Dissertations / Theses: 'Catalytic studies of glycogen'

1

Martin, Jennifer Louise. "Molecular interactions involving glycogen phosphorylase." Thesis, University of Oxford, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.253306.

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2

Barford, D. "Crystallographic studies on glycogen phosphorylase b." Thesis, University of Oxford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.233473.

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3

McLaughlin, P. J. "Crystallographic studies on glycogen phosphorylase b." Thesis, University of Oxford, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.370290.

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4

Hu, Shu-Hong. "Crystallographic studies on activated glycogen phosphorylase." Thesis, University of Oxford, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.291283.

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5

Duke, Elizabeth Mary Helen. "X-ray diffraction studies on glycogen phosphorylase." Thesis, University of Oxford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.336092.

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6

Mitchell, Edward Peter. "Cryocrystallographic and mechanistic studies on glycogen phosphorylase." Thesis, University of Oxford, 1994. https://ora.ox.ac.uk/objects/uuid:d562f4f6-0a93-43a6-ad74-d480697d1b8c.

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Glycogen phosphorylase (GPb) regulates the degradation of glycogen to glucose-1-phosphate and catalyses the first step of the reaction. Many studies have provided insights into the essentials of the catalytic mechanism. Previous time resolved crystallographic work using heptenitol has revealed a putative phosphate binding site at the active site of phosphorylase. Using nojirimycin tetrazole, a transition state analogue, complexed with phosphate and both T and R state GPb crystals, this work has conclusively located the phosphate binding site and the concomitant active site conformational changes. This has confirmed the previous heptenitol results. Using R state crystals complexed with tetrazole and phosphate, data were collected to 2.5Ã resolution, higher than for the original 2.8Ã resolution native structure, and used to position water molecules in the R state model. Further to this, direct observation of the phosphate ion orientation was made possible using flash-frozen T state crystals to collect 1.7Ã resolution data at 100K. As part of this cryocrystallographic work the relationship of cryoprotectant concentration with crystal mosaicity was established, aiding the systematic search for flash-freezing cryoprotectant conditions for all protein crystals. Collection of a new native T state data set to 1.5Ã resolution was made possible using the flash-freezing technique. Refinement has produced a new higher precision native model (R factor currently 22.8%) containing additional N terminal residues (14-18) and 330 new water molecules. A molecule of glycerol, the cryoprotectant, was located at the active site. This study represents a considerable improvement over the 1.9Ã resolution room temperature native data, and is also the first time such high resolution data have been collected from such a large enzyme. In a further analysis of the phosphate binding properties, a link between structure, atomic charges and the ability of a ligand to bind phosphate at the phosphorylase active site was established. In order of phosphate binding ability, the nojirimycin tetrazole, nitroglucal, glucal and glucose complexes with T state GPb and phosphate were structurally analysed. As the charge difference between the pyranose ring oxygen (or equivalent atom) and anomeric atom becomes more negative (charges estimated using MOPAC) the tendency to bind phosphate decreases. The ligand must possess a half-chair conformation as this is essential to bind phosphate; glucose, having the most negative charge difference and a full chair conformation, does not bind phosphate significantly in the crystal. A novel surface binding site for nitroglucal (covalently linked to His 73) was also located during this work. As part of an ongoing search for potential drugs for diabetes, two gluco-hydantoin inhibitors of GPb were investigated. One proved to be the best inhibitor to date, and the inhibition was rationalised using the structural results from this work. A new improved inhibitor has been proposed on the basis of these results.

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7

Varvill, Katherine Mary. "X-ray crystallographic studies on glycogen phosphorylase b." Thesis, University of Oxford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.352921.

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8

Watson, Kimberly Ann. "Crystallographic studies on phosphorylase : sugar recognition properties." Thesis, University of Oxford, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.259849.

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9

Khan, M. "Catalytic studies on zeolites." Thesis, City University London, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375832.

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10

Maeda, Kenji. "Extended studies in catalytic hydroboration." Thesis, University of Oxford, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.246529.

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11

Copplestone, Francis A. "Catalytic studies of perovskite oxides." Thesis, University of Oxford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.358591.

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12

Daniells, S. T. "Model and experimental catalytic studies." Thesis, Queen's University Belfast, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.403269.

