Revista CENIC. Ciencias Químicas ISSN: 1015-8553 [email protected] Centro Nacional de Investigaciones Científicas Cuba

Pino, Jorge A.; Quijano, Clara Elizabeth Volatile compounds of arazá fruit (Eugenia stipitata McVaught) Revista CENIC. Ciencias Químicas, vol. 38, núm. 3, 2007, pp. 363-366 Centro Nacional de Investigaciones Científicas La Habana, Cuba

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Volatile compounds of arazá fruit (Eugenia stipitata McVaught)

Jorge A. Pino y Clara Elizabeth Quijano*

Instituto de Investigaciones para la Industria Alimenticia, Carretera al Guatao kilómetro 3½, La Habana, Código Postal 19200, Cuba. E-mail: [email protected]. *Universidad de los Andes, Facultad de Ciencias, Departamento de Química, Cra. 1a Este No. 18-A-10 Edif. (Q-826), Bogotá, . E-mail: [email protected]

Recibido: 8 de diciembre de 2006. Aceptado: 19 de febrero de 2007.

Palabras clave: Eugenia stipitata, Myrtaceae, arazá, compuestos volátiles, octanoato de etilo, decanoato de etilo, dodecanoato de etilo. Key words: Eugenia stipitata, Myrtaceae, arazá, volatile compounds, ethyl octanoate, ethyl decanoate, ethyl dodecanoate.

RESUMEN. El arazá (Eugenia stipitata McVaugh) es nativo de la parte peruana INTRODUCTION de la selva amazónica. La fruta es una esfera, caracterizada por su intenso aro- ma y sabor ácido, así como color de la piel verde a amarillo al madurar. La parte Colombia has a natural diversity comestible, una pulpa cremosa blanca se come fresca o es usada para preparar of tropical fruits with distinctive ex- jugos, mermeladas, helados y licores. Los compuestos volátiles se aislaron del otic flavors appealing to the pro- arazá mediante extracción líquida-líquida continua con el uso de pentano- ducer that they could be an impor- diclorometano [1 : 1 (v/v)] durante 8 h y se analizaron por cromatografía de gases tant source of income. However, the capilar con detector de ionización con llama de hidrógeno y cromatografía de volatile composition responsible for gases-espectrometría de masas con el uso de columnas capilares del tipo HP- their flavors has not yet been char- Innowax. El extracto concentrado obtenido mostró notas aromáticas similares acterized widely. Among them, arazá al aroma de la fruta fresca, descrito como dulce-verdoso-frutal. Como resultado, (Eugenia stipitata McVaught), be- se obtuvieron 7,9 mg de compuestos volátiles por kilogramo de fruta fresca. En longing to the Myrtaceae family, is total, se identificaron 27 ésteres, 20 terpenos, cinco alcoholes, seis compuestos an indigenous Amazonian tree wide- carbonílicos, cinco ácidos, tres hidrocarburos, dos lactonas y dos compuestos spread in different regions of Colom- azufrados. De los 70 constituyentes identificados, 53 se reportan por primera bia. This fruit is also known as araça- vez en esta fruta. Los ésteres (54,8 % del total de la composición) fueron la clase boi in or as pichi or sororia in de compuestos más abundante. El octanoato de etilo, dodecanoato de etilo y Peru. The fruit, characterized by its decanoato de etilo fueron los componentes mayoritarios. Otros compuestos sig- nificativos fueron: el etanol, 1-hexanol, globulol, ácido 2-metilbutanoico, ácido intense aroma and acid flavor, is hexanoico, ácido octanoico, 3-metil-2-buten-1-ol y 2-furfural. round, about 12-15 cm in diameter, 800 g maximum weight, and green ABSTRACT. The arazá (Eugenia stipitata McVaugh) is native from the Peru- to yellow peel at maturity. The ed- vian part of the Amazonian forest. The fruit is a sphere, characterized by its ible part, a creamy-white pulp, is intense aroma and acid flavor and green to yellow peel at maturity. The edible eaten fresh or is used to prepare part, a creamy-white pulp, is eaten fresh or is used to prepare juices, marma- juices, marmalades, ice creams and lades, ice creams and liquors. Volatile compounds were isolated from arazá by liquors.1-3 continuous liquid-liquid extraction using pentane-dichloromethane [1 : 1 (v/v)] As far it is known, there are for 8 h, and analyzed by GC-FID and GC-MS using HP-Innowax fused silica only two reports on the composi- column. The concentrated extract showed aroma notes resembling the flavor of tion of the volatile compounds of fresh fruit, described as sweet-green-fruity. A total amount of 7.9 mg of volatile 4,5 compounds per kilogram of fresh fruit was obtained. In total, 27 esters, 20 terpe- this fruit. In both works, 30 and nes, five alcohols, six carbonyls, five acids, three hydrocarbons, two lactones 65 volatiles were identified, re- and two sulfur-compounds were identified. Of the 70 components identified, 53 spectively. are reported for the first time in this fruit. Esters (54.8 % of the total composi- The main purpose of this study tion) were the most abundant compound class. Ethyl octanoate, ethyl dodecanoate was to identify additional arazá fruit and ethyl decanoate were found to be the major constituents. Other significant (Eugenia stipitata McVaught) com- compounds were: ethanol, 1-hexanol, globulol, 2-methylbutanoic acid, hexanoic pounds that may contribute to its acid, octanoic acid, 3-methyl-2-buten-1-ol and 2-furfural. delicate flavor.

