Esters, volatile aroma

Many microbial metabolites are volatile compounds and in terms of their sensory properties can be broken into two broad categories odorants and tastants (Table 1). Tastants include salty, sour, sweet, and bitter compounds such as amino acids, peptides, and sugars. Primary odorants typically are quite volatile and include carbonyl compounds, esters, and terpenes. There is considerable overlap between the two categories lactones, for example, have both taste and odor properties. In keeping with the theme of this symposium, volatile aroma substances will be the primary focus. 

The esters of aliphatic monocarboxylic acids are the most numerous of the neutral volatile aroma compounds in alcoholic beverages. Because of the relatively high volatility of the esters it has often been proposed that esters have a noticeable influence on the odor of a beverage. 

Many esters occur naturally Those of low molecular weight are fairly volatile and many have pleasing odors Esters often form a significant fraction of the fragrant oil of fruits and flowers The aroma of oranges for example contains 30 different esters along with 10 carboxylic acids 34 alcohols 34 aldehydes and ketones and 36 hydrocarbons... 

Volatiles or Aroma. The essential oil, or aroma, of tea provides much of the pleasing flavor and scent of green and black tea beverages. Despite this, volatile components comprise only - 1% of the total mass of the tea leaves and tea infusions. Black tea aroma contains over 300 characterizing compounds, the most important of which are terpenes, terpene alcohols, lactones, ketones, esters, and spiro compounds (30). The mechanisms for the formation of these important tea compounds are not fully understood. The respective chemistries of the aroma constituents of tea have been reviewed... 

CgHioO, Mr 122.17, mp 20°C, Z pioi.skPa 203°C, df 1.0135, ng 1.5275, has been identified as a volatile component of food (e.g., in tea aroma and mushrooms). The alcohol is a colorless liquid with a dry, roselike odor, slightly reminiscent of hawthorn. It can be prepared by catalytic hydrogenation of acetophenone. 1-Phenylethyl alcohol is used in small quantities in perfumery and in larger amounts for the production of its esters, which are more important as fragrance materials. 

More than 350 volatile compounds have been identified in apples [44]. Only a few of these volatiles have been identified as being responsible for apple aroma [45]. The most abundant volatile components in apples are esters (78-92% of total volatiles), alcohols (6-16% of total volatiles), aldehydes, ketones and ethers [35, 45], which are present in various amounts in different cultivars [46]. Esters are the principal compounds responsible for apple odour (Table 7.1, Fig 7.1)... 

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,... 

The berry or the small fruits consist of strawberry, raspberry, blackberry, black currant, blueberry, cranberry and elderberry. The volatiles responsible for the flavour of small fruits are esters, alcohols, ketones, aldehydes, terpenoids, furanones and sulfur compounds (Table 7.3, Figs. 7.1-7.7). As fruit ripen, the concentration of aroma volatiles rapidly increases, closely following pigment formation [43]. 

Sugars, acids and aroma compounds contribute to the characteristic strawberry flavour [85]. Over 360 different volatile compounds have been identified in strawberry fruit [35]. Strawberry aroma is composed predominately of esters (25-90% of the total volatile mass in ripe strawberry fruit) with alcohols, ketones, lactones and aldehydes being present in smaller quantities [85]. Esters provide a fruity and floral characteristic to the aroma [35,86], but aldehydes and furanones also contribute to the strawberry aroma [85, 87]. Terpenoids and sulfur compounds may also have a significant impact on the characteristic strawberry fruit aroma although they normally only make up a small portion of the strawberry volatile compounds [88, 89]. Sulfur compounds, e.g. methanethiol. 

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 aroma of intact black currant fruit is mostly produced by anabolic pathways of the plant, and production of fruit volatiles occurs mainly during a short ripening period [112]. The aroma profile of black currant shares similarities with that of other berry fruits, although terpenes are more abundantly present in black currant [107]. Black currant is mainly used for the production of juice. Over 150 volatile compounds have been reported from either black currant berries and/or juice, of which the major groups are monoterpenes, sesquiterpenes, esters and alcohols [107]. Processing of berries to juice has been shown to lead to major changes in the aroma composition [113-118]. 

Important aroma compounds of black currant berries have been identified mainly by GC-O techniques by Latrasse et al. [119], Mikkelsen and Poll [115] and Varming et al. [7] and those of black currant nectar and juice by Iversen et al. [113]. The most important volatile compounds for black currant berry and juice aroma include esters such as 2-methylbutyl acetate, methyl butanoate, ethyl butanoate and ethyl hexanoate with fruity and sweet notes, nonanal, /I-damascenone and several monoterpenes (a-pinene, 1,8-cineole, linalool, ter-pinen-4-ol and a-terpineol) as well as aliphatic ketones (e.g. l-octen-3-one) and sulfur compounds such as 4-methoxy-2-methyl-butanethiol (Table 7.3, Figs. 7.3, 7.4, 7.6). 4-Methoxy-2-methylbutanethiol has a characteristic catty note and is very important to blackcurrant flavour [119]. 

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. 

Banana (Musa sapientum L.) is one of the most common tropical fruits, and one of Central America s most important crops. It is grown in all tropical regions and is one of the oldest known fruits [45]. From a consumer perspective, bananas are nutritious with a pleasant flavour and are widely consumed throughout the world [57]. Esters predominate in the volatile fraction of banana (Fig. 8.2). Acetates are present in high concentrations in the fruit and generally possess a low threshold. Isopentyl acetate and isobutyl acetate are known as the two most important impact compounds of banana aroma. Alcohols are the second most important group of volatiles in banana extracts. 3-Methyl-1-butanol, 2-pentanol, 2-methyl-1-propanol, hexanol, and linalool are the alcohols present in higher concentrations in the fresh fruit [45]. 

