- Email: [email protected]
Essential oil composition of four Psiadia species from Reunion Island: A chemotaxonomic study
Biochemical Systematics and Ecology 33 (2005) 705e714 www.elsevier.com/locate/biochemsyseco
Essential oil composition of four Psiadia species from Reunion Island: A chemotaxonomic study Anne Gauvin *, Jacqueline Smadja Laboratoire de Chimie des Substances Naturelles et des Sciences des Aliments, Faculte´ des Sciences et Technologies, Universite´ de la Re´union, 15 Avenue Rene´ Cassin, BP 7151, St Denis Messag Cedex 9, La Re´union 97 715, France Received 5 May 2004; accepted 24 December 2004
Abstract The essential oils of four wild species of Psiadia (Psiadia anchusifolia, Psiadia argentea, Psiadia boivinii, Psiadia salaziana; Asteraceae) endemic to Reunion Island were obtained by hydrodistillation and subjected to detailed GC/MS analysis in order to determine possible similarities among them and also the differences in their chemical compositions depending on the stage of the life cycle (vegetative and flowering). A total of 57 compounds were identified including two unusual components 7,7-dimethyl-2-methylenebicyclo[3.3.1]heptan-6-ol acetate (1) and 6,6,8,9-tetramethyltricyclo[3.3.3.0]-undec-7-en-2-ol (2) which, until now, have been found only in species of the genus Psiadia. For P. anchusifolia, P. argentea and P. salaziana, the qualitative and quantitative composition of the oils appeared to be constant in the different
* Corresponding author. Tel.: C33 262 262 938197; fax: C33 262 262 938183. E-mail address: [email protected] (A. Gauvin). 0305-1978/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.bse.2004.12.013
706
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
stages of their development. In contrast, considerable differences were found to exist in the composition of essential oils of P. boivinii. Ó 2005 Elsevier Ltd. All rights reserved. Keywords: Psiadia anchusifolia; Psiadia argentea; Psiadia boivinii; Psiadia salaziana; Asteraceae; Essential oil composition; 7,7-Dimethyl-2-methylenebicyclo[3.3.1]heptan-6-ol acetate; 6,6,8,9-Tetramethyltricyclo[3.3.3.0]-undec-7-en-2-ol; Chemotaxonomy
1. Introduction The genus Psiadia Jacq. (Asteraceae) includes more than 60 species (Bosser et al., 1993; Scott, 1991). One species can be found in Sri Lanka and Southern India; several species are native to Arabia, East and South Africa, with a single species, now extinct, formerly found in St Helena. This genus is also particularly well represented in Madagascar with 28 species and in the Mascarene Islands (Reunion, Mauritius, Roderick) with 26 species. Psiadia species are of particular interest as some of them are commonly used in traditional pharmacopoeia. Therefore, many papers about the secondary metabolites of Psiadia species can be found in the literature (Abou-Zaid et al., 1991; Al-Yahya et al., 1987; Canonica et al., 1967, 1969a,b; El-Domiaty et al., 1993; El-Feraly et al., 1990; Fortin et al., 2001; Jakobsen et al., 2001; Juma et al., 2001; Midiwo et al., 1997; Mossa et al., 1992; Robin et al., 1998; Wang et al., 1989a,b, 1992). The volatile constituents of a few species have also been examined, for example, Psiadia altissima (Ramanoelina et al., 1994), Psiadia arabica (Mekkawi et al., 1984; Mossa et al., 1983), Psiadia arguta (Gurib-Fakim et al., 2000), Psiadia lithospermifolia (Gurib-Fakim et al., 1995), Psiadia salviifolia (Dennis, 1973), and Psiadia viscosa (Gurib-Fakim et al., 1995). As part of our research on the aromatic Psiadia of the Mascarenes (Gurib-Fakim et al., 2000; Gauvin et al., 2004), we report on the chemical composition of the volatile oils obtained from Psiadia anchusifolia, Psiadia argentea, Psiadia boivinii, and Psiadia salaziana collected during the flowering and vegetative phases in Reunion Island, for comparison and for chemotaxonomic purposes. As far as we know, the volatile constituents of these four Psiadia species endemic to Reunion Island, have not been previously investigated.
2. Material and methods 2.1. Plant material The plant materials, collection places, dates and plant life-cycle stages (vegetative; flowering) are given in Table 1. The plants were identified by Pr. Dominique Strasberg and voucher specimens have been deposited in the herbarium of Reunion Island (REU).
707
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714 Table 1 Plant material, collection places, dates, life-cycle stages and oil yields of Psiadia species Species
Voucher number
Part
Collection places (altitudes)
Date
Life-cycle stages
Oil yield (%)
P. anchusifolia
DIV18
Leaves
April 2000 November 2001
Vegetative Flowering
0.089 0.088
P. argentea
DIV19
Aerial parts
April 2000 November 2001
Vegetative Flowering
0.020 0.015
P. boivinii
DIV17
Leaves
April 2000 November 2001
Vegetative Flowering
0.002 0.008
P. salaziana
DIV16
Leaves
Reunion Island: volcano area (2300 m) Reunion Island: volcano area (2300 m) Reunion Island: forest of Belouve-Be´bour (1500 m) Reunion Island: volcano area (2300 m)
April 2000 November 2001
Vegetative Flowering
0.120 0.065
2.2. Sampling and essential oil extraction Sampling of the four species of Psiadia was done by a randomised collection of 10e15 individuals. For each development stage (vegetative, flowering), the essential oils were isolated two times from 2 ! 500 g of the fresh leaves or the fresh aerial parts of the plants by hydrodistillation for 4 h using a modified Clevenger apparatus. The oils were taken up in dichloromethane, dried over anhydrous sodium sulphate and kept at 4 C. Yields of essential oil are reported in Table 1. 2.3. Gas chromatographyemass spectrometry analyses GCeMS analyses were carried out using a HewlettePackard chromatograph type 6890 series coupled to an HP 6890 mass selective detector. The MS detector was used in the EI mode with an ionization voltage of 70 eV. Two capillary columns were used under the following conditions: (i) HP-5MS (30 m ! 0.25 mm i.d., film thickness: 0.25 mm); oven temperature programme 60 C rising at 4 C/min to 200 C, held for 30 min; ion source temperature, 280 C; injector temperature, 250 C; split ratio, 1:20; carrier gas, helium; flow rate, 1.1 mL/min. (ii) Supelcowax (60 m ! 0.20 mm i.d., film thickness: 0.20 mm); oven temperature programme 60 C rising at 4 C/min to 230 C, held for 30 min; ion source temperature, 280 C; injector temperature, 250 C; split ratio, 1:20; carrier gas, helium; flow rate, 0.7 mL/min. 2.4. Identification and quantification Retention indices of all the constituents were determined on both phases by Kovats method using n-alkanes as standards. Constituents of the volatile oil were
708
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
identified by comparison of their retention indices and their mass spectral fragmentation pattern with those reported in the literature (Adams, 2001) and stored on MS Library (NBS75K). The quantification of the components was performed on the basis of their GC peak areas on the Supelcowax column.
