2. Phytochemical composition of fig fruit, leaf, and the alcoholic products, liqueurs, and spirits

Phytochemicals or plant secondary metabolites are non-nutritive plant metabolites which are essential for plant survival and proper growth and reproduction [23]. Many of these components have bioactivities toward animal biochemistry and metabolism with the ability to provide health benefits. F. carica plant owns the highest diversity of compounds with the higher quantities of all classes of compounds (except aldehydes and monoterpenes) mainly in leaves, followed by fruits pulps and peels [2, 9, 24].

Phytochemical studies on raw materials (fruits and leaves) and derived products (wine, liqueur, and spirit) of F. carica revealed the presence of numerous bioactive compounds including volatiles, organic acids, phytosterols, triterpenoids, fatty acids, phenolic acids, flavonoids, coumarins, and few other classes of secondary metabolites shown in Figure 2.

#### 2.1 Volatile compounds

Aroma is an important attribute of the sensory appreciation of a product and is usually used as a criterion for its quality assessment. It is a defining element of the

Figs and leaves are used in their primary and processed form to produce different traditional and industrial products (infusions, jams, wines, spirits, liqueurs, etc.). The fig is a very perishable product, and for this reason it is mainly utilized as dried fruit [6]. Either way, dry or fresh figs are well known for their nutritive value due to the high contents in minerals (mainly calcium and others like copper, manganese, magnesium, potassium, etc.), fats (source of energy), sugars, and other non-nutritive components such as water, fiber, and antioxidants like phenolic compounds [1, 6, 7]. On the other hand, infusions, decoctions, or other preparations

Modern Fruit Industry

Manufacturing process of Ficus carica L. wine, liqueur, and spirit from raw materials to the final beverage.

Figure 1.

116

distinct flavor of individual foods. The ripening period has an important role in the volatile composition, and many volatiles are produced during different developmental stages of plant tissues such as flowering, ripening, or maturation [1]. These volatiles are known as primary aromas, and they are responsible for varietal aromas [25]. These compounds are accumulated in plant storage sites and are released from the surface of the leaf, making this part of the F. carica the largest holder of compounds (except aldehydes and monoterpenes, in highest amounts in fruits [9]). On the other hand, in products such as wine, spirits, and liqueurs elaborated from fruits of F. carica, other types of aromas come from the different processing steps. Secondary aromas (the greatest pool of volatiles) are mainly produced by yeast as metabolism by-products, while tertiary aromas of finished alcoholic beverages are compounds that illustrate the changes made in the sample matrix during the storage and maturity stages [25].

Fruits [1, 2, 26, 27] and leaves [2, 8] of F. carica as well as derived products such as the alcoholic beverages, fig liqueurs [28], and spirits [14, 15, 17] consist of various volatile compounds which are identified and distributed by distinct chemical classes, such as terpenes (monoterpenes and sesquiterpenes), alcohols, aldehydes, ketones, esters, and miscellaneous compounds.

#### 2.1.1 Terpenes

Terpenes, such as monoterpenes (C10) and sesquiterpenes (C15), are the largest class of plant secondary metabolites, as can be seen in Figure 2. The high vapor pressures of these compounds, at normal atmospheric conditions, allow their significant release into the air [1]. Monoterpenes such as linalool (1) and epoxylinalool (34) (more important than linalool) are related with their important role in the attraction of specific pollinators, the fig/wasp linkage [1]. Although sesquiterpenes represented just the 3% of the total volatiles in Tunisian cultivars, it was the main class of compounds identified in leaves, and germacrene D, β-caryophyllene, and τ-elemene are the major compounds detected [9].

