Analytical strategy for class-selective determination and structural characterization of phytoprostanes involving molecularly imprinted polymer extraction coupled with UHPLC-HRMS/MS analysis

Phytoprostanes (PhytoPs) represent crucial biomarkers of oxidative stress in plants and bioactive components of significant nutritional interest. Generated through the non-enzymatic peroxidation of α-linolenic acid, these compounds serve as sensitive indicators of environmental stress and lipid degradation. However, their analysis in food systems remains a complex analytical challenge. This study presents a novel analytical strategy for the selective extraction and comprehensive profiling of phytoprostanes (PhytoPs) in complex food matrices. A class-selective molecularly imprinted polymer (MIP) was rapidly synthesized (5 min) via a green sonochemical procedure, utilizing 4-cyclopentene-1,3-dione as a dummy template. The resulting material was applied in a dispersive solid-phase extraction (dSPE) protocol coupled with UHPLC-MS/MS, demonstrating high selectivity and sensitivity with recoveries between 76% and 93% and minimal matrix interference (≤ −14%). Integration of a UHPLC-HRMS/MS workflow enabled the putative identification of numerous PhytoPs for which commercial standards are currently unavailable.