Origin-based polyphenolic fingerprinting of Theobroma cacao in unfermented and fermented beans

- Principal component analysis can distinguish between cocoa origins.
- Several phenolic biomarkers to distinguish between fermented and unfermented cocoa
- Larger A-type proanthocyanidins degrade rapidly upon fermentation.
- Proanthocyanidin glycosides detected in phenolic extracts of cocoa.

A comprehensive analysis of cocoa polyphenols from unfermented and fermented cocoa beans from a wide range of geographic origins was carried out to catalogue systematic differences based on their origin as well as fermentation status. This study identifies previously unknown compounds with the goal to ascertain, which of these are responsible for the largest differences between bean types. UHPLC coupled with ultra-high resolution time-of-flight mass spectrometry was employed to identify and relatively quantify various oligomeric proanthocyanidins and their glycosides amongst several other unreported compounds. A series of biomarkers allowing a clear distinction between unfermented and fermented cocoa beans and for beans of different origins were identified. The large sample set employed allowed comparison of statistically significant variations of key cocoa constituents.

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