In Vitro Faecal Fermentation of Monomeric and Oligomeric Flavan‐3‐ols: Catabolic Pathways and Stoichiometry

Scope 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). Methods and Results 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 production (≃1.5% and 6.0% at 5 and 24 h faecal incubation, respectively) despite the different DPs. Conclusion The flavan‐3‐ol structure strongly affects the colonic catabolism of the native compounds, influencing the profile of PVLs and PVAs produced in vitro. This study opens new perspectives to further elucidate the colonic fate of oligomeric flavan‐3‐ols and their availability in producing bioactive catabolites. Monomeric and oligomeric flavan‐3‐ols occur widely in our diet. This study involved a 24 h in vitro faecal fermentation of flavan‐3‐ols by human gut microbiota to assess the role of the degree of polymerization, A/B‐linkage type and galloyl moieties on microbiota‐derived catabolite production. Up to 32 colonic catabolites, directly related to the microbial catabolism of parent compounds, were identified. Catabolite pathways and stoichiometric balances in their production were highlighted.