Middle-East Journal of Scientific Research 11 (6): 808-813, 2012 ISSN 1990-9233 © IDOSI Publications, 2012

GC and GC/MS Analysis of Essential Oil of Five Species from Côte D’ivoire

1G.D. Diomandé, 11 A.M. Koffi, Z.F. Tonzibo, 1 G. Bedi and 2 G. Figueredo

1Laboratoire de Chimie Organique Biologique¸ UFR-SSMT, Université de Cocody, BP 582 Abidjan 22, Côte d’Ivoire 2Laboratoire de Chimie des Hétérocycles et Glucides, Université Blaise Pascale de Clermont Ferrand, Campus des Cézeaux, 63177 Aubière, France

Abstract: The leaves and of five Aframomum species, namely A. elliotii, A. strobilaceum, A. geocarpum, A. longiscarpum and A. sceptrum were subjected for hydrodistillation carried out with Clevenger apparatus type. Higher yields were found in the leaves varying between 0.28% and 0.42%, while the oil shown lower yields accounting for 0.13-0.19%. The results of the analysis of volatile oils by GC and GC/MS have showed 52 identified components with the total proportion ranged from 96.3to 97.9%. The chemical composition of the leaves oil was dominated by hydrocarbon compounds such as -pinene, -caryophyllene, -humulene, -selinene, -selinene and germacrene A. Meanwhile, the rhizomes oil characterized with oxygenated components, namely , linalool and caryophyllene oxide accompanied by a few hydrocarbon constituents.

Key world: Aframomum species Essential oil composition -pinene Linalool -caryophyllene 1,8-cineole

INTRODUCTION Biological investigations carried out on Aframomum species revealed antimicrobial, antifungal, analgesic, The Zingiberaceae constitute a family of terrestrial aphrodisiac, antioxidant and antiprotozoal properties rhizomal with over 1400 species distributed in over [8-11]. From this , non-volatile constituents have 50 genera [1]. They are mostly found in tropical areas been isolated and could be divided into four main groups, (Asia and Africa) [2]. In West and Central Africa of comprising labdane diterpenoids, flavonoids, the Zingiberaceae family are widespread in humid forest sesquiterpinoids and arylalkanoids [12-15]. Furthermore, regions. They are distributed among eight genera five of essential oil composition of Aframomum species has been which are indigenous or endemic (Aulotandra, , investigated; the literature reported the predominance of Kampferia, Reneilmia and Aframomum). The three others monoterpenoids, sesquiterpinoids and a few diterpenoids (Pheaeomeri, Zingiber and Curcuma) have been [17-20]. introduced. However, there is no report available in the literature The genus Aframomum occurring in this paper was on the description of essential oil for our selected species, represented in West and Central Africa by approximately namely A. elliotii (Bak.)K. Schum., A. strobilaceum (Sm.) 50 species that can be distinguished from the other genera Hepper, A. geocarpum Lock and Hall and A. by the generally large size. They are perennials and longiscarpum (Hook) K. Shum. Except for the rhizome oil aromatics when any part of the is crushed [3, 4]. of A. sceptrum (Oliv.et Hamb.) K. Shum collected in south Generally, Aframomum species are used for culinary of Côte d’Ivoire and more recently was reported as being preparations [5, 6]. This genus is wildly used in traditional rich in â-pinene (12.7%), caryophyllene oxide (10.0%) and medicine to treat several diseases; for certain species cyperene (6.0%) [9]. whole plant is used for treatment of the cough [5], Therefore, this paper reports the investigations of the the roots of Aframomum exscapum are taken in Côte chemical composition of the leaves and rhizome oils from d’Ivoire with citron as a purgative and anthelmintic [7]. these Aframomum species growing in Côte d’Ivoire.

Corresponding Author: Zanahi Félix Tonzibo, Laboratoire de Chimie Organique Biologique, UFR-SSMT, Université de Cocody, BP 582 Abidjan 22, Côte d’Ivoire. Tel: + (225)02773902. 808 Middle-East J. Sci. Res., 11 (6): 808-813, 2012

Table 1: the yields, localities, plant parts and oil color of selected Aframomum species. Plant species plant parts localities harvest date yield (v/w %) oil color Voucher specimen Reference number leaves 0,36 Pale yellow AKE Assi 12134 A. Elliotii rhizomes Dabou February 2008 0,17 yellow A. longiscarpum leaves 0,42 Pale yellow AKE Assi 9995 rhizomes Dabou February 2008 0,19 yellow A. geocarpum leaves 0,33 Pale yellow AKE Assi 12009 rhizomes Forêt de Yapo February 2008 0,13 yellow A. sceptrum leaves Tabou 0,28 Pale yellow AKE Assi 12967 rhizomes February 2008 0,15 Yellow A strobilaceum leaves Campus Cocody July 2008 0,3 Pale yellow AKE Assi 7358 Dabou: South of Côte d’Ivoire; Petit Yapo: South-East of Côte d’Ivoire; Tabou: South-West of Côte d’Ivoire; Campus de cocody: locality of Abidjan (South of Côte d’Ivoire.

