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Aroma volatiles of pequi fruit (Caryocar brasiliense Camb.)
ARTICLE IN PRESS Journal of Food Composition and Analysis 21 (2008) 574– 576
Contents lists available at ScienceDirect
Journal of Food Composition and Analysis journal homepage: www.elsevier.com/locate/jfca
Short Communication
Aroma volatiles of pequi fruit (Caryocar brasiliense Camb.) Jose´ Guilherme S. Maia a,, Eloisa Helena A. Andrade a, Milton Helio L. da Silva b a b
´, 66075-900 Bele ´m, PA, Brazil Faculdade de Engenharia Quı´mica, Universidade Federal do Para ˆnica, Museu Paraense Emı´lio Goeldi, 66040-170 Bele´m, PA, Brazil Coordenac- ˜ ao de Bota
a r t i c l e in f o
a b s t r a c t
Article history: Received 8 May 2007 Received in revised form 16 April 2008 Accepted 16 May 2008
The aroma volatiles of Caryocar brasiliense, the ‘‘pequi’’ fruit, were analyzed by GC and GC–MS. It is rich on vitamins, lipids and proteins and an edible fruit after cooking. The ‘‘pequi’’ flavor has been used to aromatize many foods eaten up in the Central West and South Eastern of Brazil. The ethyl esters prevailed in the aroma concentrate of ‘‘pequi’’ followed by other analogous esters, saturated fatty acids and long chain hydrocarbons. The major component was ethyl hexanoate (52.9%) followed of minor amounts of ethyl octanoate (4.6%), tetrahydrofurfurylalcohol (4.3%), ethyl butanoate (4.1%), butyl palmitate (3.7%), isobutyl stearate (2.6%) and 3-methylvaleric acid (2.6%). The fatty acids and their derivatives varied from C-8 (caprylic acid and ethyl octanoate) to C-18 (stearyl acetate and isobutyl stearate). The existing homologous series of hydrocarbons ranged from C-11 (undecane) to C-26 (hexacosane). & 2008 Elsevier Inc. All rights reserved.
Keywords: Caryocar brasiliense Caryocaraceae Pequi GC–MS Aroma volatiles Ethyl hexanoate
1. Introduction The genus Caryocar L. comprises 16 species and together with Anthodiscus Meyer (10 species) belongs the Caryocaraceae, a small family with occurrence in Central and South America. The Caryocar brasiliense Camb. grows naturally in savanna woodlands (Brazilian cerrado) of Central West and South Eastern Region of Brazil. It is a tree, 10 m high (C. brasiliense subsp brasiliense Camb.) or sometimes a small shrub (C. brasiliense subsp intermedium (Wittmack) Prance and Freitas da Silva) known as ‘‘pequi’’, an indigenous word that means your endocarp is covered by numerous slender thorns (Prance and Freitas da Silva, 1973). The leaves and the fruit oil of C. brasiliense are used in the folk medicine of the Brazilian cerrado region to treat cold, cough, bronchitis, edema and burns, and the seeds are considered as aphrodisiacs (Vieira and Martins, 2000). The species is economically exploited for the fatty oil contained in the mesocarp used as butter substitute and the fruit kernel for cooking. In the leaves of C. brasiliense were identified some triterpenes (Oliveira et al., 1968). In the fruits and stem bark of C. villosum, the ‘‘piquia´’’ of Amazon Region, were found triterpenoid saponins (Magid et al., 2006a, b). The fruit pulp of ‘‘pequi’’ is edible after cooking and rich on vitamins, lipids and proteins. It is commonly used to flavor rice and chicken, and to produce home-made sweets and an alcoholic
Corresponding author. Tel.: +55 91 32017836; fax: +55 91 3235 3043.
