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 | |
| State | Published - May 23 2012 |
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ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Ground-state electronic destabilization via hyperconjugation in aspartate aminotransferase. / Griswold, Wait R.; Castro, Joan Nieto; Fisher, Andrew J; Toney, Michael D.
In: Journal of the American Chemical Society, Vol. 134, No. 20, 23.05.2012, p. 8436-8438.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ground-state electronic destabilization via hyperconjugation in aspartate aminotransferase
AU - Griswold, Wait R.
AU - Castro, Joan Nieto
AU - Fisher, Andrew J
AU - Toney, Michael D.
PY - 2012/5/23
Y1 - 2012/5/23
N2 - 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.
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.
UR - http://www.scopus.com/inward/record.url?scp=84861371017&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84861371017&partnerID=8YFLogxK
U2 - 10.1021/ja302809e
DO - 10.1021/ja302809e
M3 - Article
C2 - 22551424
AN - SCOPUS:84861371017
VL - 134
SP - 8436
EP - 8438
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 20
ER -