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Updated: Aug 12, 2026

Monitoring Equilibrium Changes in RNA Structure by 'Peroxidative' and 'Oxidative' Hydroxyl Radical Footprinting
Published on: October 17, 2011
The generation of 5'-deoxyadenosyl radicals by adenosylmethionine-dependent radical enzymes
1Department of Biochemistry and Biophysics, University of Pennsylvania, 905B Stellar-Chance Laboratory, 422 Curie Boulevard, Philadelphia, PA 19104-6059, USA. jjarrett@mail.med.upenn.edu
Abstract:
Adenosylmethionine-dependent radical enzymes provide a novel mechanism for generating the highly oxidizing 5'-deoxyadenosyl radical in an anaerobic reducing environment. Recent studies suggest a unique covalent interaction between adenosylmethionine and a catalytic iron-sulfur cluster that may promote inner-sphere electron transfer to the sulfonium, resulting in the reductive cleavage of a C[bond]S and the generation of a 5'-deoxyadenosyl radical. The utilization of this radical as a catalytic and stoichiometric oxidant in many different enzyme reactions reflects the broad diversity of radical enzymes throughout biology.
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