Correspondencia: Dra.Clara Elizabeth Quijano Celís Universidad de los Andes, Facultad de Ciencias, Departamento de Química, Cra. 1a Este No. 18-A-10 Edif. (Q-826), Bogotá, Colombia. E-mail: [email protected] 363 Revista CENIC Ciencias Químicas, Vol. 38, No. 3, 2007.

MATERIALS AND METHODS extraction and analyzed by GC-FID were identified. Of the 70 compo- Fresh mature arazá fruits were and GC-MS. A valid aroma concen- nents identified, 53 are reported for picked from bushes grown in Caquetá, trate was prepared by using an es- the first time. Colombia, and transported by airplane tablished procedure with an accept- According to class of compounds, to the laboratory within 24 h after har- able extraction efficiency (> 80 % esters dominate the volatiles profile. vest. The fruits were allowed to ripen recovery) and low danger of artifact These compounds that constitute at room temperature. After separation formation.10-12 The concentrated ex- over 54.8 % of the total volatiles in- of the skin and seeds the pulp was tract showed aroma notes resem- clude many ethyl and hexyl esters. gently bended in a commercial bling the flavor of fresh fruit, de- Of them, ethyl octanoate, ethyl blender. The blended pulp was im- scribed as sweet-green-fruity. dodecanoate and ethyl decanoate mediately subjected to extraction. Table 1 presents identified com- were found to be the major ones. In Isolation of volatile compounds pounds with their concentrations. one previous result about arazá fruit, was made by the following proce- Quantitations were based upon the amount of esters was low,4 dure: an aliquot of blended pulp GC-FID peak integration data, so whereas in the other report they (1 kg) was diluted with distilled wa- accuracy is potentially limited by were in significant amounts. These ter (1 L) and centrifuged at 10 000 r a number of factors, including co- discrepancies may be related to the /min for 20 min . Decanol (0.25 mg) elution of two or more components stage of ripeness of the fruit when was added as internal standard be- and differences in FID response fac- sampled, different cultivars or geo- fore the liquid-liquid extraction. The tors among compounds. The quan- graphical regions and the isolation supernatant was continuously ex- titative data (Table 1) shows that to- method. Two identified lactones, δ- tracted with pentane-dichloromethane tally 7.9 mg of volatile compounds decalactone and γ-dodecalactone, were [1 : 1 (v/v)] for 8 h . The organic phase per kilogram of fresh fruit were ob- reported for the first time in arazá was dried over anhydrous sodium sul- tained. fruit. fate and concentrated to 0.2 mL on