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Dissertations / Theses on the topic 'Isotope kinetic effect'

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Published: 14 March 2023

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1

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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2

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
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3

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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4

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.<br>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, creatin
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5

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 an
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6

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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7

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
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8

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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9

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
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10

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
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11

Giebel, Brian M. "Advancement and Application of Gas Chromatography Isotope Ratio Mass Spectrometry Techniques for Atmospheric Trace Gas Analysis." Scholarly Repository, 2011. http://scholarlyrepository.miami.edu/oa_dissertations/610.

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The use of gas chromatography isotope ratio mass spectrometry (GC-IRMS) for compound specific stable isotope analysis is an underutilized technique because of the complexity of the instrumentation and high analytical costs. However stable isotopic data, when coupled with concentration measurements, can provide additional information on a compounds production, transformation, loss, and cycling within the biosphere and atmosphere. A GC-IRMS system was developed to accurately and precisely measure δ13C values for numerous oxygenated volatile organic compounds (OVOCs) having natural and anthropoge
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12

Hoeven, Robin. "Investigating the contribution of protein dynamics to catalysis in protochlorophyllide oxidoreductase." Thesis, University of Manchester, 2015. https://www.research.manchester.ac.uk/portal/en/theses/investigating-the-contribution-of-protein-dynamics-to-catalysis-in-protochlorophyllide-oxidoreductase(029dda21-023f-4fdb-a980-26db7eab4833).html.

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Enzyme dynamics has been established to play a crucial role in catalysis, and it has therefore become an important area of research to better understand enzymatic rate enhancements. The light-activated enzyme protochlorophyllide oxidoreductase (POR) is a well-studied model system where dynamics are known to be important for catalysis. The catalytic reaction involves a sequential hydride and proton transfer to reduce the C17-C18 double bond in the protochlorophyllide (Pchlide) substrate with NADPH as a cofactor to yield the chlorophyllide (Chlide) product. Both H-transfer steps are established
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13

Wang, Zhen. "Catalytic mechanisms of thymidylate synthases: bringing experiments and computations together." Diss., University of Iowa, 2012. https://ir.uiowa.edu/etd/2654.

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The relationship between protein structure, motions, and catalytic activity is an evolving perspective in enzymology. An interactive approach, where experimental and theoretical studies examine the same catalytic mechanism, is instrumental in addressing this issue. We combine various techniques, including steady state and pre-steady state kinetics, temperature dependence of kinetic isotope effects (KIEs), site-directed mutagenesis, X-ray crystallography, and quantum mechanics/molecular mechanics (QM/MM) calculations, to st
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14

Huang, Min. "Elucidation des Mécanismes de O- et C-glycosylation par des Moyens Chimiques et Spectroscopiques." Phd thesis, Université Paris Sud - Paris XI, 2012. http://tel.archives-ouvertes.fr/tel-00923152.

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L'effet isotopique cinétique (KIE) est un outil puissant pour obtenir un aperçu sur le mécanisme d'une grande variété réactions. Nous avons observé différentes mesures de l'effet isotopique cinétique primaire du 13C pour la formation des α-, et β-mannopyranosides et des α- et β-glucopyranosides, en partant du sulfoxyde de glycosyle protégé par le groupement 4,6-O-benzylidène, par la spectroscopie RMN à ultrahaut champ (13C à 200 MHz et 1H à 800 MHz). Nous avons aussi calculé les KIE pour ces réactions en collaboration avec le Prof. Pratt à l'Université d'Ottawa. Les valeurs expérimentale et ca
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15

Piansawan, Tammarat [Verfasser]. "Temperature Dependence of Carbon Kinetic Isotope Effect for the Oxidation Reaction of Ethane by Hydroxyl Radicals Under Atmospherically Relevant Conditions: Experimental and Theoretical Studies / Tammarat Piansawan." Wuppertal : Universitätsbibliothek Wuppertal, 2016. http://d-nb.info/1120337615/34.

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16

Ryberg, Per. "Concerted or Stepwise? : β-Elimination, Nucleophilic Substitution, Copper Catalysed Aziridination and Ruthenium Catalysed Transfer Hydrogenation Studied by Kinetic Isotope Effects and Linear Free-Energy Relationships". Doctoral thesis, Uppsala universitet, Avdelningen för organisk kemi, 2002. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-2008.

