Gamma-irradiation and UV-C light-induced lipid peroxidation: a Fourier transform-infrared absorption spectroscopic...

Fourier transform-infrared spectroscopy of dry, multibilayer films has been used to study gamma-radiation and UV-C light induced lipid peroxidation in 1,2-dilinoleoyl-sn-glycero-3-phosphocholine liposomes. The observed spectral changes were compared with the results obtained from measurement of hydroperoxides, conjugated dienes and to the formation of thiobarbituric acid reactive substances, such as malondialdehyde (MDA) or MDA-like substances. Upon irradiation a decrease in intensity of the asymmetric C - H stretching vibration (va(CH2)) of the isolated cis C = C - H groups (3010 cm-1) was observed. Directly correlated with the decrease of the va(CH2) absorption was a shift of the asymmetric phosphate ester stretching vibration (va(P = O)) towards smaller wavenumbers (1260-->1244 cm-1), indicating that the lipid peroxidation induced molecular alterations in the fatty acid chains influence the packing of the phospholipids in dry multibilayer films. In addition, the formation of a new absorption band at 1693 cm-1 could be detected, the intensity of which was comparable with the formation of thiobarbituric acid reactive substances and, therefore, attributed to the (C = O) stretching of alpha, beta unsaturated aldehydes. Dose-dependent studies using ionizing radiation showed that the decrease of va(CH2) was directly correlated with an increase in absorption of the conjugated dienes at 234 nm and with the formation of hydroperoxides suggesting that the absorption at 3010 cm-1 is solely due to isolated cis C = C - H groups and hence subject to the early stages of the radical chain reaction. UV-C light induced lipid peroxidation revealed a non-linear decrease of I3010, which was directly correlated with the formation of hydroperoxides. The observed early saturation of the conjugated dienes was attributed to an early photodecomposition of the conjugated double bonds.