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13

Sutton, Jonathan Mark. "Synthetic studies towards catalytic antibody generation." Thesis, University of Bath, 1998. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.242814.

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14

Boopalachandran, Praveenkumar. "Catalytic studies of supported Pd-Au catalysts." Texas A&M University, 2006. http://hdl.handle.net/1969.1/3826.

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Although Pd-Au high-surface area catalysts are used in industry to improve activity and selectivity, a thorough understanding of the nature of these enhancements is lacking. A molecular-level understanding of catalytic reactions under actual reaction conditions is the ultimate goal. This thesis is mainly focused on the application of Pd-Au supported catalysts for vinyl acetate synthesis and CO oxidation reactions using highsurface area catalysts. We have attempted to improve the conventional Pd-Au based catalyst by synthesizing novel acetate-based and polymer-based catalysts. The corresponding catalytic reactivity and selectivity were measured and compared to conventional Pd-Au based catalyst systems. Subsequent characterization was performed using characterization techniques, such as, X-ray diffraction (XRD) and transmission electron microscopy (TEM). From our bimetallic catalytic studies, it was evident that the addition of Au to Pd leads to increased reactivity and selectivity. This surface modification is an important factor in the altered reaction kinetics for vinyl acetate (VA) synthesis and CO oxidation reactions. Promoted and unpromoted Pd-Au/SiO2/K+ catalyst were used for VA synthesis and the effect of pre-adsorbed O2, acetic acid and the role of oxygen were explored. The VA reaction rate of novel acetate-based Pd-Au/SiO2 catalyst was 3.5 times higher than conventional Pd-Au catalysts. Also, 100% selectivity was obtained for acetate-based Pd-Au/SiO2 at 130 oC and the VA formation rate was comparable to that of conventional Pd-Au catalysts. Therefore, the acetate-based Pd-Au/SiO2 catalyst seems very promising and can be explored further. Also, Pd(1):Au(4)/SiO2 catalysts demonstrate 100% CO conversion at much lower temperatures (90 oC) compared with other Pd-Au based catalysts. Furthermore, we were successful in obtaining sufficient CO oxidation activity with increased metal loading (5 wt%) and these catalysts did not deactivate under above-ambient reaction temperature conditions, which make 1:4 Pd- Au/SiO2 catalyst a good candidate for further exploration in CO oxidation reactions.

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15

Mandani, Faisal Mohammad. "Kinetic and deactivation studies during catalytic dehydrogenation." Thesis, University of Salford, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.305913.

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16

Weatherup, Robert Stewart. "In situ studies of catalytic graphene growth." Thesis, University of Cambridge, 2013. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.608143.

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17

Seal, L. H. "Studies on glycogen in the nervous systems of Haemopis sanguisuga (L) and Planorbis corneus (L)." Thesis, University of Salford, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.372154.

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18

Toufaili, Faissal-Ali el. "Catalytic and mechanistic studies of polyethylene terephthalate synthesis." [S.l.] : [s.n.], 2006. http://deposit.ddb.de/cgi-bin/dokserv?idn=979236096.

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19

O'Neal, Claire J. "Structural studies of the cholera toxin catalytic subunit /." Thesis, Connect to this title online; UW restricted, 2005. http://hdl.handle.net/1773/8592.

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20

Ekström, Jesper. "Transition metal hydrides : biomimetic studies and catalytic applications /." Stockholm : Department of Organic Chemistry, Stockholm University, 2007. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-7187.

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21

Ekström, Jesper. "Transition Metal Hydrides : Biomimetic Studies and Catalytic Applications." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2007. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-7187.

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In this thesis, studies of the nature of different transition metal-hydride complexes are described. The first part deals with the enantioswitchable behaviour of rhodium complexes derived from amino acids, applied in asymmetric transfer hydrogenation of ketones. We found that the use of amino acid thio amide ligands resulted in the formation of the R-configured product, whereas the use of the corresponding hydroxamic acid- or hydrazide ligands selectively gave the S-alcohol. Structure/activity investigations revealed that the stereochemical outcome of the catalytic reaction depends on the ligand mode of coordination. In the second part, an Fe hydrogenase active site model complex with a labile amine ligand has been synthesized and studied. The aim of this study was to find a complex that efficiently catalyzes the reduction of protons to molecular hydrogen under mild conditions. We found that the amine ligand functions as a mimic of the loosely bound ligand which is part of the active site in the hydrogenase. Further, an Fe hydrogenase active site model complex has been coupled to a photosensitizer with the aim of achieving light induced hydrogen production. The redox properties of the produced complex are such that no electron transfer from the photosensitizer part to the Fe moiety occurs. In the last part of this thesis, the development of a protocol for the transfer hydrogenation of ketones to secondary alcohols without the involvement of transition metal catalysts is described. A variety of ketones were efficiently reduced in 2-propanol using catalytic amounts of alkali alkoxide under microwave irradiation.

