Characterization of Key Aroma Compounds in a Commercial Rum and an Australian Red Wine by Means of a New Sensomics-Based Expert System (SEBES)-An Approach To Use Artificial Intelligence in Determining Food Odor Codes.

Although to date more than 10 000 volatile compounds have been characterized in foods, a literature survey has previously shown that only 226 aroma compounds, assigned as key food odorants (KFOs), have been identified to actively contribute to the overall aromas of about 200 foods, such as beverages, meat products, cheeses, or baked goods. Currently, a multistep analytical procedure involving the human olfactory system, assigned as Sensomics, represents a reference approach to identify and quantitate key odorants, as well as to define their sensory impact in the overall food aroma profile by so-called aroma recombinates. Despite its proven effectiveness, the Sensomics approach is time-consuming because repeated sensory analyses, for example, by GC/olfactometry, are essential to assess the odor quality and potency of each single constituent in a given food distillate. Therefore, the aim of the present study was to develop a fast, but Sensomics-based expert system (SEBES) that is able to reliably predict the key aroma compounds of a given food in a limited number of runs without using the human olfactory system. First, a successful method for the quantitation of nearly 100 (out of the 226 known KFOs) components was developed in combination with a software allowing the direct use of the identification and quantitation data for the calculation of odor activity values (OAV; ratio of concentration to odor threshold). Using a rum and a wine as examples, the quantitative results obtained by the new SEBES method were compared to data obtained by applying an aroma extract dilution analysis and stable isotope dilution assays required in the classical Sensomics approach. A good agreement of the results was found with differences below 20% for most of the compounds considered. By implementing the GC × GC data analysis software with the in-house odor threshold database, odor activity values (ratio of concentration to odor threshold) were directly displayed in the software pane. The OAVs calculated by the software were in very good agreement with data manually calculated on the basis of the data obtained by SIDA. Thus, it was successfully shown that it is possible to characterize key food odorants with one single analytical platform and without using the human olfactory system, that is, by "artificial intelligence smelling".

Quantitation of Gingerols in Human Plasma by Newly Developed Stable Isotope Dilution Assays and Assessment of Their Immunomodulatory Potential.

In a pilot study with two volunteers, the main pungent and bioactive ginger (Zingiber officinale Roscoe) compounds, the gingerols, were quantitated in human plasma after ginger tea consumption using a newly established HPLC-MS/MS(ESI) method on the basis of stable isotope dilution assays. Limits of quantitation for [6]-, [8]-, and [10]-gingerols were determined as 7.6, 3.1, and 4.0 nmol/L, respectively. The highest plasma concentrations of [6]-, [8]-, and [10]-gingerols (42.0, 5.3, and 4.8 nmol/L, respectively) were reached 30-60 min after ginger tea intake. Incubation of activated human T lymphocytes with gingerols increased the intracellular Ca(2+) concentration as well as the IFN-γ secretion by about 20-30%. This gingerol-induced increase of IFN-γ secretion could be blocked by the specific TRPV1 antagonist SB-366791. The results of the present study point to an interaction of gingerols with TRPV1 in activated T lymphocytes leading to an augmentation of IFN-γ secretion.

Characterization of the Key Odorants in Commercial Cold-Pressed Oils from Unpeeled and Peeled Rapeseeds by the Sensomics Approach.

By application of aroma extract dilution analysis (AEDA) on the volatile fraction isolated from commercial cold-pressed rapeseed oil prepared from unpeeled seeds, 35 odor-active constituents in the flavor dilution (FD) factor range of 8-8192 were detected. The identification experiments showed that the earthy, pea-like-smelling 2-isopropyl-3-methoxypyrazine showed the highest FD factor of 8192, followed by 1-octene-3-one (FD 4096) and (E,Z)-2,6-nonadienal with an FD of 2048. After quantitation of the 16 key odorants showing FD factors ≥32 by stable isotope dilution assays and a determination of their odor thresholds in deodorized sunflower oil, odor activity values (OAV; ratio of concentration to odor threshold) could be calculated. The results indicated 2-isopropyl-3-methoxypyrazine, (E,E)-2,4-nonadienal (deep-fried, fatty), and (E,Z)-2,6-nonadienal (cucumber-like) with the highest OAVs. To confirm that the key aroma compounds were correctly identified and quantitated, a recombination experiment was performed by mixing the reference odorants in the same concentrations as they occurred in the rapeseed oil using odorless sunflower oil as the matrix. The recombinate showed a very good agreement with the overall aroma of the oil. In a commercial rapeseed oil prepared from peeled seeds, the same odorants were identified; however, in particular, the FD factor of dimethyl sulfide (DMS) was clearly higher. Quantitation of DMS in 10 commercial rapeseed oils from either peeled and unpeeled seeds revealed significant differences in DMS, but no influence of the peeling process on the amounts of DMS was found. The data can serve as a basis for the quality assessment of cold-pressed rapeseed oil.

Characterization of the Key Aroma Compounds in Two Commercial Rums by Means of the Sensomics Approach.

