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. 2014 Feb 10;53(7):1887-90.
doi: 10.1002/anie.201310480. Epub 2014 Jan 20.

A mass spectrometric approach for probing the stability of bioorganic radicals

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A mass spectrometric approach for probing the stability of bioorganic radicals

Lei Tan et al. Angew Chem Int Ed Engl. .

Abstract

Glycyl radicals are important bioorganic radical species involved in enzymatic catalysis. Herein, we demonstrate that the stability of glycyl-type radicals (X-(.) CH-Y) can be tuned on a molecular level by varying the X and Y substituents and experimentally probed by mass spectrometry. This approach is based on the gas-phase dissociation of cysteine sulfinyl radical (X-Cys SO .-Y) ions through homolysis of a Cα Cβ bond. This fragmentation produces a glycyl-type radical upon losing CH2 SO, and the degree of this loss is closely tied to the stability of the as-formed radical. Theoretical calculations indicate that the energy of the Cα Cβ bond homolysis is predominantly affected by the stability of the glycyl radical product through the captodative effect, rather than that of the parent sulfinyl radical. This finding suggests a novel experimental method to probe the stability of bioorganic radicals, which can potentially broaden our understanding of these important reactive intermediates.

Keywords: captodative effect; mass spectrometry; radical ions; radicals.

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