Non-enzymatic lipid oxidation products in biological systems: Assessment of the metabolites from polyunsaturated fatty acids

•Analysis of isoprostanes and related compounds in biological system is discussed.•Methodology of GC-MS and LC-MS/MS analysis techniques is explained.•The advantages of GC-MS and LC-MS/MS analysis and its strengths are explored.•The use of GC-MS and LC-MS/MS analysis in biological system is discussed. Metabolites of non-enzymatic lipid peroxidation of polyunsaturated fatty acids notably omega-3 and omega-6 fatty acids have become important biomarkers of lipid products. Especially the arachidonic acid-derived F2-isoprostanes are the classic in vivo biomarker for oxidative stress in biological systems. In recent years other isoprostanes from eicosapentaenoic, docosahexaenoic, adrenic and α-linolenic acids have been evaluated, namely F3-isoprostanes, F4-neuroprostanes, F2-dihomo-isoprostanes and F1-phytoprostanes, respectively. These have been gaining interest as complementary specific biomarkers in human diseases. Refined extraction methods, robust analysis and elucidation of chemical structures have improved the sensitivity of detection in biological tissues and fluids. Previously the main reliable instrumentation for measurement was gas chromatography–mass spectrometry (GC–MS), but now the use of liquid chromatography–tandem mass spectrometry (LC–MS/MS) and immunological techniques is gaining much attention. In this review, the types of prostanoids generated from non-enzymatic lipid peroxidation of some important omega-3 and omega-6 fatty acids and biological samples that have been determined by GC–MS and LC–MS/MS are discussed.