title: MgF3-and AlF4-transition state analogue complexes of yeast phosphoglycerate kinase.
abstract: The phospho-transfer mechanism of yeast phosphoglycerate kinase (PGK) has been probed through formation of trifluoromagnesate (MgF3-) and tetrafluoroaluminate (AlF4-) transition state analogue complexes and analyzed using19F,1H waterLOGSY and1H chemical shift perturbation NMR spectroscopy. We observed the first19F NMR spectroscopic evidence for the formation of metal fluoride transition state analogues of yeast PGK and also observed significant changes to proton chemical shifts of PGK in the presence, but not in the absence, of fluoride upon titration of ligands, providing indirect evidence of the formation of a closed ternary transition state. WaterLOGSY NMR spectroscopy experiments using an uncompetitive model were used in an attempt to measure ligand binding affinities within the transition state analogue complexes.
authors.affiliation: a College of Pharmacy, Dalhousie University, 5968 College Street, Halifax, NS B3H 4R2, Canada.
authors.forename: Nicole E
authors.initials: NE
authors.lastname: McCormick
authors.affiliation: b Department of Chemistry, Dalhousie University, 6274 Coberg Road, Halifax, NS B3H 4R2, Canada.
authors.forename: Stephanie M
authors.initials: SM
authors.lastname: Forget
authors.affiliation: b Department of Chemistry, Dalhousie University, 6274 Coberg Road, Halifax, NS B3H 4R2, Canada.
authors.forename: Raymond T
authors.initials: RT
authors.lastname: Syvitski
authors.affiliation: a College of Pharmacy, Dalhousie University, 5968 College Street, Halifax, NS B3H 4R2, Canada.|b Department of Chemistry, Dalhousie University, 6274 Coberg Road, Halifax, NS B3H 4R2, Canada.
authors.forename: David L
authors.initials: DL
authors.lastname: Jakeman
mesh_terms: D017607:Aluminum Compounds / Q000737:chemistry*; D005459:Fluorides / Q000737:chemistry*; D007554:Isotopes; D007700:Kinetics; D017616:Magnesium Compounds / Q000737:chemistry*; D019906:Nuclear Magnetic Resonance, Biomolecular; D010710:Phosphates / Q000737:chemistry; D010735:Phosphoglycerate Kinase / Q000737:chemistry*; D011522:Protons; D012441:Saccharomyces cerevisiae / Q000737:chemistry* / Q000201:enzymology; D029701:Saccharomyces cerevisiae Proteins / Q000737:chemistry*; D012996:Solutions; D013816:Thermodynamics
chemical_list: D017607:Aluminum Compounds; D007554:Isotopes; D017616:Magnesium Compounds; D010710:Phosphates; D011522:Protons; D029701:Saccharomyces cerevisiae Proteins; D012996:Solutions; C012980:fluorophosphate; C050992:tetrafluoroaluminate; C031288:magnesium fluoride; D010735:Phosphoglycerate Kinase; D005459:Fluorides
keywords: 19F NMR spectroscopy; MgF3−/AlF4−; complexe d’analogue d’état de transition; complexes de fluorures métalliques; metal fluoride complexes; phosphoglycérate kinase de levure; spectroscopie RMN du 19F; transition state analogue complex; yeast phosphoglycerate kinase