α-Pinene (31), one of the main monoterpenes mentioned in different works, has only been found in fruits, while the sesquiterpenes β-elemene (39), β-cubebene (60), α-ylangene (61), β-bourbonene (62), (+)-ledene (viridiflorene) (66), and αgurjunene (67) are compounds exclusively identified in leaves [1, 2, 9]. The monoterpenes citronellol acetate (7), (E)-geranyl acetone (12), (+)-sylvestrene (16), pmentha-1,3,8-triene (17), cumene (26), o- and p-cymene (27, 28), and nerol oxide (33) and the sesquiterpenes (E)-nerolidol (35), farnesyl acetate (36), α-curcumene (37), β-bisabolene (38), τ-elemene (40), ()-δ-cadinol (45), cadina-1 (10),4-diene (48), cadalene (49), α-calacorene (50), valencene (51), acoradiene (53), δ-guaiene (α-bulnesene) (55), α-guaiene (56), isocaryophyllene (57), γ-patchoulene (65), and α-cedrene (68) are compounds only identified in Portuguese monovarietal fig spirits [14]. Linalool acetate (2), geraniol (4), (Z)-8-hydroxylinalool (5), neral (β-citral) (6), geranyl vinyl ether (8), ethyl linalool (9), nerol (10), dihydrocitronellol (11), geranial (α-citral) (13), ocimene (14), p-menth-3-ene (19), α-terpinolene (21), α-terpineol (23), pulegone (24), isodihydrocarveol (25), borneol (30), and (Z)- or (E)-linalool oxide (34), as monoterpenes, and cadina-1,4-diene (47) and dihydroactinidiolide (52), as sesquiterpenes, were identified in synthetic liqueurs elaborated from different Greek F. carica varieties [28].

On the other hand, common terpenes were found in different F. carica parts and/or fig spirits and synthetic liqueurs. Menthol (18), τ-muurolene (44), and τ-cadinene (46) are common compounds found in fruit and leaves [2, 9]. The

Figure 2.

119

Chemical structures of different phytochemicals (volatile compounds, organic acids, triterpenoids, sterols, fatty

acids, phenolic acids, flavonoids, and coumarins) present in fig fruits, leaves, spirits, and liqueurs.

Chemical and Biological Characteristics of Ficus carica L. Fruits, Leaves...

DOI: http://dx.doi.org/10.5772/intechopen.86660

#### Chemical and Biological Characteristics of Ficus carica L. Fruits, Leaves... DOI: http://dx.doi.org/10.5772/intechopen.86660

#### Figure 2.

distinct flavor of individual foods. The ripening period has an important role in the volatile composition, and many volatiles are produced during different developmental stages of plant tissues such as flowering, ripening, or maturation [1]. These volatiles are known as primary aromas, and they are responsible for varietal aromas [25]. These compounds are accumulated in plant storage sites and are released from

compounds (except aldehydes and monoterpenes, in highest amounts in fruits [9]). On the other hand, in products such as wine, spirits, and liqueurs elaborated from fruits of F. carica, other types of aromas come from the different processing steps. Secondary aromas (the greatest pool of volatiles) are mainly produced by yeast as metabolism by-products, while tertiary aromas of finished alcoholic beverages are compounds that illustrate the changes made in the sample matrix during the storage

Fruits [1, 2, 26, 27] and leaves [2, 8] of F. carica as well as derived products such as the alcoholic beverages, fig liqueurs [28], and spirits [14, 15, 17] consist of various volatile compounds which are identified and distributed by distinct chemical classes, such as terpenes (monoterpenes and sesquiterpenes), alcohols, aldehydes,

Terpenes, such as monoterpenes (C10) and sesquiterpenes (C15), are the largest class of plant secondary metabolites, as can be seen in Figure 2. The high vapor pressures of these compounds, at normal atmospheric conditions, allow their significant release into the air [1]. Monoterpenes such as linalool (1) and epoxylinalool (34) (more important than linalool) are related with their important role in the attraction of specific pollinators, the fig/wasp linkage [1]. Although sesquiterpenes represented just the 3% of the total volatiles in Tunisian cultivars, it was the main class of compounds identified in leaves, and germacrene D, β-caryophyllene, and

α-Pinene (31), one of the main monoterpenes mentioned in different works, has only been found in fruits, while the sesquiterpenes β-elemene (39), β-cubebene (60), α-ylangene (61), β-bourbonene (62), (+)-ledene (viridiflorene) (66), and αgurjunene (67) are compounds exclusively identified in leaves [1, 2, 9]. The monoterpenes citronellol acetate (7), (E)-geranyl acetone (12), (+)-sylvestrene (16), pmentha-1,3,8-triene (17), cumene (26), o- and p-cymene (27, 28), and nerol oxide (33) and the sesquiterpenes (E)-nerolidol (35), farnesyl acetate (36), α-curcumene (37), β-bisabolene (38), τ-elemene (40), ()-δ-cadinol (45), cadina-1 (10),4-diene (48), cadalene (49), α-calacorene (50), valencene (51), acoradiene (53), δ-guaiene (α-bulnesene) (55), α-guaiene (56), isocaryophyllene (57), γ-patchoulene (65), and α-cedrene (68) are compounds only identified in Portuguese monovarietal fig spirits [14]. Linalool acetate (2), geraniol (4), (Z)-8-hydroxylinalool (5), neral (β-citral) (6), geranyl vinyl ether (8), ethyl linalool (9), nerol (10), dihydrocitronellol (11), geranial (α-citral) (13), ocimene (14), p-menth-3-ene (19),

