Ground-state electronic destabilization via hyperconjugation in aspartate aminotransferase

Wait R. Griswold; Joan Nieto Castro; Andrew J Fisher; Michael D. Toney

doi:10.1021/ja302809e

Ground-state electronic destabilization via hyperconjugation in aspartate aminotransferase

Wait R. Griswold, Joan Nieto Castro, Andrew J Fisher, Michael D. Toney

Chemistry

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

Binding isotope effects for l-aspartate reacting with the inactive K258A mutant of PLP-dependent aspartate aminotransferase to give a stable external aldimine intermediate are reported. They provide direct evidence for electronic ground-state destabilization via hyperconjugation. The smaller equilibrium isotope effect with deazaPLP-reconstituted K258A indicates that the pyridine nitrogen plays an important role in labilizing the Cα-H bond.

Original language	English (US)
Pages (from-to)	8436-8438
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	134
Issue number	20
DOIs	https://doi.org/10.1021/ja302809e
State	Published - May 23 2012

ASJC Scopus subject areas

Chemistry(all)
Catalysis
Biochemistry
Colloid and Surface Chemistry

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abstract = "Binding isotope effects for l-aspartate reacting with the inactive K258A mutant of PLP-dependent aspartate aminotransferase to give a stable external aldimine intermediate are reported. They provide direct evidence for electronic ground-state destabilization via hyperconjugation. The smaller equilibrium isotope effect with deazaPLP-reconstituted K258A indicates that the pyridine nitrogen plays an important role in labilizing the Cα-H bond.",

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AU - Castro, Joan Nieto

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AU - Toney, Michael D.

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AB - Binding isotope effects for l-aspartate reacting with the inactive K258A mutant of PLP-dependent aspartate aminotransferase to give a stable external aldimine intermediate are reported. They provide direct evidence for electronic ground-state destabilization via hyperconjugation. The smaller equilibrium isotope effect with deazaPLP-reconstituted K258A indicates that the pyridine nitrogen plays an important role in labilizing the Cα-H bond.

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