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Metal fluorides as analogues for studies on phosphoryl transfer enzymes

Jin, Yi, Richards, Nigel G. J., Waltho, Jonathan P. and Blackburn, G. Michael 2017. Metal fluorides as analogues for studies on phosphoryl transfer enzymes. Angewandte Chemie - International Edition 56 (15) , pp. 4110-4128. 10.1002/anie.201606474

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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 AlF30 moieties, 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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Uncontrolled Keywords: 19F NMR spectroscopy; enzyme mechanisms; metal fluorides; phosphoryl transfer; transition-state analogues
Publisher: Wiley-Blackwell
ISSN: 1433-7851
Date of First Compliant Deposit: 10 April 2017
Date of Acceptance: 21 March 2017
Last Modified: 21 Mar 2018 02:30

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