Chemical Composition Of The Essential Oil Of Cionura Erecta (Asclepiadaceae) Inflorescences
By Myrianthopoulos, Vassilios; Fokialakis, Nikolas; Melliou, Eleni; Mitaku, Sofia
The essential oil of the inflorescence of Cionura erecta (L.) Griseb. was analyzed by GC and GC/MS. Seventy-two components were identified. The major components of the oil were safranal (16.8%), (Z)-3-hexenyl benzoate (6.1%), heneicosane (5.7%) linalool (4.8%), linalool (4.8%) and tricosane (4.4%).
Key Word Index
Cionura erecta, Asclepiadaceae, essential oil composition, safranal.
Cionura erecta (L.) Griseb. (syn. Cynanchum erectum L., Marsdenia erecta (L.) R. Br.) is an unpleasant smelling plant with stems up to one meter and clusters of white flowers (1). It is widespread in the Mediterranean region and it inhabits wastelands, river gravels and maritime sands. Its poisonous properties are traditionally known since antiquity. It has been used to exterminate harmful animals and the name “Apocynon,” given to this plant by Dioscorides, refers to that particular usage (2). As part of our investigation of the essential oils of Greek flora (3-4) we report here the analysis of the essential oil of C. erecta inflorescences, which to our knowledge has never been reported earlier.
Plant material: The studied plant was collected during its flowering period in June 2000 at the side of the road connecting Psatha and Villia (Attiki region) at 300 m height. It was identified by Dr. E. Kalpoutzakis and deposited as a voucher specimen (sample no. P-K 009) at the Herbarium of the Laboratory of Pharmacognosy, University of Athens.
OtI distillation: Fresh plant inflorescence (500 g) was subjected to hydrodistillation for 3 h, with 3 L water, in a Clevenger- modified apparatus with a water-cooled oil receiver to reduce overheating artefacts. The distillation afforded O, ImI of a sharp smelling oil (yield 0,02%).
GC Analysis: The oil was first analyzed by GC-FID carried out on a Perkin-Elmer Clarus 500 gas Chromatograph, fitted with a HP 5MS 30m x 0.25mm x 0.25 m film thickness capillary column. The column temperature was programmed from 60-280C at a rate of 3C /min. The injector and detector temperatures were programmed at 230C and 300C, respectively. Helium was used as the carrier gas at a flow rate 1 mL/ min.
GCMS Analysis: CC analysis was carried out using a Hewlett- Packard 5973-6890 operating on EI mode (equipped with a HP 5MS 30m x 0.25mm x 0.25m film thickness capillary column). Helium was used as carrier gas (2mL/min).The initial temperature of the column was 60C and then it was heated to 280C at a 3C/min rate. GC/MS analyses were also performed on a Finnigan GCQ Plus ion trap mass spectrometer with an external ion source in both the EI and chemical ionization (CI) modes, using CH^sub 4^ as the CI ionization reagent and with the same column and conditions as above.
Identification of components: The identification of the components was based on comparison of their EIMS spectra and their retention indices obtained using n-alkanes (C^sub 9^-C^sub 25^) with computer library spectra Wiley 275 and literature (5). Additionally, the identity of all compounds was performed by comparison of the expected molecular weights with the results obtained from the CI spectra. The compounds 3,5 dimethyl1,2,4-trithiolane (6), methyl hexadecanoate (7), 4-vinylphenol (7), 2-amylfuran (8), dihydroedulan I (8), the theaspiranes (9), 2-ethylhexanol (10), hexadecanal (10) and β-isophorone (11), were identified by comparison of the RI values with those reported in the specified literature references.
Table I. Percentage composition of Clonura erecta inflorescence oil.
Results and discussion
The analysis of C. erecta oil led to the identification of seventy-two components, representing the 91.3% of the total. The major component was safranal (16.8%), while in relatively high percentages the following components were also identified: (Z)-S- hexenyl benzoate (6.1%), heneicosane (5.7%), Iinalool (4.8%), 3- hexenol (4.7%), tricosane (4.4%), nonanal (4.3%), geraniol (3.2%) and heptanal (3.4%).
The occurrence of sulphur-containing compounds was assumed before the analysis, due to the characteristic odor of the flowers of the plant. Three such compounds were identified (2,4,5-trimethyl thiazole, 5-ethyl-2,4-dimethylthiazole and 3,5-dimethyl-l,2,4 trithiolane) in relatively small amounts (0.2%, 0.1% and
Among the other constituents of the oil, some of them like the theaspiranes are not often encountered in the volatiles; bibliography. Up until 1990, the natural theaspirane appeared in literature as a mixture of two isomers (R and S). Since 1990, several studies describe the enantioresolution of four theaspirane isomers using multidimensional GC/MS (12-13). These four isomers in a DB-5 GC column are eluted as two pairs of enantiomers which have identical chromatographic data. The (2S.5R) and (2S.5R) pair of enantiomers has a retention index 1304 and the (2R.5S) and (2S.5R) pair has a retention index 1325. The rate of the enantiomers in each pair varies, depending on the natural source but complete absence of one of the enantiomers has not been described (9).