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22

Smith, Virginia Clare Moncrieff. "Mechanistic studies of catalytic C-C bond formation." Thesis, University of Oxford, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.240383.

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23

Winstanley, Alastair W. "Characterisation and catalytic studies of ZSM-5 zeolite." Thesis, University of Nottingham, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334462.

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24

Dimitratos, Nikolaos. "Catalytic studies of heteropoly compounds on propane oxidation." Thesis, University of Liverpool, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.272683.

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25

Chellappa, Anand S. "Methane conversion to methanol : homogeneous and catalytic studies /." free to MU campus, to others for purchase, 1997. http://wwwlib.umi.com/cr/mo/fullcit?p9842517.

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26

Hart, Abarasi. "Advanced studies of catalytic upgrading of heavy oils." Thesis, University of Birmingham, 2014. http://etheses.bham.ac.uk//id/eprint/5297/.

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Heavy oil and bitumen are known to constitute high-boiling molecules which gives them characteristic high viscosity, high density/low API gravity, low yields of fuel distillates, and high heteroatom content compared to light oil. Upgrading therefore refers to the breaking down of heavy oil into oil with similar characteristics as light crude oil. The toe-to-heel air injection (THAI) and its catalytic add-on CAPRI (CAtalytic upgrading PRocess \(In-situ\)) were developed to achieve this objective down-hole. In this study, the CAPRI process was explored with the objective of controlling catalyst deactivation due to coking while increasing the extent of upgrading. The effects of reaction temperature and weight hourly space velocity on the extent of upgrading were studied in the range of 350-425\(^o\)C and 9.1-28 h\(^-\)\(^1\), respectively. In order to control premature deactivation of the catalysts due to coke and metal deposition, the following were investigated activated carbon guard-bed on top of the catalyst bed, hydrogen-addition, steam environment as a source of hydrogen-donor, and nanoparticulate catalyst. It was found that high reaction temperature of 425\(^o\)C and lower WHSV (9.1 h\(^-\)\(^1\)) improved the cracking as well as increase API gravity (~3-7\(^o\)), viscosity reduction of (81.9 %), demetallisation (9.3-12.3 %), desulphurisation (5.3-6.6 %), and higher yield of fuel distillates, respectively compared to upgrading at 350 and 400\(^o\)C. In spite of the improvement in produced oil at 425 \(^o\)C, the carbon-rejection was high (51-56.6 wt.%) compared to (42-47.8 wt.%) and (48-50.3 wt.%) when reaction was carried out at 350 and 400\(^o\)C for 25 hours operations.

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27

Ajmera, Sameer K. (Sameer Kumar) 1975. "Microchemical systems for kinetic studies of catalytic processes." Thesis, Massachusetts Institute of Technology, 2002. http://hdl.handle.net/1721.1/16821.