E-mail address: [email protected] (J.G.S. Maia). 0889-1575/$ - see front matter & 2008 Elsevier Inc. All rights reserved. doi:10.1016/j.jfca.2008.05.006
liqueur known as ‘‘licor de pequi’’ (Arau´jo, 1995). The high raw fat content of ‘‘pequi’’ fruit is approximately 65.0% in the dry matter. The nutritive value of the fruit is determined by the lipid fraction where the main fatty acids are oleic acid (54.0%) and palmitic acid (39.0%) (Handro and Barradas, 1971). A valuable amount of the carotenoids a- and b-carotenes, b-criptoxantin and zeaxantin was observed in the ‘‘pequi’’ fruit (Rodriguez-Amaya et al., 1995; Carvalho and Burger, 1960; Silva et al., 1994). The essential oils of seeds and leaves of C. brasiliense were previously reported. The main compound found in the seed oil was ethyl hexanoate and in the leaf oil were octacosane, heptadecane and hexadecanol (Passos et al., 2003). The aim of this study was to analyze the chemical composition of the aroma concentrate obtained from the fruit of C. brasiliense whose flavor is used to aromatize many foods eaten up in the Central West and South Eastern Region of Brazil.
2. Material and methods 2.1. Plant material The fruits of C. brasiliense were collected in the municipality of Chapada dos Guimara˜es, Mato Grosso state, Brazil. The fruits were transported to the laboratory after they fall in down. After removal of the shells and separated the seeds, the fresh macerated pulp (100 g) was mixed with water (20 mL) and submitted to simultaneous distillation-extraction (SDE) for 3 h, using a Chrompak
ARTICLE IN PRESS J.G.S. Maia et al. / Journal of Food Composition and Analysis 21 (2008) 574–576
575
Fig. 1. Gas chromatogram of aroma concentrate of C. brasiliense.
micro-steam distillation extractor (Likens–Nickerson apparatus) and pentane (2 mL) as organic mobile phase. Three extractions of the fruits were made and then analyzed by GC and GC–MS.
Table 1 Volatile constituents of the fruit of Caryocar brasiliense Constituents
c
2.2. GC and GC– MS analysis The identification of components was performed in a GC–MS Finnigan INCOS XL instrument, with the following conditions: a WCOT DB-5 ms (30 m 0.25 mm i.d.; 0.25 mm film thickness) fused silica capillary column; temperature programmed: 40–60 1C (2 1C/min), 60–260 1C (4 1C/min); injector temperature: 220 1C; carrier gas: helium, adjusted to a linear velocity of 32 cm/s (measured at 100 1C); injection type: splitless (2 mL of the pentane soln.); split flow was adjusted to 20:1; septum sweep was a constant 10 mL/min; EI-MS: electron energy, 70 eV; ion source temperature and connections parts: 180 1C. The MS scanning range was 34–400 amu. The quantitative data of volatile constituents was obtained by peak area normalization using a HP 5890 GC/FID instrument, operated under the same GC–MS conditions, except for the carrier gas that was hydrogen produced by a Packard hydrogen generator and a WCOT CP-Sil CB (25 m 0.25 mm; 0.25 mm film thickness) fused silica capillary column.
3. Results and discussion Individual components were identified by comparison of both mass spectrum and GC retention data with those of authentic compounds previously analyzed and stored in the data system. Other identification were made by comparison of mass spectra with those in the data system libraries and cited in the literature (Adams, 2001; Jennings and Shibamoto, 1980). The retention indices were calculated for all compounds using a homologous series of n-alkanes under the same operational conditions. They were arranged in order of GC elution on DB-5 ms column. The Fig. 1 shows the gas chromatogram of aroma concentrate of C. brasiliense. The sixty volatile constituents and their percentage contents identified in the aroma concentrate of C. brasiliense are listed in Table 1. It is a remarkable mixture of carboxylic esters, saturated fatty acids, saturated long chain hydrocarbons and terpenes. The major component found in C. brasiliense was ethyl hexanoate (52.9%) followed of minor amounts of ethyl octanoate (4.6%), tetrahydrofurfurylalcohol (4.3%), ethyl butanoate (4.1%), butyl palmitate (3.7%), isobutyl stearate (2.6%) and 3-methylvaleric acid (2.6%).