Another noteworthy point in the analysis, is the presence of three compounds which act as pheromones in certain insect species. Tetradecanal and hexadecanal are referred as constituents of the Lepidopteran family sex pheromone, and (Z)-tricosene as a potent sex pheromone and a promising attractant for luring the house fly Musca domestica (14-15).
Finally, safranal, the main constituent of the oil of the plant which has been reported to possess cytotoxic (16) activity, is found mainly in the stigmas of Crocus sativus or saffron (17). Taking into consideration the fact that it takes in excess of 70,000 C. sativus flowers to yield just one pound (0.45 kg) of saffron spice, C. erecta which is widespread, can be an alternative source for obtaining safranal.
1. T.G. Tutin, Flora Europaea. vol 3, pp. 73, Cambridge University Press: Cambridge, (1968).
2. H. Baumann, Greek wild flora and plant lore In ancient Greece, p. 124 Herbert Press, London, (1996)
3. N. Aligiannis, E. Kalpoutzakis, I. Chinou, S. Mitaku, E. Gikas and A. Tsarbopoulos, Composition and Antimicrobial Activity of the Essential oil of Five Taxa ofSlderltls from Greece. J.Agric.Food.Chem., 49, 811-815 (2001).
4. N. Foklalakis, P. Magiatisand S. Mitaku, Essential Oil Contituents of Valeriana italica and Valeriane tuberose. Stereochemlcal and Conformational Study of 15-Acetoxyvaleranone. Z.Naturforsch. 57c, 791-796 (2002).
5. R.P. Adams, Identification of Essential oil Components by Gas Chromatography/Mass spectrometry. Allured Publishing, Carol Stream, IL. (1995).
6. H.Weenen, W.Koolhaas and A. Apriyantono, Sulphur-Containing Volatiles of Durian Fruits (Durio zibethinusMurr.). J.Agric.FoodChem. 44, 3291-3293 (1996).
7. R. Boulanger, D. Chassagne and J. Crouzet, Free and Bound Flavour Components of Amazonian Fruits. 1 :Bacuri. Flav.Fragr.J., 14, 303-311 (1999).
8. E. Campeol, G. Flaminl, S. Chertconl, S. Catalane and R. Cremonini, Volatile Compounds from Three Cultivars of Olea europaea from Italy. J.Agric.Food Chem., 49, 5409-5411 (2001).
9. Q. Schmldt, G. Full, P. Wlnterhalter and P. Schreier, Synthesis and Enantiodifterentiation oflsomeric Theaspiranes. J.Agric.Food Chem., 40, 1188-1192 (1992).
10. D. Ansorena, O. Gimeno, I. Astiasaran and J. Bello, Analysis of Volatile Compounds by GC-MS of a dry fermented sausage: chorizo de Pamplona Foor Res.Internat., 34, 67-75 (2001).
11. K.R.Cadwallader, H.H. Baek and M.Cai, Characterization of Saffron Flavor by Aroma extract dilution analysis. In: Spices. Flavor Chemistry and Antioxldant Properties. Edits., S.J.Risch and C- T Ho, p 66-79, ACS Symposium Series 660, Amer.Chem.Soc., Washington, DC (1997).
12. E. Gulchard, A. Hollnagel, A. Mosandl and H. G. Schmarr, Stereoisomeric flavour compounds. Part XL. Stereodifferentiation of some chlral volatiles on apermethylatedp-cyclodextrlnphase. HRC &CC., 13, 299-301 (1990).
13. P.Werkhoff, S.Brennecke and W.Bretschnelder,Progress in the chirospecific analysis of naturally occurring flavour and fragrance compounds. Chem. Mikrobiol. Technol.Lebensm., 38, 452-455 (1991).
14. Dictionary of Natural Products. Chapman and Hall (1997).
15. J. Chapman, J. Knapp, P. Howse and D. Goulson, An evaluation of (Z)-9-tricosene and food odours for attracting house files, Musca domestics, to baited targets In deep-pit poultry units. Entomol.Experim.Applic., 89, 183-192(1998).
16. J. Escribano, G. L. Alonso, M. Coca-Prados and J. A. Femandez, Crocln, safranal and picrocrodn from saffron (Crocus sativus L) Inhibit the growth of human cancer cells In vitro. Cancer Lett., 100,23-30 (1996).
17. C. D. Kanakis, D. J. Daferera, P. A.Tarantills and M. G. Polissiou, Qualitative determination of volatile compounds and quantitative evaluation of safranal and 4-hydroxy-2,6,6-trlmethyl-1- cyclohexene-1-cart)oxaldehyde (HTCC) In Greek saffron. J.Agric.Food Chem., 52,4515-4521 (2004).
Vassilios Myrianthopoulos, Nikolas Fokialakis, Eleni Melliou and Sofia Mitaku*
Department of Pharmacognosy and Natural Products Chemistry, Faculty of Pharmacy,
University of Athens, Panepistimiopolis Zografou, 157 71 Athens, Greece
* Address for correspondence
Received: July 2005
\Revised: October 2005
Accepted: October 2005
Vol. 19, May/June 2007
1041-2905/07/0003-0266$14.00/0- 2007 Allured Publishing Corp.
Copyright Allured Publishing Corporation May/Jun 2007
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