Type I Photosensitized Oxidation of Methionine†

Methionine (Met) is an essential sulfur-containing amino acid, sensitive to oxidation. The oxidation of Met can occur by numerous pathways, including enzymatic modifications and oxidative stress, being able to cause relevant alterations in protein functionality. Under UV radiation, Met may be oxidized by direct absorption (below 250 nm) or by photosensitized reactions. Herein, kinetics of the reaction and identification of products during photosensitized oxidation were analyzed to elucidate the mechanism for the degradation of Met under UV-A irradiation using pterins, pterin (Ptr) and 6-methylpterin (Mep), as sensitizers. The process begins with an electron transfer from Met to the triplet-excited state of the photosensitizer (Ptr or Mep), to yield the corresponding pair of radicals, Met radical cation (Met(center dot+)) and the radical anion of the sensitizer (Sens(center dot-)). In air-equilibrated solutions, Met(center dot+)incorporates one or two atoms of oxygen to yield methionine sulfoxide (MetO) and methionine sulfone (MetO(2)), whereas Sens(center dot-)reacts with O(2)to recover the photosensitizer and generate superoxide anion (O-2(center dot-)). In anaerobic conditions, further free-radical reactions lead to the formation of the corresponding dihydropterin derivatives (H(2)Ptr or H(2)Mep).

Automated summary

Methionine is a sulfur-containing amino acid that is sensitive to oxidation. Under UV-A irradiation, the use of pterins as sensitizers can lead to the oxidation of methionine, resulting in the formation of different products.