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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2002.
Includes bibliographical references.
This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Silicon microfabrication techniques and scale-up by replication have for decades fueled spectacular advances in the electronics industry. More recently, with the rise of microfluidics, microfabrication has enabled the development of microchemical systems for a variety of chemical and biological applications. This work focuses on the development of these systems for improved gas phase heterogeneous catalysis research. The catalyst development process often requires fundamental information such as reaction rate constants, activation energies, and reaction mechanisms to gauge and understand catalyst performance. To this end, we have examined the ability of microreactors with a variety of geometries to efficiently obtain accurate kinetic information. This work primarily focuses on microfabricated packed-bed reactors that utilize standard catalyst particles and briefly explores the use of membrane based reactors to obtain kinetic information. Initial studies with microfabricated packed-beds led to the development of a microfabricated silicon reactor that incorporates a novel cross-flow design with a short pass multiple flow-channel geometry to reduce the gradients that often confound kinetics in macroscale reactors. The cross-flow geometry minimizes pressure drop though the particle bed and incorporates a passive flow distribution system composed of an array of shallow flow channels. Combined experiments and modeling confirm the even distribution of flow across the wide catalyst bed with a pressure drop [approx.] 1600 times smaller than typical microfabricated packed-bed configurations.
(cont.) Coupled with the inherent heat and mass transfer advantages at the sub-millimeter length scale achievable through microfabrication, the cross-flow microreactor has been shown to operate in near-gradientless conditions and is an advantageous design for catalyst testing. The ability of microfabricated packed-beds to obtain accurate catalytic information has been demonstrated through experiments with phosgene generation over activated carbon, and CO oxidation and acetylene hydrogenation over a variety of noble metals on alumina. The advantages of using microreactors for catalyst testing is quantitatively highlighted throughout this work.
by Sameer K. Ajmera.
Ph.D.

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28

Huang, Zhenyu. "Magnetic resonance studies of catalysts and catalytic reactors." Thesis, University of Cambridge, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.612201.

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29

Cochrane, Heather Dunlop. "Surface studies of catalytic cerias using atomic resolution TEM." Thesis, University of Oxford, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.276508.

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30

Hayward, J. J. "Studies in modern organic chemistry : catalytic, technological and structural." Thesis, University of Cambridge, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.603905.

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This thesis describes work done within the Ley group on a variety of projects, with a particular focus upon modern methods of synthesis. Chapter 1 initially describes work directed towards examining the use of the proline tetrazole catalyst 1.16 as a catalyst for aminations of carbonyl compounds. A novel ionic liquid-based system was developed to investigate this reaction as an oscillatory flow process. Chapter 2 gives an overview of the three enabling technologies that are of principal interest to the Ley group in general and this thesis in particular – microwave chemistry, polymer-supported reagents and flow chemistry (Fig 8888A). Chapter 3 describes the total synthesis of Siphonazole B. Our approach to this molecule was designed to make use of the enabling technologies described above, but also to evaluate them – particularly flow-based methods. With this in mind a left-hand fragment synthesis is devised and executed in the flow domain, and several approaches to the left-hand fragment investigated, culminating in the completed total synthesis. Siphonazole B is a bis-oxazole natural product, a class of molecules that has been of interest to our group for some time. Oxazoles and other aromatic heterocycles are ubiquitous within organic chemistry, whether one considers natural products (such as the siphonazoles) or pharmaceuticals (Fig 8888B). Chapter 4 chronicles our studies towards a new synthesis of thiazolothiophenes. During the course of these studies we describe a new class of conjugated betaines (shown above) which appear to exhibit an unusual S ^…. S interaction in the solid state, which we have investigated crystallographically and computationally.

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31

Jenta, Tuah R.-J. "Catalytic studies of lipase in microemulsion-based reaction media." Thesis, University of East Anglia, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334698.

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32

Harrison, Richard John. "Studies on some niobocene derivatives and their catalytic activity." Thesis, University of Warwick, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.245940.

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33

Slater, David Alan. "Surface science studies of catalytic promoters on Cu(110)." Thesis, University of Southampton, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.277505.

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34

Baddeley, Christopher John. "Structural, electronic and catalytic studies of Au/Pd systems." Thesis, University of Cambridge, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.309333.

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35

Zieleniuk, Candace A. "Anion binding and catalytic studies of metal salen complexes." [Gainesville, Fla.] : University of Florida, 2009. http://purl.fcla.edu/fcla/etd/UFE0024865.

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36

Kagawa, Reiko. "Structural studies of the catalytic mechanism of F₁-ATPase." Thesis, University of Cambridge, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.615879.

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37

Kyriakou, Georgios. "Catalytic studies on Cu-based model and dispersed systems." Thesis, University of Cambridge, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.616017.

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38

Inada, Youichi. "Studies on catalytic activity of thiolate-bridged diruthenium complexes." 京都大学 (Kyoto University), 2006. http://hdl.handle.net/2433/143980.

