Isolation and Characterization of Novel Oligomeric Proanthocyanidins in Chokeberries Using High-Resolution Mass Spectrometry and Investigation of Their Antioxidant Potential

Chokeberries, which belong to the rose family (Rosaceae), have received increasing research attention due to their high content of secondary metabolites, especially oligomeric proanthocyanidins (OPCs). OPC-rich extracts are attributed to various positive health effects, including antioxidant or anti-inflammatory properties, which is why they are sold as food supplements. However, knowledge about the antioxidant properties of single OPCs is quite limited. Several separation steps with different separation techniques were performed to isolate OPCs from a pre-produced extract. More than 90 analytes were detected in the enriched fractions, which include eight OPCs, four cinchonains and one hexoside, including their respective isomers. For the characterization of the OPCs, high-resolution mass spectrometry coupled with liquid chromatography (LC-HRMS) was used. Based on the fragment spectra of the MS2 experiments, conclusions about the fragmentation pathways and the structure of six new OPCs could be drawn. After isolating trimers, tetramers and pentamers, it was possible to test the antioxidant effect in relation to the individual degrees of polymerization (DP) or structures. The Trolox-equivalent antioxidant capacity (TEAC) test showed that all OPCs investigated exhibit antioxidant effects and a first correlation between the antioxidant effect and the DP could be postulated, which suggests new possibilities for the design of food supplements.