PNP Diminishes Guanosine Glycosidic Bond Strength Through Restrictive Ring Pucker as a Precursor to Phosphorylation

dc.contributor.authorBarnett, Christopher B
dc.contributor.authorNaidoo, Kevin J
dc.date.accessioned2016-08-24T13:05:45Z
dc.date.available2016-08-24T13:05:45Z
dc.date.issued2013
dc.date.updated2016-08-24T13:04:26Z
dc.description.abstractPurine nucleoside phosphorylase is a transferase that catalyzes the addition of phosphate and removal of a purine base from guanosine and similar nucleosides. Here the interplay between sugar puckering conformation, the enzyme, and the perceived course of the reaction is examined using QM/MM FEARCF dynamics simulations. The enzyme biases the guanosine sugar ring toward a flattened 4E conformer as a step that is critical to the success of the phosphorylation reaction. The C4′ endo conformer allows the nonbonded ring oxygen orbital to align and donate electrons into the antibonding glycosidic bond orbital, thus weakening the bond. This conformational preference is due to sustained and directed noncovalent interactions anchored by the phosphate nucleophile’s hydrogen bonds to the sugar C2′ and C3′ hydroxyls. In so doing, PNP alters the solution sugar ring pucker preferences as part of its catalytic reaction barrier lowering function.en_ZA
dc.identifierhttp://dx.doi.org/10.1021/jp3109013
dc.identifier.apacitationBarnett, C. B., & Naidoo, K. J. (2013). PNP Diminishes Guanosine Glycosidic Bond Strength Through Restrictive Ring Pucker as a Precursor to Phosphorylation. <i>The Journal of Physical Chemistry</i>, http://hdl.handle.net/11427/21519en_ZA
dc.identifier.chicagocitationBarnett, Christopher B, and Kevin J Naidoo "PNP Diminishes Guanosine Glycosidic Bond Strength Through Restrictive Ring Pucker as a Precursor to Phosphorylation." <i>The Journal of Physical Chemistry</i> (2013) http://hdl.handle.net/11427/21519en_ZA
dc.identifier.citationBarnett, C. B., & Naidoo, K. J. (2013). PNP Diminishes Guanosine Glycosidic Bond Strength Through Restrictive Ring Pucker as a Precursor to Phosphorylation. The Journal of Physical Chemistry B, 117(20), 6019-6026.en_ZA
dc.identifier.issn0022-3654en_ZA
dc.identifier.ris TY - Journal Article AU - Barnett, Christopher B AU - Naidoo, Kevin J AB - Purine nucleoside phosphorylase is a transferase that catalyzes the addition of phosphate and removal of a purine base from guanosine and similar nucleosides. Here the interplay between sugar puckering conformation, the enzyme, and the perceived course of the reaction is examined using QM/MM FEARCF dynamics simulations. The enzyme biases the guanosine sugar ring toward a flattened 4E conformer as a step that is critical to the success of the phosphorylation reaction. The C4′ endo conformer allows the nonbonded ring oxygen orbital to align and donate electrons into the antibonding glycosidic bond orbital, thus weakening the bond. This conformational preference is due to sustained and directed noncovalent interactions anchored by the phosphate nucleophile’s hydrogen bonds to the sugar C2′ and C3′ hydroxyls. In so doing, PNP alters the solution sugar ring pucker preferences as part of its catalytic reaction barrier lowering function. DA - 2013 DB - OpenUCT DP - University of Cape Town J1 - The Journal of Physical Chemistry LK - https://open.uct.ac.za PB - University of Cape Town PY - 2013 SM - 0022-3654 T1 - PNP Diminishes Guanosine Glycosidic Bond Strength Through Restrictive Ring Pucker as a Precursor to Phosphorylation TI - PNP Diminishes Guanosine Glycosidic Bond Strength Through Restrictive Ring Pucker as a Precursor to Phosphorylation UR - http://hdl.handle.net/11427/21519 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/21519
dc.identifier.urihttp://pubs.acs.org/doi/abs/10.1021/jp3109013
dc.identifier.vancouvercitationBarnett CB, Naidoo KJ. PNP Diminishes Guanosine Glycosidic Bond Strength Through Restrictive Ring Pucker as a Precursor to Phosphorylation. The Journal of Physical Chemistry. 2013; http://hdl.handle.net/11427/21519.en_ZA
dc.languageengen_ZA
dc.publisherThe Journal of Physical Chemistryen_ZA
dc.publisher.institutionUniversity of Cape Town
dc.sourceThe Journal of Physical Chemistryen_ZA
dc.source.urihttp://pubs.acs.org/journal/jpcbfk
dc.subject.otherGuanosine
dc.subject.otherGlycosidic
dc.subject.otherPrecursor
dc.subject.otherPhosphorylation
dc.titlePNP Diminishes Guanosine Glycosidic Bond Strength Through Restrictive Ring Pucker as a Precursor to Phosphorylationen_ZA
dc.typeJournal Articleen_ZA
uct.type.filetypeText
uct.type.filetypeImage
uct.type.publicationResearchen_ZA
uct.type.resourceArticleen_ZA
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