Photosensitization of Methyl Linoleate Oxidation by Tryptophan in Peptides

The ability of tryptophan in peptides to photosensitize the oxidation of methyl linoleate (ML) was evaluated. Purified ML was irradiated (λ > 270 nm) alone or in the presence of a tryptophan‐containing peptide in ethanol solution. Oxidation was monitored by measuring the dienc hydroperoxides formed from ML by high performance liquid chromatography. N‐acetylphenylalanyltryptophan (NAPT) and N‐acetyltryptophan were about 2‐fold more effective as photosensitizers than leucyltryptophan and tryptophylleucine. N‐acetylphenylalanyltryptophan photolyzed in ethanol to form multiple photoproducts including N‐formylkynurenine‐type compounds. However, the NAPT photoproducts did not photosensitize the oxidation of ML and N‐formylkynurenine was about 8% as effective as NAPT. Sodium azide partially quenched the photooxidation sensitized by NAPT.