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This thesis describes the use of kinetic isotope effects, linear free energy relationships and stereochamical studies to distinguish between different mechanistic alternatives and to obtain information about transition state structure. In the first part fluorine and deuterium kinetic isotope effects were determined for the base promoted HF elimination from 4-fluoro-4-(4’-nitrophenyl)butane-2-on. During this work a new method for the determination of fluorine kinetic isotope effects was developed. The results from the study demonstrates that the reaction proceeds via an E1cBip mechanism. In the
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17

Wang, Zhihong. "Kinetic isotope effects, dynamic effects, and mechanistic studies of organic reactions." Texas A&M University, 2005. http://hdl.handle.net/1969.1/4886.

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Several organic reactions that could potentially involve coarctate transition states were investigated by a combination of experimental and theoretical studies. In the thermal fragmentation of ∆-1,3,4-oxadiazolines, the mechanism supported by kinetic isotope effects and theoretical calculations is a three-step process that does not demonstrate any special stabilization in coarctate transition states. Rather than undergoing a direct coarctate conversion to product, the mechanism avoids coarctate steps. The last step is a concerted coarctate reaction, but being concerted may be viewed as be
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18

Guo, Weifu Blake Geoffrey A. Eiler John. "Carbonate clumped isotope thermometry : application to carbonaceous chondrites and effects of kinetic isotope fractionation /." Diss., Pasadena, Calif. : California Institute of Technology, 2009. http://resolver.caltech.edu/CaltechETD:etd-12182008-115035.

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19

Li, Jiayue. "The preservation of protein dynamics from bacteria to human dihydrofolate reductase." Diss., University of Iowa, 2019. https://ir.uiowa.edu/etd/6984.

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Protein motions are complex, including occurring at different time scales, and their roles in enzyme-catalyzed reactions have always been of great interest among enzymologists. In order to characterize the potential factors that play a role on the chemical step of enzymatic reactions, variants of dihydrofolate reductase have been used as a benchmark system to study the motions of proteins correlated with the chemical step. A “global dynamic network” of coupled residues in Escherichia coli dihydrofolate reductase (ecDHFR), which assists in catalyzing the chemical step, has been demonstrated thr
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20

Jenson, David L. Jenson. "Proton-coupled electron transfer and tyrosine D of phototsystem II." Diss., Atlanta, Ga. : Georgia Institute of Technology, 2009. http://hdl.handle.net/1853/29667.

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Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2010.<br>Committee Chair: Bridgette Barry; Committee Member: Ingeborg Schmidt-Krey; Committee Member: Jake Soper; Committee Member: Nils Kroger; Committee Member: Wendy Kelly. Part of the SMARTech Electronic Thesis and Dissertation Collection.
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21

Backstrom, Nicholas. "Primary Kinetic Isotope Effects in Intramolecular Deprotonation of Carbon Acids." Thesis, University of Manchester, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.511907.

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22

Hothi, Parvinder. "Multiple ligand binding and kinetic isotope effects in methanol dehydrogenase." Thesis, University of Leicester, 2004. http://hdl.handle.net/2381/29691.

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The reaction of PQQ-dependent methanol dehydrogenase (MDH) has been studies by steady-state and stopped-flow kinetic methods, with particular reference to multiple ligand binding and kinetic isotope effects (KIEs). Phenazine ethosulphate (PES; an artificial electron acceptor) and cyanide (a suppressant of endogenous activity), but not ammonium (an activator of MDH), compete for binding at the catalytic methanol-binding site. MDH activity is dependent on activation by ammonium, bit is inhibited at high ammonium concentrations. Glycine ethyl ester (GEE; an alternative activator) does not inhibit
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23

Christian, Chad F. "The experimental and theoretical determination of combinatorial kinetic isotope effects for mechanistic analysis." [College Station, Tex. : Texas A&M University, 2007. http://hdl.handle.net/1969.1/ETD-TAMU-1253.

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24

Ussing, Bryson Richard. "Systematic examination of dynamically driven organic reactions via kinetic isotope effects." Texas A&M University, 2006. http://hdl.handle.net/1969.1/4877.

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Organic reactions are systematically examined experimentally and theoretically to determine the role dynamics plays in the outcome of the reaction. It is shown that trajectory studies are of vital importance in understanding reactions influenced by dynamical motion. This dissertation discusses how a combination of kinetic isotope effects, theoretical calculations, and quasiclassical dynamics trajectories aid in the understanding of the solvolysis of p-tolyldiazonium cation in water, the cycloadditions of cyclopentadiene with diphenylketene and dichloroketene, and the cycloaddition of 2- methyl
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25

Roston, Daniel Harris. "The use of kinetic isotope effects in studies of hydrogen transfers." Diss., University of Iowa, 2013. https://ir.uiowa.edu/etd/1498.