a In total, 27 esters, 20 terpenes, In the terpene group, many Kuderna-Danish evaporator with a five alcohols, six carbonyls, five ac- monoterpene and sesquiterpenes 15-cm Vigreux column. Extractions ids, three hydrocarbons, two lac- were identified, with the major rep- were made by triplicate. tones and two sulfur-compounds resentatives being globulol and An HP 6890 GC with a FID, equip- ped with an HP-Innowax fused silica column (60 m X 0.25 mm X 0.25 µm film thickness) was employed. The Table 1. Volatile constituents of arazá fruit. column temperature was program- med as follows: 50 oC hold 4 min, to Cnompound Identificatio 2 RI3 Amount 220 oC at 4 oC/min, then hold 10 min. (µg/kg) Nitrogen carrier gas was used at a Ethyl acetate1 M4S, GC 832 4 flow rate of 1 mL/min . The injector Ethanol1 M8S, GC 869 56 and detector were maintained at 230 oC . Sample injection volume was α-Pinene M2S, GC 1t01 1 µL with a split ratio of 1 : 10. Lin- Ethyl butanoate1 M1S, GC 1002 1 ear retention indices were calculated Ethyl 2-methylbutanoate1 M0S, GC 1404 1 using n-paraffin standards.6 β An HP 6890 Series II equipped -Pinene M5S, GC 1t11 with a mass selective detector HP- MCyrcene M0S, G 1t14 5973N and the same capillary col- 2-Methyl-2-pentenal1 M2S 1015 6 umn and temperature program as in 1 GC-FID technique was used. He- Ethyl hexanoate M0S, GC 1t22 lium carrier gas was used at a flow 3-Methyl-2-buten-1-ol1 M1S, GC 1523 29 rate of 1 mL/min . Mass spectra were (E)-β-COcimene M1S, G 1824 3 recorded in the electron-impact Hexyl acetate1 M1S, GC 1026 15 mode at 70 eV by 1.8 scans/s . Detec- tion was performed in the scan mode TCerpinolene M0S, G 1t27 between 30 and 400 Daltons. 3-Hydroxy-2-butanone1 M5S, GC 1427 5 Compounds were identified by HCexyl propanoate M1S, G 1432 5 comparing their spectra to those of 1 authentic standards, those in NIST Hexyl isobutanoate M5S, GC 1232 3 library or literature7-9 and also, in 1C-Hexanol M0S, G 1334 31 many cases, by comparison of their (CZ)-3-Hexenol M1S, G 1336 12 GC linear retention indices to those Methyl octanoate1 M8S, GC 1537 2 of standard compounds. Quantitative analysis was made 1-Tetradecane1 M5S, GC 1339 14 by the internal standard method Hexyl 2-methylbutanoate1 M8S, GC 1340 18 from the electronic integration of ECthyl octanoate M1S, G 1142 103 the FID peak areas without the use 1 of correction factors. Ethyl 2-methylthioacetate M5S 1242 16 2-Furfural1 M9S, GC 1043 30 RESULTS AND DISCUSSION α-Copaene M5S, GC 1t47 The volatile compounds of arazá 1 fruit were obtained by liquid-liquid 1-Pentadecane M9S, GC 1849 2 364 Revista CENIC Ciencias Químicas, Vol. 38, No. 3, 2007.

