FLAVOUR AND FRAGRANCE JOURNALFlavour Fragr. J. 2002; 17: 401–403Published online in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/ffj.1116

Volatile constituents of star apple (Chrysophyllumcainito L.) from Cuba

Jorge Pino,1* Rolando Marbot2 and Aristides Rosado2

1 Instituto de Investigaciones para la Industria Alimenticia, Carretera del Guatao km 3 12 , La Habana 19200, Cuba

2 Centro Nacional de Investigaciones Cientificas, La Habana, Cuba

Received 16 October 2001Revised 10 January 2002Accepted 14 January 2002

ABSTRACT: The volatile constituents of the star apple (Chrysophyllum cainito L.) growing in Cuba were analysedby GC–MS. One hundred and four compounds were identified in the aroma concentrate, of which (E)-2-hexenal,1-hexanol, limonene, linalool, ˛-copaene and hexadecanoic acid were found to be the major constituents. Thepresence of many terpenic compounds is thought to contribute to the unique flavour of the star apple fruit.Copyright 2002 John Wiley & Sons, Ltd.

KEY WORDS: Chrysophyllum cainito L.; Sapotaceae; star apple; fruit volatiles; (E)-2-hexenal; 1-hexanol;limonene; linalool; ˛-copaene; hexadecanoic acid

Introduction

The star apple, locally called ‘caimito’, is the speciesChrysophyllum cainito L., which grows in many placesin Cuba. Probably native to Central America and theWest Indies, this fruit belongs to the botanical familySapotaceae. It is produced on an evergeeen tree growingto a height of about 20 m. Fruit maturation takes placein about 180 days. The fruits are globose, 5–8 cm indiameter, solitary; with external colour purple or lightgreen and internal colour purple or white. The soft fleshof the ripe fruit has a pleasant sweet flavour. It is usuallyeaten fresh and also in preserves and beverages. Sincethe volatile components of the star apple have not beenexamined to date, the objective of the present studywas to characterize the former in order to facilitate anunderstanding of what constitutes to unique aroma ofthis fruit.

Experimental

Materials and Isolation of the VolatileConstituents

Samples of ripe fruits of the variety Blanco werecollected from a home garden in Havana in April2001. A voucher specimen of the plant is deposited in

* Correspondence to: Jorge Pino, Instituto de Investigaciones para laIndustria Alimenticia, Carretera del Guatao km 3 1

2 , La Habana 19200,Cuba.

the Herbarium of the National Botanic Garden. Afteraddition of an internal standard (methyl undecanoate,2 mg), pulp (200 g) was blended with distilled water(800 ml) and simultaneously distilled and extracted for90 min in a Likens–Nickerson microapparatus with25 ml diethyl ether (previously redistilled and checkedas to purity). The volatile concentrate was dried overanhydrous sodium sulphate and concentrated to 0.6 mlon a Kuderna–Danish evaporator with a 12 cm Vigreuxcolumn and then to 0.2 ml with a gentle nitrogenstream.

Analysis of the Volatile Constituents

The extract was analysed by GC using a Hewlett-Packard6890 gas chromatograph equipped with a flame ion-ization detector (FID). The separations were performedusing an SPB-5 column (30 m ð 0.25 mm i.d., 0.25 µmfilm thickness, Supelco Inc., Bellefonte, PA). The ini-tial temperature was 60 °C (2 min) and the column wasthen programmed at 4 °C/min to 250 °C (20 min). Thecarrier gas was helium at a flow rate of 1 ml/min. Thetemperature of the injector and detector was 250 °C. Theinjection was made in the split mode (1 : 10 ratio). Lin-ear retention indices (LRI) were calculated against thoseof n-paraffins.1

GC–MS analyses were performed on a Hewlett-Packard series 6890 (series II) gas chromatograph linkedto a HP-5973 mass-selective detector. The chromato-graphic conditions were the same as those described forGC–FID. The detector was operated in electron impact

Copyright 2002 John Wiley & Sons, Ltd.

