTS FOR THE CONCENTRATION OF TRITIUM. Office of Scientific and Technical Information (OSTI), December 2001. http://dx.doi.org/10.2172/827401.

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Brown, G. M., and T. J. Meyer. Utilization of kinetic isotope effects for the concentration of tritium. 1997 annual progress report. Office of Scientific and Technical Information (OSTI), September 1997. http://dx.doi.org/10.2172/13743.

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Brown, G. M., and T. J. Meyer. Utilization of kinetic isotope effects for the concentration of tritium. 1998 annual progress report. Office of Scientific and Technical Information (OSTI), June 1998. http://dx.doi.org/10.2172/13744.

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