Compositional characteristics of the essential oil of Artemisia campestris var. glutinosa

Compositional characteristics of the essential oil of Artemisia campestris var. glutinosa

Biochemical Systematics and Ecology 30 (2002) 1065–1070 www.elsevier.com/locate/biochemsyseco Compositional characteristics of the essential oil of A...

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Biochemical Systematics and Ecology 30 (2002) 1065–1070 www.elsevier.com/locate/biochemsyseco

Compositional characteristics of the essential oil of Artemisia campestris var. glutinosa Fabien Juteau a, Ve´ronique Masotti a,∗, Jean-Marie Bessie`re b, Josette Viano a a

Laboratoire Dynamique et Ressources du Ve´ge´tal, E.A. 2202-Biodiversite´—Universite´ de Provence, UFR DENTES et SVTE, case 17, 3 place Victor Hugo, F-13331 Marseilles cedex 3, France b Ecole Nationale Supe´rieure de Chimie de Montpellier, CNRS URA 1193, 8 rue Ecole Normale, F-34296 Montpellier, France Received 21 November 2001; accepted 22 January 2002

Abstract The chemical variations of the essential oil from the aerial parts of Artemisia campestris var. glutinosa have been studied. Plant material has been harvested at each phenological status (vegetative, before anthesis, full flowering and seed-bearing). Analysis by GC and GC/MS of the essential oils have allowed to identify 51 components. The main components were γterpinene, capillene, 1-phenyl-2,4-pentadiyne, spathulenol, methyleugenol, p-cymene and βpinene. Aromatic polyacetylens have been characterized for the first time in this species. Flowering involves an increase of these compounds in the essential oil.  2002 Elsevier Science Ltd. All rights reserved. Keywords: Artemisia campestris var. glutinosa; Asteraceae; Essential oil composition; Phenology; γ-Terpinene; Capillene; 1-Phenyl-2,4-pentadiyne

1. Introduction The present study reports on the volatile constituents isolated from the aerial parts of Artemisia campestris L. var. glutinosa (Gay ex Bess.) Y.R. Ling over several phenological stages. Commonly known as ‘field wormwood’, this taxon belongs in



Corresponding author. Tel.: +33-4-91-10-62-61; fax: +33-4-91-10-63-66. E-mail address: [email protected] (V. Masotti).

0305-1978/02/$ - see front matter  2002 Elsevier Science Ltd. All rights reserved. PII: S 0 3 0 5 - 1 9 7 8 ( 0 2 ) 0 0 0 5 2 - 2

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the genus Artemisia (family Asteraceae), to the Dracunculus section which also contains A. capillaris (oriental wormwood) and A. dracunculus (tarragon). A. campestris var. glutinosa (syn. A. glutinosa Gay ex Bess; A. campestris ssp. glutinosa Gay ex Bess.) is a perennial undershrub widespread all over Europe, from Siberia to Great Britain and in Northern Africa. In France, this polymorphic species is present at altitudes ranging from sea level to 1800 m, throughout open and sandy places, but particularly on maritime sands of the Mediterranean area (Tutin et al., 1976). Numerous studies in the literature have reported the composition of oils isolated from various species of Artemisia. Volatile constituents of A. campestris var. glutinosa have been identified: the major constituents are reported as ar-curcumene, caryophyllene oxide, p-cymene, β-pinene and germacrene D (De Pascual-Teresa et al., 1981a), or β-pinene, germacrene D and bicyclogermacrene (Bellomaria et al., 2001). 2. Materials and methods 2.1. Plant material Aerial parts of A. campestris var. glutinosa were harvested in the Camargue (50 km west of Marseilles, southern France), respectively in May (vegetative plants) August (before anthesis), September (full flowering plants) and November (seedbearing plants) of 2000. The plants were gathered at sea level, in a sandy area (dune) just above a temporary salt marsh. A voucher specimen (MARS-2000.4) is deposited in the herbarium of the University of Provence. The aerial parts were harvested on numerous representative plants, early in the morning, and the material was taken immediately to the laboratory to be shade-dried at ambient temperature, with ventilation. Drying time was approx. 72 h. 2.2. Isolation of the essential oil Dried material was powdered in a Tecator Cyclone Mill (mesh width 1 mm) and 100 g were immediately hydrodistillated in a Clevenger type apparatus for 2 h (AFNOR, 1986). The yields are based on dry weight of each sample. The yields decreased from vegetative (1.4%), blooming, and full-flowering plants (1.1%), to seed-bearing plants (0.5%). The essential oil was stored at 4 °C in the dark, until the moment of analysis. 2.3. Gas chromatographic analysis Capillary gas chromatography was carried out using a Varian (Model 3900GC) chromatographic system with a flame ionisation detector (FID), equipped with a CP SIL 8CB fused silica capillary column (30 m × 0.25 mm, 0.25 µm film thickness). Oven temperature was programmed from 50 to 220 °C at 3 °C/min, after an isothermal step at 50 °C for 2 min. The carrier gas was He, with a flow rate of 0.5

