Character-impact compounds

As these examples indicate, the characteristic flavor of a food, fruit, etc., usually derives from a complex mixture of components. In a few cases, one unique sulfur compound is a character-impact compound, a material recognized as having the same organoleptic character as the material itself. Although some 670 compounds, of which more than 100 are sulfur-containing, have been identified in roast coffee, one material, furfurylmercaptan (2-furylmethanethiol) is considered to be a character-impact compound.43,44 The threshold level for detection of 2-furylmethanethiol in water is 0.005 ppb, and at levels of 0.01-0.5 ppb, it has the very characteristic aroma of freshly roasted coffee. However, as in many other cases, there is a concentration effect. At levels from 1-10 ppb the aroma is that of staled coffee with a sulfury note .43 Hence, 2-furylmethanethiol has a two headed property - at low concentrations it is a character impact compound and at higher levels it is an off-flavor component. 

Peaches and nectarines are members of the same species (Prunus persica). There is controversy over whether nectarine is a separate and distinct fruit or merely a variety of peach [68]. Nectarines lack skin fuzz or pubescence. Approximately 100 volatile compounds have been identified in peaches and nectarines, including alcohols, aldehydes, alkanes, esters, ketones, lactones and terpenes [14, 15, 17, 64, 65, 68-71]. Among them, lactones, particularly y-decalactone and d-decalactone, have been reported as character-impact compounds in peaches and nectarines where they process a strong peach-like aroma [66]. Lactones act in association with Ce aldehydes, aliphatic alcohols and terpenes (Table 7.2,... 

Approximately 230 volatile compounds have been identified in raspberry fruit [35]. The aroma of raspberries is composed of a mixture of ketones and aldehydes (27%) and terpenoids (30%), alcohols (23%), esters (13%) and furanones (5%). The raspberry ketone (Fig. 7.5) along with a-ionone and jS-ionone have been found to be the primary character-impact compounds in raspberries. Other compounds such as benzyl alcohol, (Z)-3-hexen-l-ol, acetic acid, linalool, geraniol, a-pinene, jS-pinene, a-phellandrene, jS-phellandrene and jS-caryophyllene contribute to the overall aroma of mature red raspberries [101-105]. The most important character-impact compounds of raspberries are summarised in Table 7.3. 

The most important character-impact compounds of elderberries are summarised in Table 7.3. 

The kiwi fruit is a cultivar group of the species Actinidia deliciosa. More than 80 compounds have been identified in fresh and processed kiwi [137]. Methyl acetate, methyl butanoate, ethyl butanoate, methyl hexanoate and ( )-2-hexenal have the most prominent effect on consumer acceptability of kiwi fruit flavour [137-140]. The volatile composition of kiwi fruit is very sensitive to ripeness, maturity and storage period [138, 139]. Bartley and Schwede [140] found that ( )-2-hexenal was the major aroma compound in mature kiwi fruits, but on further ripening ethyl butanoate began to dominate. Ripe fruits had sweet and fruity flavours, which were attributed to butanoate esters, while unripe fruits had a green grassy note due to ( )-2-hexenal [140]. The most important character-impact compounds of kiwi fruits are summarised in Table 7.4. 

The fruit of pumpkin (Cucurbita pepo) is eaten boiled or baked. About 30 compounds have been identified in the volatile extracts of raw pumpkin, with the major classes of compounds being aliphatic alcohols and carbonyl compounds, furan derivatives and sulfur-containing compounds. Hexanal, ( )-2-hexenal, (Z)-3-hexen-l-ol and 2,3-butanedione have been identified as important for the flavour of freshly cooked pumpkins (Table 7.7) [35] however, studies using GC-O techniques are needed to get a better understanding of the character-impact compounds of pumpkins. 

Raw potato possesses little aroma. Approximately 50 compounds have been reported to contribute to raw potato aroma. Raw potatoes have a high content of LOX, which catalyses the oxidation of unsaturated fatty acids into volatile degradation products (Scheme 7.2) [187]. These reactions occur as the cells are disrupted, e.g. during peeling or cutting. Freshly cut, raw potatoes contain ( ,Z)-2,4-decadienal, ( ,Z)-2,6-nonadienal, ( )-2-octenal and hexanal, which are all products of LOX-initiated reactions of unsaturated fatty acids [188,189]. It is reported that two compounds represent typical potato aroma in raw potato methional and ( ,Z)-2,6-nonadienal [189]. Other important volatiles in raw potatoes produced via the LOX pathway are l-penten-3-one, heptanal, 2-pen-tyl furan, 1-pentanol and ( , )-2,4-heptadienal [189]. Pyrazines such as 3-iso-propyl-2-methoxypyrazine could be responsible for the earthy aroma of potato [35]. Some of the most important character-impact compounds of raw potatoes are summarised in Table 7.8. Aroma compounds from cooked, fried and baked potatoes have previously been reviewed [35]. 

