A stereoelectronic and thermodynamic study of b-D-methyl glucose conformational changes related to anomeric centre reactivity

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dc.contributor.advisorNaidoo, Kevinen_ZA
dc.contributor.advisorBarnett, Christopher, Bevanen_ZA
dc.contributor.authorYusuf, Sabena Shaiken_ZA
dc.date.accessioned2014-11-05T03:56:49Z
dc.date.available2014-11-05T03:56:49Z
dc.date.issued2014en_ZA
dc.descriptionIncludes bibliographical references.en_ZA
dc.description.abstractThe major part of this thesis focuses on investigating the rationale for ring deformation of -D-methyl glucose in glycosidase reactions (for example, cellulose hydrolysis). The investigation is computational and is done in isolation from the enzyme binding pocket and incoming nucleophile. What is the effect of the C1-O1 bond breaking process on key glucose properties is the central question asked and answered in this thesis. A battery of ab initio methods is used to uncover details of the glucose ring pucker free energy volumes. The free energy volumes were computed using the Free Energy from Adaptive Reaction Coordinate Forces (FEARCF) method. The bond stretch of the C1-O1 bond in -D-methyl glucose serves as a sugar model for hydrolysis, following the DN*AN mechanism. The FEARCF method has been employed as it was previously shown to generate molecular sampling traversing all of pucker phase space resulting in a multidimensional free energy surfaces (or volumes). Density functional theory and post SCF analysis have been used to investigate the stereoelectronic changes that occur during ring deformation. In particular, changes involving the anomeric carbon, that is the C1-O1, C1-O5 bond distances, electron densities and charges of the C1, O5 and O1 atoms.en_ZA
dc.identifier.apacitationYusuf, S. S. (2014). <i>A stereoelectronic and thermodynamic study of b-D-methyl glucose conformational changes related to anomeric centre reactivity</i>. (Thesis). University of Cape Town ,Faculty of Science ,Department of Chemistry. Retrieved from http://hdl.handle.net/11427/9197en_ZA
dc.identifier.chicagocitationYusuf, Sabena Shaik. <i>"A stereoelectronic and thermodynamic study of b-D-methyl glucose conformational changes related to anomeric centre reactivity."</i> Thesis., University of Cape Town ,Faculty of Science ,Department of Chemistry, 2014. http://hdl.handle.net/11427/9197en_ZA
dc.identifier.citationYusuf, S. 2014. A stereoelectronic and thermodynamic study of b-D-methyl glucose conformational changes related to anomeric centre reactivity. University of Cape Town.en_ZA
dc.identifier.ris TY - Thesis / Dissertation AU - Yusuf, Sabena Shaik AB - The major part of this thesis focuses on investigating the rationale for ring deformation of -D-methyl glucose in glycosidase reactions (for example, cellulose hydrolysis). The investigation is computational and is done in isolation from the enzyme binding pocket and incoming nucleophile. What is the effect of the C1-O1 bond breaking process on key glucose properties is the central question asked and answered in this thesis. A battery of ab initio methods is used to uncover details of the glucose ring pucker free energy volumes. The free energy volumes were computed using the Free Energy from Adaptive Reaction Coordinate Forces (FEARCF) method. The bond stretch of the C1-O1 bond in -D-methyl glucose serves as a sugar model for hydrolysis, following the DN*AN mechanism. The FEARCF method has been employed as it was previously shown to generate molecular sampling traversing all of pucker phase space resulting in a multidimensional free energy surfaces (or volumes). Density functional theory and post SCF analysis have been used to investigate the stereoelectronic changes that occur during ring deformation. In particular, changes involving the anomeric carbon, that is the C1-O1, C1-O5 bond distances, electron densities and charges of the C1, O5 and O1 atoms. DA - 2014 DB - OpenUCT DP - University of Cape Town LK - https://open.uct.ac.za PB - University of Cape Town PY - 2014 T1 - A stereoelectronic and thermodynamic study of b-D-methyl glucose conformational changes related to anomeric centre reactivity TI - A stereoelectronic and thermodynamic study of b-D-methyl glucose conformational changes related to anomeric centre reactivity UR - http://hdl.handle.net/11427/9197 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/9197
dc.identifier.vancouvercitationYusuf SS. A stereoelectronic and thermodynamic study of b-D-methyl glucose conformational changes related to anomeric centre reactivity. [Thesis]. University of Cape Town ,Faculty of Science ,Department of Chemistry, 2014 [cited yyyy month dd]. Available from: http://hdl.handle.net/11427/9197en_ZA
dc.language.isoengen_ZA
dc.publisher.departmentDepartment of Chemistryen_ZA
dc.publisher.facultyFaculty of Scienceen_ZA
dc.publisher.institutionUniversity of Cape Town
dc.titleA stereoelectronic and thermodynamic study of b-D-methyl glucose conformational changes related to anomeric centre reactivityen_ZA
dc.typeMaster Thesis
dc.type.qualificationlevelMasters
dc.type.qualificationnameMScen_ZA
uct.type.filetypeText
uct.type.filetypeImage
uct.type.publicationResearchen_ZA
uct.type.resourceThesisen_ZA
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