Publication Details

Khairallah, G. N., Maccarone, A. T., Pham, H. T., Benton, T. M., Ly, T., da Silva, G., Blanksby, S. J. & O'Hair, R. A. J. (2015). Radical formation in the gas-phase ozonolysis of deprotonated cysteine. Angewandte Chemie International Edition, 54 (44), 12947-12951.


Although the deleterious effects of ozone on the human respiratory system are well-known, many of the precise chemical mechanisms that both cause damage and afford protection in the pulmonary epithelial lining fluid are poorly understood. As a key first step to elucidating the intrinsic reactivity of ozone with proteins, its reactions with deprotonated cysteine [Cys−H]− are examined in the gas phase. Reaction proceeds at near the collision limit to give a rich set of products including 1) sequential oxygen atom abstraction reactions to yield cysteine sulfenate, sulfinate and sulfonate anions, and significantly 2) sulfenate radical anions formed by ejection of a hydroperoxy radical. The free-radical pathway occurs only when both thiol and carboxylate moieties are available, implicating electron-transfer as a key step in this reaction. This novel and facile reaction is also observed in small cys-containing peptides indicating a possible role for this chemistry in protein ozonolysis.

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