Near-infrared (NIR) Raman spectroscopy has been used to observe the spectrum changes of linolenic acid during the iron-dependent lipid peroxidation reactions. The intensity of several bands including those at 726, 977, 1264, 1658, and 3014 cm−1 decreased after lipid peroxidation. Other notable changes after lipid peroxidation include the appearance of a couple of new bands at 1165 and 1638 cm−1. The Raman spectrum change was suppressed by an antioxidant, 21-aminosteroid. Harmonic ab initio vibrational analysis was performed for two model structures: one for the pure linolenic acid and another for a peroxidation product. The calculations by the Hartree–Fock (HF) method and a density functional theory (DFT) indicate that a new band which appeared at 1638 cm−1 after lipid peroxidation is due to the rearrangement of skeletal double bonds.
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