3. Results and discussion The taxonomy of the genus Psiadia is rather complex. Thus, in the Mascarenes, the taxonomic scheme established by Scott (1991) is built on the segregation of the genus into five groups mostly based on morphological characters. The four taxa investigated here are endemic to Reunion Island and belong to two different groups. P. anchusifolia and P. boivinii belong to the group of shrubs or small trees, densely hairy; the hairs are often brownish. The inflorescences are much branched, bearing larger heads containing numerous florets; the phyllaries are lanceolated and rather stiff; the female florests are sparsely hispid with very short ray; the achenes are compressed. P. argentea and P. salaziana belong to the group of subshrubs. The leaves are small, sessile and often densely hairy; the heads are large and subspherical, solitary or in groups of three; the phyllaries are generally herbaceous and lanceolated; the female florest possesses a short or no ray; the achenes are compressed. The essential oils of these four species of Psiadia were obtained by hydrodistillation during the vegetative (April) and flowering (November) phases. The oil yields are reported in Table 1 and were found to be low especially for P. boivinii. Moreover, the yields were about the same in April and November, except for P. salaziana which gave a slightly higher percentage of essential oil during the vegetative phase. The identified volatile components are listed according to their chemical structures in Table 2. The table also includes their retention indices and the percentage composition. Altogether, 57 compounds were identified amounting to 58.5e82.9% of the total oils. For P. anchusifolia, P. argentea and P. salaziana, the qualitative and quantitative composition of the oils appeared to be not dependent on the stage of plant development. Moreover, the oils of these three species were characterized by a large presence of terpenoids mainly oxygenated mono- (12.8e45.8%) and sesquiterpenes (28.4e39.3%). The main similarities in their composition are also related to the high percentages of the two unusual components: compound 1 (12.0e41.4%) among the oxygenated monoterpene fraction, compound 2 (19.2e39.3%) among the oxygenated sesquiterpene fraction. These two major components were detected and isolated for the first time from P. anchusifolia (Gauvin et al., 2004) and were identified as
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
709
7,7-dimethyl-2-methylenebicyclo[3.3.1]heptan-6-ol acetate for 1 and 6,6,8,9-tetramethyltricyclo[3.3.3.0]-undec-7-en-2-ol for 2. This is the second report on the occurrence of these rare terpenoids in nature.
OH
O
O
1
2
In contrast, the essential oils of P. boivinii showed a different composition pattern depending on the stage of plant development. During the vegetative stage, the essential oil was dominated by oxygenated sesquiterpenes (28.8%) and sesquiterpene hydrocarbons (14.4%). The rest being mainly oxygenated monoterpenes (10.9%). Like P. anchusifolia, P. argentea and P. salaziana, the two major constituents of this oil were the oxygenated sesquiterpene 2 (19.6%) and the oxygenated monoterpene 1 (5.2%). The chemical composition of the essential oil of P. boivinii collected during flowering, was quite distinguishable. The oil was characterized by a great prevalence of mono- (29.8%) and sesquiterpene (24.5%) hydrocarbons, b-pinene (10.6%), (E )-b-ocimene (10.0%), germacrene D (8.5%) and b-elemene (5.6%) being the main components. It is worth mentioning that the oil was not completely devoid of terpenoids 1 and 2 as they were detected in low concentrations (4.9 and 2.0%, respectively). The occurrence of the unusual terpenoids 1 and 2 in P. anchusifolia, P. argentea, P. boivinii and P. salaziana supposes that the four species have the same biosynthetic pathway and it may also suggest that both 1 and 2 could be used as a chemotaxonomic tool for the characterization of some Psiadia species. However, chemical variations related to environmental conditions are frequently encountered in aromatic plants. Further investigations are therefore needed to prove that the occurrence of terpenoids 1 and 2 in the four species depends more on the genetic similarities between the plants than the environmental conditions. To complete this chemotaxonomic study, it would also be interesting to find other species of Psiadia with compounds 1 and 2 in their essential oil composition.
