UVA irradiation of fatty acids and their oxidized products substantially increases their ability to generate singlet oxygen

UVA radiation plays an important role for adverse reactions in human tissue. UVA penetrates epidermis and dermis of skin being absorbed by various biomolecules, especially endogenous photosensitizers. This may generate deleterious singlet oxygen ((1)O2) that oxidizes fatty acids in cell membranes, lipoproteins, and other lipid-containing structures such as the epidermal barrier. Indications exist that fatty acids are not only the target of (1)O2 but also act as potential photosensitizers under UVA irradiation, if already oxidized. Five different fatty acids in ethanol solution (stearic, oleic, linoleic, linolenic and arachidonic acid) were exposed to UVA radiation (355 nm, 100 mW) for 30 seconds. (1)O2 luminescence was detected time-resolved at 1270 nm and confirmed in spectrally-resolved experiments. The more double bonds fatty acids have the more (1)O2 photons were detected. In addition, fatty acids were continuously exposed to broadband UVA for up to 240 min. During that time span, UVA absorption and (1)O2 luminescence substantially increased with irradiation time, reached a maximum and decreased again. HPLC-MS analysis showed that the amount of peroxidized fatty acids and the (1)O2 generation increased and decreased in parallel. This indicates the high potential of peroxidized fatty acids to produce (1)O2 under UVA irradiation. In conclusion, fatty acids along with peroxidized products are weak endogenous photosensitizers but become strong photosensitizers under continuous UVA irradiation. Since fatty acids and their oxidized products are ubiquitous in living cells and in skin, which is frequently and long-lasting exposed to UVA radiation, this photosensitizing effect may contribute to initiation of deleterious photooxidative processes in tissue.