METERIAL AND MATHODS Identification of Compounds: Compounds were identified by computer search using their mass spectra either with Plant Material: The Table 1 shows the different yields; the known components or published spectra [21] and by plant parts, harvest localities and voucher specimen comparison of their retention indices with those of known reference number of our selected Aframomum species, compounds [22]. namely A. elliotii (Bak.)K. Schum., A. strobilaceum (Sm.) Hepper, A. geocarpum Lock and Hall and A. RESULTS AND DISCUSSION longiscarpum (Hook) K. Shum. and A. sceptrum (Oliv.et Hamb.) K. Shum. The voucher specimens were The hydrodistillation of the leaves and rhizomes of deposited with the Centre National Floristique of Abidjan the five Aframomum species collected from different (Côte d’Ivoir. localities of Côte d’Ivoire gave yellowish oil. The Table 1 showed highly yields in the leaves of Aframomum species Extraction of Essential Oil: Each sample (500 g by fresh (0.33%-0.42%), with slight yields obtained from the material) of the 5 species was submitted to hydroditillation rhizome oils accounting for 0.13-0.17%. The results of the for 3 h, using a Clevenger-type apparatus. The oils qualitative and quantitative oil analyses were listed in obtained by decantation were dried over anhydrous order of elution in the DB-5 column. Generally, 49 sodium sulfate and then stored in sealed vials protected components were identified; accounting for 96.3-97.9% of from the light at –20°C before GLC analysis. volatile constituents. The chemical composition of the leaves oil obtained from Aframomum species showed Analysis of the Essential Oils certain homogeneity, characterized by the predominance GC: The essential oils were analysed on a AGILENT gas of hydrocarbon components (48.5-95.4%), with highly chromatograph Model 6890, equipped with a DB5 MS proportion of -pinene (11.3-44.3%) being followed by column (30m X 0.25mm; 0,25 m), programming from 50°C -caryophyllene (24-58.1%). Meanwhile, the composition (5 min) to 300°C at 5°C/min, 5 min hold. Hydrogen as of rhizome oils was constituted mainly by oxygenated carrier gas (1.0 ml/min); injection in split mode (1:60); components, due to the high amounts of eucalyptol injector and detector temperature were 280 and 300°C (11.3-17.1%) and linalool (8.8-45.3%). Nevertheless, a respectively. The essential oil was diluted in hexane: 1/3 difference was noted in the composition of rhizome oil obtained from A. sceptrum, with the predominance of GC/MS: The essential oils were analysed on a AGILENT sesquiterpene hydrocarbons, this oil was characterized gas chromatograph Model 7890, coupled to a AGILENT by high amounts of -caryophyllene, -cubebene and MS model 5975, equipped with a DB5 MS column -elemene. As regard to the main components of the (20m X 0,20mm, 0,20 m), programming from 50°C (5 min) chemical composition of our samples, it could be divided to 300°C at 8°C/min, 5 min hold. Helium as carrier gas into several types of oils. (1.0 ml/min); injection in split mode (1:250); injector and Concerning the leaves, Table 2 shown the oils rich in detector temperature were 250 and 280°C respectively. combination of -pinene and -caryophyllene especially The MS was mode electron impact at 70 eV; electron in A. elliotii and A. longiscarpum with (44.3%; 26.2%) multiplier, 1500 V; ion source temperature, 230°C; mass and (42.6%; 25.4%) respectively. When, the oil of spectra data were acquired in the scan mode in m/z range A. geocarpum was characterized by -pinene (11.3%), 33-450. -caryophyllene (58.1%) and -humulene (15%).

