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Molecular probes for the evaluation of three isomerase enzyme mechanisms in secondary metabolism
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dc.contributor.advisor | O'Hagan, David | |
dc.contributor.author | Nasomjai, Pitak | |
dc.coverage.spatial | 267 | en_US |
dc.date.accessioned | 2010-04-09T09:44:22Z | |
dc.date.available | 2010-04-09T09:44:22Z | |
dc.date.issued | 2010 | |
dc.identifier | uk.bl.ethos.552357 | |
dc.identifier.uri | http://hdl.handle.net/10023/866 | |
dc.description.abstract | This thesis is focused on an investigation of the mechanisms of three enzymatically mediated carbon skeleton isomerisation reactions. Chapter 1 provides an overview of some representative examples of the carbon skeleton rearrangement reactions in enzymology. Chapter 2 describes the preparation and use of fluorolittorines to explore the mechanism of the rearrangement of the tropane alkaloid littorine to hyoscyamine which is a reaction mediated by the cytochrome P450 enzyme. Chapter 3 describes the synthesis of D-ribose-1-phosphonates and the cyclic phosphonates (phostone) that are candidate inhibitors of the enzymatic isomerisation of 5-fluoro-5-deoxy-ribose-1-phosphate (5-FDRP) to 5-fluoro-5-deoxy-ribulose-1-phosphate (5-FDRulP), an important step in fluorometabolite biosynthesis pathway in Streptomyces cattleya. Chapter 4 describes the synthesis of 5-hydroxy-3,4-dioxohexylphosphonate and [5-13C]-5-hydroxy-3,4-dioxohexylphosphonate. These compounds are proposed as candidates for the transition state of the retro-aldol/aldol mechanism of the enzymatic isomerisation of 1-deoxy-D-xylulose-5-phosphate (DXP) to 2-C-methylerythitol-phophate-2-phosphate (MEP) in the biosynthesis of isopentenyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP). The influence of pH on tautomerisation of [5-13C]-5-hydroxy-3,4-dioxohexylphosphonate is also described. Chapter 5 describes the general chemical and biochemical methodologies utilised in this research project. | en_US |
dc.language.iso | en | en_US |
dc.publisher | University of St Andrews | |
dc.rights | Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported | |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/3.0/ | |
dc.subject | Isomerisation | en_US |
dc.subject | Alkaloid | en_US |
dc.subject | Cytochrome P450 | en_US |
dc.subject | Fluorometabolite | en_US |
dc.subject | 5-fluoro-5-deoxyribulose-1-phosphate | en_US |
dc.subject | Phostone | en_US |
dc.subject | 2-C-methylerythitol-phophate-2-phosphate | en_US |
dc.subject.lcc | QD281.R35N2 | |
dc.subject.lcsh | Isomerization | en_us |
dc.subject.lcsh | Enzymology | en |
dc.subject.lcsh | Metabolism, Secondary | en |
dc.title | Molecular probes for the evaluation of three isomerase enzyme mechanisms in secondary metabolism | en_US |
dc.type | Thesis | en_US |
dc.contributor.sponsor | Royal Thai Government | en_US |
dc.type.qualificationlevel | Doctoral | en_US |
dc.type.qualificationname | PhD Doctor of Philosophy | en_US |
dc.publisher.institution | The University of St Andrews | en_US |
dc.publisher.department | School of Chemistry | en_US |
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