Retention index (RI)a Observed
1,2-Dimethylcyclohexane (tent.)b 1-Octene Ethyl butanoate Tetrahydrofurfurylalcohol Ethyl 2methylpropanoate Ethyl 2-methylbutanoate Ethyl isovalerate Methyl hexanoate 3-Methylvaleric acid Propyl isovalerate Ethyl hexanoate Limonene Phenylacetaldehyde Ethyl (E)-2-hexenoate Isopentyl butanoate Terpinolene Propyl hexanoate Ethyl heptanoate Undecane Isopentyl isobutanoate Ethyl 3hydroxyhexanoate Isobutyl hexanoate Ethyl benzoate Caprylic acid Ethyl octanoate Dodecane Ethyl (E)-2-octenoate (tent.)a Isopentyl hexanoate Geraniol Safrole a-Copaene Ethyl decanoate Tetradecane b-Caryophyllene Germacrene D Pentadecane (E)-b-Farnesene d-Cadinene Lauric acid Hexadecane Heptadecane 2,6,10-Trimethyldodecane (tent.)a Myristic acid Octadecane
769 794 804 820 838
d
Relative % d
Adams
NIST (2005)
–
–
0.4
– – 833 841
0.1 4.1 4.3 0.2 0.5 1.0 0.5 2.6 0.3 52.9 0.1 0.4 0.4 0.1 0.1 0.5 0.6 0.1 0.1 0.3
788 802 – –
843 855 925 944 948 1000 1028 1040 1045 1058 1088 1092 1096 1098 1102 1125
–
997 1024 1036 1038 1052 1086 – 1097 1100 – 1121
850 – – 946 949 – – – – – – 1091 – – 1105 –
1132 1173 1195 1197 1200 1244
– 1169 – 1196 1200 –
1140 – 1187 – – –
0.3 0.1 0.4 4.6 0.1 0.2
1250 1253 1286 1377 1396 1400 1417 1484 1500 1505 1522 1563 1599 1701 1703
– 1249 1285 1374 1395 1400 1417 1484 1500 1506 1522 – 1600 1700 –
1252 – – – – – – – – – – 1566 – – –
1.0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.6 0.4 0.2 0.1
1764 1800
– 1800
1760 –
0.5 0.4
849 921 – –
ARTICLE IN PRESS 576
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taldehyde are probably the key components for the aroma of ‘‘pequi’’ fruit.
Table 1 (continued ) Constituents
Retention index (RI) c
14-Methyl pentadecanoate (tent.)a Palmitic acid Butyl myristate Ethyl palmitate Eicosane Heneicosane Butyl palmitate Docosane Stearyl acetate Tricosane Isobutyl stearate Tetracosane 1-Eicosanol (tent.)a Pentacosane 4-Methyldocosane (tent.)a Hexacosane Total
a
d
Relative %
Observed
Adams
NIST (2005)
1922
–
–
1960 1984 1993 1998 2098 2185 2199 2210 2302 2388 2400 2408 2499 2559 2600
– – – 2000 2100 – 2200 – 2300 – 2400 – 2500 – 2600
1957 1978 1991 – – 2174 – 2198 – 2384 – – – – –
d
Acknowledgments 0.1
0.9 0.2 0.1 0.2 0.3 3.7 0.7 0.7 1.1 2.6 1.6 0.2 2.1 0.1 2.1 96,1
a (RI)—Values obtained by comparison of retention time and mass spectrum, using the same column phase (5%-phenyl-methylpolysiloxane). b (tent.)—Tentative, using mass spectra data bases. c On DB5ms column. d See references.
