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The effect of magnesium ions on triphosphate hydrolysis
Univ Southern Calif, Dept Chem, Los Angeles, CA 90089 USA..
Uppsala University, Disciplinary Domain of Science and Technology, Biology, Department of Cell and Molecular Biology, Structure and Molecular Biology.
Univ Sheffield, Dept Chem, Sheffield S3 7HF, S Yorkshire, England..
Uppsala University, Disciplinary Domain of Science and Technology, Biology, Department of Cell and Molecular Biology, Structure and Molecular Biology.ORCID iD: 0000-0002-3190-1173
2017 (English)In: Pure and Applied Chemistry, ISSN 0033-4545, E-ISSN 1365-3075, Vol. 89, no 6, 715-727 p.Article in journal (Refereed) Published
Abstract [en]

The role of metal ions in catalyzing phosphate ester hydrolysis has been the subject of much debate, both in terms of whether they change the transition state structure or mechanistic pathway. Understanding the impact of metal ions on these biologically critical reactions is central to improving our understanding of the role of metal ions in the numerous enzymes that facilitate them. In the present study, we have performed density functional theory studies of the mechanisms of methyl triphosphate and acetyl phosphate hydrolysis in aqueous solution to explore the competition between solvent-and substrate-assisted pathways, and examined the impact of Mg2+ on the energetics and transition state geometries. In both cases, we observe a clear preference for a more dissociative solvent-assisted transition state, which is not significantly changed by coordination of Mg2+. The effect of Mg2+ on the transition state geometries for the two pathways is minimal. While our calculations cannot rule out a substrate-assisted pathway as a possible solution for biological phosphate hydrolysis, they demonstrate that a significantly higher energy barrier needs to be overcome in the enzymatic reaction for this to be an energetically viable reaction pathway.

Place, publisher, year, edition, pages
2017. Vol. 89, no 6, 715-727 p.
Keyword [en]
acetyl phosphate, density functional theory (DFT), ICPOC-23, metals in biology, methyl triphosphate, phosphate hydrolysis
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-329730DOI: 10.1515/pac-2016-1125ISI: 000403321500004OAI: oai:DiVA.org:uu-329730DiVA: diva2:1143312
Funder
EU, FP7, Seventh Framework Programme, 306474Knut and Alice Wallenberg Foundation
Available from: 2017-09-21 Created: 2017-09-21 Last updated: 2017-09-21Bibliographically approved

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Blaha-Nelson, DavidKamerlin, Shina C. Lynn

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