402 J. PINO, R. MARBOT AND A. ROSADO

Table 1. Volatile constituents of star apple

Constituents LRIa Means ofidentificationb

Concentration(mg/kg)

Acetaldehyde 435 A <0.01Ethanol 500 A 0.021-Propanol 568 A 0.01Diacetyl 612 A <0.01Ethyl acetate 615 A 0.031-Butanol 715 A <0.011-Penten-3-ol 719 C <0.01Acetoin 720 A 0.013-Methyl-1-butanol 736 A <0.01Pyridine 752 A 0.02(Z)-2-Pentenol 767 C <0.01Toluene 776 A <0.012,3-Hexanedione 786 A <0.01Hexanal 801 A 0.04Furfural 807 A 0.01Ethyl (E)-2-butenoate 835 B <0.01(Z)-2-Hexenal 841 B <0.01(E)-2-Hexenal 848 A 0.25(Z)-3-Hexen-1-ol 850 A <0.011-Hexanol 869 A 0.09Isopentyl acetate 876 A <0.01Styrene 880 C <0.01p-Xylene 884 A <0.01Heptanal 899 A <0.01Methional 909 C 0.01Methyl 2-hydroxy-2-methylbutanoate

923 C <0.01

Methyl hexanoate 933 A <0.01˛-Pinene 939 A <0.01Ethyl3-hydroxybutanoate

945 A 0.01

Ethyl (E)-tiglate 953 A <0.01Benzaldehyde 961 A <0.01Sabinene 976 A <0.01ˇ-Pinene 980 A <0.01Methyl 2-furoate 983 C <0.01Hexanoic acid 986 A <0.01Myrcene 991 A <0.012-Pentylfuran 991 C <0.01Ethyl hexanoate 996 A <0.01υ-3-Carene 1011 A <0.012-Acetylthiazole 1014 A <0.01p-Cymene 1026 A <0.01Limonene 1031 A 0.17Benzyl alcohol 1032 A <0.01(Z)-ˇ-Ocimene 1040 A <0.01Cyclohexyl acetate 1043 A 0.05Propylenzene 1048 C <0.01(E)-ˇ-Ocimene 1050 A <0.01Ethyl 2-furoate 1056 A <0.01�-Terpinene 1062 A 0.01Acetophenone 1065 A <0.011-Octanol 1070 A <0.01p-Tolualdehyde 1079 A <0.01Terpinolene 1088 A <0.01Methyl benzoate 1091 A <0.01Linalool 1098 A 0.09Nonanal 1102 A 0.012-Phenethyl alcohol 1110 A <0.01Dehydrosabina ketone 1117 B 0.01Methyl octanoate 1126 A <0.01Ethyl3-hydroxyhexanoate

1133 B <0.01

C10H18O 1142 — 0.01Menthone 1154 B 0.02(E)-2-Nonenal 1161 A <0.01Ethyl benzoate 1170 A 0.03Terpinen-4-ol 1177 A 0.01

Table 1. (Continued)

Constituents LRIa Means ofidentificationb

Concentration(mg/kg)

p-Cymen-8-ol 1183 A <0.01˛-Terpineol 1189 A 0.02Hexyl butanoate 1191 A <0.01Methyl chavicol 1195 A <0.01Ethyl octanoate 1196 A <0.01Decanal 1204 A <0.01Ethyl nicotinate 1218 C <0.01Benzothiazole 1221 A <0.012,3-Dihydrobenzofuran 1224 C 0.01Nerol 1228 A <0.013-Isopropylbenzal-dehyde

1234 A <0.01

Hexyl2-methylbutanoate

1247 B <0.01

p-Anisaldehyde 1252 A <0.01Geraniol 1257 A 0.01Ethyl salicylate 1267 A <0.01(E)-Anethole 1283 A 0.01Dihydroedulan I 1286 C <0.01Lavandulyl acetate 1289 B <0.01Thymol 1290 A <0.01Ethyl 6-methyl-2,4-heptadienoate