Compounds
RIa
Hydrocarbons Alcohols n-Hexanol 3-Hexen-1-ol 2-Hexen-1-ol Total Aldehydes Hexenal n-Octanal n-Nonanal Total Terpenoids Monoterpene hydrocarbons a-Pinene b-Pinene Myrcene a-Phellandrene Limonene b-Phellandrene (Z )-b-ocimene (E )-b-ocimene p-Cymene Total Oxygenated monoterpenes cis-Linalool oxide trans-Linalool oxide Linalool cis-Chrysanthenyl acetate 1
%b HP-5MS
P. anchusifolia
P. argentea
P. boivinii
P. salaziana
April
November
April
November
April
November
April
November
1311 1345 1364
e e e
e 0.4 e 0.4
e 1.2 e 1.2
e e e e
e e e e
0.5 3.0 0.5 4.0
0.2 0.4 e 0.6
e t e t
e t e t
1061 1266 1366
e e 1095
e e e e
e e e e
0.7 t 1.3 2.0
e e 0.7 0.7
e e e e
e e e e
e e e e
e e e e
1016 1092 1136 1148 1184 1196 1211 1228 1251
e 970 987 e 1024 1024 1032 1042 1023
e 0.2 0.3 t t t 0.2 1.8 t 2.5
e 0.2 t e t t e t t 0.2
e e e e e e e e e e
e 0.3 0.9 e t e e e t 1.2
e e e e t e e e t t
1.2 10.6 1.7 e 4.8 e 0.5 10.0 1.0 29.8
e 0.5 3.6 e 0.4 t t 0.5 t 5.0
e 1.1 5.2 e 0.3 t t 0.7 t 7.3
1410 1438 1500 1540 1646
1065 1080 1091 1256 1313
e e t 0.8 12.0
e e t 0.8 14.1
t t 0.3 2.3 18.2
t e 0.3 4.1 41.4
1.2 1.0 3.2 0.3 5.2
t t 1.0 e 4.9
e e t 1.5 21.2
e e t 1.3 18.6
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
Supelcowax
710
Table 2 Volatile constituents identified in the essential oils of Psiadia species from Reunion Island
1719 1762
1375 1237
e e 12.8
e e 14.9
t e 20.8
t e 45.8
e t 10.9
e e 5.9
e e 22.7
e e 19.9
1483 1515 1518 1525 1564 1569 1580 1583 1655 1668 1671 1695 1703 1706 1711 1733 1739 1807 1890 1931
1368 1372 1382 1378 1429 1386 1422 e 1444 1466 1483 1476 1491 1476 1487 1514 1505 1512 1533 1554
t 0.9 t t t 0.9 t 0.6 0.9 e 2.7 4.0 0.3 e 0.5 0.5 e e e e 11.3
0.6 1.5 0.2 0.4 t 1.2 m m 1.0 e 2.7 3.3 0.6 e 1.0 1.0 e e e e 13.5
t 1.0 e t e 1.0 t e e t e e e t e t t m m t 2.0
t 0.5 e t e 1.0 t e e e e e e t e e e t t t 1.5
0.7 2.9 e 0.6 e 3.4 0.5 e e 2.1 e e 0.6 1.4 m t 1.3 0.5 0.4 t 14.4
0.5 1.8 1.5 m e 5.6 0.6 1.0 e 0.5 e 8.5 1.1 0.3 0.4 2.2 0.2 0.3 t t 24.5
1.2 1.4 0.5 0.5 e 1.1 2.3 1.5 1.8 e 0.6 3.1 0.5 e 0.3 0.5 t t e e 15.3
1.0 1.5 0.4 0.4 e 0.7 1.9 1.0 1.3 e 1.1 2.6 0.8 e 0.4 1.6 0.4 0.4 e e 15.5
1854 1903 1964 1977 2018 2031 2109 2147
1487 1510 1583 e 1601 1549 1580 1635
0.7 2.4 e 0.6 e 2.6 20.5 0.7
0.8 1.7 e 0.2 e 1.4 19.2 0.6
t e 2.3 e 1.0 t 39.3 m
e e 0.7 e 0.3 0.2 28.3 0.3
e e e 0.4 0.7 e 19.6 1.9
0.6 0.6 e e 0.3 e 2.0 1.0
1.2 3.8 0.8 t 0.6 0.7 26.6 1.3
0.6 2.4 0.6 t m m 28.5 1.1
711
(continued on next page)
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
trans-Myrtanol acetate Cuminaldehyde Total Sesquiterpene hydrocarbons a-Copaene b-Maalienec b-Cubebene a-Isocomene a-trans-Bergamotene b-Elemene b-Copaenec b-Caryophyllene a-Humulene g-Muurolene d-Selinene Germacrene D a-Muurolene b-Selinene a-Selinene d-Cadinene g-Cadinene trans-Calamene a-Calacorene b-Calacorene Total Oxygenated sesquiterpenes Epicubebol Cubebol Caryophyllene oxide Nerolidold Humulene epoxide II Elemol 2 T-muurolol
712
Table 2 (continued) Compounds
RIa Supelcowax
HP-5MS
P. anchusifolia
P. argentea
P. boivinii
April
November
April
November
April
November
April
P. salaziana November
2171 2188 2191 2196 2217
1665 1649 1650 e e
7.0 4.6 0.9 1.2 0.6 41.8
6.3 5.6 0.6 1.6 0.6 38.6
e e 0.6 e e 43.2
e e 0.7 e e 30.5
e 0.6 2.7 0.8 1.7 28.4
e e 1.4 0.4 6.3
1.6 1.2 1.2 0.7 t 39.7
2.8 2.4 1.3 0.5 t 40.2
Miscellaneous compounds (E )-b-damascone 1786 b-Ionone 1907 Total
1406 1478
e e e
e e e
e t t
e t t
0.4 e 0.4
0.4 e 0.4
e e e
e e e
68.8
68.4
68.0
79.7
58.1
67.5
82.7
82.9
% Identification a b c d
Retention indices relative to C8eC22 n-alkanes on the Supelcowax capillary column and on the HP-5MS column. Relative percentage obtained from peak area on the Supelcowax column; m: mixture; t: trace (!0.1%). Tentatively identified. Correct isomer non-identified.