The root of parsnip Pastinaca sativa) is eaten boiled or baked. The major classes of compounds identified in raw and cooked parsnip are monoterpenoids, aliphatic sulfur compounds, and 3-alkyl-2-methoxypyrazines [35]. To the best of our knowledge, no investigations have been performed to elucidate the character-impact compounds in parsnip by modern GC-O techniques however, it has been suggested that volatile compounds such as terpinolene, myristicin and 3-sec-butyl-2-methoxypyrazine maybe important contributors to the flavour of parsnip owing to either their high concentrations or their low threshold values, or both [35]. 

Fig. 8.2 Esters as character-impact compounds 4 isobutyl acetate in passion frml 5 isopentyl acetate in banana 6 ethyl butanoate in cupuacu 7 ethyl (32)-hexenoate and 8 ethyl-3-(methylthio)propanoate in pineapple...

Search for natural character-impact compounds Improved biocatalysts by evolutionary and rational enzyme engineering and metabolic engineering... 

Esters also constitute a group of important flavour compounds. They are the main aroma components found in fruits (apples, pears,. ..). For example, bananas contain 12-18 ppm acetates. The price of the pure flavour compounds, when isolated from fruit, can range between 10,000 and 100,000 US /kg In the past, research has been carried out by our group about the microbial production of fruity esters by the yeast Hansenula mrakii and the fungus Geotrichum penicillatum [10]. A fermentation was developed whereby fusel oil was continuously converted into a mixture of 3-methylbutyl acetate (isoamyl acetate) and 2-methylbutyl acetate, the character impact compounds of banana flavour. 

By AEDA the four odorants shown in Figure 9 were detected with the highest FD-factors in dill herb [33], A mixture of these compounds, dissolved in water at the same concentration ratios occurring in the herb (Table 16) very much resembled the typical odor of the dill herb. If (S)-a-phellandrene or the dill ether (B and A Fig. 9), respectively, were omitted, the mixture lost its typical odor note. On the contrary, omission of myristicin and methyl 3-methylbutanoate (D and C Fig. 9) did not significantly influence the overall dill herb aroma of the model mixture [33, 66], The data indicated that (S)-a-phellandrene and the dill ether are the character impact compounds of the dill herb. Since, on the basis of AEDA or calculation of OAVs further odorants have been shown to contribute to the dill herb flavor [33, 66], the results of the simulation experiments revealed that obviously the two monoterpenes are able to mask the flavor contributions of these compounds. 

Aqueous solutions of unsaturated carbonyls are hydrolyzed under alkaline conditions to produce additional carbonyl-containing compounds. Alkaline conditions traditionally used to accelerate this reaction cascade can be replaced with elevated temperatures and pressures without greatly affecting the overall hydrolysis of these unsaturated carbonyls. Water-mediated retro-aldol degradation of alpha/beta unsaturated carbonyls appears to be significant as a means to thermally-generate flavor-active carbonyls, as well as lead to deterioration of character-impact compounds possessing these features. 

The composition of the volatile fraction of bread depends on the bread ingredients, the conditions of dough fermentation and the baking process. This fraction contributes significantly to the desirable flavors of the crust and the crumb. For this reason, the volatile fraction of different bread types has been studied by several authors. Within the more than 280 compounds that have been identified in the volatile fraction of wheat bread, only a relative small number are responsible for the different notes in the aroma profiles of the crust and the crumb. These compounds can be considered as character impact compounds. Approaches to find out the relevant aroma compounds in bread flavors using model systems and the odor unit concept are emphasized in this review. A new technique denominated "aroma extract dilution analysis" was developed based on the odor unit concept and GC-effluent sniffing. It allows the assessment of the relative importance of the aroma compounds of an extract. The application of this technique to extracts of the crust of both wheat and rye breads and to the crumb of wheat bread is discussed. 

