title: Metal Fluorides as Analogues for Studies on Phosphoryl Transfer Enzymes.
abstract: The 1994 structure of a transition-state analogue with AlF4-and GDP complexed to G1α, a small G protein, heralded a new field of research into the structure and mechanism of enzymes that manipulate the transfer of phosphoryl (PO3-) groups. The number of enzyme structures in the PDB containing metal fluorides (MFx) as ligands that imitate either a phosphoryl or a phosphate group was 357 at the end of 2016. They fall into three distinct geometrical classes: 1) Tetrahedral complexes based on BeF3-that mimic ground-state phosphates; 2) octahedral complexes, primarily based on AlF4-, which mimic "in-line" anionic transition states for phosphoryl transfer; and 3) trigonal bipyramidal complexes, represented by MgF3-and putative AlF30moieties, which mimic the geometry of the transition state. The interpretation of these structures provides a deeper mechanistic understanding into the behavior and manipulation of phosphate monoesters in molecular biology. This Review provides a comprehensive overview of these structures, their uses, and their computational development.
authors.affiliation: Department of Chemistry, University of York, York, YO10 5DD, UK.
authors.forename: Yi
authors.initials: Y
authors.lastname: Jin
authors.affiliation: School of Chemistry, Cardiff University, Cardiff, CF10 3AT, UK.
authors.forename: Nigel G
authors.initials: NG
authors.lastname: Richards
authors.affiliation: Manchester Institute of Biotechnology, Manchester, M1 7DN, UK.
authors.forename: Jonathan P
authors.initials: JP
authors.lastname: Waltho
authors.affiliation: Department of Molecular Biology and Biotechnology, University of Sheffield, Sheffield, S10 2TN, UK.
authors.forename: G Michael
authors.identifier: 0000-0002-3941-0459
authors.initials: GM
authors.lastname: Blackburn
mesh_terms: D017607:Aluminum Compounds / Q000737:chemistry* / Q000378:metabolism; D000818:Animals; D005459:Fluorides / Q000737:chemistry* / Q000378:metabolism; D006801:Humans; D008958:Models, Molecular; D010710:Phosphates / Q000737:chemistry / Q000378:metabolism*; D010735:Phosphoglycerate Kinase / Q000378:metabolism*; D010744:Phosphoric Monoester Hydrolases / Q000378:metabolism*
chemical_list: D017607:Aluminum Compounds; D010710:Phosphates; C050992:tetrafluoroaluminate; D010735:Phosphoglycerate Kinase; D010744:Phosphoric Monoester Hydrolases; C022394:phosphoserine phosphatase; D005459:Fluorides
keywords: 19F NMR spectroscopy; enzyme mechanisms; metal fluorides; phosphoryl transfer; transition-state analogues