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
Bulnesol a-Eudesmol a-Cadinol b-Eudesmol Selin-11-en-4-a-ol Total
%b
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
713
Acknowledgements Financial support from the Conseil Re´gional of Reunion Island is gratefully acknowledged. References Abou-Zaid, M.M., El-Karemy, Z., El-Negoumy, S.I., Altosaar, I., Saleh, N.A.M., 1991. The flavonoids of Psiadia punctulata. Bull. Chem. Soc. Ethiop. 5, 37e40. Adams, R.P., 2001. Identification of Essential Oils by Gas Chromatography/Quadrupole Mass Spectroscopy. Allured Publishing Corporation, Carol Stream, Illinois, USA. Al-Yahya, M.A., Hifnawy, M.S., Mossa, J.S., El-Feraly, F.S., McPhail, D.R., McPhail, A.T., 1987. X-ray structure of psiadiarabin, a flavone from Psiadia arabica. Phytochemistry 26, 2648e2649. Bosser, J., Gue´ho, J., Jeffrey, C., 1993. In: Antoine, R., Bosser, J., Ferguson, I.K. (Eds.), Flore des Mascareignes. La Re´union, Maurice, Rodrigues, 109. Compose´es. ORSTOM, Paris, pp. 80e103. Canonica, L., Rindone, B., Scolastico, C., Ferrari, G., Casagrande, C., 1967. Structure and stereochemistry of psiadiol, a new diterpenoid. Tetrahedron Lett. 28, 2639e2643. Canonica, L., Rindone, B., Scolastico, C., Ferrari, G., Casagrande, C., 1969a. Gazz. Chim. Ital. 99, 260. Canonica, L., Rindone, B., Scolastico, C., Ferrari, G., Casagrande, C., 1969b. Gazz. Chim. Ital. 99, 276. Dennis, R., 1973. Essential oil of Psiadia salviifolia. Phytochemistry 12, 2705e2708. El-Domiaty, M.M., El-Feraly, F.S., Mossa, J.S., McPhail, A.T., 1993. Diterpenes from Psiadia arabica. Phytochemistry 34, 467e471. El-Feraly, F.S., Mossa, J.S., Al-Yahya, M.A., Hifnawy, M.S., Hafez, M.M., Hufford, C.D., 1990. Two flavones from Psiadia arabica. Phytochemistry 29, 3372e3373. Fortin, H., Tomasi, S., Jaccard, P., Robin, V., Boustie, J., 2001. A prenyloxycoumarin from Psiadia dentata. Chem. Pharm. Bull. 49, 619e621. Gauvin, A., Susperregui, A., Barth, P., Remy, L., De´le´ris, G., Smadja, J., 2004. An acetylated monoterpene and a sesquiterpene alcohol from Psiadia anchusifolia. Phytochemistry 65, 897e901. Gurib-Fakim, A., Bourrel, C., Kodja, H., Govinden, J., 1995. Chemical composition of the essential oils of Psiadia lithospermifolia (Lam.) Cordem. and P. viscosa (Lam.) A.J. Scott of the Asteraceae family. J. Essent. Oil Res. 7, 533e535. Gurib-Fakim, A., Gauvin, A., Smadja, J., Govinden-Soulange, J., Kodja, H., 2000. Composition of the essential oil of the endemic Psiadia arguta Pers. (Voigt) from Mauritius. J. Essent. Oil Res. 12, 556e 558. Jakobsen, T.H., Marcussen, H.V., Adsersen, A., Strasberg, D., Smitt, U.W., Jaroszewski, J.W., 2001. 3-Methoxyflavones and a novel coumarin from Psiadia dentata. Biochem. Syst. Ecol. 29, 963e965. Juma, B.F., Yenesew, A., Midiwo, J.O., Waterman, P.G., 2001. Flavones and phenylpropenoids in the surface exudate of Psiadia punctulata. Phytochemistry 57, 571e574. Mekkawi, A.G., Mossa, J.S., Hifnawy, M.S., Karawya, M.S., 1984. Essential oil of Psiadia arabica Jaub. et Spach. Pharmazie 39, 419e420. Midiwo, J.O., Owuor, F.A.O., Juma, B.F., Waterman, P.G., 1997. Diterpenes from the leaf exudate of Psiadia punctulata. Phytochemistry 45, 117e120. Mossa, J.S., Mekkawi, A.G., Hifnawy, M.S., Karawya, M.S., 1983. Essential oil of Psiadia arabica Jaub. Et. sp. In: IX International Congress of Essentials Oils. Essential Oil Technical Paper, Book 4, Singapore pp. 45e47. Mossa, J.S., El-Domiaty, M.M., Al-Meshal, I.A., El-Feraly, F.S., Hufford, C.D., McPhail, D.R., McPhail, A.T., 1992. A flavone and diterpene from Psiadia arabica. Phytochemistry 31, 2863e2868. Ramanoelina, P.A.R., Rasoarahona, J.R.E., Masotti, V., Viano, J., Gaydou, E.M., Bianchini, J.P., 1994. Chemical composition of the leaf oil of Psiadia altissima (Compositeae). J. Essent. Oil Res. 6, 565e570. Robin, V., Boustie, J., Amoros, M., Girre, L., 1998. In-vitro antiviral activity of seven Psiadia species, Asteraceae: isolation of two antipoliovirus flavonoids from Psiadia dentata. Pharm. Pharmacol. Commun. 4, 61e64.
714
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
Scott, A.J., 1991. Notes on Compositae-Astereae for the ‘‘Flore des Mascareignes’’. Kew Bull. 2, 339e353. Wang, Y., Hamburger, M., Gueho, J., Hostettmann, K., 1989a. Antimicrobial flavonoids from Psiadia trinervia and their methylated and acetylated derivatives. Phytochemistry 28, 2323e2327. Wang, Y., Hamburger, M., Hostettmann, K., 1989b. Antifungal methylated flavonols from Psiadia trinervia. Planta Med. 55, 109. Wang, Y., Hamburger, M., Gueho, J., Hostettmann, K., 1992. Cyclohexanecarboxylic-acid derivatives from Psiadia trinervia. Helv. Chim. Acta 75, 269e275.