Since in particular the cracker-like crust odor note was lacking in the synthetic mixture, it was concluded that the character impact compound for this odor note occurs in a concentration in the bread too low to be detected by headspace analysis. Later on the basis of its aroma quality and its very low odor threshold of 0.04 ppb (water), Mulders et al. (19) proposed 2-[(methyldithio)methyl] furan (4 in Figure 1) as the compound which should be responsible for the "golden brown" crust aroma of white bread. 

In the case of wheat bread, 2-acetyl-l-pyrroline appeared with the highest FD-factor, followed by 2(E)-nonenal, 3-methylbutanal, diacetyl and 2(Z)-nonenal. These results confirm that the 2-acetyl-l-pyrroline is the "character impact compound of the wheat bread crust odor. 

The investigation of a series of model meat systems has demonstrated the important role of volatile sulfur-containing heterocyclic components substituted with sulfur in the 3-position. One of these 3-substituted sulfur compounds, 2-methy1-3-methy1thio-furan was identified recently in the volatiles from cooked beef aroma (5J and from a heated yeast extract composition (6J and is considered a meaty character impact compound. 

It is worth noting that ACPY was found to be the character-impact compound of cooked rice224 and was subsequently shown to play an important role in the more aromatic varieties of rice.225... 

The dog units were labeled furaneol units because this compound is found in large quantity in many fruits (26). Besides being intensely sweet, this compound also has a fragrant odor and is a character impact compound for many fruits. It is believed that this dog furaneol taste system is specific for fruit and is linked with the seed dispersing function of the dog. The presence of this taste system and its absence is readily detectable in the natural eating behavior of canines and felids. In a natural environment canines will supplement their small animal diet with fruit of the season, unlike felids. Nucleotide responsive units are relatively rare in taste systems. The only other vertebrate nucleotide taste system that has been described is in the puffer fish (27). This fish facial nerve taste system, like that in the cat, also responded to a wide variety of nucleotides and to inorganic phosphate compounds. In invertebrates, nucleotide taste systems have been described for blood sucking animals where they are common (28). 

In our opinion, the predominant contribution to flavor seems to come from sulfurous and carbonyl-containing volatiles. While many of the sulfur-containing volatiles are known to have meaty aromas, volatile carbonyl compounds generally are formed by lipid autoxidation/degradation and do not possess meaty flavor notes. However, it has been indicated that the carbonyl compounds are responsible for the "chickeny" aroma of cooked chicken (17). Thus, lipid autoxldatlon appears to yield the character impact compounds for chicken (18). 

The tastes of all natural foods are imparted by complex flavour mixtures consisting of a multitude of different single substances. The total sensoric impression is, however, imparted already by a few significant components, so-called character impact compounds. The biotechnical reaction therefore only has to yield sufficient amounts of these compounds in the correct proportion. 

A professional description of flavours uses as precise descriptors as possible. Chemical analytical results are combined with sensory analysis of the identified components to assess the relative importance and contribution to the flavour profile. Key ingredients or character impact compounds (CIC) are important components sine qua non to impart the typical, product characteristic, flavour, e.g. anethol for anise, eugenol for clove, 3-methyl butyl acetate for banana or ethyl butyrate to improve the juiciness of orange juice. 

M. Glintert, R. Emberger, R. Hopp, M. Kbpsel, W. SUberzahn and P. Werkhoff. Chirospecific analysis in flavor and essential oil chemistry Part A. Filbertone - the character impact compound of hazel-nuts. Z. Lebensm. Unters. Forsch., 192. 108-110 (1991). 

Glintert, M., Emberger, R., Hopp, R., Kopsel, M., Silberzahn, W., Werkhoff, R. (1991) Chirospe-cific analysis in flavour and essential oil chemistry. Rart A. EUbertone the character impact compound of hazelnuts. Z. Lebensm. Unters. Eorsch. 192. 108-110... 

Unsaturated esters may also be derived from the products of B-oxidation of unsaturated fatty acids. Methyl-and ethyl decadienoates are known as character impact compounds of Bartlett pears and all presumptive intermediates of the pathway were identified by Jennings et al. (JLZ UL) binoleyl-CoA is transformed into (E,Z)-2,4-decadienoyl-CoA by B-oxidation. The further degradation... 

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