α-terpinolene (21), α-terpineol (23), pulegone (24), isodihydrocarveol (25), borneol (30), and (Z)- or (E)-linalool oxide (34), as monoterpenes, and cadina-1,4-diene (47) and dihydroactinidiolide (52), as sesquiterpenes, were identified in synthetic

On the other hand, common terpenes were found in different F. carica parts and/or fig spirits and synthetic liqueurs. Menthol (18), τ-muurolene (44), and τ-cadinene (46) are common compounds found in fruit and leaves [2, 9]. The

liqueurs elaborated from different Greek F. carica varieties [28].

the surface of the leaf, making this part of the F. carica the largest holder of

and maturity stages [25].

Modern Fruit Industry

2.1.1 Terpenes

118

ketones, esters, and miscellaneous compounds.

τ-elemene are the major compounds detected [9].

Chemical structures of different phytochemicals (volatile compounds, organic acids, triterpenoids, sterols, fatty acids, phenolic acids, flavonoids, and coumarins) present in fig fruits, leaves, spirits, and liqueurs.

monoterpenes β-pinene (32) and eucalyptol (29) and the sesquiterpene (E)-αbergamotene (54) were identified in different fig cultivars from different countries and also in fig liqueurs, while the monoterpenes linalool (1) and linalool oxide (furanoid) (epoxylinalool) (34) were isolated in fig fruits and spirits [2, 9, 28].

class of volatiles (95% of total volatiles), particularly the fatty acid ethyl esters such as ethyl decanoate, ethyl octanoate, and ethyl dodecanoate. The second and third major compounds identified in fruits from Tunisian varieties were butyl acetate (108) and isoamyl acetate (107) with banana odor [1]. This last compound was also present in fig spirits [14]. Other ester identified in fruits was ethyl salicylate (113). Methyl butanoate (106), hexyl acetate (110), and ethyl benzoate (111) were found in leaves [2, 9], while methyl hexanoate (109) was a common compound in fruits and leaves and methyl salicylate (113) in fruits, leaves, and spirits [2, 9, 14]. Many methyl and ethyl esters and other esters were identified in fig spirits and are common to other alcoholic beverages. The study comparing dried and fresh fig spirits showed that dried fig spirits presented ethyl acetate (105) in higher proportion than fresh fig spirits. This compound results from the growth of

Chemical and Biological Characteristics of Ficus carica L. Fruits, Leaves...

DOI: http://dx.doi.org/10.5772/intechopen.86660

acetic acid bacteria during the fermentation in aerobic conditions [14].

in leaves were other volatile compounds detected in different fig samples.

2.2 Organic acids, phytosterols, triterpenoids, and fatty acids

while the quinic acid (121) was reported only in leaves [2, 9].

The norisoprenoid β-cyclocitral (114) present in leaves and fruits [2, 9] and βdamascenone (115) characteristic of different fig spirits and synthetic fig liqueurs [14, 28] and finally the phenylpropanoids [(eugenol (116), cinnamic alcohol (117), cinnamic aldehyde (118)] and indole (120) in fruits [9] and s-nonalactone (119) [2]

Some organic acids isolated from fruits and leaves of F. carica were the shikimic (122), malic (123), oxalic (124), fumaric (125), and citric (126) acids [2, 9, 24, 29],

Phytosterols are found in most plant foods, with the highest concentrations occurring in vegetable oils. Sterols (modified triterpenes) like β-sitosterol (137) [24] and the triterpenoids methyl maslinate (127), oleanolic acid (128), taraxasterol (129), w-taraxasterol ester, calotropenyl acetate (130), bauerenol (131),

24-methylenecycloartanol (132), lupeol (133), and lupeol acetate (135) have been reported in fig leaves [2, 9], and betulinic acid (134) in fruits [3], while stigmasterol