Essential oil composition of four Psiadia species from Reunion Island: A chemotaxonomic study Anne Gauvin *, Jacqueline Smadja Laboratoire de Chimie des Substances Naturelles et des Sciences des Aliments, Faculte´ des Sciences et Technologies, Universite´ de la Re´union, 15 Avenue Rene´ Cassin, BP 7151, St Denis Messag Cedex 9, La Re´union 97 715, France Received 5 May 2004; accepted 24 December 2004
Abstract The essential oils of four wild species of Psiadia (Psiadia anchusifolia, Psiadia argentea, Psiadia boivinii, Psiadia salaziana; Asteraceae) endemic to Reunion Island were obtained by hydrodistillation and subjected to detailed GC/MS analysis in order to determine possible similarities among them and also the differences in their chemical compositions depending on the stage of the life cycle (vegetative and flowering). A total of 57 compounds were identified including two unusual components 7,7-dimethyl-2-methylenebicyclo[3.3.1]heptan-6-ol acetate (1) and 6,6,8,9-tetramethyltricyclo[3.3.3.0]-undec-7-en-2-ol (2) which, until now, have been found only in species of the genus Psiadia. For P. anchusifolia, P. argentea and P. salaziana, the qualitative and quantitative composition of the oils appeared to be constant in the different
* Corresponding author. Tel.: C33 262 262 938197; fax: C33 262 262 938183. E-mail address: [email protected] (A. Gauvin). 0305-1978/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.bse.2004.12.013
706
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
stages of their development. In contrast, considerable differences were found to exist in the composition of essential oils of P. boivinii. Ó 2005 Elsevier Ltd. All rights reserved. Keywords: Psiadia anchusifolia; Psiadia argentea; Psiadia boivinii; Psiadia salaziana; Asteraceae; Essential oil composition; 7,7-Dimethyl-2-methylenebicyclo[3.3.1]heptan-6-ol acetate; 6,6,8,9-Tetramethyltricyclo[3.3.3.0]-undec-7-en-2-ol; Chemotaxonomy
1. Introduction The genus Psiadia Jacq. (Asteraceae) includes more than 60 species (Bosser et al., 1993; Scott, 1991). One species can be found in Sri Lanka and Southern India; several species are native to Arabia, East and South Africa, with a single species, now extinct, formerly found in St Helena. This genus is also particularly well represented in Madagascar with 28 species and in the Mascarene Islands (Reunion, Mauritius, Roderick) with 26 species. Psiadia species are of particular interest as some of them are commonly used in traditional pharmacopoeia. Therefore, many papers about the secondary metabolites of Psiadia species can be found in the literature (Abou-Zaid et al., 1991; Al-Yahya et al., 1987; Canonica et al., 1967, 1969a,b; El-Domiaty et al., 1993; El-Feraly et al., 1990; Fortin et al., 2001; Jakobsen et al., 2001; Juma et al., 2001; Midiwo et al., 1997; Mossa et al., 1992; Robin et al., 1998; Wang et al., 1989a,b, 1992). The volatile constituents of a few species have also been examined, for example, Psiadia altissima (Ramanoelina et al., 1994), Psiadia arabica (Mekkawi et al., 1984; Mossa et al., 1983), Psiadia arguta (Gurib-Fakim et al., 2000), Psiadia lithospermifolia (Gurib-Fakim et al., 1995), Psiadia salviifolia (Dennis, 1973), and Psiadia viscosa (Gurib-Fakim et al., 1995). As part of our research on the aromatic Psiadia of the Mascarenes (Gurib-Fakim et al., 2000; Gauvin et al., 2004), we report on the chemical composition of the volatile oils obtained from Psiadia anchusifolia, Psiadia argentea, Psiadia boivinii, and Psiadia salaziana collected during the flowering and vegetative phases in Reunion Island, for comparison and for chemotaxonomic purposes. As far as we know, the volatile constituents of these four Psiadia species endemic to Reunion Island, have not been previously investigated.
2. Material and methods 2.1. Plant material The plant materials, collection places, dates and plant life-cycle stages (vegetative; flowering) are given in Table 1. The plants were identified by Pr. Dominique Strasberg and voucher specimens have been deposited in the herbarium of Reunion Island (REU).
707
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714 Table 1 Plant material, collection places, dates, life-cycle stages and oil yields of Psiadia species Species
Voucher number
Part
Collection places (altitudes)
Date
Life-cycle stages
Oil yield (%)
P. anchusifolia
DIV18
Leaves
April 2000 November 2001
Vegetative Flowering
0.089 0.088
P. argentea
DIV19
Aerial parts
April 2000 November 2001
Vegetative Flowering
0.020 0.015
P. boivinii
DIV17
Leaves
April 2000 November 2001
Vegetative Flowering
0.002 0.008
P. salaziana
DIV16
Leaves
Reunion Island: volcano area (2300 m) Reunion Island: volcano area (2300 m) Reunion Island: forest of Belouve-Be´bour (1500 m) Reunion Island: volcano area (2300 m)
April 2000 November 2001
Vegetative Flowering
0.120 0.065
2.2. Sampling and essential oil extraction Sampling of the four species of Psiadia was done by a randomised collection of 10e15 individuals. For each development stage (vegetative, flowering), the essential oils were isolated two times from 2 ! 500 g of the fresh leaves or the fresh aerial parts of the plants by hydrodistillation for 4 h using a modified Clevenger apparatus. The oils were taken up in dichloromethane, dried over anhydrous sodium sulphate and kept at 4 C. Yields of essential oil are reported in Table 1. 2.3. Gas chromatographyemass spectrometry analyses GCeMS analyses were carried out using a HewlettePackard chromatograph type 6890 series coupled to an HP 6890 mass selective detector. The MS detector was used in the EI mode with an ionization voltage of 70 eV. Two capillary columns were used under the following conditions: (i) HP-5MS (30 m ! 0.25 mm i.d., film thickness: 0.25 mm); oven temperature programme 60 C rising at 4 C/min to 200 C, held for 30 min; ion source temperature, 280 C; injector temperature, 250 C; split ratio, 1:20; carrier gas, helium; flow rate, 1.1 mL/min. (ii) Supelcowax (60 m ! 0.20 mm i.d., film thickness: 0.20 mm); oven temperature programme 60 C rising at 4 C/min to 230 C, held for 30 min; ion source temperature, 280 C; injector temperature, 250 C; split ratio, 1:20; carrier gas, helium; flow rate, 0.7 mL/min. 2.4. Identification and quantification Retention indices of all the constituents were determined on both phases by Kovats method using n-alkanes as standards. Constituents of the volatile oil were
708
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
identified by comparison of their retention indices and their mass spectral fragmentation pattern with those reported in the literature (Adams, 2001) and stored on MS Library (NBS75K). The quantification of the components was performed on the basis of their GC peak areas on the Supelcowax column.
