Ground-state electronic destabilization via hyperconjugation in aspartate aminotransferase.

نویسندگان

  • Wait R Griswold
  • Joan Nieto Castro
  • Andrew J Fisher
  • Michael D Toney
چکیده

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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عنوان ژورنال:
  • Journal of the American Chemical Society

دوره 134 20  شماره 

صفحات  -

تاریخ انتشار 2012