Application of 1H NMR for the characterisation of cocoa beans of different geographical origins and fermentation levels

• We used 1H NMR to study a wide number of cocoa beans with different characteristics.
• Bean fermentation degree was the most important parameter influencing cocoa chemistry.
• Chemometric classification according to the degree of fermentation was achieved.
• Quantitative 1H NMR data on differently fermented beans were provided and discussed.
• Possibilities to classify beans also according to geographical origin were showed.

This study reports for the first time the use of 1H NMR technique combined with chemometrics to study the metabolic profile of cocoa (Theobroma cacao L.) beans of different varieties, origin and fermentation levels. Results of PCA applied to cocoa bean 1H NMR dataset showed that the main factor influencing the cocoa bean metabolic profile is the fermentation level. In fact well fermented brown beans form a group clearly separated from unfermented, slaty, and underfermented, violet, beans, independently of the variety or geographical origin. Considering only well fermented beans, the metabolic profile obtained by 1H NMR permitted to discriminate between some classes of samples. The National cocoa of Ecuador, known as Arriba, showed the most peculiar characteristics, while the samples coming from the African region showed some similar traits. The dataset obtained, representative of all the classes of soluble compounds of cocoa, was therefore useful to characterise fermented cocoa beans as a function of their origin and fermentation level.