3. Results and discussion The taxonomy of the genus Psiadia is rather complex. Thus, in the Mascarenes, the taxonomic scheme established by Scott (1991) is built on the segregation of the genus into five groups mostly based on morphological characters. The four taxa investigated here are endemic to Reunion Island and belong to two different groups. P. anchusifolia and P. boivinii belong to the group of shrubs or small trees, densely hairy; the hairs are often brownish. The inflorescences are much branched, bearing larger heads containing numerous florets; the phyllaries are lanceolated and rather stiff; the female florests are sparsely hispid with very short ray; the achenes are compressed. P. argentea and P. salaziana belong to the group of subshrubs. The leaves are small, sessile and often densely hairy; the heads are large and subspherical, solitary or in groups of three; the phyllaries are generally herbaceous and lanceolated; the female florest possesses a short or no ray; the achenes are compressed. The essential oils of these four species of Psiadia were obtained by hydrodistillation during the vegetative (April) and flowering (November) phases. The oil yields are reported in Table 1 and were found to be low especially for P. boivinii. Moreover, the yields were about the same in April and November, except for P. salaziana which gave a slightly higher percentage of essential oil during the vegetative phase. The identified volatile components are listed according to their chemical structures in Table 2. The table also includes their retention indices and the percentage composition. Altogether, 57 compounds were identified amounting to 58.5e82.9% of the total oils. For P. anchusifolia, P. argentea and P. salaziana, the qualitative and quantitative composition of the oils appeared to be not dependent on the stage of plant development. Moreover, the oils of these three species were characterized by a large presence of terpenoids mainly oxygenated mono- (12.8e45.8%) and sesquiterpenes (28.4e39.3%). The main similarities in their composition are also related to the high percentages of the two unusual components: compound 1 (12.0e41.4%) among the oxygenated monoterpene fraction, compound 2 (19.2e39.3%) among the oxygenated sesquiterpene fraction. These two major components were detected and isolated for the first time from P. anchusifolia (Gauvin et al., 2004) and were identified as
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
709
7,7-dimethyl-2-methylenebicyclo[3.3.1]heptan-6-ol acetate for 1 and 6,6,8,9-tetramethyltricyclo[3.3.3.0]-undec-7-en-2-ol for 2. This is the second report on the occurrence of these rare terpenoids in nature.
OH
O
O
1
2
In contrast, the essential oils of P. boivinii showed a different composition pattern depending on the stage of plant development. During the vegetative stage, the essential oil was dominated by oxygenated sesquiterpenes (28.8%) and sesquiterpene hydrocarbons (14.4%). The rest being mainly oxygenated monoterpenes (10.9%). Like P. anchusifolia, P. argentea and P. salaziana, the two major constituents of this oil were the oxygenated sesquiterpene 2 (19.6%) and the oxygenated monoterpene 1 (5.2%). The chemical composition of the essential oil of P. boivinii collected during flowering, was quite distinguishable. The oil was characterized by a great prevalence of mono- (29.8%) and sesquiterpene (24.5%) hydrocarbons, b-pinene (10.6%), (E )-b-ocimene (10.0%), germacrene D (8.5%) and b-elemene (5.6%) being the main components. It is worth mentioning that the oil was not completely devoid of terpenoids 1 and 2 as they were detected in low concentrations (4.9 and 2.0%, respectively). The occurrence of the unusual terpenoids 1 and 2 in P. anchusifolia, P. argentea, P. boivinii and P. salaziana supposes that the four species have the same biosynthetic pathway and it may also suggest that both 1 and 2 could be used as a chemotaxonomic tool for the characterization of some Psiadia species. However, chemical variations related to environmental conditions are frequently encountered in aromatic plants. Further investigations are therefore needed to prove that the occurrence of terpenoids 1 and 2 in the four species depends more on the genetic similarities between the plants than the environmental conditions. To complete this chemotaxonomic study, it would also be interesting to find other species of Psiadia with compounds 1 and 2 in their essential oil composition.