Dried and fresh fruits of F. carica showed polyunsaturated fatty acids with 84 and 69% of total fatty acids, respectively. Linoleic acid (139), in fresh and dried fruits, was the only polyunsaturated fatty acid identified. With respect to monoun-

Among the different chemical structures found in F. carica, one of the most important for biological uses is the phenolic compounds. These play many physiological roles in plants and are also favorable to human health [2]. Fruits and leaves presented qualitative differences in phenolic acids. Leaves were richer in phenolic derivatives formed by conjugation with sugars (the hydroxybenzoic derivatives:

deoxyhexoside, and the dihydroxybenzoic acids hexoside/hexoside pentoside) and organic acids including malic (the hydroxybenzoic derivative, syringic acid malate, and the hydroxycinnamic derivatives, caffeoylmalic acid, coumaroylmalic acid, sinapic acid malate, and ferulic acid malate) and quinic acid (the hydroxycinnamic derivative coumaroylquinic acid) [31, 32]. The signal of hydroxycinnamics was higher in extracts from leaves. On the other hand, in general, free forms of

saturated fatty acids, oleic acid (138) is the most abundant in fruits [9].

gallic acid di-pentoside, syringic acid hexoside, vanillic acid hexoside

2.1.3 Miscellaneous compounds

(136) was reported in both [29, 30].

121

2.3 Phenolic acids, flavonoids, and coumarins

Other common terpenes were identified in different fig samples such as αterpinene (20) in fig spirits and synthetic liqueurs; limonene (15), α-cubenene (59), copaene (63), and germacrene D (41) in fig fruits, leaves, and spirits; α-guaiene (57), aromadendrene (64), and α-muurolene (43) in fig leaves and spirits; and finally, β-caryophyllene (58) in fruit, leaves, spirits, and synthetic liqueurs, while α-caryophyllene (42) in fig leaves, spirits, and synthetic liqueurs [1, 2, 9, 14, 28].

#### 2.1.2 Alcohols, aldehydes, ketones, and esters

Alcohols, ketones, and esters are the more developed compound classes in ripened fruits, representing 41% of total aroma [1].

Different alcohols were identified in fruits [(Z)-3-hexen-1-ol (78)], leaves [2-methyl-1-butanol (76) and 1-heptanol (80)], spirits [methanol (69), ethanol (70), 1-propanol (71), 1-butanol (72), 2-methyl-propanol (isobutyl alcohol) (74), 1-hexanol (79), octanol (81), and decanol (83), among others], in both fruits and leaves [1-penten-3-ol (75), benzyl alcohol (85), and (E)-2-nonen-1-ol (82)] [2, 9], leaves and spirits [1-heptanol (80)] [9, 14], and finally in raw materials and spirits [3-methylbutanol (77), phenylethyl alcohol (84)] [2, 9, 14, 15]. Methanol (69), a toxic compound formed by hydrolytic demethoxylation of esterified methoxyl groups of the pectin polymer by pectic enzymes, with a marked maximum methanol content in fruit spirits of 1500 g/hL of pure alcohol (Regulation (EC) No 110/ 2008), was present in fresh and dried fig spirits [14]. It should be emphasized that its concentration depends on the technological characteristics of the manufacturing process. Higher quantities were found in spirits prepared from fresh figs because this compound is naturally present in fruits and decreased in spirits prepared using fermentations with immobilized yeast cell technology [15]. In addition, greater amounts of higher alcohols [2-butanol (73) + 1-propanol (71) + 2-methyl-propanol (74) + butanol (72) + 2-methylbutanol (76) + 3-methylbutanol (77)] were also found in samples of spirits made from dried figs (approx. > 350 g/hL absolute alcohol), being indicative of worse quality of these samples [14].

The aldehydes present exclusively in fruits are heptanal (92), octanal (95), nonanal (96), 2-methyl-butanal (87), (Z)-2-heptenal (93), (E, E)-2,4-heptadienal (94), (E)-2-octenal (97), and (E, Z)-2,6-nonadienal (98) [2, 9]. Furfural (99) and 5-hydroxymethylfurfural (100), toxic compounds originated during the fired potstill distillation process at high temperatures, and acetaldehyde (86) were identified in spirits [14, 15]. Meanwhile, common aldehydes identified in fruits and leaves were 2-methyl-butanal (87), 3-methyl-butanal (88), (E)-2-pentenal (89), hexanal (90), and (E)-2-hexenal (91); benzaldehyde (101) was present in fruits and spirits [2, 9].

