Formation of short-chain glycerol-bound oxidation products and oxidised monomeric triacylglycerols during deep-frying and occurrence in used frying

Heating fats and oils at high temperature in the presence of air, a common procedure in culinary practices such as frying, results in a complex mixture of oxidation products. These compounds may impair the nutritional value of the food. Among them, there is a growing interest in the group of oxidised triacylglycerol monomers because of their high absorbability. The main structures in this group include triacylglycerols (TG) containing short-chain acyl groups formed by homolytic beta-scission of the alkoxy radicals coming from allylic hydroperoxides. In addition there are TG containing oxidised fatty acyl groups of molecular weight similar to that of their parent TG, i.e., epoxy, keto and hydroxy fatty acyl groups. In this review, the main routes of formation of oxidised TG monomers are detailed. Also, the most relevant advances in the analysis of intact TG molecules by high-performance liquid chromatography coupled with mass spectrometry are discussed. Special attention is paid to the present analytical possibilities for accurate quantification of the most important oxidised compounds formed at high temperature. Both the need to convert fats and oils into simpler derivatives, thus concentrating the compounds bearing the oxidised structure, and the methylation procedure selected to avoid artefact formation are justified. Typical concentrations of short-chain fatty acids, short-chain aldehydic acids, short-chain diacids, and monoepoxy fatty acids, ketoacids and hydroxyacids in frying oils from restaurants and fried-food outlets, with polar lipids levels at the limit of rejection for human consumption, are given.