1296 B <0.01

4-Vinylguaiacol 1312 A 0.01Methyl decanoate 1326 A <0.01Benzyl butanoate 1345 A <0.014-Butan-4-olide 1369 C 0.01˛-Copaene 1376 A 0.13iso-italicene 1397 B <0.01cis-˛-Bergamotene 1415 B 0.02C15H24 1425 — 0.02(E)-ˇ-Farnesene 1458 A 0.01�-Muurolene 1477 A <0.01ar-Curcumene 1483 A 0.03Bicyclogermacrene 1494 B <0.01˛-Muurolene 1499 A 0.01ˇ-Bisabolene 1509 A <0.01υ-Cadinene 1524 A <0.01Dodecanoic acid 1568 A 0.01�-Cadinol 1640 A 0.01Tetradecanoic acid 1771 A 0.02Methyl hexadecanoate 1926 A <0.01Hexadecanoic acid 1973 A 0.11Octadecanoic acid 2172 A 0.01

a Retention index on SPB-5 column.b The reliability of the identification proposal is indicated by the following: A,mass spectrum and Kovats index agreed with standards; B, mass spectrum andKovats index agreed with literature data; C, mass spectrum agreed with massspectral database.Mass spectra of unknown compounds [m/z(rel. int. %)]:C10H18O, 93(100), 91(77), 77(50), 41(40), 43(40), 79(30), 117(29), 121(28),136(28).C15H24, 119(100), 93(53), 105(70), 91(38), 41(30), 79(27), 69(25), 121(20),161(13), 204(12).

mode (70 eV) at 230 °C. Detection was performed in thescan mode between 30 and 400 amu at a scan rate of 1.5scan/s.

Compounds were identified by comparing their spec-tra to those of the Wiley library or our IDENT library(Instituto de Investigaciones para la Industria Alimenti-cia, Cuba) and also by comparison of their GC Kovatsindex to those of standard compounds and data from theliterature.2,3

Copyright 2002 John Wiley & Sons, Ltd. Flavour Fragr. J. 2002; 17: 401–403

VOLATILE CONSTITUENTS OF CHRYSOPHYLLUM CAINITO 403

Results and Discussion

The volatile constituents of star apple fruit were obtainedby simultaneous steam distillation–solvent extractionand analysed by GC and GC–MS using fused silicacapillary columns. Table 1 summarizes the qualitativeand quantitative analyses of the fruit volatiles accordingto order of elution on the SPB-5 column. The yield oftotal volatiles, estimated by the addition of a measuredamount of internal standard to the pulp, was approxi-mately 1.54 mg/kg fruit pulp.

Among 120 constituents separated, 104 were eitherpositively or tentatively identified, all of them beingreported for the first time as volatile components of starapple. The chemical classes represented in the volatilesof the fruit were as follows. Terpenoids comprised thelargest class of volatiles (36.4%); the composition of theother classes of compounds was as follows: aldehydesand ketones, 20.1%; acids, 9.7%; esters, 7.8%; alcohols,7.1%; N-compounds, 1.3%; and others, 17.5%.

The major constituents found in star apple volatileswere (E)-2-hexenal (0.25 mg/kg), 1-hexanol (0.09 mg/kg), limonene (0.17 mg/kg), linalool (0.09 mg/kg),˛-copaene (0.13 mg/kg) and hexadecanoic acid(0.11 mg/kg).

Some compounds present, e.g. furfural and somefuranes, are probably degradation products of ascorbicacid and sugars. It has been reported that acid treat-ment and even distillation induce the oxidation of ascor-bic acid.4 Nevertheless, the concentrate was found, onappropriate redilution with water, to possess the charac-teristic star apple aroma.

As sensory evaluation was not carried out in thisstudy, it is not possible to say which of the identi-fied components contribute most to the flavour, but itis our opinion that the terpenoids should play an impor-tant role.

References

1. Majlat P, Erdos Z, Takacs J. Calculation and application ofretention indices in programmed temperature gas chromatography.J. Chromatogr. 1974; 91: 89–110.

2. MacLafferty FW, Staffer DB. The Wiley/NBS Registry of MassSpectral Data . Wiley: New York, 1989.

3. Adams RP. Identification of Essential Oil Components by GasChromatography/Mass Spectroscopy . Allured: Carol Stream, IL,1995.

4. Tatum JH, Shaw PE, Berry RE. Degradation products fromascorbic acid. J. Agric. Food Chem. 1969; 17: 38–40.

Copyright 2002 John Wiley & Sons, Ltd. Flavour Fragr. J. 2002; 17: 401–403