Compounds
RIa
Hydrocarbons Alcohols n-Hexanol 3-Hexen-1-ol 2-Hexen-1-ol Total Aldehydes Hexenal n-Octanal n-Nonanal Total Terpenoids Monoterpene hydrocarbons a-Pinene b-Pinene Myrcene a-Phellandrene Limonene b-Phellandrene (Z )-b-ocimene (E )-b-ocimene p-Cymene Total Oxygenated monoterpenes cis-Linalool oxide trans-Linalool oxide Linalool cis-Chrysanthenyl acetate 1
%b HP-5MS
P. anchusifolia
P. argentea
P. boivinii
P. salaziana
April
November
April
November
April
November
April
November
1311 1345 1364
e e e
e 0.4 e 0.4
e 1.2 e 1.2
e e e e
e e e e
0.5 3.0 0.5 4.0
0.2 0.4 e 0.6
e t e t
e t e t
1061 1266 1366
e e 1095
e e e e
e e e e
0.7 t 1.3 2.0
e e 0.7 0.7
e e e e
e e e e
e e e e
e e e e
1016 1092 1136 1148 1184 1196 1211 1228 1251
e 970 987 e 1024 1024 1032 1042 1023
e 0.2 0.3 t t t 0.2 1.8 t 2.5
e 0.2 t e t t e t t 0.2
e e e e e e e e e e
e 0.3 0.9 e t e e e t 1.2
e e e e t e e e t t
1.2 10.6 1.7 e 4.8 e 0.5 10.0 1.0 29.8
e 0.5 3.6 e 0.4 t t 0.5 t 5.0
e 1.1 5.2 e 0.3 t t 0.7 t 7.3
1410 1438 1500 1540 1646
1065 1080 1091 1256 1313
e e t 0.8 12.0
e e t 0.8 14.1
t t 0.3 2.3 18.2
t e 0.3 4.1 41.4
1.2 1.0 3.2 0.3 5.2
t t 1.0 e 4.9
e e t 1.5 21.2
e e t 1.3 18.6
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
Supelcowax
710
Table 2 Volatile constituents identified in the essential oils of Psiadia species from Reunion Island
1719 1762
1375 1237
e e 12.8
e e 14.9
t e 20.8
t e 45.8
e t 10.9
e e 5.9
e e 22.7
e e 19.9
1483 1515 1518 1525 1564 1569 1580 1583 1655 1668 1671 1695 1703 1706 1711 1733 1739 1807 1890 1931
1368 1372 1382 1378 1429 1386 1422 e 1444 1466 1483 1476 1491 1476 1487 1514 1505 1512 1533 1554
t 0.9 t t t 0.9 t 0.6 0.9 e 2.7 4.0 0.3 e 0.5 0.5 e e e e 11.3
0.6 1.5 0.2 0.4 t 1.2 m m 1.0 e 2.7 3.3 0.6 e 1.0 1.0 e e e e 13.5
t 1.0 e t e 1.0 t e e t e e e t e t t m m t 2.0
t 0.5 e t e 1.0 t e e e e e e t e e e t t t 1.5
0.7 2.9 e 0.6 e 3.4 0.5 e e 2.1 e e 0.6 1.4 m t 1.3 0.5 0.4 t 14.4
0.5 1.8 1.5 m e 5.6 0.6 1.0 e 0.5 e 8.5 1.1 0.3 0.4 2.2 0.2 0.3 t t 24.5
1.2 1.4 0.5 0.5 e 1.1 2.3 1.5 1.8 e 0.6 3.1 0.5 e 0.3 0.5 t t e e 15.3
1.0 1.5 0.4 0.4 e 0.7 1.9 1.0 1.3 e 1.1 2.6 0.8 e 0.4 1.6 0.4 0.4 e e 15.5
1854 1903 1964 1977 2018 2031 2109 2147
1487 1510 1583 e 1601 1549 1580 1635
0.7 2.4 e 0.6 e 2.6 20.5 0.7
0.8 1.7 e 0.2 e 1.4 19.2 0.6
t e 2.3 e 1.0 t 39.3 m
e e 0.7 e 0.3 0.2 28.3 0.3
e e e 0.4 0.7 e 19.6 1.9
0.6 0.6 e e 0.3 e 2.0 1.0
1.2 3.8 0.8 t 0.6 0.7 26.6 1.3
0.6 2.4 0.6 t m m 28.5 1.1
711
(continued on next page)
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
trans-Myrtanol acetate Cuminaldehyde Total Sesquiterpene hydrocarbons a-Copaene b-Maalienec b-Cubebene a-Isocomene a-trans-Bergamotene b-Elemene b-Copaenec b-Caryophyllene a-Humulene g-Muurolene d-Selinene Germacrene D a-Muurolene b-Selinene a-Selinene d-Cadinene g-Cadinene trans-Calamene a-Calacorene b-Calacorene Total Oxygenated sesquiterpenes Epicubebol Cubebol Caryophyllene oxide Nerolidold Humulene epoxide II Elemol 2 T-muurolol
712
Table 2 (continued) Compounds
RIa Supelcowax
HP-5MS
P. anchusifolia
P. argentea
P. boivinii
April
November
April
November
April
November
April
P. salaziana November
2171 2188 2191 2196 2217
1665 1649 1650 e e
7.0 4.6 0.9 1.2 0.6 41.8
6.3 5.6 0.6 1.6 0.6 38.6
e e 0.6 e e 43.2
e e 0.7 e e 30.5
e 0.6 2.7 0.8 1.7 28.4
e e 1.4 0.4 6.3
1.6 1.2 1.2 0.7 t 39.7
2.8 2.4 1.3 0.5 t 40.2
Miscellaneous compounds (E )-b-damascone 1786 b-Ionone 1907 Total
1406 1478
e e e
e e e
e t t
e t t
0.4 e 0.4
0.4 e 0.4
e e e
e e e
68.8
68.4
68.0
79.7
58.1
67.5
82.7
82.9
% Identification a b c d
Retention indices relative to C8eC22 n-alkanes on the Supelcowax capillary column and on the HP-5MS column. Relative percentage obtained from peak area on the Supelcowax column; m: mixture; t: trace (!0.1%). Tentatively identified. Correct isomer non-identified.
