Tentative identification and quantification of TAG core aldehydes as dinitrophenylhydrazones in autoxidized...

The molecular species of TAG core aldehydes (aldehydes still esterified to parent molecules) were detected and quantified in dietary-quality sunflowerseed oil autoxidized for 0-18 d at 60 degrees C in the dark. The analyses were performed by reversed-phase HPLC with UV (358 nm) absorption or light scattering and electrospray ionization-MS (ESI/MS) detection following preparation of the dinitrophenylhydrazone derivatives. Aldehyde production, as estimated by UV and ESI/MS, increased gradually over the 18-d period following a rapid initial destruction of the core aldehydes accumulated during storage of the commercial oil at 10 degrees C for 3 mon. The contents of hydroperoxides and hydroperoxide core aldehyde combinations were estimated to account for about 5% of total TAG, quantified as area in the chromatographic trace, after 18 d of autoxidation as estimated by an evaporative light scattering detector (ELSD). The major species of core aldehydes were tentatively identified as 9-oxononanoyl (70%)-, 12-oxo-9,10-epoxydodecenoyl (10%)-, and 13-oxo-9,11-tridecadienoyl (5%)-containing acylglycerols, plus smaller amounts of simple and mixed chain-length dialdehydes, and hydroxy and epoxy monoaldehyde-containing acylglycerols (15% of total). Quantitatively, the core aldehydes made up 2-12 g/kg of oil by UV detection and 2-9 g/kg of oil by ESI/MS detection, whereas the hydroperoxides measured in the unreduced state by HPLC with ELSD were estimated at 200 g/kg after 18 d of autoxidation. The major hydroperoxides of sunflowerseed oil were as previously identified.