Generation of isoprenoid compounds, notably prist-1-ene, via photo- and autoxidative degradation of vitamin E

In order to mimic the photodegradation of vitamin E during phytoplankton senescence and study the behaviour of the resulting photoproducts during cell lysis, vitamin E dispersed in seawater was irradiated with solar light in the presence of hematoporphyrin as sensitizer. Under these conditions, singlet oxygen-mediated photooxidation and free radical oxidation (autoxidation) acted simultaneously on the substrate, affording 4,8,12-trimethyltridecanal, 4,8,12-trimethyltridecanoic acid, 6,10,14-trimethylpentadecan-2-one, α-tocopherylquinone, 4,8,12,16-tetramethylheptadecan-4-olide, 2,3-epoxy-α-tocopherylquinone and 5,6-epoxy-α-tocopherylquinone as minor products. Different mechanisms were proposed to explain the formation of these different isoprenoids. The main products (85% of the degraded substrate) appeared to be previously described diastereoisomeric trimeric oxidation products of vitamin E, whose pyrolysis during gas chromatography-mass spectrometry (GC-MS) afforded 2,6,10,14-tetramethylpentadec-1-ene (prist-1-ene). On the basis of their greater ability to produce prist-1-ene during pyrolysis than intact vitamin E and their highly favoured production in phytoplanktonic cells, these trimers are proposed as likely sources of this isoprenoid alkene, previously identified in many pyrolysates from immature kerogens.