通过天冬氨酸转氨酶中的超共轭作用导致基态电子去稳定化。
Ground-state electronic destabilization via hyperconjugation in aspartate aminotransferase.
机构信息
Department of Chemistry, University of California - Davis, 95616, United States.
出版信息
J Am Chem Soc. 2012 May 23;134(20):8436-8. doi: 10.1021/ja302809e. Epub 2012 May 10.
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.
摘要
本文报道了 L-天冬氨酸与 PLP 依赖型天冬氨酸转氨酶的无活性 K258A 突变体反应生成稳定的外部亚胺中间物的结合同位素效应。它们为通过超共轭作用导致电子基态去稳定提供了直接证据。用去氮 PLP 重建的 K258A 的较小平衡同位素效应表明吡啶氮在稳定 Cα-H 键方面起着重要作用。
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