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Kyoto University (京都大学)
0048
新制・課程博士
博士(工学)
甲第12283号
工博第2612号
新制||工||1368(附属図書館)
24119
UT51-2006-J276
京都大学大学院工学研究科物質エネルギー化学専攻
(主査)教授光藤武明, 教授檜山爲次郎, 教授大江浩一
学位規則第4条第1項該当

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39

Trant, Aoife Geraldine. "Structural and catalytic studies of novel Au/Ni enantioselective catalysts." Thesis, St Andrews, 2008. http://hdl.handle.net/10023/854.

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40

Schröder, Olga. "Catalytic center of [NiFe] hydrogenases EPR, ENDOR and FTIR studies /." [S.l.] : [s.n.], 2001. http://deposit.ddb.de/cgi-bin/dokserv?idn=962310204.

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41

Bordes, Pastor Isabel. "Theoretical Studies of the Catalytic Mechanism of the Dihydroxyacetone Kinase." Doctoral thesis, Universitat Jaume I, 2017. http://hdl.handle.net/10803/436901.

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Dihydroxyacetone kinases (DHAKs) catalyse the transfer of the phosphoryl group from adenosine triphosphate (ATP) to dihydroxyacetone (Dha) generating Dha phosphate (Dha-P), a very important specie for C-C bond formation in nature. Kinases are present in humans and they are involved in cancer progression, inflammation and autoimmune disorders. In this Doctoral Thesis, it has been studied the molecular mechanism of the phosphoryl transfer from ATP to Dha in aqueous solution and in the DHAK of Escherichia coli employing the quantum mechanical/molecular mechanical (QM/MM) hybrid methodology. In addition, in collaboration with a experimental group of Madrid, it has been performed the tuning of the phosphoryl donor specificity in the DHAK from Citrobacter freundii, from ATP to inorganic polyphosphate, a very advantageous compound. It has been analyzed the binding effects of this compound with the enzyme and also the chemical reaction with the Dha.
Las dihidroxiacetona quinasas (DHAKs) catalizan la transferencia del grupo fosfato desde el adenosin trifosfato (ATP) a la dihidroxiacetona (Dha), generando Dha fosfato (Dha-P), una especie importante para la formación de enlaces C-C en la naturaleza. Las quinasas están presentes en el cuerpo humano e involucradas en el cáncer, la inflamación y los desórdenes autoinmunes. En esta Tesis Doctoral, se ha estudiado el mecanismo de reacción de transferencia de fosfato desde el ATP a la Dha en disolución acuosa y en la DHAK de Escherichia coli empleando la metodología híbrida mecánica cuántica/mecánica molecular (QM/MM). Además, en colaboración con un grupo experimental de Madrid, se ha estudiado la modificación de la especificidad en la DHAK de Citrobacter freundii, desde el ATP al polifosfato inorgánico como dador de fosfatos, un compuesto con grandes ventajas. Se han analizado los efectos de unión de este compuesto con dicha enzima, además de estudiar la reacción química con la Dha.

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42

Glavas, Suzana. "Studies on the catalytic acid/base residues of glutamate racemase." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0017/NQ46348.pdf.

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43

Cao, Chundi. "In situ infared [i.e. infrared] studies of catalytic partial oxidation." Diss., Manhattan, Kan. : Kansas State University, 2008. http://hdl.handle.net/2097/887.

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44

Kelly, Brian Daniel. "AMINO ACID DERIVED TRANSITION METAL COMPLEXES: STRUCTURAL AND CATALYTIC STUDIES." Diss., The University of Arizona, 2009. http://hdl.handle.net/10150/193634.

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A group of ligands were designed based on a minimalist reduction of the structure of metalloproteins. It was thought that a modular design with facile synthesis could lead to a new family of privileged ligands. Towards this goal a series of tri-, tetra, and penta-dentate ligands were synthesized. The ligands had a common chiral core based on inexpensive amino acid starting materials. A modular diamine backbone was adjusted to control the size, bite angle and electronic nature of the binding pocket. The ligands were capped with Schiff base imines to provide an initial binding point for the metal and to create steric bulk at one face of the complex.The tetra-dentate ligands were shown to efficiently bind zinc(II), copper((II), nickel(II), and palladium(II). In the case of the penta-dentate ligands the series was extended to cobalt(II), manganese(II) and iron(II). The tri-dentate ligands did not form isolated metal complexes. The structures of these complexes were confirmed by NMR, ESR and X-ray crystallography. The chiral copper complexes were applied to a model asymmetric acylation reaction. The results were disappointing as the reactions showed no stereoselectivity.

