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Dissertations / Theses on the topic 'Kinetic solvent isotope effect'

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Published: 5 June 2025

Last updated: 1 August 2025

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1

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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2

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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3

Belhadj, Hamza [Verfasser]. "Solvent isotope effect (D2O) in photocatalytic systems / Hamza Belhadj." Hannover : Technische Informationsbibliothek (TIB), 2017. http://d-nb.info/1150536683/34.

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4

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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5

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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6

Yidan, Shen. "Solvent Isotope Effect and Hydrogen Bond Effect on The Self-assembly Process of Macroions." University of Akron / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=akron1522256710854143.

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7

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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8

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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9

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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10

Kumwimba, Ghislain Mutamba. "Effect of process variables on the kinetic and thermodynamic parameters of platinum solvent extraction by cyanex 921." Thesis, Cape Peninsula University of Technology, 2012. http://hdl.handle.net/20.500.11838/870.

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Thesis(MTech( Engineering))--Cape Peninsula University of Technology, 2012<br>Platinum is a precious metal which may be processed under acidic conditions. Accordingly, the extraction of platinum from an acidic chloride media is of immense practical importance. In this study, the extraction of platinum was investigated in a Pt(IV)-HCl-Cyanex 921 matrix in order to establish the effect of temperature, extractant concentration, pH and the initial platinum concentration which had been used in the evaluated solvent extraction (SX) process. The extractant phase contained a mixture of Cyanex 921 and

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11

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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12

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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13

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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14

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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15

Di, Menno Di Bucchianico Daniele. "The effect of solvent on the thermal and catalysed decomposition of hydrogen peroxide: an experimental and model analysis." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2020.

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L'obiettivo di questo lavoro è quello di studiare l'effetto del solvente organico sulla decomposizione del perossido di idrogeno attraverso un'analisi sperimentale e di modellazione cinetica. L’analisi sperimentale esamina la decomposizione termica e la decomposizione catalizzata da γ-allumina in assenza e presenza di acetato di etile come solvente. Determinati attraverso cerimetria, i dati di concentrazione del perossido di idrogeno nei sistemi acquoso-solido e acquoso-organico-solido sono stati esaminati rispetto a parametri di reazione, come temperatura, massa di catalizzatore, rapporto in

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16

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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17

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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18

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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19

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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20

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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21

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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22

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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23

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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24

MAGALHAES, WELINGTON F. "Influence de parametres physico-chimiques sur les reactions du positonium en solution." Université Louis Pasteur (Strasbourg) (1971-2008), 1987. http://www.theses.fr/1987STR13218.

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25

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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26

McCord, Bruce Royston. "Solvent and ion-pairing effects on the chlorine kinetic isotope effect of t-butyl chloride." 1986. http://catalog.hathitrust.org/api/volumes/oclc/15288226.html.

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Thesis (Ph. D.)--University of Wisconsin--Madison, 1986.<br>Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 155-160).

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27

Headley, George William. "Solvent dependence of the oxygen kinetic isotope effect on the decarboxylation of 4-pyridylacetic acid." 1988. http://catalog.hathitrust.org/api/volumes/oclc/18229919.html.

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Thesis (M.S.)--University of Wisconsin--Madison, 1988.<br>Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaf 44).

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28

Cash, Michael T. "Kinetic isotope effect in the [beta]-subunit mechanism of tryptophan synthase ; excited state tautomerization of azaindole." 2003. http://purl.galileo.usg.edu/uga%5Fetd/cash%5Fmichael%5Ft%5F200308%5Fms.

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29

Chen, Min-ta, та 陳明達. "The mechanism study of the free radical SH2’reaction by secondary α-Deuterium kinetic isotope effect". Thesis, 2006. http://ndltd.ncl.edu.tw/handle/00159285591733226251.

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碩士<br>義守大學<br>生物技術與化學工程研究所碩士班<br>94<br>The reactions of free radical addition to allylic compounds are believed to proceed the SH2'' mechanism. The secondary α-ducterium kinetic isotope effect of 3-d-allyl chloride and 3,3-d2-allyl chloride in free radical SH2'' reaction have been determined. The secondary α-ducterium kinetic isotope effects of 3,3-d2-allyl chloride and 3-d-allyl chloride were measured as 0.78 and 0.89 respectively. These inverse KIE indicate that the rate-determining-step is the radical addition to double bond in SH2'' reaction. The secondary α-ducterium of 1,1-d2-allyl c

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30

Oyola, Yatsandra. "The Dynamic Effect in the Hydroboration of Alkenes." Thesis, 2010. http://hdl.handle.net/1969.1/ETD-TAMU-2010-12-8813.

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The hydroboration of simple alkenes with BH3 preferentially occurs in an anti- Markovnikov fashion. The standard explanation for this preference, reproduced in all general organic chemistry textbooks, is that the selectivity arises from a greater stability for the anti-Markovnikov transition state. This explanation presupposes the applicability of the transition-state theory model for reactivity and selectivity. This dissertation explores the applicability of transition state theory to selectivity in hydroborations and finds that in some cases transition state theory fails to accurately accoun

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31

Jye-Shiow-Chuang and 莊志秀. "Studies on the Solvolytic Reactivity and the Kinetic Isotope Effect in the Solvolysis of 4-Nitro-4''-Substituted Benzhydryl Substrates." Thesis, 2000. http://ndltd.ncl.edu.tw/handle/77866664552131979412.