Two rums differing in their overall aroma profile and price level (rum A, high price; rum B, low price) were analyzed by means of the Sensomics approach. Application of aroma extract dilution analysis (AEDA) on a distillate of volatiles prepared from rum A revealed 40 aroma-active compounds in the flavor dilution (FD) factor range from 8 to 2048. The identification experiments indicated cis-whiskey lactone, vanillin, decanoic acid, and 2- and 3-methylbutanol with the highest FD factors. The AEDA of a distillate prepared from rum B showed only 26 aroma-active compounds in the same FD factor range. Among them, in particular, ethyl butanoate, 1,1-diethoxyethane, ethyl (S)-2-methylbutanoate, and decanoic acid appeared with the highest FD factors. Thirty-seven compounds having at least an FD factor ≥32 in one of the two rums were quantitated using stable isotope dilution assays or enzyme kits (2 compounds). The calculation of odor activity values (OAVs; ratio of concentration to respective odor threshold) indicated ethanol, vanillin, ethyl (S)-2-methylbutanoate, and (E)-ß-damascenone with the highest OAVs in rum A, whereas ethanol, 2,3-butanedione, 3-methylbutanal, and ethyl butanoate revealed the highest OAVs in rum B. Most compounds were present in similar concentrations in both rums, but significant differences were determined for vanillin, cis-whiskey lactone, and 4-allyl-2-methoxyphenol (all higher in rum A) and 3-methylbutanal, 2,3-butanedione, and ethyl butanoate (all higher in rum B). Finally, the aromas of both rums were successfully simulated by a recombinate using reference odorants in the same concentrations as they naturally occurred in the spirits.

Characterization of the key aroma compounds in a commercial Amontillado sherry wine by means of the sensomics approach.

An aroma extract dilution analysis (AEDA) carried out on the volatile fraction isolated by extraction/solvent-assisted flavor evaporation (SAFE) distillation from a commercial Amontillado sherry wine revealed 37 odor-active compounds with flavor dilution (FD) factors in the range of 16-4096. Among them, 2-phenylethanol (flowery, honey-like) and ethyl methylpropanoate (fruity) showed the highest FD factors, followed by ethyl (2S,3S)-2-hydroxy-3-methylpentanoate (fruity) reported for the first time in sherry wine. A total of 36 aroma-active compounds located by AEDA were then quantitated by a stable isotope dilution assay, and their odor activity values (OAVs; ratio of concentration to odor threshold) were calculated. The highest OAV was displayed by 1,1-diethoxyethane (2475; fruity), followed by 2- and 3-methylbutanals (574; malty) and methylpropanal (369; malty). Aroma reconstitution experiments and a comparative aroma profile analysis revealed that the entire orthonasal aroma profile of the Amontillado sherry wine could be closely mimicked.

Assessment of the aroma impact of major odor-active thiols in pan-roasted white sesame seeds by calculation of odor activity values.

Eleven odor-active thiols, namely, 2-methyl-1-propene-1-thiol, (Z)-3-methyl-1-butene-1-thiol, (E)-3-methyl-1-butene-1-thiol, (Z)-2-methyl-1-butene-1-thiol, (E)-2-methyl-1-butene-1-thiol, 2-methyl-3-furanthiol, 3-mercapto-2-pentanone, 2-mercapto-3-pentanone, 4-mercapto-3-hexanone, 3-mercapto-3-methylbutyl formate, and 2-methyl-3-thiophenethiol, recently identified in an extract prepared from white sesame seeds, were quantitated in sesame using stable isotope dilution analyses. For that purpose, the following deuterium-labeled compounds were synthesized and used as internal standards in the quantitation assays: [2H6]-2-methyl-1-propene-1-thiol, [2H3]-(E)- and [2H3]-(Z)-2-methyl-1-butene-1-thiol, [2H3]-2-methyl-3-furanthiol, [2H2]-3-mercapto-2-pentanone, [2H3]-4-mercapto-3-hexanone, [2H6]-3-mercapto-3-methylbutyl formate, and [2H3]-2-methyl-3-thiophenethiol. On the basis of the results obtained, odor activity values (OAVs) were calculated as ratio of the concentration and odor threshold of the individual compounds in cooking oil. According to their high OAVs, particularly the 3-methyl-1-butene-1-thiols (OAV: 2400) and the 2-methyl-1-butene-1-thiols (OAV: 960) were identified as the most odor-active compounds in pan-roasted white sesame seeds. These compounds were therefore suggested to be mainly responsible for the characteristic but rather unstable sulfury aroma of freshly pan-roasted white sesame seeds.

Quantitation of key peanut aroma compounds in raw peanuts and pan-roasted peanut meal. Aroma reconstitution and comparison with commercial peanut products.

By means of stable isotope dilution assays (SIDA), 26 odor-active compounds, previously characterized by GC-olfactometry (GC-O), were quantitated in raw peanuts, and the concentrations of 38 odorants were determined in pan-roasted peanut meal. On the basis of the quantitative data and odor thresholds determined in vegetable oil, the odor activity values (OAVs) of the most important aroma compounds in raw as well as in pan-roasted peanut meal were calculated. 3-Isopropyl-2-methoxypyrazine, acetic acid, and 3-(methylthio)propanal showed the highest OAVs in raw peanuts, whereas methanethiol, 2,3-pentanedione, 3-(methylthio)propanal, and 2- and 3-methylbutanal as well as the intensely popcorn-like smelling 2-acetyl-1-pyrroline revealed the highest OAV in the pan-roasted peanut meal. Aroma recombination studies confirmed the importance, in particular, of methanethiol and of lipid degradation products in the characteristic aroma of the freshly roasted peanut material. To evaluate additive effects on the overall aroma, the concentrations of eight pyrazines, previously not detected by GC-O among the odor-active volatiles, were additionally quantitated in the pan-roasted peanut meal. A sensory experiment in which the eight pyrazines were added to the recombinate clearly revealed that these volatiles did not show an impact on the overall aroma. Finally, selected odorants were quantitated in commercial peanut products to confirm their important role in peanut aroma.