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The present dissertation seeks to deepen our understanding of hydrogen transfers and especially C-H bond activations in enzymes. Hydrogen transfers are ubiquitous in chemistry and biology and a thorough understanding of how they occur and what factors influence them will facilitate developments in biomimetic catalysis, rational drug design, and other fields. A particular difficulty with H-transfers is the importance of nuclear quantum effects to the reaction, particularly tunneling. The overall scope of the work here aims to examine how experimental kinetic isotope effects (KIEs) can be interp
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26

Sobrado, Pablo. "Studies of the chemical mechanisms of flavoenzymes." Texas A&M University, 2003. http://hdl.handle.net/1969/565.

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27

Owens, Simon. "Kinetics and mechanisms of hydrogen isotope exchange over solid storage media." Thesis, University of Bath, 2015. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.687343.

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Hydrogen isotope separation systems using palladium (Pd) are currently being designed for both reactor designs with the aim of separating and purifying the reactor exhaust products which contain valuable unspent hydrogen isotopes. Hydrogen isotope exchange in Pd offers an efficient, ambient condition process that can produce pure isotopic species in a process far simpler and less costly than the current state of the art cryogenic distillation processes. The method is applicable whether separating hydrogen (protium), deuterium or tritium and any combination of these. If practical fusion devices
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28

Frantom, Patrick Allen. "Studies of the chemical and regulatory mechanisms of tyrosine hydroxylase." Texas A&M University, 2006. http://hdl.handle.net/1969.1/3817.

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Tyrosine hydroxylase (TyrH) catalyzes the pterin-dependent hydroxylation of tyrosine to form dihydroxyphenylalanine. The enzyme requires one atom of ferrous iron for activity. Using deuterated 4-methylphenylalanine substrates, intrinsic primary and secondary isotope effects of 9.6 ± 0.9 and 1.21 ± 0.08 have been determined for benzylic hydroxylation catalyzed by TyrH. The large, normal secondary isotope effect is consistent with a mechanism involving hydrogen atom abstraction to generate a radical intermediate. The similarity of the isotope effects to those measured for benzylic hydroxylatio
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29

Kellerman, Daniel. "Application of Internal Competition Kinetics to Probe the Catalytic Strategies of RNA 2’-O-transphosphorylation." Case Western Reserve University School of Graduate Studies / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=case1449150064.

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30

Ma, Li. "Study of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Hydride Transfer Reactions in Solution." Thesis, Southern Illinois University at Edwardsville, 2018. http://pqdtopen.proquest.com/#viewpdf?dispub=10843728.

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<p> It has been accepted that hydrogen-transfer reactions take place through a quantum mechanical tunneling mechanism, where H tunnels through its classical energy barrier in light of its wave form. There are several H-tunneling models proposed, including the contemporary Marcus-like H-tunneling model, which explains that the donor-acceptor distance (DAD) in the tunneling ready state (TRS) is shorter for a heavier isotope (e.g. deuterium (D)) then a lighter isotope (e.g., protium (H)). This model has been used to explain the kinetic isotopic effect observations in H-tunneling processes to prov
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31

Pudney, Christopher R. "Kinetic isotope effects as probes of the mechanism of enzymatic hydrogen transfer." Thesis, University of Manchester, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.492045.

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32

Nowlan, Daniel Thomas. "Mechanisms of transition-metal catalyzed additions to olefins." Texas A&M University, 2003. http://hdl.handle.net/1969.1/2308.

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Transition metal catalyzed reactions have an important place in synthetic chemistry, but the mechanistic details for many of these reactions remain undetermined. Through a combination of experimentally determined 13C kinetic isotope effects (KIEs) and density functional theory (DFT) calculations, some of these reactions have been investigated. The cyclopropanation of an olefin catalyzed by rhodium (II) tetrabridged complexes has been shown to proceed through an asynchronous, but concerted mechanism. DFT does not provide an accurate transition structure for the reaction of an unstabilized carbe
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33

Leavitt, William Davie. "On the mechanisms of sulfur isotope fractionation during microbial sulfate reduction." Thesis, Harvard University, 2014. http://dissertations.umi.com/gsas.harvard:11511.