In general, the aroma volatiles are metabolized of amino acids, lipids and carbohydrates (Sanz et al., 1997). Most of volatiles in ‘‘pequi’’ aroma are alkyl esters. We believe that its production is dependent of the availability of C2–C8 acid and alcohol unities, in turn, generated by the oxidation of unsaturated fatty acids by enzymes of the plant. Similarly, we assume that the saturated fatty acids and hydrocarbons found in ‘‘pequi’’ were produced after hydrogenation and decarboxylation of the unsaturated fatty acids. The ethyl esters prevailed in the aroma concentrate of ‘‘pequi’’ followed by other analogous esters. The odor description of ethyl hexanoate (fruity, sweet, pineapple), ethyl octanoate (fruity, floral) and ethyl butanoate (fruity, apple) pointing them to a high contribution to the characteristics of the aroma of ‘‘pequi’’ fruit (Rezende and Fraga, 2003; Qian and Reineccius, 2003). Similarly, they are also described as important odorants in wines, milks and cheeses (Drazenka et al., 2005; Moio et al., 1993; Takeoka et al., 1995). Phenylacetaldehyde which has a floral honey-like aroma (Qian and Reineccius, 2003) may also be a significant contributor to ‘‘pequi’’ aroma, despite their low percentage content. The fatty acids and their derivatives varied in the aroma concentrate from C-8 (caprylic acid and ethyl octanoate) to C-18 (stearyl acetate and isobutyl stearate). The existing homologous series of hydrocarbons ranged from C-11 (undecane) to C-26 (hexacosane). In this study we are showing that ethyl hexanoate followed by ethyl octanoate, tetrahydrofurfurylalcohol, ethyl butanoate, butyl palmitate, isobutyl stearate, 3-methylvaleric acid and phenylace-
The authors are grateful to PPBio/MCT and CNPq for financial support. References Adams, R.P., 2001. Identification of Essential Oil Components by Gas Chromatography/Mass Spectroscopy. Allured Publishing Corporation, Carol Stream, IL. Arau´jo, F.D., 1995. A review of Caryocar brasiliense (Caryocaraceae)—an economically valuable species of the central Brazilian cerrados. Economic Botany 49, 40–48. Carvalho, M.C., Burger, O.N., 1960. Contribuic- a˜o ao estudo do pequi de Brası´lia. Colec-a˜o Estudo e Pesquisa Alimentar 50, 7–15. Drazenka, K., Ulrich, D., Lovric, T., 2005. Characterization of odor-active compounds in croatian Rhine Riesling wine. European Food Research and Technology 222, 5–6. Handro, W., Barradas, M.M., 1971. Sobre os o´leos do fruto e da semente do pequi–Caryocar brasiliense Camb. (Caryocaraceae). In: III Simpo´sio sobre o Cerrado, Universidade De Sa˜o Paulo, Editora Edgard Blu¨cher Ltda, Sa˜o Paulo, pp. 110–113. Jennings, W., Shibamoto, T., 1980. Qualitative Analysis of Flavour and Fragrance Volatiles by Glass Capillary Gas Chromatography. Academic Press, New York. Magid, A.A., Voutquenne, N.L., Harakat, D., Pouny, I., Caron, C., Moretti, C., Lavaud, C., 2006a. Triterpenoid saponins from the fruits of Caryocar villosum. Journal of Natural Products 69, 919–926. Magid, A.A., Voutquenne, N.L., Renimel, I., Harakat, D., Moretti, C., Lavaud, C., 2006b. Triterpenoid saponins from the stem bark of Caryocar villosum. Phytochemistry 67, 2096–2102. Moio, L., Langlois, D., Etievant, P., Addeo, F., 1993. Powerful odorants in bovine, ovine, caprine and water buffalo milk determined by means of gas chromatography–olfactometry. Journal of Dairy Research 60, 215–222. NIST/EPA/NIH Mass Spectral Library (NIST 05) ASCII Version, 2005. National Institute of Standards and Technology, Mass Spectrometry