The first major compound found in non-pollinated and pollinated figs was the ketone 3-hydroxy-2-butanone (acetoin) (102) [1]. Other ketones, 6-methyl-5 hepten-2-one (104) and 3-pentanone (103), were identified in, respectively, fruits (pulps and peels) and leaves of Portuguese fig varieties [2, 9].

Esters are the major contributors to fruit aroma and are the most important in ripe figs. They are produced through the esterification of alcohols and acyl-CoAs derived from both fatty acid and amino acid metabolism, in a reaction catalyzed by the enzyme alcohol-o-acyltransferase [1]. These compounds are much less developed in non-pollinated fruits, and its content decreases when using immobilized cell application during the fermentation process. In spirits, esters represent the largest

Chemical and Biological Characteristics of Ficus carica L. Fruits, Leaves... DOI: http://dx.doi.org/10.5772/intechopen.86660

class of volatiles (95% of total volatiles), particularly the fatty acid ethyl esters such as ethyl decanoate, ethyl octanoate, and ethyl dodecanoate. The second and third major compounds identified in fruits from Tunisian varieties were butyl acetate (108) and isoamyl acetate (107) with banana odor [1]. This last compound was also present in fig spirits [14]. Other ester identified in fruits was ethyl salicylate (113). Methyl butanoate (106), hexyl acetate (110), and ethyl benzoate (111) were found in leaves [2, 9], while methyl hexanoate (109) was a common compound in fruits and leaves and methyl salicylate (113) in fruits, leaves, and spirits [2, 9, 14]. Many methyl and ethyl esters and other esters were identified in fig spirits and are common to other alcoholic beverages. The study comparing dried and fresh fig spirits showed that dried fig spirits presented ethyl acetate (105) in higher proportion than fresh fig spirits. This compound results from the growth of acetic acid bacteria during the fermentation in aerobic conditions [14].

#### 2.1.3 Miscellaneous compounds

monoterpenes β-pinene (32) and eucalyptol (29) and the sesquiterpene (E)-αbergamotene (54) were identified in different fig cultivars from different countries and also in fig liqueurs, while the monoterpenes linalool (1) and linalool oxide (furanoid) (epoxylinalool) (34) were isolated in fig fruits and spirits [2, 9, 28]. Other common terpenes were identified in different fig samples such as αterpinene (20) in fig spirits and synthetic liqueurs; limonene (15), α-cubenene (59), copaene (63), and germacrene D (41) in fig fruits, leaves, and spirits; α-guaiene (57), aromadendrene (64), and α-muurolene (43) in fig leaves and spirits; and finally, β-caryophyllene (58) in fruit, leaves, spirits, and synthetic liqueurs, while α-caryophyllene (42) in fig leaves, spirits, and synthetic liqueurs [1, 2, 9, 14, 28].

Alcohols, ketones, and esters are the more developed compound classes in

Different alcohols were identified in fruits [(Z)-3-hexen-1-ol (78)], leaves [2-methyl-1-butanol (76) and 1-heptanol (80)], spirits [methanol (69), ethanol (70), 1-propanol (71), 1-butanol (72), 2-methyl-propanol (isobutyl alcohol) (74), 1-hexanol (79), octanol (81), and decanol (83), among others], in both fruits and leaves [1-penten-3-ol (75), benzyl alcohol (85), and (E)-2-nonen-1-ol (82)] [2, 9], leaves and spirits [1-heptanol (80)] [9, 14], and finally in raw materials and spirits [3-methylbutanol (77), phenylethyl alcohol (84)] [2, 9, 14, 15]. Methanol (69), a toxic compound formed by hydrolytic demethoxylation of esterified methoxyl groups of the pectin polymer by pectic enzymes, with a marked maximum methanol content in fruit spirits of 1500 g/hL of pure alcohol (Regulation (EC) No 110/ 2008), was present in fresh and dried fig spirits [14]. It should be emphasized that its concentration depends on the technological characteristics of the manufacturing process. Higher quantities were found in spirits prepared from fresh figs because this compound is naturally present in fruits and decreased in spirits prepared using fermentations with immobilized yeast cell technology [15]. In addition, greater amounts of higher alcohols [2-butanol (73) + 1-propanol (71) + 2-methyl-propanol (74) + butanol (72) + 2-methylbutanol (76) + 3-methylbutanol (77)] were also found in samples of spirits made from dried figs (approx. > 350 g/hL absolute

2.1.2 Alcohols, aldehydes, ketones, and esters

Modern Fruit Industry

ripened fruits, representing 41% of total aroma [1].

alcohol), being indicative of worse quality of these samples [14].

