Essential oil composition of four Psiadia species from Reunion Island: A chemotaxonomic study

Biochemical Systematics and Ecology 33 (2005) 705e714

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Essential oil composition of fourPsiadia species from ReunionIsland: 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 Reunion,

15 Avenue Rene Cassin, BP 7151, St Denis Messag Cedex 9,

La Reunion 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 byhydrodistillation and subjected to detailed GC/MS analysis in order to determine possiblesimilarities 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 identifiedincluding 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).

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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 thecomposition of essential oils of P. boivinii.

� 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, nowextinct, formerly found in St Helena. This genus is also particularly well representedin 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 intraditional pharmacopoeia. Therefore, many papers about the secondary metabolitesof Psiadia species can be found in the literature (Abou-Zaid et al., 1991; Al-Yahyaet 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 volatileconstituents 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-Fakimet al., 2000; Gauvin et al., 2004), we report on the chemical composition of thevolatile oils obtained from Psiadia anchusifolia, Psiadia argentea, Psiadia boivinii,and Psiadia salaziana collected during the flowering and vegetative phases inReunion Island, for comparison and for chemotaxonomic purposes. As far as weknow, the volatile constituents of these four Psiadia species endemic to ReunionIsland, 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. DominiqueStrasberg and voucher specimens have been deposited in the herbarium of ReunionIsland (REU).

707A. Gauvin, J. Smadja / Biochemical Systematics and Ecology 33 (2005) 705e714

2.2. Sampling and essential oil extraction

Sampling of the four species of Psiadia was done by a randomised collection of10e15 individuals. For each development stage (vegetative, flowering), the essentialoils were isolated two times from 2! 500 g of the fresh leaves or the fresh aerialparts of the plants by hydrodistillation for 4 h using a modified Clevenger apparatus.The oils were taken up in dichloromethane, dried over anhydrous sodium sulphateand 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 type6890 series coupled to an HP 6890 mass selective detector. The MS detector was usedin the EI mode with an ionization voltage of 70 eV. Two capillary columns were usedunder 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 for30 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 mmi.d., film thickness: 0.20 mm); oven temperature programme 60 �C rising at 4 �C/minto 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 byKovats method using n-alkanes as standards. Constituents of the volatile oil were

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 Reunion Island:

volcano area

(2300 m)

April 2000 Vegetative 0.089

November 2001 Flowering 0.088

P. argentea DIV19 Aerial

parts

Reunion Island:

volcano area

(2300 m)



P. boivinii DIV17 Leaves Reunion Island:

forest of

Belouve-Bebour

(1500 m)



P. salaziana DIV16 Leaves Reunion Island:

volcano area

(2300 m)




identified by comparison of their retention indices and their massspectral fragmentation pattern with those reported in the literature (Adams,2001) and stored on MS Library (NBS75K). The quantification of the com-ponents was performed on the basis of their GC peak areas on the Supelcowaxcolumn.

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 thegenus into five groups mostly based on morphological characters. The four taxainvestigated here are endemic to Reunion Island and belong to two differentgroups.

P. anchusifolia and P. boivinii belong to the group of shrubs or small trees, denselyhairy; the hairs are often brownish. The inflorescences are much branched, bearinglarger heads containing numerous florets; the phyllaries are lanceolated and ratherstiff; the female florests are sparsely hispid with very short ray; the achenes arecompressed.

P. argentea and P. salaziana belong to the group of subshrubs. The leavesare small, sessile and often densely hairy; the heads are large and subspherical,solitary or in groups of three; the phyllaries are generally herbaceous andlanceolated; the female florest possesses a short or no ray; the achenes arecompressed.

The essential oils of these four species of Psiadia were obtained by hydro-distillation during the vegetative (April) and flowering (November) phases. The oilyields 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 forP. salaziana which gave a slightly higher percentage of essential oil during thevegetative phase.

The identified volatile components are listed according to their chemicalstructures in Table 2. The table also includes their retention indices and the per-centage composition. Altogether, 57 compounds were identified amounting to58.5e82.9% of the total oils.