Data Center, Gaithersburg, MD, USA. Oliveira, M.M., Gilbert, B., Mors, W.B., 1968. Triterpenes in Caryocar brasiliense. Anais da Academia Brasileira de Cieˆncias 40, 451–453. Passos, X.S., Castro, A.C.M., Pires, J.S., Garcia, A.C.F., Campos, F.C., Fernandes, O.F.L., Paula, J.R., Ferreira, H.D., Santos, S.C., Ferri, P.H., Silva, M.R.R., 2003. Composition and antifungal activity of the essential oils of Caryocar brasiliensis. Pharmaceutical Biology 41, 319–324 (Formerly International Journal of Pharmacognosy). Prance, G.T., Freitas da Silva, M., 1973. Caryocaraceae, Flora Neotropica, Monograph no. 12. Qian, M., Reineccius, G.A., 2003. Quantification of aroma compounds in parmigiano reggiano cheese by a dynamic headspace gas chromatography–mass spectrometry technique and calculation of odor activity value. Journal Dairy Science 86, 770–776. Rezende, C.M., Fraga, S.R.G., 2003. Chemical and aroma determination of the pulp and seeds of murici (Byrsonima crassifolia L). Journal of Brazilian Chemical Society 14, 425–428. Rodriguez-Amaya, D.B., Godoy, H.T., Mercadante, A.Z., Ramos, D.M.R., 1995. Carotenoid composition of underexploited Brazilian fruits. In: Proceedings of the Nineth World Congress of Food Science and Technology, International Union of Food Science and Technology, Budapest. Sanz, C., Olias, J.M., Perez, A.G., 1997. Aroma biochemistry of fruits and vegetables. In: Phytochemistry of Fruit and Vegetables. Oxford University Press Inc, New York, pp. 125–155. Silva, J.A., Silva, D.B., Junqueira, N.T.V., Andrade, L.R.M., 1994. Frutas Nativas dos Cerrados. Embrapa/Cpac, Brazil. Takeoka, G.R., Buttery, R.G., Turnbaugh, J.G., Benson, M., 1995. Odour thresholds of various branched esters. Lebensmittel-Wissenschaft und Technologie 28, 153–156. Vieira, R.F., Martins, M.V.M., 2000. Recursos gene´ticos de plantas medicinais do cerrado: uma compilac- a˜o de dados. Revista Brasileira de Plantas Medicinais 3, 13–36.
Contents lists available at ScienceDirect
Journal of Food Composition and Analysis journal homepage: www.elsevier.com/locate/jfca
Short Communication
Aroma volatiles of pequi fruit (Caryocar brasiliense Camb.) Jose´ Guilherme S. Maia a,, Eloisa Helena A. Andrade a, Milton Helio L. da Silva b a b
´, 66075-900 Bele ´m, PA, Brazil Faculdade de Engenharia Quı´mica, Universidade Federal do Para ˆnica, Museu Paraense Emı´lio Goeldi, 66040-170 Bele´m, PA, Brazil Coordenac- ˜ ao de Bota
a r t i c l e in f o
a b s t r a c t
Article history: Received 8 May 2007 Received in revised form 16 April 2008 Accepted 16 May 2008
The aroma volatiles of Caryocar brasiliense, the ‘‘pequi’’ fruit, were analyzed by GC and GC–MS. It is rich on vitamins, lipids and proteins and an edible fruit after cooking. The ‘‘pequi’’ flavor has been used to aromatize many foods eaten up in the Central West and South Eastern of Brazil. The ethyl esters prevailed in the aroma concentrate of ‘‘pequi’’ followed by other analogous esters, saturated fatty acids and long chain hydrocarbons. The major component was ethyl hexanoate (52.9%) followed of minor amounts of ethyl octanoate (4.6%), tetrahydrofurfurylalcohol (4.3%), ethyl butanoate (4.1%), butyl palmitate (3.7%), isobutyl stearate (2.6%) and 3-methylvaleric acid (2.6%). The fatty acids and their derivatives varied from C-8 (caprylic acid and ethyl octanoate) to C-18 (stearyl acetate and isobutyl stearate). The existing homologous series of hydrocarbons ranged from C-11 (undecane) to C-26 (hexacosane). & 2008 Elsevier Inc. All rights reserved.
