Investigating the Role of Antioxidant Compounds in Riboflavin-Mediated Photo-Oxidation of Methionine: A 1H-NMR Approach

摘要

Riboflavin (RF) is a well-known photosensitizer, responsible for the light-induced oxidation of methionine (Met) leading to the spoilage of wine. An NMR approach was used to investigate the role of gallic acid (GA) and sulfur dioxide (SO_(2)) in the RF-mediated photo-oxidation of Met. Water solutions of RF and Met, with and without GA or SO_(2), were exposed to visible light for increasing time in both air and nitrogen atmospheres. Upon light exposure, a new signal appeared at 2.64 ppm that was assigned to the S(O)CH_(3) moiety of methionine sulfoxide. Its formation rate was lower in a nitrogen atmosphere and even lower in the presence of GA, supporting the ability of this compound in quenching the singlet oxygen. In contrast, SO_(2) caused relevant oxidation of Met, moderately observed even in the dark, making Met less available in donating electrons to RF. The competition of GA versus Met photo-oxidation was revealed, indicating effectiveness of this antioxidant against the light-dependent spoilage of wine. A pro-oxidant effect of SO_(2) toward Met was found as a possible consequence of radical pathways involving oxygen.