The pentacovalent phosphorus intermediate of a phosphoryl transfer reaction - PubMed (original) (raw)
. 2003 Mar 28;299(5615):2067-71.
doi: 10.1126/science.1082710. Epub 2003 Mar 13.
Affiliations
- PMID: 12637673
- DOI: 10.1126/science.1082710
The pentacovalent phosphorus intermediate of a phosphoryl transfer reaction
Sushmita D Lahiri et al. Science. 2003.
Abstract
Enzymes provide enormous rate enhancements, unmatched by any other type of catalyst. The stabilization of high-energy states along the reaction coordinate is the crux of the catalytic power of enzymes. We report the atomic-resolution structure of a high-energy reaction intermediate stabilized in the active site of an enzyme. Crystallization of phosphorylated beta-phosphoglucomutase in the presence of the Mg(II) cofactor and either of the substrates glucose 1-phosphate or glucose 6-phosphate produced crystals of the enzyme-Mg(II)-glucose 1,6-(bis)phosphate complex, which diffracted x-rays to 1.2 and 1.4 angstroms, respectively. The structure reveals a stabilized pentacovalent phosphorane formed in the phosphoryl transfer from the C(1)O of glucose 1,6-(bis)phosphate to the nucleophilic Asp8 carboxylate.
Comment in
- Chemistry. Seeing is believing.
Knowles J. Knowles J. Science. 2003 Mar 28;299(5615):2002-3. doi: 10.1126/science.1084036. Epub 2003 Mar 13. Science. 2003. PMID: 12637674 No abstract available. - Comment on "The pentacovalent phosphorus intermediate of a phosphoryl transfer reaction".
Blackburn GM, Williams NH, Gamblin SJ, Smerdon SJ. Blackburn GM, et al. Science. 2003 Aug 29;301(5637):1184; author reply 1184. doi: 10.1126/science.1085796. Science. 2003. PMID: 12947182 No abstract available.
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