Keywords: Caryocar brasiliense Caryocaraceae Pequi GC–MS Aroma volatiles Ethyl hexanoate
1. Introduction The genus Caryocar L. comprises 16 species and together with Anthodiscus Meyer (10 species) belongs the Caryocaraceae, a small family with occurrence in Central and South America. The Caryocar brasiliense Camb. grows naturally in savanna woodlands (Brazilian cerrado) of Central West and South Eastern Region of Brazil. It is a tree, 10 m high (C. brasiliense subsp brasiliense Camb.) or sometimes a small shrub (C. brasiliense subsp intermedium (Wittmack) Prance and Freitas da Silva) known as ‘‘pequi’’, an indigenous word that means your endocarp is covered by numerous slender thorns (Prance and Freitas da Silva, 1973). The leaves and the fruit oil of C. brasiliense are used in the folk medicine of the Brazilian cerrado region to treat cold, cough, bronchitis, edema and burns, and the seeds are considered as aphrodisiacs (Vieira and Martins, 2000). The species is economically exploited for the fatty oil contained in the mesocarp used as butter substitute and the fruit kernel for cooking. In the leaves of C. brasiliense were identified some triterpenes (Oliveira et al., 1968). In the fruits and stem bark of C. villosum, the ‘‘piquia´’’ of Amazon Region, were found triterpenoid saponins (Magid et al., 2006a, b). The fruit pulp of ‘‘pequi’’ is edible after cooking and rich on vitamins, lipids and proteins. It is commonly used to flavor rice and chicken, and to produce home-made sweets and an alcoholic
Corresponding author. Tel.: +55 91 32017836; fax: +55 91 3235 3043.
E-mail address: [email protected] (J.G.S. Maia). 0889-1575/$ - see front matter & 2008 Elsevier Inc. All rights reserved. doi:10.1016/j.jfca.2008.05.006
liqueur known as ‘‘licor de pequi’’ (Arau´jo, 1995). The high raw fat content of ‘‘pequi’’ fruit is approximately 65.0% in the dry matter. The nutritive value of the fruit is determined by the lipid fraction where the main fatty acids are oleic acid (54.0%) and palmitic acid (39.0%) (Handro and Barradas, 1971). A valuable amount of the carotenoids a- and b-carotenes, b-criptoxantin and zeaxantin was observed in the ‘‘pequi’’ fruit (Rodriguez-Amaya et al., 1995; Carvalho and Burger, 1960; Silva et al., 1994). The essential oils of seeds and leaves of C. brasiliense were previously reported. The main compound found in the seed oil was ethyl hexanoate and in the leaf oil were octacosane, heptadecane and hexadecanol (Passos et al., 2003). The aim of this study was to analyze the chemical composition of the aroma concentrate obtained from the fruit of C. brasiliense whose flavor is used to aromatize many foods eaten up in the Central West and South Eastern Region of Brazil.
2. Material and methods 2.1. Plant material The fruits of C. brasiliense were collected in the municipality of Chapada dos Guimara˜es, Mato Grosso state, Brazil. The fruits were transported to the laboratory after they fall in down. After removal of the shells and separated the seeds, the fresh macerated pulp (100 g) was mixed with water (20 mL) and submitted to simultaneous distillation-extraction (SDE) for 3 h, using a Chrompak
ARTICLE IN PRESS J.G.S. Maia et al. / Journal of Food Composition and Analysis 21 (2008) 574–576
575
Fig. 1. Gas chromatogram of aroma concentrate of C. brasiliense.
micro-steam distillation extractor (Likens–Nickerson apparatus) and pentane (2 mL) as organic mobile phase. Three extractions of the fruits were made and then analyzed by GC and GC–MS.
