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American Chemical Society, Journal of the American Chemical Society, 20(134), p. 8436-8438, 2012

DOI: 10.1021/ja302809e

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Ground State Electronic Destabilization via Hyperconjugation in Aspartate Aminotransferase

Journal article published in 2012 by Wait R. Griswold, Joan Nieto Castro, Andrew J. Fisher ORCID, Michael D. Toney
This paper is available in a repository.
This paper is available in a repository.

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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.