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Underlying all applications of sulfur isotope analyses is our understanding of isotope systematics. This dissertation tests some fundamental assumptions and assertions, drawn from equilibrium theory and a diverse body of empirical work on biochemical kinetics, as applied to the multiple sulfur isotope systematics of microbial sulfate reduction. I take a reductionist approach, both in the questions addressed and experimental approaches employed. This allows for a mechanistic, physically consistent interpretation of geological and biological sulfur isotope records. The goal of my work here i
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34

Rungsrisuriyachai, Kunchala. "On the Catalytic Roles of HIS351, ASN510, and HIS466 in Choline Oxidase and the Kinetic Mechanism of Pyranose 2-Oxidase." Digital Archive @ GSU, 2010. http://digitalarchive.gsu.edu/chemistry_diss/36.

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Choline oxidase (E.C. 1.1.3.17) from Arthrobacter globiformis catalyzes the four-electron oxidation of choline to glycine betaine (N,N,N-trimethylglycine) via two sequential, FAD-dependent reactions in which betaine aldehyde is formed as an enzyme-bound intermediate. In each oxidative half-reaction, molecular oxygen acts as electron acceptor and is converted into hydrogen peroxide. Biochemical, structural, and mechanistic studies on the wild-type and a number of mutant variants of choline oxidase have recently been carried out, allowing for the depiction of the mechanism of alcohol oxidation c
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35

Lai, Chung-Jeng. "Fumarate Activation and Kinetic Solvent Isotope Effects as Probes of the NAD-Malic Enzyme Reaction." Thesis, University of North Texas, 1992. https://digital.library.unt.edu/ark:/67531/metadc278864/.

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The kinetic mechanism of activation of the NAD-malic enzyme by fumarate and the transition state structure for the oxidation malate for the NAD-malic enzyme reaction have been studied. Fumarate exerts its activating effect by decreasing the off-rate for malate from the E:Mg:malate and E:Mg:NAD:malate complexes. The activation by fumarate results in a decrease in K_imalate and an increase in V/K_malate by about 2-fold, while the maximum velocity remains constant. A discrimination exists between active and activator sites for the binding of dicarboxylic acids. Activation by fumarate is proposed
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36

Guo, Qi. "Enzyme dynamics and their role in formate dehydrogenase." Diss., University of Iowa, 2016. https://ir.uiowa.edu/etd/2216.

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How the fast (femtosecond-picosecond, fs-ps) protein dynamics contribute to enzymatic function has gained popularity in modern enzymology. With multiple experimental and theoretical studies developed, the most challenging part is to assess both the chemical step kinetics and the relevant motions at the transition state (TS) on the fast time scale. Formate dehydrogenase (FDH), which catalyzes a single hydride transfer reaction, is a model system to address this specific issue. I have crystallized and solved the structure of FDH from Candida boidinii (CbFDH) in complex with NAD+ and azide. With
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37

Lavigne, André. "Oxydations cupro-catalysees des amines aliphatiques : etudes mecanistiques et applications synthetiques." Paris 6, 1987. http://www.theses.fr/1987PA066470.

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Preparation de nitriles a partir d'amines primaires et d'alpha -aminoacides. Les acides amines monosubstutitues rch(nh::(2))co::(2)h donnent le nitrile rcn, alors que les acides amines disubstitues rr'c(nh::(2))co::(2)h conduisent a l'azine rr'c=n-n=cr'r. Les mecanismes proposes font intervenir le cuivre (iii), forme in situ a partir du cuivre (i) et de l'oxygene
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38

Ralph, Erik C. "The chemical mechanisms of flavin-dependent amine oxidases and the plasticity of the two-his one-carboxylate facial triad in tyrosine hydroxylase." [College Station, Tex. : Texas A&M University, 2006. http://hdl.handle.net/1969.1/ETD-TAMU-1043.

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39

Uluisik, Rizvan C. "Effects of Temperature on the Kinetic Isotope Effects for Proton and Hydride Transfers in the Active Site Variant of Choline Oxidase Ser101Ala." Digital Archive @ GSU, 2013. http://digitalarchive.gsu.edu/chemistry_theses/56.