Table 1 Volatile constituents of the fruit of Caryocar brasiliense Constituents
c
2.2. GC and GC– MS analysis The identification of components was performed in a GC–MS Finnigan INCOS XL instrument, with the following conditions: a WCOT DB-5 ms (30 m 0.25 mm i.d.; 0.25 mm film thickness) fused silica capillary column; temperature programmed: 40–60 1C (2 1C/min), 60–260 1C (4 1C/min); injector temperature: 220 1C; carrier gas: helium, adjusted to a linear velocity of 32 cm/s (measured at 100 1C); injection type: splitless (2 mL of the pentane soln.); split flow was adjusted to 20:1; septum sweep was a constant 10 mL/min; EI-MS: electron energy, 70 eV; ion source temperature and connections parts: 180 1C. The MS scanning range was 34–400 amu. The quantitative data of volatile constituents was obtained by peak area normalization using a HP 5890 GC/FID instrument, operated under the same GC–MS conditions, except for the carrier gas that was hydrogen produced by a Packard hydrogen generator and a WCOT CP-Sil CB (25 m 0.25 mm; 0.25 mm film thickness) fused silica capillary column.
3. Results and discussion Individual components were identified by comparison of both mass spectrum and GC retention data with those of authentic compounds previously analyzed and stored in the data system. Other identification were made by comparison of mass spectra with those in the data system libraries and cited in the literature (Adams, 2001; Jennings and Shibamoto, 1980). The retention indices were calculated for all compounds using a homologous series of n-alkanes under the same operational conditions. They were arranged in order of GC elution on DB-5 ms column. The Fig. 1 shows the gas chromatogram of aroma concentrate of C. brasiliense. The sixty volatile constituents and their percentage contents identified in the aroma concentrate of C. brasiliense are listed in Table 1. It is a remarkable mixture of carboxylic esters, saturated fatty acids, saturated long chain hydrocarbons and terpenes. The major component found in C. brasiliense was ethyl hexanoate (52.9%) followed of minor amounts of ethyl octanoate (4.6%), tetrahydrofurfurylalcohol (4.3%), ethyl butanoate (4.1%), butyl palmitate (3.7%), isobutyl stearate (2.6%) and 3-methylvaleric acid (2.6%).
Retention index (RI)a Observed
1,2-Dimethylcyclohexane (tent.)b 1-Octene Ethyl butanoate Tetrahydrofurfurylalcohol Ethyl 2methylpropanoate Ethyl 2-methylbutanoate Ethyl isovalerate Methyl hexanoate 3-Methylvaleric acid Propyl isovalerate Ethyl hexanoate Limonene Phenylacetaldehyde Ethyl (E)-2-hexenoate Isopentyl butanoate Terpinolene Propyl hexanoate Ethyl heptanoate Undecane Isopentyl isobutanoate Ethyl 3hydroxyhexanoate Isobutyl hexanoate Ethyl benzoate Caprylic acid Ethyl octanoate Dodecane Ethyl (E)-2-octenoate (tent.)a Isopentyl hexanoate Geraniol Safrole a-Copaene Ethyl decanoate Tetradecane b-Caryophyllene Germacrene D Pentadecane (E)-b-Farnesene d-Cadinene Lauric acid Hexadecane Heptadecane 2,6,10-Trimethyldodecane (tent.)a Myristic acid Octadecane
769 794 804 820 838
d
Relative % d
Adams
NIST (2005)
–
–
0.4
– – 833 841
0.1 4.1 4.3 0.2 0.5 1.0 0.5 2.6 0.3 52.9 0.1 0.4 0.4 0.1 0.1 0.5 0.6 0.1 0.1 0.3
788 802 – –
843 855 925 944 948 1000 1028 1040 1045 1058 1088 1092 1096 1098 1102 1125
–
997 1024 1036 1038 1052 1086 – 1097 1100 – 1121
850 – – 946 949 – – – – – – 1091 – – 1105 –
1132 1173 1195 1197 1200 1244
– 1169 – 1196 1200 –
1140 – 1187 – – –
0.3 0.1 0.4 4.6 0.1 0.2
1250 1253 1286 1377 1396 1400 1417 1484 1500 1505 1522 1563 1599 1701 1703
– 1249 1285 1374 1395 1400 1417 1484 1500 1506 1522 – 1600 1700 –
1252 – – – – – – – – – – 1566 – – –
1.0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.6 0.4 0.2 0.1
1764 1800
– 1800
1760 –
0.5 0.4
849 921 – –
ARTICLE IN PRESS 576
J.G.S. Maia et al. / Journal of Food Composition and Analysis 21 (2008) 574–576
taldehyde are probably the key components for the aroma of ‘‘pequi’’ fruit.