(pulps and peels) and leaves of Portuguese fig varieties [2, 9].

spirits [2, 9].

120

The aldehydes present exclusively in fruits are heptanal (92), octanal (95), nonanal (96), 2-methyl-butanal (87), (Z)-2-heptenal (93), (E, E)-2,4-heptadienal (94), (E)-2-octenal (97), and (E, Z)-2,6-nonadienal (98) [2, 9]. Furfural (99) and 5-hydroxymethylfurfural (100), toxic compounds originated during the fired potstill distillation process at high temperatures, and acetaldehyde (86) were identified in spirits [14, 15]. Meanwhile, common aldehydes identified in fruits and leaves were 2-methyl-butanal (87), 3-methyl-butanal (88), (E)-2-pentenal (89), hexanal (90), and (E)-2-hexenal (91); benzaldehyde (101) was present in fruits and

The first major compound found in non-pollinated and pollinated figs was the ketone 3-hydroxy-2-butanone (acetoin) (102) [1]. Other ketones, 6-methyl-5 hepten-2-one (104) and 3-pentanone (103), were identified in, respectively, fruits

Esters are the major contributors to fruit aroma and are the most important in ripe figs. They are produced through the esterification of alcohols and acyl-CoAs derived from both fatty acid and amino acid metabolism, in a reaction catalyzed by the enzyme alcohol-o-acyltransferase [1]. These compounds are much less developed in non-pollinated fruits, and its content decreases when using immobilized cell application during the fermentation process. In spirits, esters represent the largest

The norisoprenoid β-cyclocitral (114) present in leaves and fruits [2, 9] and βdamascenone (115) characteristic of different fig spirits and synthetic fig liqueurs [14, 28] and finally the phenylpropanoids [(eugenol (116), cinnamic alcohol (117), cinnamic aldehyde (118)] and indole (120) in fruits [9] and s-nonalactone (119) [2] in leaves were other volatile compounds detected in different fig samples.

#### 2.2 Organic acids, phytosterols, triterpenoids, and fatty acids

Some organic acids isolated from fruits and leaves of F. carica were the shikimic (122), malic (123), oxalic (124), fumaric (125), and citric (126) acids [2, 9, 24, 29], while the quinic acid (121) was reported only in leaves [2, 9].

Phytosterols are found in most plant foods, with the highest concentrations occurring in vegetable oils. Sterols (modified triterpenes) like β-sitosterol (137) [24] and the triterpenoids methyl maslinate (127), oleanolic acid (128), taraxasterol (129), w-taraxasterol ester, calotropenyl acetate (130), bauerenol (131), 24-methylenecycloartanol (132), lupeol (133), and lupeol acetate (135) have been reported in fig leaves [2, 9], and betulinic acid (134) in fruits [3], while stigmasterol (136) was reported in both [29, 30].

Dried and fresh fruits of F. carica showed polyunsaturated fatty acids with 84 and 69% of total fatty acids, respectively. Linoleic acid (139), in fresh and dried fruits, was the only polyunsaturated fatty acid identified. With respect to monounsaturated fatty acids, oleic acid (138) is the most abundant in fruits [9].

#### 2.3 Phenolic acids, flavonoids, and coumarins

Among the different chemical structures found in F. carica, one of the most important for biological uses is the phenolic compounds. These play many physiological roles in plants and are also favorable to human health [2]. Fruits and leaves presented qualitative differences in phenolic acids. Leaves were richer in phenolic derivatives formed by conjugation with sugars (the hydroxybenzoic derivatives: gallic acid di-pentoside, syringic acid hexoside, vanillic acid hexoside deoxyhexoside, and the dihydroxybenzoic acids hexoside/hexoside pentoside) and organic acids including malic (the hydroxybenzoic derivative, syringic acid malate, and the hydroxycinnamic derivatives, caffeoylmalic acid, coumaroylmalic acid, sinapic acid malate, and ferulic acid malate) and quinic acid (the hydroxycinnamic derivative coumaroylquinic acid) [31, 32]. The signal of hydroxycinnamics was higher in extracts from leaves. On the other hand, in general, free forms of

