Molecular Aroma Composition of Vanilla Beans from Different Origins.

The demand for natural Vanilla has increased rapidly, creating the need for more potential sources of high-quality Vanilla essence. Understanding the geographical influences on the aroma profile of Vanilla is essential. This study demonstrates the first comparative analysis of odorant compositions in the three most important Vanilla varieties: Vanilla planifolia, Vanilla pompona, and Vanilla tahitensis from different origins. Following the screening for odor-active molecules through gas chromatography-olfactometry and aroma extract dilution analysis (GC-O and AEDA), selected compounds were quantified using stable isotope dilution assays (SIDA) and their dose over threshold values (DoTs) were calculated. Vanillin was confirmed as the most important odor-active compound due to its highest DoT value, especially in the V. planifolia sample. Meanwhile, 4-methoxybenzyl alcohol and 4-methoxybenzaldehyde showed higher DoT factors than vanillin in V. pompona and partially in V. tahitensis samples. This indicates their role as discriminative odorants for these varieties. The heightened DoT values of 3-hydroxy-4,5-dimethyl-2(5H)-furanone in Uganda Vanilla samples unveil geographical influences on the odorant profile within V. planifolia species. Additionally, 2-methyl-3-(methyldithio)furan was identified for the first time in Vanilla samples with diverse DoT values from different species and origins.

Decoding the Fine Flavor Properties of Dark Chocolates.

Fine flavor properties of chocolates such as fruity, floral, and cocoa-like were decoded on a molecular level for the first time. The molecular compositions of six chocolates made out of liquors that were referenced with specific sensory attributes were analyzed. After the screening for odor-active molecules by aroma extract dilution analysis, selected compounds were quantitated with the overall aim to decode the distinct fine flavor attributes on a molecular level. Acidic and fruity flavor notes were associated with high dose over threshold factors (DoT factors) of acetic acid and fruity smelling esters such as ethyl 2-methylbutanaote, ethyl 3-methylbutanoate, and 3-methylbutyl acetate, respectively. Cocoa-like and roasty flavor notes were associated with high DoT factors for 2-methylbutanal, 3-methylbutanal, 4-hydroxy-2,5-dimethylfuran-3(2H)-one, and dimethyltrisulfane. The floral and astringent flavors were linked to high DoT factors of (-)-epicatechin, procyanidin B2, procyanidin C1, and 2-phenylethan-1-ol.

Use of molecular networking to identify 2,5-diketopiperazines in chocolates as potential markers of bean variety.

2,5-diketopiperazines are cyclic dipeptides found, among others, in chocolate. Although those compounds are contributing greatly to its pleasant bitterness, they can also be seen as interesting markers of cocoa beans processing. To evaluate the influence of bean variety and processing technology on the quantity of 2,5-diketopiperazines formed in chocolates, HPLC-MS/MS analyses were conducted, and a molecular network was built with the MS2 data. This approach eases the identification of 2,5-diketopiperazines within complex datasets and allows to visualize the chemical diversity of all samples. Using this methodology, 33 dark chocolates were analysed. 18 different diketopiperazine were identified and quantified. Among them, cyclo(L-ile-L-val), cyclo(L-leu-L-ile) and cyclo(L-phe-L-phe) were, to the best of our knowledge, detected for the first time in chocolate. The molecular network allows the clear visualization of differences between samples. The principal component analysis revealed the clustering of small batch chocolate samples according to bean variety, suggesting that bean genotype has a strong influence on the 2,5-diketopiperazines content of bean-to-bar chocolates, regardless of the degree of roasting or the technological process used by the small producers. The presence of two unique diastereoisomers in the classical chocolates bought in the supermarket indicates that the beans have probably undergone a more intense heat treatment. This study proposes the use of 2,5-diketopiperazines as potential markers of cocoa beans variety, as well as an indicator of post-harvest processing and processing technology, and highlights the potential of the molecular networks in the field of food and drink innovation as a promising tool to understand the complex chemistry of flavours.

Impact of Water on Odor-Active Compounds in Fermented and Dried Cocoa Beans and Chocolates Made thereof.

The impact of water on odor-active compounds in fermented and dried cocoa beans as well as in chocolate either produced by a novel processing (NPC) or a traditional processing (TPC) technology from the same batch of cocoa beans was investigated in this study. Quantitation of selected key odorants revealed significantly higher concentrations of Strecker aldehydes such as 3-(methylsulfanyl)propanal (66-fold) and phenylacetaldehyde (50-fold) after water treatment of the cocoa beans. The comparison of the two chocolates showed that higher amounts of the Strecker aldehydes 2-methylbutanal, 3-methylbutanal, and phenylacetaldehyde are released with water in the NPC (24-fold to 39-fold), compared to the TPC (7.3-fold-11-fold). In addition to Strecker aldehydes, the concentrations of many further characteristic key odorants of cocoa and chocolate increased after water treatment. Based on the results, a more intense retronasal odor perception of the analyzed compounds is expected due to their release during consumption in contact with saliva.