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Comptes Rendus

Chemical composition of essential oil of Pinus halepensis Miller growing in Algeria
Comptes Rendus. Chimie, Volume 8 (2005) no. 11-12, pp. 1939-1945.

Résumés

The chemical composition of the volatile oil extracted by hydrodistillation from the needles of Pinus halepensis Miller, grown in natural habitats in Sidi Feradj (Algiers region), was obtained with yield 0.52% and analysed by GC and GC–MS. More than 41 compounds, representing 67.02% of total oil, were identified. The oil was found to be rich in β-caryophyllene (40.31%), α-humulene (7.92%) and aromadendrene (7.1%). .

La composition chimique de l'huile essentielle extraite par hydrodistillation (rendement: 0,52%) des aiguilles fraîches de Pinus halepensis Mill. récoltées à Sidi Feradj (région d'Alger), a été analysée par CPG et CPG–SM. Quarante et un constituants, représentant 67,02% de l'huile totale, ont été identifiés. Les constituants majoritaires sont le β-caryophyllène (40,31%), l'α-humulene (7,92%) et l'aromadendrene (7,1%). .

Métadonnées
Reçu le :
Accepté le :
Publié le :
DOI : 10.1016/j.crci.2005.05.007
Keywords: Pinus halepensis, Pinaceae, Aleppo pine, Essential oil chemical composition, β-Caryophyllene, α-Humulene
Mots clés : Pinus halepensis, Pinaceae, Pin d'Alep, Composition chimique de l'huile essentielle, β-caryophyllène, α-humulene

Tahar Dob 1, 2 ; Tayeb Berramdane 1 ; Chaabane Chelgoum 2

1 Laboratoire de molécules bio-active et valorisation de la biomasse, École normale supérieure, BP 92, Kouba-Algiers, Algeria
2 Laboratoire de chromatographie, faculté de chimie, USTHB, Algiers, Algeria
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     author = {Tahar Dob and Tayeb Berramdane and Chaabane Chelgoum},
     title = {Chemical composition of essential oil of {\protect\emph{Pinus} halepensis} {Miller} growing in {Algeria}},
     journal = {Comptes Rendus. Chimie},
     pages = {1939--1945},
     publisher = {Elsevier},
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Tahar Dob; Tayeb Berramdane; Chaabane Chelgoum. Chemical composition of essential oil of Pinus halepensis Miller growing in Algeria. Comptes Rendus. Chimie, Volume 8 (2005) no. 11-12, pp. 1939-1945. doi : 10.1016/j.crci.2005.05.007. https://comptes-rendus.academie-sciences.fr/chimie/articles/10.1016/j.crci.2005.05.007/

Version originale du texte intégral

1 Introduction

The genus Pinus (Pinaceae) comprises 250 species and is widespread in the northern hemisphere, especially in the Mediterranean region, Caribbean area, Asia, Europe, North and Central America [1–4].

The medicinal and aromatic properties of the chemical compounds (e.g., turpentine, resins and essential oil…) of pine make it one of the most popular plants throughout all civilisation. Pine is also still widely used in traditional therapeutic practice in world and has an economic importance [5–7].

The chemical composition of various pine species has been the subject of numerous studies, the majority of the studies focused on North American and Central European species [6,8–10] and only a limited number of chemically oriented reports dealt with Mediterranean pine species [11–13]. Most bibliographical studies of chemical, biological, antimicrobial activities and genetic side of P. halepensis have been reported [11–22].

As part of an extensive phytochemical analysis of P. halepensis growing in Algeria, we have oriented our first investigation towards the chemical composition of the essential oil obtained from the needles of P. halepensis Mill. collected in Algiers region (Sidi Feradj) in Algeria.

2 Experimental

2.1 Plant material

The needles of P. halepensis Mill. were collected in May 2002, at the forest of Sidi Feradj (Algiers). The plant was authenticated by Mr A. Beloued in botanical department, National Agronomic Institute of Algiers (N.A.I), Algeria (Herbarium No. P. 105). The samples were dried in shad ventilated place.

2.2 Oil isolation

The needles were cut into small pieces and separately hydrodistilled for 2 h in a Clevenger-type apparatus with water cooled receiver, in order to reduce hydrodistillation overheating artifacts. The essential oil was taken up in diethyl ether and dried over sodium sulphate and reduced at room temperature under vacuum on rotatory evaporator. The oil obtained was stored at (+4 °C) until analysis.

2.3 Analysis of essential oil

2.3.1 Gas chromatography

GC analysis was performed on a Chrompack CP 9002 chromatograph using fused silica capillary columns with two different stationary phases DB-1 and PEG. The various parameters fixed for DB-1 column are: 30 m × 0.32 mm i.d.; film thickness 0.25 μm column; temp. prog., 50 °C for 3 min then 2 °C/min to 260 °C for 5 min; detector heaters 280 °C; injector heaters 250 °C; nitrogen was used as carrier gas at a flow rate of 1 ml/min in the split mode (Split ratio 1:50), with an injection vol. 0.2 μl. For PEG the parameters are: 30 m × 0.32 mm i.d.; film thickness 0.25 μm column; temp. prog., 50 °C for 3 min then 2 °C/min to 220 °C for 15 min; others parameters as the same for the DB-1 column. Components were quantified as area percentages of total volatiles from the GC–FID system without correction factors.

In order to determine retentions indices (RI) a series of n-alkanes (C5–C28) mixture was analysed under the same operative conditions on DB-1 and PEG columns and the sample indices were calculated following Van den Dool and Kratz [23].