Table 1 (continued ) Constituents
Retention index (RI) c
14-Methyl pentadecanoate (tent.)a Palmitic acid Butyl myristate Ethyl palmitate Eicosane Heneicosane Butyl palmitate Docosane Stearyl acetate Tricosane Isobutyl stearate Tetracosane 1-Eicosanol (tent.)a Pentacosane 4-Methyldocosane (tent.)a Hexacosane Total
a
d
Relative %
Observed
Adams
NIST (2005)
1922
–
–
1960 1984 1993 1998 2098 2185 2199 2210 2302 2388 2400 2408 2499 2559 2600
– – – 2000 2100 – 2200 – 2300 – 2400 – 2500 – 2600
1957 1978 1991 – – 2174 – 2198 – 2384 – – – – –
d
Acknowledgments 0.1
0.9 0.2 0.1 0.2 0.3 3.7 0.7 0.7 1.1 2.6 1.6 0.2 2.1 0.1 2.1 96,1
a (RI)—Values obtained by comparison of retention time and mass spectrum, using the same column phase (5%-phenyl-methylpolysiloxane). b (tent.)—Tentative, using mass spectra data bases. c On DB5ms column. d See references.
In general, the aroma volatiles are metabolized of amino acids, lipids and carbohydrates (Sanz et al., 1997). Most of volatiles in ‘‘pequi’’ aroma are alkyl esters. We believe that its production is dependent of the availability of C2–C8 acid and alcohol unities, in turn, generated by the oxidation of unsaturated fatty acids by enzymes of the plant. Similarly, we assume that the saturated fatty acids and hydrocarbons found in ‘‘pequi’’ were produced after hydrogenation and decarboxylation of the unsaturated fatty acids. The ethyl esters prevailed in the aroma concentrate of ‘‘pequi’’ followed by other analogous esters. The odor description of ethyl hexanoate (fruity, sweet, pineapple), ethyl octanoate (fruity, floral) and ethyl butanoate (fruity, apple) pointing them to a high contribution to the characteristics of the aroma of ‘‘pequi’’ fruit (Rezende and Fraga, 2003; Qian and Reineccius, 2003). Similarly, they are also described as important odorants in wines, milks and cheeses (Drazenka et al., 2005; Moio et al., 1993; Takeoka et al., 1995). Phenylacetaldehyde which has a floral honey-like aroma (Qian and Reineccius, 2003) may also be a significant contributor to ‘‘pequi’’ aroma, despite their low percentage content. The fatty acids and their derivatives varied in the aroma concentrate from C-8 (caprylic acid and ethyl octanoate) to C-18 (stearyl acetate and isobutyl stearate). The existing homologous series of hydrocarbons ranged from C-11 (undecane) to C-26 (hexacosane). In this study we are showing that ethyl hexanoate followed by ethyl octanoate, tetrahydrofurfurylalcohol, ethyl butanoate, butyl palmitate, isobutyl stearate, 3-methylvaleric acid and phenylace-
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