Aécio Luis De Sousa Dias ^1* Emmanuelle Meudec ^2,3 Arnaud Verbaere ^2,3* Sophie Lair ^4* Jean-Claude Boulet ^2,3* Nicolas Sommerer ^2,3*

• ¹ INRAE Occitanie Montpellier, Montpellier, France
• ² SPO, Université de Montpellier, INRAE, Institut Agro, Montpellier, Languedoc-Roussillon, France
• ³ INRAE, PROBE Research Infrastructure, PFP Polyphenol analysis facility, Montpellier, Languedoc-Roussillon, France
• ⁴ Valrhona, Tain-l'Hermitage, France

This study aimed to evaluate the color and the discriminating compounds for two types of cocoa beans (black and brown beans) related to 70% dark chocolates of black and brown colors from a previous work of our group. Color analysis and untargeted high-resolution mass spectrometry-based metabolomic analysis were performed on 8 beans of each type. Mass spectral data processing, univariate and multivariate statistical methods were conducted for classification of beans and selection of discriminant features. The results showed that the color difference already observed for black and brown chocolates preexists in the beans. Black and brown beans had 45 and 50 discriminant features, respectively, of which 16 and 41 were phenolic compounds. Most of them were also previously identified as discriminating compounds for black and brown chocolates. Black beans predominantly contained glycosylated flavanols, ranging from monomers to trimers, with dimers and trimers being A-type procyanidins, along with a phenolic acid (protocatechuic acid), and an O-glycosylated flavonol (quercetin-3-O-glucoside). In contrast, brown beans mostly contained non-glycosylated B-type procyanidins ranging from dimers to decamers, but also dimers and trimers of A-type procyanidins, and a glycosylated and sulfated flavanol ((epi)catechin hexoside-sulfate). These markers may be useful for quality control purposes and may contribute to the selection of beans that yield black or brown dark chocolates.