Fatty acid isomerism: analysis and selected biological functions

Abstract

The biological functions of fatty acids and the lipids in which they are esterified are determined by their chain length, double bond position and geometry and other structural motifs such as the presence of methyl branches. Unusual isomeric features in fatty acids of human foods such as conjugated double bonds or chain branching found in dairy products, some seeds and nuts, and marine foods potentially have important effects on human health. Recent advancements in identifying fatty acids with unusual double bond positions and pinpointing the position of methyl branches have empowered the study of their biological functions. We present recent advances in fatty acid structural elucidation by mass spectrometry in comparison with the more traditional methods. The double bond position can be determined by purely instrumental methods, specifically solvent-mediated covalent adduct chemical ionization (SM-CACI) and ozone induced dissociation (OzID), with charge inversion methods showing promise. Prior derivatization using the Paternò-Büchi (PB) reaction to yield stable structures that, upon collisional activation, yield the double bond position has emerged. The chemical ionization (CI) based three ion monitoring (MRM) method has been developed to simultaneously identify and quantify low-level branched chain fatty acids (BCFAs), unattainable by electron ionization (EI) based methods. Accurate identification and quantification of unusual fatty acid isomers has led to research progress in the discovery of biomarkers for cancer, diabetes, nonalcoholic fatty liver disease (NAFLD) and atherosclerosis. Modulation of eicosanoids, weight loss and the health significance of BCFAs are also presented. This review clearly shows that the improvement of analytical capacity is critical in the study of fatty acid biological functions, and stronger coupling of the methods discussed here with fatty acid mechanistic research is promising in generating more refined outcomes.