For P. anchusifolia, P. argentea and P. salaziana, the qualitative and quantitativecomposition of the oils appeared to be not dependent on the stage of plantdevelopment. Moreover, the oils of these three species were characterized by a largepresence of terpenoids mainly oxygenated mono- (12.8e45.8%) and sesquiterpenes(28.4e39.3%). The main similarities in their composition are also related to the highpercentages of the two unusual components: compound 1 (12.0e41.4%) among theoxygenated monoterpene fraction, compound 2 (19.2e39.3%) among the oxygen-ated sesquiterpene fraction. These two major components were detected and isolatedfor the first time from P. anchusifolia (Gauvin et al., 2004) and were identified as


7,7-dimethyl-2-methylenebicyclo[3.3.1]heptan-6-ol acetate for 1 and 6,6,8,9-tetrame-thyltricyclo[3.3.3.0]-undec-7-en-2-ol for 2. This is the second report on theoccurrence of these rare terpenoids in nature.

In contrast, the essential oils of P. boivinii showed a different composition patterndepending on the stage of plant development. During the vegetative stage, theessential oil was dominated by oxygenated sesquiterpenes (28.8%) and sesquiterpenehydrocarbons (14.4%). The rest being mainly oxygenated monoterpenes (10.9%).Like P. anchusifolia, P. argentea and P. salaziana, the two major constituents of thisoil 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 duringflowering, was quite distinguishable. The oil was characterized by a great prevalenceof 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 maincomponents. It is worth mentioning that the oil was not completely devoid ofterpenoids 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 biosynthe-tic pathway and it may also suggest that both 1 and 2 could be used asa chemotaxonomic tool for the characterization of some Psiadia species. However,chemical variations related to environmental conditions are frequently encounteredin aromatic plants. Further investigations are therefore needed to prove that theoccurrence of terpenoids 1 and 2 in the four species depends more on the geneticsimilarities between the plants than the environmental conditions. To complete thischemotaxonomic study, it would also be interesting to find other species of Psiadiawith compounds 1 and 2 in their essential oil composition.

O

O

OH

1 2

Table 2

Volatile constituents identified in the essential oils of Psiadia species from Reunion Island

