Procyanidin A2 and Its Degradation Products in Raw, Fermented, and Roasted Cocoa

Cocoa is known as an important source of flavan-3-ols, but their fate from the bean to the bar is not yet clear. Here, procyanidin A2 found in native cocoa beans (9-13 mg/kg) appeared partially epimerized into A2(E1) through fermentation, whereas a second epimer (A2(E2)) emerged after roasting. At m/z 575, dehydrodiepicatechin A was revealed to be the major HPLC peak before fermentation, whereas F1, a marker of well-conducted fermentations, becomes the most intense after roasting.RP-HPLC-ESI(-)-HRMS/MS analysis performed on a procyanidin A2 model medium after 12 h at 90 degrees C revealed many more degradation products than those identified in fermented cocoa, including the last epimer of A2, A2 open structure intermediates (m/z 577), and oxidized A -type dimers (m/z 573).