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Oxidative Degradation of Pyruvate Formate-Lyase

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journal contribution
posted on 2000-02-17, 00:00 authored by James W. Gauld, Leif A. Eriksson
The reaction mechanisms of oxidative degradation of the anaerobic radical enzyme pyruvate formate-lyase (PFL) have been examined at the theoretical hybrid Hartree−Fock/density functional theory level B3-LYP. It is concluded that the most likely scenario involves O2 addition at the glycyl radical site, followed by H abstraction/transfer from C419 and subsequent rearrangements to generate an α-hydroxyglycine and the sulfinyl radical R−SO, observed by EPR spectroscopy. In addition, the present model accounts for alternative fragmentations observed in wild-type PFL, and the formation and degradation of Gly−O-O in the absence of C419 (as observed in C419A and C419AC418A mutants).