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Table 2: chemical composition of essential oils of the selected Aframomum species from Côte d`Ivoire A.elliotti A.strobilaceum A. geocarpum A. longiscarpum A. sceptrum ------Method of KI Compounds LRL L R L R L R identification 934 _-_ Pinene 5.1 2 1.4 1.4 2.3 5.2 5.3 5.8 0.8 KI,MS 974 Sabinene 0.5 - - - 1.5 0.7 0.4 3.2 - KI,MS 979 -Pinene 44.3 16.3 2 11.3 22.7 42.6 40.2 15.1 7.8 KI,MS 990 Myrcene - 0.6 - - - - 0.6 0.7 - KI,MS 1026 p - Cymene - - - - 2.3 - - - - KI,MS 1030 Limonene 0.8 3.5 0.3 - 2.6 0.7 3 2.4 - KI,MS 1034 1,8 -Cineole 1.1 17.1 1.1 - 5.1 - 11.3 12.1 - KI,MS 1100 Linalool 3.8 45.3 0.3 - 8.8 4.5 27.4 - - KI,MS 1144 trans Pinocarveol --- - 1 - - - - KI,MS 1150 Camphor --- - 1 - - - - KI,MS 1165 Borneol - - - - 2.6 - - - - KI,MS 1183 Terpinen-4-ol - - - - 3.7 - - - - KI,MS 1198 -Terpineol 1.4 7 - - 5.1 1.6 4.2 - 0.7 KI,MS 1286 Bornyl actate 2.6 - 0.2 - - 0.6 - - 0.8 KI,MS 1325 Myrtenyl acetate 0.8 1 - 1.7 1.1 3.4 1.3 3.8 1.5 KI,MS 1338 _-_Elemene ------0.5 10.4 KI,MS 1349 -Cubebene - - 0.2 - - - - - KI,MS 1379 _-_Copaene - - 1.4 0.3 - - - - 0.8 KI,MS 1387 _-_Bourbonene 0.6 - - - - 0.8 - - - KI,MS 1391 - Cubebene 0.8 - 4.1 0.5 - 1.3 - KI,MS 1407 Cyperene --- - 11.8 - - - 1.5 KI,MS 1424 -Caryophyllene 26.2 2.2 31.6 58.1 3.3 25.4 3.1 KI,MS 1435 - Copaene ------0.8 - KI,MS 1438 - Guaeine - - 0.2 ------KI,MS 1453 (E) -_ - Farnesene - - 0.9 ------KI,MS 1460 -Humulene 2.1 - 3.8 15 0.8 2.3 - 10.1 6.7 KI,MS 1464 allo Aromadendrene - - 0.3 ------KI,MS 1474 5-epi-Aristolochene 1.2 - - - - 1.5 - - 2.5 KI,MS 1476 -Chamigrene - - 0.5 ------KI,MS 1479 _- Muurolene ------1.7 KI,MS 1485 Germacrene D 0.8 - 1 0.8 0.9 1.4 - 1.5 KI,MS 1488 Aristolochene - 1 ------2.3 KI,MS 1490 -Selinene 0.6 - 15.8 1.1 - 1.5 - 0.3 4 KI,MS 1496 Valencene ------1.8 KI,MS 1500 -Selinene 0.7 - 10.9 0.6 - 1.7 - 0.5 3.6 KI,MS 1506 - Bisabolene - - 2.1 --- - - KI,MS 1513 Germacrene A - - 10.8 ---- KI,MS 1521 - Cadinene - - 0.5 ------KI,MS 1525 Calamenene trans - - 2 0.7 - - - 0.9 KI,MS 1551 Elemol - - - 2.5 0.7 - - 3.3 1.5 KI,MS 1562 (E)-Nerolidol - 0.7 1.6 0.5 - - - KI,MS 1578 Spathulenol 1.1 - - - - 0.9 - - - KI,MS 1588 Caryophyllene oxide 1.2 0.5 3.5 1.1 10.5 - 1.1 1.5 4.8 KI,MS 1616 Humulene epoxide II - - 0.3 - 1.4 - - - 0.9 KI,MS 1639 - Eudesmol - - - 1 1,6 - - 0.8 - KI,MS 1643 Caryophylla -4(12) 1 - 0.5 - 0.9 0.8 - - 0.8 KI,MS 8(13)-diene -5-_ -ol 1656 - Eudesmol - 0.2 - 2 2.1 0.8 - - 1 KI,MS 1661 Intermedeol 0.7 0.4 0.2 - 1.8 - - 1.8 - KI,MS Monoterpene hydrocarbons 50.7 22.4 3.7 12.7 31.4 49.2 49.5 27.2 8.6 Oxygenated monoterpenes 9.7 70.4 1.6 1.7 28.4 10.1 44.2 15.9 3 Sesquiterpene hydrocarbons 33 3.9 87.7 76.4 17.5 35.9 3.1 46.3 75.5 Oxygenated sesquiterpenes 4 1.1 4.5 7.1 19 2.5 1.1 8.1 9.7 Total 97.4 97.8 97.5 97.9 96.3 97.7 97.9 97.5 96.8 L : leaves ; R : rhizomes, KI: Kovats Indices on DB5 column MS: Mass Spectrometry