hydroxycinnamic acids such as caffeic acid (141), and the hydroxybenzoic acids, gallic (148) and syringic (149) acids, were only present in fruits [32]. Also the ferulic acid hexoside and the coumaroyl and ferulic hexosides were present in fruits. Moreover, the following compounds were common to both leaves and fruits: the hydroxybenzoic acids, di-/hydroxybenzoic acids and vanillic acid; the hydroxybenzoic derivatives, dihydroxybenzoic acid attached to hexoside/hexoside pentoside/pentoside/di-pentoside, vanillic acid glucoside, and gallic acid dipentoside; and the hydroxycinnamic acids, ferulic acid (140) and the chlorogenic (3-O-caffeoylquinic acid) (144) and neochlorogenic (5-O-caffeoylquinic acid) (145) acids. The common hydroxycinnamic derivatives present in fruits and leaves were caffeoylquinic acid hexoside, dihydrocaffeic acid hexose, and the sinapic acid hexoside [2, 9, 24, 32].

(5-methoxypsoralen) (188) were isolated from F. carica fruits and leaves [32].

murrayacarpin B (185) and the furocoumarins hydroxypsoralen, hydroxypsoralen

ypsoralen, oxypeucedanin, psoralic acid glucoside and marmesin (191) were iso-

The leaves and fruits of F. carica are important in traditional medicine [24]. Many biological activities have been evaluated and confirmed on F. carica extracts, and the bioassay-guided fractionation in most cases allowed to assign the chemical structures responsible of such biological effects, thereby ratifying some of its folkloric uses [9]. In this section we analyzed the potential health-promoting constitu-

Among the different phytochemicals studied in F. carica, phenolic compounds are among the most important with antioxidant capacity (AC). Many of these compounds are able to act as antioxidants by different ways: reducing agents, hydrogen donators, free radical scavengers, singlet oxygen quenchers, and so

6-sulfonate)] and DPPH (1,1-diphenyl-2-picrylhydrazyl) assays and the total phenolic content (TPC) by Folin–Ciocalteu method were evaluated in different fig spirits and liqueurs [34]. Fig liqueurs showed high values of TPC and AC (ABTS), close to the values of other fruit spirits with highest AC such as green walnut, carob pod, and mulberry. Fig spirits presented high (third value of 15 samples) AC by ABTS assay and among the highest TPC values. However, no DPPH scavenging

The maximum total flavonoid content (25.04 mg/g) with marked scavenging activities against hydroxyl and superoxide anion free radicals in a concentrationdependent manner were found in ethanolic (40%) leaf extracts of F. carica (solid to liquid ratio 1:60 g/mL, temperature extraction of 60°C, and 50 min of ultrasonic

Several works studied the AC of fruit extracts. Extracts from six commercial fig varieties were evaluated for AC by ferric reducing antioxidant method (FRAP) and also for TPC and total flavonoid content (TFC) and amount and profile of anthocyanins. The extracts exhibiting the highest AC contained the highest levels of TPC and TFC and anthocyanins (cyanidin-3-O-rutinoside as the main compound) [2, 6]. In another work, two fruit extracts [water (WE) and crude hot water-soluble polysaccharide (PS)] were evaluated for AC using the in vitro scavenging abilities



Simple coumarins 6-carbaxyl-umbelliferone, phellodenol A (184), and

Chemical and Biological Characteristics of Ficus carica L. Fruits, Leaves...

3. Biological studies in fruit, leaf, and fig spirits and liqueurs

ents of fig fruits, leaves, and derived products, fig liqueurs, and spirits [6].

hexoside, 40

,50

3.1 Antioxidant capacity

3.1.1 Fig spirits and liqueurs

3.1.2 Leaf extracts

treatment) [6].

123

3.1.3 Fruit extracts

The antioxidant capacity (AC) by ABTS [2,2<sup>0</sup>

activity was shown for fig liqueurs and spirits.

forth [2].

lated from leaves [2, 9, 31, 32].