A wide range of volatile compounds from Indian mango were identified by pioneer group research [20,21]. Esters, lactones, monoterpenes, sesquiterpenes, and furanones were among the volatiles. It has been suggested that the ratio of palmitic to palmitoleic acids determines the flavour quality of the ripe fruit, a ratio of less than 1 resulting in strong aroma and flavour [44]. 

Charentais cantaloupe melon Cucumismelo L. var. cantalupensis Naud.) was characterised by abundant sweetness and a good aromatic flavour [68]. The aroma volatiles of Charentais-type cantaloupe melons, as with other cantaloupes, comprise a complex mixture of compounds including esters, saturated and unsaturated aldehydes and alcohols, as well as sulfur compounds [26, 65]. Among these compounds, volatile esters were quantitatively the most important and therefore represent key contributors to the aroma [68]. The linear saturated and unsaturated aldehydes seem to originate from the degradation of linolenic and linoleic acids [26, 32, 33, 67]. 

The aroma volatiles of some melon species consist of a complex mixture of esters together with other components, including C9 unsaturated aldehydes, alcohols, and acetates whose sensory properties have been described as melonlike [10,31-33,35]. Several esters and alcohols were described among the volatiles of muskmelons [33, 34]. 

Papaya is a native fruit from America and is widely planted throughout the tropics [41], and is a crop of economic importance to tropical countries [11]. It has become a commercially important fresh fruit crop, particularly in the USA and Europe [51]. Papaya possesses a characteristic aroma, which is due to several volatile components, such as alcohols, esters, aldehydes, and sulfur compounds [11]. 

Later, the chemical characterisation of the volatiles from yellow passion fruit essence and from the juice of the fruit was done by GC-MS and GC-olfactom-etry (GC-O) [27]. Esters were the components found in the largest concentrations in passion fruit juice and essence extracted with methylene chloride. Analysis by GC-O yielded a total of 66 components which appeared to contribute to the aroma of passion fruit juice and its aqueous essence. Forty-eight compounds were identified in the pulp of Brazilian yellow passion fruits (Passiflora edulis f. flavicarpa) [48]. The predominant volatile compounds belonged to the classes of esters (59%), aldehydes (15%), ketones (11%), and alcohols (6%). 

The volatile compounds of juices made from freshly cut pineapple fruits from different cultivars from Costa Rica, Ghana, Honduras, Cote d Ivoire, the Philippines, Reunion, South Africa, and Thailand were studied in comparison to that of commercial water phases/recovery aromas, juice concentrates as well as commercially available juices [12]. The qualitative pineapple fruit flavour profile showed several methyl esters, some characteristic sulfur-containing esters, and various hydroxy esters were responsible for the typical pineapple flavour profile. 

Volatile constituents of cupuacu were isolated by steam distillation-extraction of pulp or juice [2].The identification of volatile constituents was based on mass spectral analysis. The pleasant aroma compounds were mainly esters (Fig. 8.2). Targe amounts of ethyl butanoate and small amounts of ethyl acetate, butyl acetate, and butyl isobutanoate were described. 

Fig. 23.4 Organophilic pervaporation (PV) for in situ recovery of volatile flavour compounds from bioreactors. The principle of PV can be viewed as a vacuum distillation across a polymeric barrier (membrane) dividing the liquid feed phase from the gaseous permeate phase. A highly aroma enriched permeate is recovered by freezing the target compounds out of the gas stream. As a typical silicone membrane, an asymmetric poly(octylsiloxane) (POMS) membrane is exemplarily depicted. Here, the selective barrier is a thin POMS layer on a polypropylene (PP)/poly(ether imide) (PEI) support material. Several investigations of PV for the recovery of different microbially produced flavours, e.g. 2-phenylethanol [119], benzaldehyde [264], 6-pentyl-a-pyrone [239], acetone/buta-nol/ethanol [265] and citronellol/geraniol/short-chain esters [266], have been published...

An extensive list of volatile compounds in apples and other fruits was included in a review by Nursten (222). White (223) reported that the principal components of the aroma of apples were alcohols (92% ) methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-l-propa-nol, 2-methyl-l-butanol, and 1-hexanol. The other constituents included 6% carbonyl compounds and 2% esters. Later, MacGregor et al. (224) tentatively identified 30 volatile components of McIntosh apple juice including four aldehydes, one ketone, 11 alcohols, 10 esters, and four fatty acids. The major organic volatiles in several different extractants of Delicious apple essence were identified and quantitatively estimated by Schultz et al. (225). They reported from sensory tests that low molecular weight alcohols contributed little to apple aroma. Flath et al. (226) identified... 

Jennings et al (228) fractionated an extract from Bartlett pears into 32 volatile components of which five were found to contribute significantly to the characteristic pear aroma. Later studies indicated that esters of trans-2 cis-4 decadienoic acid and hexyl acetate were significant components of the Bartlett pear aroma (229, 230). More recently, numerous volatiles of Bartlett pears were separated and identified including esters of methyl, ethyl, propyl, butyl, and hexyl alcohols, and Cio to Ci8 fatty acids (231, 232). 

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