Oxidation Mechanism of Methyl Linoleate with ${\alpha}-Tocopherol$

${\alpha}-Tocopherol$이 첨가된 Methyl Linoleate의 산화물 생성 기구

Oxidation mechanisms of methyl linoleate with ${\alpha}-Tocopherol$(TML) were investigated by determining oxidized products using GC-MS during oxidation at $37^{\circ}C$ for 9 days. Oxidized products of TML were found to be methyl octanoate, methyl-8-(2-furyl)-octanoate, 9,13-trans, cis isomer and 9,13-trans, trans isomer. In previous report, oxidation products of methyl linoleate(ML) were methyl-8-(2-furyl)octanoate, 9,13-trans, cis hydroperoxide isomer, 9,13-trans, trans hydroperoxide isomer, and 9-TMSO-12,13-epoxy-10-octadecenoate. In the case of ML, 9-TMSO-12,13-epoxy-l0-octadecenoate was produced instead of methyl octanoate in TML. ${\alpha}-Tocopherol$ quinone, as a major oxidized product of ${\alpha}-Tocopherol$ was formed at the 6th day of oxidation. ${\alpha}-Tocopherol$ quinone was produced rather quickly in lipid media than aqueous media. In oxidation of methyl linoleate, it was shown that the first oxidized product was methyl-9,13-hydroxy-octadecadienoate. As second products, methyl-8-(2-furyl)-octanoate, 9-TMSO-12,13-epoxy-10-octadenoate, and methyl octanoate were oxidized from methyl-9-hydroxy-10-trans, 12-trans-octadecadienoate.

Methyl linoleate에 ${\alpha}-Tocopherol$을 첨가하여(TML) $37^{\circ}C$에서 9일간 산화시키면서 산화생성물의 확인 및 생성기구에 대하여 GC/MS를 사용하여 검토하였다. TML군에서의 산화 생성물들은 methyl octanoate와 methyl-8-(2-furyl)-octanoate 및 9,13-trans, cis isomer와 9,13-trans, trans isomer로 밝혀졌다. 전보의 methyl linoleate(ML)에서의 산화생성물과 비교하여 볼 때 9-TMSO-12,13-epoxy-10-octadecenoate 대신 methyl octanoate가 생성되었다. ${\alpha}-Tocopherol$의 주된 산화물인 ${\alpha}-Tocopherol$ quinone은 반응 6일부터 생성되었으며, ${\alpha}-Tocopherol$은 aqueous media보다 lipid media에서 산화가 빨리 진행되는 것으로 나타났다. Methyl linoleate의 산화에 의한 생성물들의 생성과정 기구를 추정한 결과, 우선 methyl-9,13-hydroxy-octadecadienoate가 생성되고 다시 methyl-9-hydroxy-10 trans, 12 trans-octadecadienoate로부터 methyl-8-(2-furyl)-octanoate와 9-TMSO-12,13-epoxy-10-ortadecenoate 및 methyl octanoate가 생성된 것으로 사료되었다.