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ml/min. Injector and detector were heated to 220 and 230 °C respectively. The injection volume was 0.1 µl for each sample. 2.4. Gas chromatography and mass spectrometry Analyses were carried out on a Hewlett-Packard (Model, 5790) capillary gas chromatograph quadrupole mass spectrometry system fitted with a DB5 fused silica capillary column (50 m × 0.2 mm, 0.25 µm film thickness). Chromatographic conditions were the same as mentioned above, the mass spectrometer was operated at 70 eV. Component identification was carried out by comparing with authentic reference compounds, spectrometric electronic libraries (Wiley 138, NBS 75K), published mass spectra (Adams, 1995) and retention indices (Jennings and Shibamoto, 1980).

3. Results and discussion The components of the essential oils are reported in Table 1. The majority of these compounds belong to the hydrocarbon fraction, with percentages ranging from 94% in the vegetative stage, to 90% before anthesis, 87% in the flowering stage and 63% in the seed-bearing stage. Among these hydrocarbon fractions, the predominant compounds were found to be monoterpenes in the vegetative stage oils and aromatic compounds in the seed stage. In the flowering stages oils (before anthesis and full flowering) the relative proportion of aromatic compounds and monoterpenes was similar. The oxygenated fraction is mainly composed of sesquiterpenes, and increases in the essential oil all the way through phenological cycle, from traces in the vegetative stage, 3% in the flowering stages (bud and full) and 17% in the seed stage. Qualitatively, the oils obtained from the different phenological stages were found to have similar compositions: the main compounds were γ-terpinene, capillene, 1phenyl-2,4-pentadiyne, spathulenol, methyleugenol, p-cymene and β-pinene. It should be noted that γ-terpinene was more abundant in the vegetative stage oil (47%) than in flowering plant oils (27% and 21%) and seed stage oil (1%); capillene was lower in the vegetative stage oil (9%), than in the flowering stage oils (27% and 22%) and the seed stage oil (33%). 1-phenyl-2,4-pentadiyne was abundant in all of the oils examined (16–27%), and his rate did not vary during the phenological cycle. The level of the other main compounds (spathulenol, methyleugenol, p-cymene and β-pinene) did not show significant variations during the phenological stages. Only in plants in seed was it possible to find 1-phenyl-2,4-pentadiynone (6%), the ketone of 1-phenyl-2,4-pentadiyne. Thus, a high proportion (36–55%) of the four essential oils was constituted by acetylenic compounds (capillene, 1-phenyl-2,4-pentadiyne and 1-phenyl-2,4pentadiynone). Only capillene and his ketone capilline had previously been identified in a genus other than Artemisia (Santolina rosmarinifolia, in De Pascual-Teresa et al., 1981b; Pala-Paul et al., 2001). In Artemisia, these compounds were previously identified in the essential oils of A. capillaris (Harada and Wasaki, 1982; Yano, 1983) and A. dracunculus (Pappas and Sturtz, 2001), both members of the Dracun-

IRa 936 973 976 989 1013 1022 1028 1028 1037 1047 1060 1087 1161 1174 1178 1180 1196 1198 1238 1255 1290 1304 1307 1384 1386 1407 1426 1445 1453

Compounds

α-Pinene Sabinene β-Pinene Myrcene α-Terpinene p-Cymene Limonene β-Phellandrene (Z)-β-Ocimene (E)-β-Ocimene γ-Terpinene Terpinolene Umbellulone Borneol Terpinene-4-ol p-Cymene-8-ol Estragol α-Terpineol (Z)-3-hexenyl isovalerate Piperitone 1-Phenyl-2,4-pentadiyne Thymol Carvacrol α-Copaene Geranyl acetate O-methyleugenol β-Caryophyllene Aromadendrene α-Himachalene

Table 1 Composition of the essential oil of A. campestris var. glutinosa

0.1 – 3.7 0.3 0.2 1.7 1.0 – 1.9 1.5 46.5 0.5 – – – – 0.9 – – – 26.9 – – trc – 4.5 – – –

Vegetative

Phenological stage

0.1 0.1 1.8 0.3 0.2 4.5 1.3 – 2.3 1.7 26.5 0.1 – 0.1 0.1 – – 0.6 0.2 – 19.1 0.1 – 0.1 0.1 4.9 0.1 0.1 0.1

Bud –b – 0.3 0.1 0.1 2.9 0.7 – 1.1 1.4 20.8 0.3 0.1 – 0.2 – 0.8 – 0.2 – 29.7 0.1 – 0.2 0.1 6.6 0.1 0.1 0.1

Flower – – – – – 2.9 – 0.4 – 1.2 1.4 – – – 0.4 0.2 0.6 – 0.4 0.4 16.2 0.4 0.4 0.1 0.3 4.7 0.3 – 0.7

Seed

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c

b

a

1461 1469 1478 1484 1485 1487 1500 1506 1510 1515 1524 1561 1575 1578 1579 1586 1602 1611 1625 1630 1640 1665

Retention index on CP SIL 8CB and according to n-paraffins. Not detected. Traces (⬍0.1%).