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
Bulnesol a-Eudesmol a-Cadinol b-Eudesmol Selin-11-en-4-a-ol Total
%b
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
713
Acknowledgements Financial support from the Conseil Re´gional of Reunion Island is gratefully acknowledged. References Abou-Zaid, M.M., El-Karemy, Z., El-Negoumy, S.I., Altosaar, I., Saleh, N.A.M., 1991. The flavonoids of Psiadia punctulata. Bull. Chem. Soc. Ethiop. 5, 37e40. Adams, R.P., 2001. Identification of Essential Oils by Gas Chromatography/Quadrupole Mass Spectroscopy. Allured Publishing Corporation, Carol Stream, Illinois, USA. Al-Yahya, M.A., Hifnawy, M.S., Mossa, J.S., El-Feraly, F.S., McPhail, D.R., McPhail, A.T., 1987. X-ray structure of psiadiarabin, a flavone from Psiadia arabica. Phytochemistry 26, 2648e2649. Bosser, J., Gue´ho, J., Jeffrey, C., 1993. In: Antoine, R., Bosser, J., Ferguson, I.K. (Eds.), Flore des Mascareignes. La Re´union, Maurice, Rodrigues, 109. Compose´es. ORSTOM, Paris, pp. 80e103. Canonica, L., Rindone, B., Scolastico, C., Ferrari, G., Casagrande, C., 1967. Structure and stereochemistry of psiadiol, a new diterpenoid. Tetrahedron Lett. 28, 2639e2643. Canonica, L., Rindone, B., Scolastico, C., Ferrari, G., Casagrande, C., 1969a. Gazz. Chim. Ital. 99, 260. Canonica, L., Rindone, B., Scolastico, C., Ferrari, G., Casagrande, C., 1969b. Gazz. Chim. Ital. 99, 276. Dennis, R., 1973. Essential oil of Psiadia salviifolia. Phytochemistry 12, 2705e2708. El-Domiaty, M.M., El-Feraly, F.S., Mossa, J.S., McPhail, A.T., 1993. Diterpenes from Psiadia arabica. Phytochemistry 34, 467e471. El-Feraly, F.S., Mossa, J.S., Al-Yahya, M.A., Hifnawy, M.S., Hafez, M.M., Hufford, C.D., 1990. Two flavones from Psiadia arabica. Phytochemistry 29, 3372e3373. Fortin, H., Tomasi, S., Jaccard, P., Robin, V., Boustie, J., 2001. A prenyloxycoumarin from Psiadia dentata. Chem. Pharm. Bull. 49, 619e621. Gauvin, A., Susperregui, A., Barth, P., Remy, L., De´le´ris, G., Smadja, J., 2004. An acetylated monoterpene and a sesquiterpene alcohol from Psiadia anchusifolia. Phytochemistry 65, 897e901. Gurib-Fakim, A., Bourrel, C., Kodja, H., Govinden, J., 1995. Chemical composition of the essential oils of Psiadia lithospermifolia (Lam.) Cordem. and P. viscosa (Lam.) A.J. Scott of the Asteraceae family. J. Essent. Oil Res. 7, 533e535. Gurib-Fakim, A., Gauvin, A., Smadja, J., Govinden-Soulange, J., Kodja, H., 2000. Composition of the essential oil of the endemic Psiadia arguta Pers. (Voigt) from Mauritius. J. Essent. Oil Res. 12, 556e 558. Jakobsen, T.H., Marcussen, H.V., Adsersen, A., Strasberg, D., Smitt, U.W., Jaroszewski, J.W., 2001. 3-Methoxyflavones and a novel coumarin from Psiadia dentata. Biochem. Syst. Ecol. 29, 963e965. Juma, B.F., Yenesew, A., Midiwo, J.O., Waterman, P.G., 2001. Flavones and phenylpropenoids in the surface exudate of Psiadia punctulata. Phytochemistry 57, 571e574. Mekkawi, A.G., Mossa, J.S., Hifnawy, M.S., Karawya, M.S., 1984. Essential oil of Psiadia arabica Jaub. et Spach. Pharmazie 39, 419e420. Midiwo, J.O., Owuor, F.A.O., Juma, B.F., Waterman, P.G., 1997. Diterpenes from the leaf exudate of Psiadia punctulata. Phytochemistry 45, 117e120. Mossa, J.S., Mekkawi, A.G., Hifnawy, M.S., Karawya, M.S., 1983. Essential oil of Psiadia arabica Jaub. Et. sp. In: IX International Congress of Essentials Oils. Essential Oil Technical Paper, Book 4, Singapore pp. 45e47. Mossa, J.S., El-Domiaty, M.M., Al-Meshal, I.A., El-Feraly, F.S., Hufford, C.D., McPhail, D.R., McPhail, A.T., 1992. A flavone and diterpene from Psiadia arabica. Phytochemistry 31, 2863e2868. Ramanoelina, P.A.R., Rasoarahona, J.R.E., Masotti, V., Viano, J., Gaydou, E.M., Bianchini, J.P., 1994. Chemical composition of the leaf oil of Psiadia altissima (Compositeae). J. Essent. Oil Res. 6, 565e570. Robin, V., Boustie, J., Amoros, M., Girre, L., 1998. In-vitro antiviral activity of seven Psiadia species, Asteraceae: isolation of two antipoliovirus flavonoids from Psiadia dentata. Pharm. Pharmacol. Commun. 4, 61e64.
714
A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714
Scott, A.J., 1991. Notes on Compositae-Astereae for the ‘‘Flore des Mascareignes’’. Kew Bull. 2, 339e353. Wang, Y., Hamburger, M., Gueho, J., Hostettmann, K., 1989a. Antimicrobial flavonoids from Psiadia trinervia and their methylated and acetylated derivatives. Phytochemistry 28, 2323e2327. Wang, Y., Hamburger, M., Hostettmann, K., 1989b. Antifungal methylated flavonols from Psiadia trinervia. Planta Med. 55, 109. Wang, Y., Hamburger, M., Gueho, J., Hostettmann, K., 1992. Cyclohexanecarboxylic-acid derivatives from Psiadia trinervia. Helv. Chim. Acta 75, 269e275.