Table 1. (continued) (E,Z)-α-farnesene. Germacrene D, reported in a previous study as the Cnompound Identificatio 2 RI3 Amount most abundant compound,4 was only (µg/kg) detected in traces in the present ECthyl 3-hydroxybutanoate M2S, G 1350 4 study. Alcohols and carbonyls com- β-Bisabolene1 M8S, GC 1t50 pounds represented 17.0 and 6.9 % Ethyl nonanoate1 M9S, GC 1951 2 of the total volatiles. Of them, etha- Ethyl (E)-2-octenoate1 M2S, GC 1553 2 nol, 1-hexanol and 3-methyl-2-buten- Ethyl 3-methylthiopropanoate1 G5C 1553 2 1-ol were the major alcohols, whereas 2-furfural was the most abundant 1 5-Methyl-2-furfural M8S, GC 1055 10 carbonyl compound. 2-Methyloctanol1 M5S, GC 1156 4 The presence of some acids (6.8 %) β-Caryophyllene M1S, GC 1t57 and n-paraffins (2.5 %) should not significantly contribute to fruit fla- Hexyl hexanoate1 M2S, GC 1859 15 vor, due to the high thresholds of 3-Hydroxy-2-methylpentanal1 M2S 1t60 these compounds.13 Two sulfur-com- ECthyl decanoate M1S, G 1662 51 pounds not reported previously, ethyl 2-methylthioacetate and ethyl (Z)-3-Hexenyl hexanoate1 M8S, GC 1563 2 3-methylthiopropanoate were iden- 1 Citronellyl acetate M8S, GC 1t65 tified. On the other hand, methyl 3- α-Humulene M9S, GC 1t68 methylthipropanoate which was pre- 5 2-Methylbutanoic acid1 M1S, GC 1069 25 viously reported, was not found in the present study. 1 1-Heptadecane M9S, GC 1669 2 Certainly, many of the found GCermacrene D M0S, G 1t71 compounds (Table 1) should make γ-Muurolene1 M3S, GC 1571 2 important contributions to the over- all arazá flavor, particularly the esters, β-Himachalene1 M6S, GC 1571 2 with their relative low threshold.13 Ethyl undecanoate1 M1S, GC 1672 1 Many of the esters found in arazá (E,Z)-α-Farnesene1 M2S, GC 1072 5 which seems to be strong contribu- Hexyl octanoate1 M0S, GC 1180 14 tors to tropical fruit aromas have also been found in a variety of other 1 Ethyl dodecanoate M8S, GC 1281 79 tropical and subtropical fruits. Ethyl HCexanoic acid M0S, G 1183 29 and hexyl esters similar to those Furfuryl hexanoate1 M5S, GC 1384 3 found in this study have been iden- tified as important contributors of 2-Hexanoyl furan1 G7C 1384 3 tropical fruit flavors in ,14 pas- 2-Phenylethyl propanoate1 M2S, GC 1085 30 sion fruit,15 guava,16 pineapple,17 lulo 2-Phenylpropyl acetate1 M6S, GC 1592 4 fruit,18 and mango.19 Ethyl tetradecanoate1 M7S, GC 2102 19 CONCLUSIONS OCctanoic acid M5S, G 2804 20 Volatile compounds were isolated 2-Phenylethyl benzoate1 M6S, GC 2905 7 from araza fruit (7.9 mg/kg of fresh Globulol1 M1S, GC 2606 21 fruit). In total, 27 esters, 20 terpenes, five alcohols, six carbonyls, five ac- 1 Spathulenol M0S, GC 2507 2 ids, three hydrocarbons, two lac- (E)-2-Hexenyl benzoate1 M8S, GC 2307 3 tones and two sulfur-compounds (E)-Cinnamyl acetate1 M9S, GC 2009 10 were identified. Of the 70 compo- nents identified, 53 are reported for γ-Eudesmol1 M5S, GC 2t13 the first time. Esters (54.8 % of the T-Cadinol1 M8S, GC 2313 8 total composition) were the most δ-Decalactone1 M5S, GC 2514 2 abundant compound class. Ethyl T-Muurolol1 M1S, GC 2815 5 octanoate, ethyl dodecanoate and ethyl decanoate were found to be the α 1 -Muurolol M5S, GC 2016 1 major constituents. Decanoic acid1 M8S, GC 2325 3 ACKNOWLEDGMENTS γ-Dodecalactone1 M6S, GC 2531 5 Grateful acknowledgements are Methyl (E)-9-octadecenoate1 M8S 2543 8 expressed to the Faculty of Sciences Dodecanoic acid1 M8S, GC 1163 4 of the University of the Andes for the financial support. We thank Jaime 1 Reported for the first time in this fruit. Campos for supplying the fruits 2 Identification: MS mass spectra, GC comparison of retention indices with standards. 3 Linear retention indices reported on HP-Innowax capillary column. used in this study. t Represents less than 10 µg/kg . BIBLIOGRAPHY 1. Do N. Ferreira S.A. Biometría de frutos de araça-boi (Eugenia stipitata 365 Revista CENIC Ciencias Químicas, Vol. 38, No. 3, 2007.

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