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Choline oxidase catalyzes the oxidation of choline to glycine betaine. The reaction includes betaine aldehyde as an intermediate. FAD is reduced by the alcohol substrate, betaine aldehyde intermediate and oxidized by molecular oxygen to give hydrogen peroxide. In this study, the Ser101Ala variant of choline oxidase was prepared to elucidate the contribution of the hydroxyl group of Ser101 in the proton and hydride transfer reactions for proper preorganization and reorganization of the active site towards quantum mechanical tunneling. The thermodynamic parameters associated with the enzyme-cata
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40

Gurevic, Ilya. "Studies on the hydride transfer and other aspects of several thymidylate synthase variants." Diss., University of Iowa, 2018. https://ir.uiowa.edu/etd/6586.

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The nucleotide 2'-deoxythymidine 5'-monophosphate (thymidylate, dTMP) is phosphorylated twice to become a substrate for DNA polymerases, which copy a cell’s genetic information in advance of cell division. The main route to dTMP is mediated by the enzyme thymidylate synthase (TSase) and goes through 2'-deoxyuridine 5'-monophosphate (dUMP); dUMP’s heterocyclic aromatic pyrimidine ring loses a proton from its C5 position and gains a methylene and a hydride from the other reactant, methylene tetrahydrofolate (MTHF). In general, intricate knowledge of an enzyme’s mechanism can yield insight that l
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41

Roberts, Kenneth M. "Mechanistic evaluation of N-dealkylation by cytochrome P450 using N,N-dimethylaniline N-oxides and kinetic isotope effects." Pullman, Wash. : Washington State University, 2009. http://www.dissertations.wsu.edu/Dissertations/Fall2009/k_roberts_113009.pdf.

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42

Mauve, Caroline. "Production et hydrolyse des amides : mécanismes chimiques, isotopie et applications : étude de la glutamine synthétase." Thesis, Paris 11, 2014. http://www.theses.fr/2014PA112397.

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La nutrition azotée des bactéries et des plantes est actuellement un sujet de grande importance, notamment pour comprendre comment améliorer les voies métaboliques aboutissant à l’assimilation de l’azote et à plus grande échelle, optimiser des apports d’engrais et augmenter le rendement des cultures. Dans ce contexte, la réaction d’amidation catalysée par la glutamine synthétase (GS), qui fixe l’ammonium (NH₄)⁺ en glutamine, est cruciale car elle est à la fois le point d’entrée de l’azote dans les végétaux, et une étape-clef du recyclage de l’azote (en particulier, NH₄⁺ photorespiratoire). Dan
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43

Hatzakorzian, Roupen. "The effect of insulin on whole body protein and glucose metabolism after cardiac surgery using stable isotope kinetics: a pilot study." Thesis, McGill University, 2012. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=107612.

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High doses of insulin are required to prevent the hyperglycemic response to open heart surgery. Insulin has been shown to produce hypoaminoacidemia during coronary artery bypass graft (CABG) surgery. The present study investigated the effect of high-dose insulin therapy on whole body protein and glucose metabolism in patients undergoing CABG surgery using stable isotope tracers [6,6-2H2]glucose and L-[1-13C]-leucine. Hyperinsulinemic-normoglycemic clamp was used to deliver high-dose insulin. The primary objective was to establish a protocol and to assess the feasibility of using stable isotope
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44

Uliaque, Cugat Katia. "Implementation of stable isotopes lipoprotein kinetic studies: effects on HDL metabolism of a Mediterranean type diet rich in MUFAs from virgin olive oil." Doctoral thesis, Universitat Rovira i Virgili, 2007. http://hdl.handle.net/10803/8658.

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The anti-atherogenic effects ascribed to a Mediterranean-type diet rich in monounsaturated<br/>fatty acids (MUFAs) from virgin olive oil are due, partly, to an increase in, or maintenance of,<br/>plasma concentrations of high density lipoprotein (HDL) cholesterol. However, the underlying<br/>mechanisms that may explain these concentrations are not well characterised, to-date.<br/>Apolipoprotein (apo) A-I (apoA-I) is the major HDL apo and its kinetic parameters, such as<br/>production rate and catabolic rate, reflect the kinetics of the HDL particle. Our working<br/>hypothesis is as follows: a
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Wu, Guanmin. "Synthesis, characterization, and kinetics of isomerization, C-H and P-C bond activation for unsaturated diphosphine-coordinated triosmium carbonyl clusters." Thesis, University of North Texas, 2008. https://digital.library.unt.edu/ark:/67531/metadc6037/.

