Strategies for UHPLC-MS/MS-Based Analysis of Different Classes of Acyl Chain Oxidation Products Resulting from Thermo-Oxidation of Sitostanyl Oleate

Phytostanyl fatty acid esters, which are being added to a variety of foods owing to their cholesterol-lowering properties, are susceptible to thermally induced oxidation reactions. Using sitostanyl oleate as an example, we, in this study, aimed at developing strategies for the detection and the quantitation of acyl chain oxidation products (ACOPs). The elaborated ultra high performance liquid chromatography-mass spectrometry MS/MS-based approach involves (i) derivatizations of hydroxy and oxo groups, (ii) combined use of atmospheric pressure chemical ionization and electrospray ionization as ionization techniques, and (iii) establishment of selective multireaction monitoring transitions. These strategies allow the identification of a broad spectrum of nonpolar short-chain as well as polar short- and long-chain hydroxy, epoxy, and oxo ACOPs. Semiquantitative assessments showed that sitostanyl 9,10-epoxystearate was the predominating ACOP resulting from thermo-oxidation of sitostanyl oleate at 180 °C for 30 min. The elaborated analytical approach paves the way to narrow the existing knowledge gap on the fate of phytostanyl fatty acid esters upon heat treatments.