On pentacovalent phosphorus intermediates of enzymatic phosphoryl transfer reactions

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The pentacovalent phosphorus intermediate of a phosphoryl transfer reaction.

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 prese...

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Comment on "The pentacovalent phosphorus intermediate of a phosphoryl transfer reaction".

The claim by Lahiri et al. (1) to have identified the pentacovalent phosphorus intermediate of a phosphoryl transfer reaction addresses an important, long-disputed problem: whether the enzyme-catalyzed transfer of phosphate is a dissociative or associative process. The apparent observation of a pentaoxy-phosphorane suggests that the transfer occurs through an associative, addition– elimination ...

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Enzyme-catalyzed phosphoryl transfer reactions.

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Biological phosphoryl-transfer reactions: understanding mechanism and catalysis.

Phosphoryl-transfer reactions are central to biology. These reactions also have some of the slowest nonenzymatic rates and thus require enormous rate accelerations from biological catalysts. Despite the central importance of phosphoryl transfer and the fascinating catalytic challenges it presents, substantial confusion persists about the properties of these reactions. This confusion exists desp...

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Environmental effects on phosphoryl group bonding probed by vibrational spectroscopy: implications for understanding phosphoryl transfer and enzymatic catalysis.

We have used vibrational spectroscopy to study bonding in monosubstituted dianionic phosphates, both to learn more about basic properties intrinsic to this important class of biological substrates and to assess the ability of vibrational spectroscopy to provide a "sensor" or probe of the local environment experienced by the phosphoryl group. We examined the bonding properties of the phosphoryl ...

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ژورنال

عنوان ژورنال: Acta Crystallographica Section A Foundations of Crystallography

سال: 2004

ISSN: 0108-7673

DOI: 10.1107/s0108767304097752