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Substitution of MeCN ligands in the activated cluster Os3(CO)10(MeCN)2 by the unsaturated diphosphine ligands (Z)-Ph2PCH=CHPPh2 (cDPPEn) or 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) proceeds rapidly at room temperature to furnish the ligand-bridged cluster 1,2-Os3(CO)10(P-P) (P-P represents cDPPEn or bpcd). Heating 1,2-Os3(CO)10(P-P) leads to the formation of the thermodynamically more stable chelating isomer 1,1-Os3(CO)10(P-P). Each compound of Os3(CO)10(P-P) has been characterized by x-ray diffraction, IR, 31P NMR and 1H NMR. Ligand isomerization kinetics have been investiga
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46

Francis, Kevin. "On the Biochemistry, Mechanism and Physiological Role of Fungal Nitronate Monooxygenase." Digital Archive @ GSU, 2011. http://digitalarchive.gsu.edu/chemistry_diss/51.

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Nitronate monooxygenase (E.C. 1.13.11.16), formerly known as 2-nitropropane dioxygenase (EC 1.13.11.32), is a flavin dependent enzyme that catalyzes the oxidation of nitronates to their corresponding carbonyl compounds and nitrite. Despite the fact that the enzyme was first isolated from Neurospora crassa 60 years ago, the biochemical and physiological properties of nitronate monooxygenase have remained largely elusive. This dissertation will present the work that established both the catalytic mechanism and physiological role of the fungal enzyme. The biological and biochemical properties of
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47

Juillet, Clara. "Mécanismes et cinétiques de perméation de l’hydrogène dans les alliages de zirconium oxydés Kinetics of hydrogen desorption from Zircaloy-4: Experimental and modelling Effect of a pre-oxidation on the hydrogen desorption from Zircaloy-4 Effect of the precipitates on the hydrogen desorption kinetics from zirconium-niobium alloys Kinetics of deuterium permeation through Zircaloy-4 in the 623 – 773 K temperature range." Thesis, université Paris-Saclay, 2020. http://www.theses.fr/2020UPAST060.

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Au cœur des réacteurs à eau pressurisée, les pastilles de combustible sont isolées du circuit primaire par des gaines en alliages de zirconium. En conditions nominales de fonctionnement, l’interaction entre ces gaines et le milieu primaire entraîne la formation d’un oxyde et l’absorption d’hydrogène par l’alliage. La désorption de l’hydrogène lors du transport de combustible usé et le relâchement du tritium issu de la réaction de fission au sein des pastilles de combustible en réacteur sont des problématiques importantes pour la sûreté. Il est impératif d’estimer la quantité de tritium suscept
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48

Bajnai, David [Verfasser], Jens [Gutachter] Fiebig, Silke [Gutachter] Voigt та Gregory D. [Gutachter] Price. "The clumped and oxygen isotope compositions of biogenic carbonate archives: kinetic effects and reconstruction of seawater temperatures and seawater δ18O / David Bajnai ; Gutachter: Jens Fiebig, Silke Voigt, Gregory D. Price". Frankfurt am Main : Universitätsbibliothek Johann Christian Senckenberg, 2019. http://d-nb.info/1193126037/34.

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Montanari, Carlo Emilio. "Development of an event-based simulator for analysing excluded volume effects in a Brownian gas." Bachelor's thesis, Alma Mater Studiorum - Università di Bologna, 2017. http://amslaurea.unibo.it/14527/.

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Il presente lavoro si pone come scopo lo sviluppo di un simulatore in C++ di dinamica molecolare utilizzando un approccio event-based, in grado di simulare la dinamica newtoniana semplice di molecole bidimensionali di forma arbitraria. Abbiamo utilizzato il simulatore NOCS per imbastire un primo tentativo di ricerca e di analisi degli effetti di volume escluso sul moto Browniano di molecole. In particolare si vogliono ricercare violazioni locali di isotropia nel moto Browniano. Nella parte teorica dell'elaborato, si analizzano gli strumenti matematici e statistici fondamentali della Kinetic Th
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Hancock, Amber N. "A Radical Approach to Syntheses and Mechanisms." Diss., Virginia Tech, 2011. http://hdl.handle.net/10919/77139.

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The critically important nature of radical and radical ion mechanisms in biology and chemistry continues to be recognized as our understanding of these unique transient species grows. The work presented herein demonstrates the versatility of kinetic studies for understanding the elementary chemical reactions of radicals and radical ions. Chapter 2 discusses the use of direct ultrafast kinetics techniques for investigation of crucially important enzymatic systems; while Chapter 3 demonstrates the value of indirect competition kinetics techniques for development of synthetic methodologies for co
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