Normal-phase high-performance liquid chromatography electrospray ionization(-) tandem mass spectrometry (NP-HPLC-ESI(-)-MS/MS) and thioacidolysis analyses recently have revealed the presence of (+)-catechin, (-)-epicatechin, procyanidin dimers, and prodelphinidin trimers in acetone/water (70/30, vol/vol) LH-20 extracts of lager beers. In this study, detailed structures were determined by reversed-phase (RP) HPLC-ESI(-)MS/MS. Four dimers were identified: three procyanidins (B1, B3, and 134) and one prodelphinidin (133). Previously detected in hop or malt, three trimers; (the procyanidin C-4 alpha-8-C-4 alpha-8-C and two prodelphinidins, GC-4 alpha-8-C-4 alpha-8-C and GC-4 alpha-8-GC-4 alpha-8-C) were distinguished for the first time in beer. As expected based on previous thioacidolysis data, most beer proanthocyanidins carried a catechin as the terminal unit.
Callemien, D., & Collin, S. (2008). Use of RP-HPLC-ESI(-)-MS/MS to differentiate various proanthocyanidin isomers in lager beer extracts. American Society of Brewing Chemists. Journal, 66(2), 109-115. https://doi.org/10.1094/ASBCJ-2008-0215-01 (Original work published 2008)