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1,8-cineole (12.1%) was added to -pinene (15.1%), rhizome oil respectively. In a comparative approach to -caryophyllene (31.3%) and -humulene (10.1%) chromatographic profile of volatile oils from these species, to constitute the chemotype of the leaves oil from it is noteworthy that the selected biosynthesis of major A. sceptrum. -caryophyllene (31.6%), -selinene (15.8%), components leading to the formation of chemotypes was -selinene (10.9%) and germacrene A (10.8%) slightly influenced by extrinsic factor such as soil, climate, characterized the oil obtained from A. strobilaceum. elevation and geographical origin. Then, as regard to the The analyses of the oils from the rhizome of A. elliotii predominance of -pinene and/or -caryophyllene and in showed a predominance of -pinene (16.3%), 1,8-cineole addition with their oxygenated derivatives in the volatile (17.1%), linalool (45.3%) accompanied by -terpineol oils of numerous species, it could find a chemical stability (7%). While, the chemotype of the oil obtained from through Aframomum genus. A. geocarpum was constituted by -pinene (22.7%), linalool (8.8%), cyperene (11.8%) and caryophyllene ACKNOWLEDGEMENTS oxide (10.5%). From the rhizome oil of A. longiscarpum, -pinene (40.2%), 1,8-cineole (11.3%) and linalool (27.4%) We acknowledge Prof. Aké ASSI and the Centre were described as major components. This combination National Floristique (CNF) de Côte d’Ivoire for their showed strikingly similarity with the chemotype of contributions in the botanical identification of A. elliotii. Finally, the rhizome oil from A. sceptrum was Aframomum species. constituted mainly by -elemene (10.4%), -cubebene (13.3%) and -caryophyllene (24%), this chemotype was REFERENCES different from this has been cited by Cheikh et al [9], which is probably due to the geographical influence. 1. Hepper, F.N., 1996. Flora of West Tropical Africa, The predominance of -pinene and -caryophyllene Published on behalf the government of Nigeria, in our oils is in good agreement with the literature reports. Ghana, Sierra-Leone and Gambia, London, pp: 3. In fact, it was found the highest amounts of -pinene in 2. Koechlin, J., 1965. Flore du Cameroun, Scistaminales. the leaves oil from several Aframomum species growing in Museum National d’histoire Naturelle, Paris. 4: 43. different regions of Africa, for example, A. pruinosum, 3. Knott, C., 1998. Orangutans in the wild. National A. citratum, A. hanburyi, A. danielli, A. giganteum, geographic Magasin, 194: 30. A. hanbury and A. latifolium [23-27]. 4. Perry, L.M., 1980. Medicinal plants of East and South On the other hand, the chemotypes dominated by East Asia. MIT Press. -caryophyllene have been also reported in the leaves oil 5. Adjanohoun, E. and A.L. Aké, 1979. Contribution au of A. corrorima, A. angustifolium, A. auriculatum and recensement des plantes médicinales de Côte A. melegueta [28-30]. D’Ivoire, Centre National de Floristique. Comparing the rhizome oil composition reported in 6. Bouquet, A., 1969. Féticheurs et Médecines literature, in addition with our samples, variability in traditionnelles du Congo (Brazzaville): Zingibéracées, chemical composition can be found. Very few studies Mémoire ORSTOM, 36: 128. reported high content of oxygenated constituents, as 7. Fasoyio, S.B., and Adegoke, G.O. (2007). caryophyllene oxide, (E)-labda-8 (17), 12-diene-15, 16-dial, Phytochemical characterization and the antimicrobial intermedeol, carotol, spathulenol, eudesmol, -biotol, property of Aframomum danielli extract. African J. kougol and 1,8-cineole [17, 31-33]. Meanwhile, to our Agricultural Research, 2(3): 76-79. knowledge linalool presented in our samples have never 8. Fasoyiro, S.B., G.O. Adegoke and O.O. Idowu, 2006. been described in the rhizome oil of Aframomum species. Characterization and partial purification of antioxidant component of ethereal fractions of Aframomum CONCLUSION danielli. World J. Chemistry, 1(1): 1-5. 9. Cheikh, Z.A., M. Adiko, S. Bouttier, C. Boriesa, The present paper shows the result of analysis of T. Okpekond, E. Poupona and P. Champy, 2011. volatile oils from five Aframomum species, to our Composition and Antimicrobial and Remarkable knowledge only the rhizome oil of A. sceptrum has been Antiprotozoal Activities of the essential oil of reported with chemical difference in comparison with our rhizomes of Aframomum sceptrum K. Schum. sample. The predominance of hydrocarbon and (Zingiberaceae), Chemistry and Biodiversity, oxygenated compounds was noted in the leaves and 8: 658-667.

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