P. boivinii P. salaziana

April November April November

0.5 0.2 e e

3.0 0.4 t t

0.5 e e e4.0 0.6 t t

e e e e

e e e ee e e e

e e e e

e 1.2 e e

e 10.6 0.5 1.1

e 1.7 3.6 5.2

e e e e

t 4.8 0.4 0.3

e e t t

e 0.5 t t

e 10.0 0.5 0.7

t 1.0 t t

t 29.8 5.0 7.3

1.2 t e e

1.0 t e e

3.2 1.0 t t

0.3 e 1.5 1.3

5.2 4.9 21.2 18.6

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Compounds RIa %b

Supelcowax HP-5MS P. anchusifolia P. argentea

April November April November

Hydrocarbons

Alcohols

n-Hexanol 1311 e e e e e

3-Hexen-1-ol 1345 e 0.4 1.2 e e

2-Hexen-1-ol 1364 e e e e eTotal 0.4 1.2 e e

Aldehydes

Hexenal 1061 e e e 0.7 e

n-Octanal 1266 e e e t en-Nonanal 1366 1095 e e 1.3 0.7

Total e e 2.0 0.7

Terpenoids

Monoterpene hydrocarbons

a-Pinene 1016 e e e e e

b-Pinene 1092 970 0.2 0.2 e 0.3

Myrcene 1136 987 0.3 t e 0.9

a-Phellandrene 1148 e t e e e

Limonene 1184 1024 t t e t

b-Phellandrene 1196 1024 t t e e(Z )-b-ocimene 1211 1032 0.2 e e e

(E )-b-ocimene 1228 1042 1.8 t e e

p-Cymene 1251 1023 t t e t

Total 2.5 0.2 e 1.2

Oxygenated monoterpenes

cis-Linalool oxide 1410 1065 e e t t

trans-Linalool oxide 1438 1080 e e t e

Linalool 1500 1091 t t 0.3 0.3

cis-Chrysanthenyl acetate 1540 1256 0.8 0.8 2.3 4.1

1 1646 1313 12.0 14.1 18.2 41.4

trans-Myrtanol acetate 1719 1375 e e t t e e e e

t e e e

10.9 5.9 22.7 19.9

0.7 0.5 1.2 1.0

2.9 1.8 1.4 1.5

e 1.5 0.5 0.4

0.6 m 0.5 0.4

e e e e

3.4 5.6 1.1 0.7

0.5 0.6 2.3 1.9

e 1.0 1.5 1.0

e e 1.8 1.3

2.1 0.5 e e

e e 0.6 1.1

e 8.5 3.1 2.6

0.6 1.1 0.5 0.8

1.4 0.3 e em 0.4 0.3 0.4

t 2.2 0.5 1.6

1.3 0.2 t 0.4

0.5 0.3 t 0.4

0.4 t e e

t t e e

14.4 24.5 15.3 15.5

e 0.6 1.2 0.6

e 0.6 3.8 2.4

e e 0.8 0.6

0.4 e t t

0.7 0.3 0.6 m

e e 0.7 m

19.6 2.0 26.6 28.5

1.9 1.0 1.3 1.1

(continued on next page)

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Cuminaldehyde 1762 1237 e e e e

Total 12.8 14.9 20.8 45.8

Sesquiterpene hydrocarbons

a-Copaene 1483 1368 t 0.6 t t

b-Maalienec 1515 1372 0.9 1.5 1.0 0.5

b-Cubebene 1518 1382 t 0.2 e ea-Isocomene 1525 1378 t 0.4 t t

a-trans-Bergamotene 1564 1429 t t e e

b-Elemene 1569 1386 0.9 1.2 1.0 1.0

b-Copaenec 1580 1422 t m t t

b-Caryophyllene 1583 e 0.6 m e e

a-Humulene 1655 1444 0.9 1.0 e e

g-Muurolene 1668 1466 e e t e

d-Selinene 1671 1483 2.7 2.7 e eGermacrene D 1695 1476 4.0 3.3 e e

a-Muurolene 1703 1491 0.3 0.6 e e

b-Selinene 1706 1476 e e t t

a-Selinene 1711 1487 0.5 1.0 e e

d-Cadinene 1733 1514 0.5 1.0 t e

g-Cadinene 1739 1505 e e t e

trans-Calamene 1807 1512 e e m t

a-Calacorene 1890 1533 e e m t

b-Calacorene 1931 1554 e e t t

Total 11.3 13.5 2.0 1.5

Oxygenated sesquiterpenes

Epicubebol 1854 1487 0.7 0.8 t e

Cubebol 1903 1510 2.4 1.7 e e

Caryophyllene oxide 1964 1583 e e 2.3 0.7

Nerolidold 1977 e 0.6 0.2 e e

Humulene epoxide II 2018 1601 e e 1.0 0.3

Elemol 2031 1549 2.6 1.4 t 0.2

2 2109 1580 20.5 19.2 39.3 28.3

T-muurolol 2147 1635 0.7 0.6 m 0.3

Table 2 (continued)

Compounds RIa %b

folia P. argentea P. boivinii P. salaziana

November April November April November April November

6.3 e e e e 1.6 2.8

5.6 e e 0.6 e 1.2 2.4

0.6 0.6 0.7 2.7 1.4 1.2 1.3

1.6 e e 0.8 - 0.7 0.5

0.6 e e 1.7 0.4 t t

38.6 43.2 30.5 28.4 6.3 39.7 40.2

e e e 0.4 0.4 e e

e t t e e e ee t t 0.4 0.4 e e

68.4 68.0 79.7 58.1 67.5 82.7 82.9

x capillary column and on the HP-5MS column.

column; m: mixture; t: trace (!0.1%).

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Supelcowax HP-5MS P. anchusi

April

Bulnesol 2171 1665 7.0

a-Eudesmol 2188 1649 4.6

a-Cadinol 2191 1650 0.9

b-Eudesmol 2196 e 1.2

Selin-11-en-4-a-ol 2217 e 0.6

Total 41.8

Miscellaneous compounds

(E )-b-damascone 1786 1406 e

b-Ionone 1907 1478 eTotal e

% Identification 68.8

a Retention indices relative to C8eC22 n-alkanes on the Supelcowab Relative percentage obtained from peak area on the Supelcowaxc Tentatively identified.d Correct isomer non-identified.


Acknowledgements

Financial support from the Conseil Regional of Reunion Island is gratefullyacknowledged.

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Essential oil composition of four Psiadia species from Reunion Island: A chemotaxonomic study