The profile of reducing sugars developed during each stage of the postharvest of cocoa beans is an important quality index; these sugars are found to be one of the main precursors of flavor and neoformed compounds. However, its quantification after extraction from different parts of the bean is a challenge due to the complexity of the matrix. The primary aim of this study was to track the formation of reducing sugars and mannitol in samples obtained from various steps of the fermentation and drying processes of cocoa beans by validating a rapid matrix-corrected chromatographic method utilizing a corona-charged aerosol detector for improved sensitivity. The analytes were extracted from ground cocoa beans by solid phase extraction without a defatting step (20 mg raw fermented and 10 mg dried). The experimental variables influencing the effective detection were evaluated at different temperatures and signal filtering levels. Method validation studies showed an average recovery between 77.8 and 120% for fermented cocoa and between 79.6 and 117.7% for dried cocoa. A linear response was achieved for fructose, glucose, sucrose, and mannitol for a concentration range of 0.1-40 mg/L, and maltose showed linearity in the range of 0.1-70 mg/L. Regression coefficients (R) were 0.9991, 0.9993, 0.9992, 0.9995 and 0.9994, respectively. This method was successfully applied to a clone mix of cocoa from Antioquia, Colombia, to confirm the hydrolysis reaction of sucrose into glucose and fructose during fermentation and drying. A quality indicator of an efficient postharvest process in this study was determined to be a glucose percentage of 0.66% w/w and a fructose percentage of 1.46% w/w, which were higher than the values reported by other studies.

The aim of this study was to compare the quality of a mixture of cocoa harvested and fermented in three subregions of Antioquia (Colombia), from the chemometric profile based on multivariate statistical analysis. A mixture of clones CCN-52, ICS-1, FLE-2, and FEC-2 harvested in Bajo Cauca, Uraba and Magdalena Medio were subjected to a spontaneous fermentation. The characterization of raw and well-fermented cocoa was performed through 38 parameters, and results were compared by a Principal Component Analysis (PCA) and a Cluster Analysis (CA), followed by a Principal Factors Analysis (PFA- CA). The CA showed that there are differences among subregions only in raw cocoa from Bajo Cauca. PCA allowed identifying the variability between raw and fermented cocoa in a representative way and these results were consistent with the chemical profile. Besides, the number of parameters to differentiate raw cocoa from different subregions was reduced (11–13 parameters) and it was possible to characterize well fermented cocoa with only 10 parameters of 38. PFA-CA consolidated in three factors a grouping to identify the cocoa quality according to the process or interest of the sensory or functional properties. Factor 1 (cocoa quality indicators with functional properties), Factor 2 (indicators of quality of the beginning of fermentation) and Factor 3 (indicators of quality of well-fermented cocoa) each one with a weight of 39, 35 and 26 respectively.

A B S T R A C TThe aim of this work was to determine the effect of temperature on the formation of acrylamide in cocoa beans during drying treatment by an experimental and computational study, in order to assess the presence of this neoformed compound from postharvest stage. The computational study was conducted on the reaction between fructose, glyoxal from glucose, and on asparagine at the M06-2X/6-31þG(d,p) level, under cocoa bean drying conditions at 323.15 to 343.15 K. The proposed reaction for acrylamide formation consisted of seven steps, which required to progress a via cyclic transition state of the four members. In addition, step III (decarboxylation) was considered to be the rate-determining step. Glucose followed an E1-like elimination and fructose exhibited an E1cb-like elimination. Computational model showed that the reaction of acrylamide formation was favored by fructose rather than glucose.The content of reducing sugars, asparagine and acrylamide in fermented and dried cocoa from two subregions of Antioquia-Colombia, as well as roasted cocoa, were evaluated by UHPLC-C-CAD and UHPLC-QqQ. The concentrations of monosaccharides measured at the end of the fermentation and drying process of cocoa nibs showed greater decreases in the levels of fructose as compared to glucose, supporting the main model hypothesis. Acrylamide formation only occurred in Bajo Cauca due to the presence of both precursors and fast drying time (72 h). Finally, it was possible to find the conditions to which acrylamide can be formed from the drying process and not only from roasting, information that can be used for future control strategies.

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