Fate of Anthocyanins through Cocoa Fermentation. Emergence of New Polyphenolic Dimers

Abstract

Fresh, ripe cocoa beans from Cameroon (German cocoa/Amelonado group and ICS 40/Trinitario group) were subjected to fermentation-like incubations in acetic acid, lactic acid, or both and to natural fermentation. Two naturally fermented samples from Cuba (UF 654/Trinitario group and C 411/Criollo group) were also investigated. Both cyanidin-3-galactoside and cyanidin-3-arabinoside (found as major anthocyanins in colored beans only) were drastically degraded through fermentation, especially in small beans and in the presence of acetic acid. On the other hand, emergence of a cyanidin-rhamnose isomer was evidenced, even in Criollo beans. In addition to the recently described structures F1 and F2 [m/z = 575 in ESI(-)], three additional polyphenolic structures [F3, F4, and F5; m/z = 557 in ESI(+)] were found after fermentation, the two former ones resulting from epicatechin oxidation. Synthesis of F5 requires an interclass reaction between cyani(di)n and epicatechin, which explains its absence in fermented Criollo beans.

Flavanol Polymerization Is a Superior Predictor of α-Glucosidase Inhibitory Activity Compared to Flavanol or Total Polyphenol Concentrations in Cocoas Prepared by Variations in Controlled Fermentation and Roasting of the Same Raw Cocoa Beans

“…These methods are based upon anthocyanin degradation and aglycone release throughout fermentation. The FI of raw unfermented beans typically range from 0.3-0.6 and increase to 1.3-1.4 during fermentation, with a value of ≥1 indicating the near-complete anthocyanin degradation and, thus, adequate and complete fermentation [2,42,43]. However, our FI values started at >1 ( Figure 1B).…”

Roasting conditions for preserving cocoa flavan‐3‐ol monomers and oligomers: interesting behaviour of Criollo clones

“…The evidence of (−)‐catechin by chiral chromatography confirmed the atypical behaviour of white beans when roasted at 150 °C. Complementary analyses are now needed to determine which anthocyanin‐derived products are most involved in the disappearance of flavan‐3‐ols in Forastero and Trinitario.…”

An overview of the physical and biochemical transformation of cocoa seeds to beans and to chocolate: Flavor formation

“…Knowledge of the phenomena that modulate the biochemical reactions that occur during the transformation of cocoa seeds is necessary to establish a control over this bioprocess, based on its proper management to produce cocoa with desired quality characteristics . In this sense, some authors have studied this bioprocess under laboratory conditions to generate a knowledge base as a guide to elucidate the dynamics of flavor formation during cocoa transformation from seeds to beans (John et al 2016;Eyamo Evina et al 2016;Kadow et al 2015;Oracz and Nebesny 2014;Yaw 2014;Amin, Jinap, and Jamilah 1998;Voigt and Biehl 1995;Biehl et al 1985). These studies are of great relevance for being pioneers in developing methodologies that allow carrying out the cocoa transformation of seeds in a controlled manner.…”

“…The latter is due to the delocalization of p electrons in the structure of the chromophore molecule with eight conjugated double bonds. In addition, alkaloids (1-2% theobromine and 1% caffeine), contribute to the definition of the sensory chocolate profile, specifically with the bitter notes (De Taeye et al 2016).…”

“…Likewise, in several works postharvest transformation processes under laboratory conditions has been explored (John et al 2016;Eyamo Evina et al 2016;Kadow et al 2015;Yaw 2014), using chemical catalysts during the process such as lactic, citric, and acetic acids, as well as under controlled atmospheric conditions (oxygen and nitrogen) and temperature. The results showed that flavor formation precursors from the proteolysis and the inversion of nonreducing sugars, as well as the decrease of polyphenols was possible with the use of chemical catalysts and controlling physicochemical variables.…”