1H NMR and SPME-GC/MS study of hydrolysis, oxidation and other reactions occurring during in vitro digestion of non-oxidized and oxidized sunflower oil. Formation of hydroxy-octadecadienoates

•Non-oxidized and slightly oxidized sunflower oils were in vitro digested.•The ongoing chemical reactions were investigated by 1H NMR and SPME-GC/MS•Oil initial oxidation level affected the hydrolysis and oxidation extent reached.•The formation of hydroperoxy- and hydroxy-octadecadienoates was evidenced.•Other reactions like Maillard and esterification also took place.

Both fresh and slightly oxidized sunflower oils, as models of omega-6 rich lipids, were submitted to in vitro gastrointestinal digestion and studied by 1H NMR and SPME-GC/MS. Changes in lipolysis degree, lipid composition and oxidative level were studied by 1H NMR. Three quantitative approaches were used and several equations were newly developed. In oxidized oil digestates slightly lower hydrolysis and a higher advance of oxidation took place during digestion. This latter was evidenced by a greater decrease of lipid unsaturation degree and enhanced generation of oxidation products (cis,trans-hydroperoxy-octadecadienoates, cis,trans- and trans,trans-hydroxy-octadecadienoates). For the first time, the generation of hydroxy-octadecadienoates during in vitro digestion is reported. Furthermore, SPME-GC/MS study of non-digested and digested samples headspaces confirmed that lipid oxidation occurred: abundances of volatile markers increased (including potentially toxic alpha,beta-unsaturated aldehydes), especially in oxidized oils digestates. Markers of Maillard-type and esterification reactions were also detected in the digestates.

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