Thermal properties and volatile compounds profile of commercial dark-chocolates from different genotypes of cocoa beans (Theobroma cacao L.) from Latin America.

There is a growing interest in the identification of chemometric markers that allow the distinction and authentication of dark-chocolates according to their cocoa geographical origin and/or genotype. However, samples derived from Latin American cocoa, including specimens from North and South America, have not been studied in this context. An exploration of the melting behavior, fat composition, bioactive content, and volatile profile of commercial darkchocolates was conducted to identify possible patterns related to the genotype and/or origin of cocoa from Latin America. The melting properties were evaluated by DSC and related to fat content and fatty acids profile. Total polyphenol, anthocyanin, methylxanthine, and catechin content were analyzed. Finally, the volatile compounds were extracted and identified by HS-SPME/GC-MS and were analyzed through Principal Component Analysis (PCA) and the Hierarchical Cluster Analysis Heatmap (HCA Heatmap). The fatty acids profile showed a relationship with the melting properties of dark chocolate. The samples exhibited two glass-transition temperatures (Tg) at ≈19 °C and ≈25.5 °C, possibly related to traces of unstable polymorphic forms of monounsaturated triacylglycerides. The analysis of bioactive compounds demonstrated great variability among samples independent of the cocoa origin, genotype, and content. The PCA and HCA Heatmaps allowed discriminating against the chocolates in relation to the cocoa origin and genotype. Compounds like tetramethylpyrazine, trimethylpyrazine, benzaldehyde, and furfural could be considered as dark-chocolate aroma markers derived from Latin American cocoas (North American region). The 2-phenylethyl alcohol, 2-methylpropanoic acid, 2,3-butanediol, 2-nonanone, and limonene for derived from South America. And the 2-phenylethyl acetate, 3-methyl-butanal, and cinnamaldehyde could allow to distinguishing between regional genotypes.