DOI: http://dx.doi.org/10.5772/intechopen.86660

Flavonols such as quercetin (151) and glycosylated flavonols such as rutin (quercetin-3-O-rutinoside) (154) (major individual phenolic identified in fruits [2]), isoquercetin (quercetin-3-O-glucoside) (155), quercetin 3-O-(60 -O-malonyl) glucoside (157), quercetin di-deoxyhexoside hexoside, and quercetin O-di-hexoside were confirmed in fresh and dried figs and leaves [32]. Nicotiflorin (kaempferol-3-O-rutinoside) (152) and quercetin-acetilglucoside (156) were reported in fruits, while astragalin (kaempferol 3-O-glucoside) (153) only in leaves [2, 3, 9, 24, 31, 33].

Free flavones such as luteolin (158) and apigenin (159) are present in fig fruits and leaves. Also, the glycosylated flavones, isoorientin (luteolin 6-C-glucoside) (160), orientin (luteolin 8-C-glucoside) (161), cynaroside (luteolin 7-O-glucoside) (162), vitexin (apigenin 8-C-glucoside) (164), isochaftoside (apigenin 6-Cglucoside 8-C-arabinoside) (165), and apigenin 6-C-hexose-8-C-pentose [which could be identified as schaftoside (apigenin 6-C-glucoside 8-C arabinoside)], were detected in both plant parts. However, apigenin 7-rutinoside (163) and luteolin 6Chexose-8C-pentose were present in fruits [2, 9, 33].

Another group of flavonoids identified was the flavanones, with the compounds eriodictyol (166) and eriodictyol hexoside in fruits and naringenin (167) in fruits and leaves. The flavanonol taxifolin (dihydroquercetin) (168) was identified in fruits [32]. The flavanols, (+)-catechin (169) in fruits and leaves and (�) epicatechin (170) in leaves, were also identified [3, 33].

Genistein (173) and hydroxygenistein methyl ether malonylhexoside in leaves and prenylhydroxygenistein, prenylgenistein (171), biochanin A (genistein 4<sup>0</sup> methyl ether) (172), and cajanin (7-methoxy 2<sup>0</sup> -hydroxy genistein) (174), in fruits and leaves, were the isoflavones identified [2, 3, 9, 24, 31, 33].

Different anthocyanin pigments, some of them containing cyanidin or pelargonidin as aglycones, as well as rutinose and glucose substituting sugars and acylation with malonic acid, were found in skin and pulp from different varieties of Iberian fresh figs with different colors (black, red, yellow, and green). These compounds include (epi)-catechin-(4-8)-cyanidin-3-glucoside, (epi)catechin-(4–8) cyanidin-3-rutinoside,(epi)catechin-(4,8)-pelargonidin 3-rutinoside, 5 carboxypyranocyanidin-3-rutinoside, cyanidin-3-malonylglicosyl-5-glucoside, cyanidin-3-malonylglucoside, cyanidin-3-glucoside (175), cyanidin-3,5-diglucoside (176), cyanidin 3-O-rutinoside (as the main anthocyanin in different commercial fig varieties [2]) (178), pelargonidin-3-glucoside (179), pelargonidin-3-rutinoside (180) and peonidin-3-rutinoside (181). In addition, 5-carboxypyranocyanidin-3 rutinoside, a cyanidin 3-rutinose dimer, and five condensed pigments containing C–C linked anthocyanins and flavanol (catechin and epicatechin) residues were identified [9].

Coumarin (182); the hydroxycoumarins esculetin hexoside, dihydroxycoumarin, umbelliferone (7-hydroxycoumarin) (183), and prenyl-7 hydroxycoumarin; and the furocoumarins psoralen (187) and bergapten

Chemical and Biological Characteristics of Ficus carica L. Fruits, Leaves... DOI: http://dx.doi.org/10.5772/intechopen.86660

(5-methoxypsoralen) (188) were isolated from F. carica fruits and leaves [32]. Simple coumarins 6-carbaxyl-umbelliferone, phellodenol A (184), and murrayacarpin B (185) and the furocoumarins hydroxypsoralen, hydroxypsoralen hexoside, 40 ,50 -dihydropsoralen (190), angelicin (isopsoralen) (189), isopentenoxypsoralen, oxypeucedanin, psoralic acid glucoside and marmesin (191) were isolated from leaves [2, 9, 31, 32].