(E)-β-Farnesene γ-Himachalene γ-Muurolene Germacrene D α-Curcumene γ-Curcumene Capillene α-Murolene (E,E)-α-Farnesene γ-Cadinene δ-Cadinene (E)-Nerolidol Spathulenol Caryophyllene oxide Globulol Salvialenone Humulene oxide 1-Phenyl-2,4-pentadiynone Epi-α-cadinol α-Muurolol α-Cadinol α-Bisabolol Total identified

0.1 – – 0.2 0.2 0.8 8.9 – 0.1 – – – – – – – – – – – – – 99.8

1.2 – – 0.6 0.4 0.8 27.2 – 0.2 0.3 0.3 0.2 2.3 – 0.4 – – – 0.1 – 0.1 – 98.9

0.7 – – 0.7 1.0 2.4 22.3 0.2 0.9 0.2 0.3 0.6 1.7 – 0.3 0.1 0.1 – 0.3 – 0.1 0.1 98.4

1.8 0.7 0.5 – 3.3 – 33.1 0.2 0.8 0.8 0.6 1.7 11.3 1.2 – 0.5 – 6.0 – 0.7 0.9 0.9 95.8

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culus section, but never in A. campestris, or any other Artemisia species. Greger (1979), proposed that aromatic polyacetylens are characteristics of species of the Dracunculus section of the Artemisia genus, and this finding supports his argument. In conclusion, the presence of aromatic polyacetylens chemotaxonomically characterise A. campestris var. glutinosa oils. Chemical variations of the essential oil composition during the phenological cycle are mainly quantitative, involving γ-terpinene and capillene. As capillene is known to be synthesised by fatty acid metabolism (from linoleic acid), and γ-terpinene originates from isoprenic condensations (from isopentenylpyrophosphate), these compounds do not share the same biosynthetic pathway. It seems that initiation of flowering gives priority to the fatty acids pathway. Further studies have been started with plants cultivated ex-situ, in order to point out the influence of environmental conditions on the composition of essential oils.

References Adams, R.P., 1995. Identification of essential oil components by gas chromatography/mass spectroscopy. Allured Publishing Corporation. Association Franc¸ aise de Normalisation (AFNOR), 1986. Huiles essentielles 5e e´ dition. AFNOR, Paris. Bellomaria, B., Valentini, G., Biondi, E., 2001. Chemotaxonomy of Artemisia variabilis Ten. and A. campestris L. spp. glutinosa (Ten.) Briq. et Cavill. (Asteraceae) from Italy. J. Essent. Oil Res. 13, 90–94. De Pascual-Teresa, J., Bellido, I.S., Gonzalez, M.S., Alberdi, M.R., Muriel, M.R., Hernandez, J.M., 1981a. Essential oil of Artemisia campestris, Linnaeus, subspecies glutinosa. Riv. Ital. EPPOS 63, 205–208. De Pascual-Teresa, J., Gonzales, M.S., De Dios, M.A., San Segundo, J.M., Vicente, S., Bellido, I.S., 1981b. Essential oil of Santolina rosmarinifolia Linnaeus. Riv. Ital. EPPOS 63, 355–356. Greger, H., 1979. Aromatic acetylenes and dehydrofalcarinone derivatives within the Artemisia dracunculus group. Phytochemistry 18, 1319–1322. Harada, R.I., Wasaki, M., 1982. Volatile components of Artemisia capillaris. Roy. Soc. Edin. Biol. Sci. B 21, 2009–2011. Jennings, W., Shibamoto, T., 1980. Qualitative Analysis of Flavor and Fragrance Volatiles by Glass Capillary Gas Chromatography. Academic Press, New York. Pala-Paul, J., Perez-Alonso, M.J., Velasco-Negueruela, A., Pala-Paul, R., Sanz, J., Conejero, F., 2001. Seasonal variation in chemical constituents of Santolina rosmarinifolia L. ssp. rosmarinifolia. Biochem. Syst. Ecol. 29, 663–672. Pappas, R.S., Sturtz, G., 2001. Unusual alkynes found in the essential oil of Artemisia dracunculus L. var. dracunculus from the Pacific northwest. J. Essent. Oil Res. 13, 187–188. Tutin, T.G., Heywood, V.H., Burges, N.A., Moore, D.M., Valentine, D.H., Walters, S.M., Webb, D.A., 1976. Flora Europaea. Cambridge University Press, Cambridge. Yano, K., 1983. Insect antifeeding phenylacetylenes from growing buds of Artemisia capillaris. J. Agric. Food Chem. 31, 667–668.