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The study evaluates the influence of flavan‐3‐ol structure on the production of phenolic catabolites, principally phenyl‐γ‐valerolactones (PVLs), and phenylvaleric acids (PVAs).

A set of 12 monomeric flavan‐3‐ols and proanthocyanidins (degree of polymerization (DP) of 2–5), are fermented in vitro for 24 h using human faecal microbiota, and catabolism is analyzed by UHPLC‐ESI‐MS/MS. Up to 32 catabolites strictly related to microbial catabolism of parent compounds are detected. (+)‐Catechin and (−)‐epicatechin have the highest molar mass recoveries, expressed as a percentage with respect to the incubated concentration (75 µmol L^–1) of the parent compound, for total PVLs and PVAs, both at 5 h (about 20%) and 24 h (about 40%) of faecal incubation. Only A‐type dimer and B‐type procyanidins underwent the ring fission step, and no differences are found in total PVL and PVA …