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碩士<br>國立臺灣大學<br>化學研究所<br>88<br>ABSTRACT The solvolytic mechanism of diarymethyl bromides(I-B) and chlorides (I-C) were examined in this work. Twenty-two substrates were solvolyzed in 12 to 22 different solvents, respectively, and the rate constants were monitored. Correlation analyses using the single-parameter Grunwald-Winstein equation, log k = mYBnX (and YxBnX), and the dual-parameter equation, log k = mYBnX (and YxBnX) + lNOTS, were performed. The results suggested that the substrates I-B-1 and I-C-1 solvolyzed with limiting SN1 mechanism, whereas nucleophilic solvent part

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32

Zimmer-De, Iuliis Marco. "Mechanisms of Platinum Group Metal Catalysis Investigated by Experimental and Theoretical Methods." Thesis, 2009. http://hdl.handle.net/1807/29959.

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The results of kinetic isotope determination and computational studies on Noyori-type catalytic systems for the hydrogenation of ketones are presented. The catalysts examined include RuH2(NHCMe2CMe2NH2)(R-binap) and RuH(NHCMe2CMe2NH2)(PPh3)2. These complexes are active catalysts for ketone hydrogenation in benzene without addition of an external base. The kinetic isotope effect (KIE) for catalysis by RuH2(NHCMe2CMe2NH2)(R-binap) was determined to be 2.0 ± (0.1). The calculated KIE for the model system RuH(NHCH2CH2NH2)(PH3)2 was 1.3, which is smaller than the experimentally observed value b

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33

Chiang, Han-Kuei, and 江函桂. "I. Wavelength-dependent photocycle activity of xanthorhodopsin in the visible region II. Solvent isotope effect on the dark adaptation of bacteriorhodopsin in purple membrane." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/qkcp79.

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碩士<br>國立清華大學<br>化學系<br>105<br>Part I. Xanthorhodopsin (xR) is a dual-chromophore proton-pump photosynthetic protein comprising one retinal Schiff base and one light-harvesting antenna salinixanthin (SX). The excitation wavelength-dependent transient population of the intermediate M demonstrates that the excitation of the retinal at 570 nm leads to the highest photocycle activity and the excitations of SX at 460 and 430 nm reduce the activity to ca. 37% relatively, suggesting an energy transfer pathway from the S2 state of the SX to the S1 state of the retinal and a quick internal vibrational r

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34

"Mechanistic studies of surface-confined electrochemical proton coupled electron transfer." Thesis, 2012. http://hdl.handle.net/10388/ETD-2012-07-506.

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Mechanistic studies of electrochemical proton coupled electron transfer (PCET) have attracted attention for many decades due to their importance in many fields ranging from electrocatalysis to biology. However, mechanistic research is confined to only a few groups, and challenges in this field can be found in both theory and experiment. The contributions to mechanistic studies of electrochemical PCET reaction in this thesis can be categorized under the following two headings: 1) mechanistic studies of an aminobenzoquinone modified monolayer system with multiple electron/proton transfer reactio

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35

Hong, Nan-Sook. "Molecular basis of the evolution of new protein functions: Kemp elimination and phosphoryl transfer reactions." Phd thesis, 2016. http://hdl.handle.net/1885/116927.

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This is a series of investigations into the molecular basis of the evolution of new protein functions. The broad objective of this work was to determine exactly how a series of single amino acid mutations, typical of an evolutionary trajectory, can result in dramatic changes in catalytic activity, specificity and protein solubility. Various strategies were employed to achieve this aim, including analysis of existing literature concerning the various models and theories relating to molecular evolution, protein crystallography, extensive enzyme kinetics an

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36

Kim, Nam Ho 1975. "Mechanistic investigations of SpnF- and SpnL-catalyzed cyclizations in the biosynthesis of spinosyn A." Thesis, 2013. http://hdl.handle.net/2152/28735.

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Spinosyn A is a particularly interesting natural product due to its structural complexity and potent insecticidal activity. The biosynthetic pathway of spinosyn A is interesting as it has two unusual features, the SpnF-catalyzed (4+2) cycloaddition and the SpnL-catalyzed cyclization to produce the perhydro-as-indacene core. The work described in this dissertation focuses on elucidating the mechanisms of the SpnF- and SpnL-catalyzed reactions. SpnF has attracted significant interest as a possible Diels-Alderase. To explain how SpnF catalyzes the formation of cyclohexene ring, three plausible me

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Koch, Christian. "Structure and function of A.nidulans PSI factor producing oxygenase A." Doctoral thesis, 2012. http://hdl.handle.net/11858/00-1735-0000-0015-9E51-F.

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38

Lording, William James. "A deeper understanding of the Diels–Alder reaction." Phd thesis, 2010. http://hdl.handle.net/1885/11776.

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The Diels-Alder reaction was discovered in 1928 and has become the most efficient and practical method for the synthesis of six-membered carbocyclic and heterocyclic rings. This thesis comprises three chapters of results and discussion with the Diels-Alder reaction as a theme. Chapter 2 details an investigation of endo:exo selectivity in the Diels-Alder reactions of 1,3-butadiene. Chapter 3 explores aspects of the intramolecular Diels-Alder reactions of some substituted 1,3,8-nonatrienes, and Chapter 4 describes the domino Diels-Alder reactions of 1,4-diiodo-1,3-butadiene. The Diels-Ald

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