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45

Mohd, Yusairie. "Studies of stability and catalytic activity of lead dioxide electrodes." Thesis, University of Southampton, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.523193.

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46

Koon, Chung Lun. "Studies of coke deposition, structure and regeneration during catalytic processing." Thesis, University of Salford, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.306081.

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47

Boucher, Guillaume. "Kinetic studies of alternative substrates for existing polyclonal catalytic antibodies." Thesis, University of Brighton, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.271976.

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48

Morisaki, Yasuhiro. "Studies on New Catalytic Reactions via η[3]-Allylruthenium Intermediates." Kyoto University, 2000. http://hdl.handle.net/2433/77933.

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49

Nichol, Tim. "Mutagenic studies into the catalytic versatility of soluble methane monooxygenase." Thesis, Sheffield Hallam University, 2011. http://shura.shu.ac.uk/16489/.

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Soluble methane monooxygenase (sMMO) is a multicomponent bacterial enzyme that catalyzes the oxidation of methane to methanol, as well as oxidizing many other adventitious substrates. A number of mutagenic studies were carried out on the sMMO enzyme of Methylosinus trichosporium OB3b in order to gain insight into sMMO and probe how structural aspects relate to function of the enzyme. Leu110 within the hydroxylase a-subunit of sMMO has been proposed as a possible gating residue, controlling access of substrate to the active site (Rosenzweig et al. 1997). A range of site directed mutants were created at the 110 position and screened for activity with a number of aromatic substrates. All mutants showed relaxed regioselectivity with all substrates assayed. However no evidence of a gating residue was found, indicating that Leu110 is more important in determining regioselectivity than substrate access to the active site. Comparison to the highly similar butane monooxygenase led to the creation of three site directed mutants: M184V F282L and C151T. M184V and C151T showed small changes in regioselectivity and reduced activity with most substrates. The M184V mutant showed relaxed regioselectivity and a novel oxidation product with the substrate mesitylene which may have implications for substrate trafficking. The F282L mutant produced a stable enzyme which had no activity with any of the substrates tested, showing Phe282 is important for the enzyme function. A random mutagenesis experiment was devised and a colorimetric screen for the oxidation of triaromatic compounds was used to screen mutant libraries for activity towards anthracene and phenanthrene. However no activity towards triaromatic compounds was detected. In order to improve the cloning strategies and to make creation of mutant libraries easier, a novel expression vector pT2ML was created. The pT2ML vector reduces the number of cloning steps required to make soluble methane monooxygenase mutants. This expression system was used to make a site directed mutants F188Aand N116G in order to complement previous site directed mutant studies, as well as a recombinant wild type mutant in order to asses the activity of the new expression system which is comparible to the wild type enzyme.

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50

Fioravanti, Emanuela. "Mycobacterium tuberculosis thymidylate kinase : structural studies of the catalytic mechanism." Université Joseph Fourier (Grenoble), 2004. http://www.theses.fr/2004GRE10061.

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La tuberculose (TB) est la cause principale de décès par maladie infectieuse dans le monde. L'identification de cibles possibles pour le développement de drogues contre la TB est une nécessité prioritaire. L'enzyme thymidylate kinase (TMPK), responsable de la phosphorylation ATP-dependante de la désoxythymidine-5'monophosphate (TMP), représente une cible possible. Huit structures du processus réactionnel ont été obtenues et indiquent que la fermeture du site actif de la TMPKMtub, associée à la fixation du substrat, et la catalyse qui suit, sont couplées à la fixation d'un ion magnésium que coordonne le TMP. L'arrangement structural du site actif de la TMPKMtub confère des propriétés uniques à cette enzyme. En particulier, le 3'-azido-3'-deoxythymidine-5'-monophosphate (AZT-MP) est un inhibiteur de la TMPKMtub. La structure du complexe TMPKMtub-AZT-MP explique le mécanisme d'inhibition. Le groupe azido de l'AZT-MP déplace l'ion métallique et la réaction ne peut plus avoir lieu.

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Dissertations / Theses on the topic 'Catalytic studies of glycogen'

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