2.3.2 Gas chromatography and mass spectrometry

Mass spectra were obtained from GC–MS analysis on a Trace MS Finnigan chromatograph system equipped with a 30 m × 0.32 mm i.d.; film thickness 0.25 μm DB-1 capillary column it was programmed from 50 °C (3 min) to 260 °C (5 min) at 2 °C/min with helium carrier gas at a flow rate of 1 ml/min and injector heater 250 °C. The mass-spectrometer was operating (full scan-mode) in the EI-mode at 70 eV.

2.3.3 Component identification

Identification of components was made on the basis of their retention indices on non-polar (DB-1) and/or on polar (PEG) columns and by computerised matching of the acquired mass spectra with those stored in the spectrometer data base using Willey mass spectral library and with the literature [13,22–25].

3 Results and discussion

The needles from Pinus halepensis collected for the present study were obtained from Algiers region (Sidi Feradj). It's collected from various parts of crowns. Since all of samples were collected in May 2002, the effect of the seasonal variation was diminished [26]. The oil was obtained from the Aleppo pine needles with a yield of 0.52% (v/w).

The chromatographic profile showed a complex mixture of components with a consistent fraction of monoterpenes and sesquiterpenes.

The list of the compounds, in order of elution on DB-1, and the quantitative data (GC–FID peak area percentages without correction factors), are reported in Table 1. More than 41 oil compounds were identified accounting for 67.02% of the total oil, while 32.98% of the oil remained unidentified (Fig. 1).

Table 1

Qualitative and quantitative composition of needles oil of P. halepensis Miller

Compound a% on DB-1R. I.b on DB-1R.I. on PEGMethod of identification
Tricyclenetr915GC, GCMS
α-Pinene1.239221036GC, GCMS
Camphenetr957GC,GCMS
Sabinene1.239601127GC, GCMS
β-Pinene0.23978GC, GCMS
Myrcene3.079971140GC, GCMS
α-Phellandrenetr10021296GC, GCMS
Hexyle acetate0.710081268GC, GCMS
δ-3-Carene0.1510111140GC, GCMS
α-Terpinene0.1110211181GC, GCMS
Limonenetr1032GC, GCMS
β-Ocimene0.2110411247GC, GCMS
γ-Terpinenetr10621231GC, GCMS
α-Terpinolene0.131088GC, GCMS
α-Pinene oxide0.0610951488GC, GCMS
Linalooltr10981566GC, GCMS
Camphortr1143GC, GCMS
Borneol0.1311651695GC, GCMS
Terpinen-4-oltr11771591GC, GCMS
p-Cymen-8-oltr11831823GC, GCMS
α-Terpineol0.0711891684GC, GCMS
α-Terpinyl acetatetr1350GC, GCMS
α-Cubebene0.171351GC, GCMS
Citronellyl acetate0.191354GC, GCMS
α-Yalangene0.6413721481GC, GCMS
(Z)-β-Caryophyllene40.3114041591GC, GCMS
α-Guaiene0.11437GC, GCMS
Aromadendrene7.114391599GC, GCMS
α-Humulene7.921454GC, GCMS
allo-Aromadendrene0.6514611685GC, GCMS
γ-Muurolene0.0614771715GC, GCMS
Germacrene-D0.4914801702GC, GCMS
Bicyclogermacrenetr14941723GC, GCMS
β-Bisabolenetr1509GC, GCMS
δ-Cadinene0.1315131777GC, GCMS
β-Sesquiphellandrene0.5315241776GC, GCMS
Z-Nerolidol0.071534GC, GCMS
Elemol0.681549GC, GCMS
δ-Cadinol0.2316222152GC, GCMS
γ-Eudesmol0.081630GC, GCMS
Monoyl oxidetr1989GC, GCMS
Monoterpene hydrocarbon6.48%
Oxygenated monoterpene0.36%
Sesquiterpene hydrocarbon58.20%
Oxygenated sesquiterpene1.06%

a Order of elution on DB-1.

b Retention indices. tr: Trace (<0.05%).

Fig. 1

Chemical composition groups of needles oil of P. halepensis.

Amounting to 67.02% of the total oil, the sesquiterpene hydrocarbons had the highest contribution (58.20%), this fraction dominated by β-caryophyllene (40.31%), followed by α-humulene (7.92%) and aromadendrene (7.10%). The monoterpene was relatively poor; it represented (6.50%) in monoterpene hydrocarbons, it is found to contain a significant percent of myrcene (3.07%), followed by α-pinene (1.23%) and sabinene (1.23%). The oil is characterised by 13 compounds could be detected in traces (< 0.05%).

Table 2 summarises previous investigations of authors on the analysis of the volatile oils from several population of P. halepensis. The chemical composition of our P. halepensis Mill. oil was dominated by β-caryophyllene, these results agree with data obtained by Roussis et al. who found that monoterpene (41.8%) was dominated in Greece pine oils with remarkable differences concerning the amounts of component: caryophyllene (19.05%) [11]. Vidrich et al. [27] have reported that β-caryophyllene (26.31%) play an important part of the Italy oil. Macchioni et al. [13] found main compounds of the needles oil of Aleppo pine grown in Italy to be: myrcene (27.9%), α-pinene (18.1%) and β-caryophylene (16.4%), with a 73.2% of monoterpenes and 21.2% of sesquiterpenes. When our results were compared with the chemical composition of essential oils obtained from the leaves of P. halepensis collected in region of Tessimsilt and Djelfa (Algeria) in 1987, remarkable differences were observed: myrcene (8.65%) and α-pinene (17.56%), dominated in later sites, respectively [19].

Table 2

Chemical composition of needles oils of P. halepensis as reported in the literature

ConstituentsOuer studyGreece [11]ItalyMorocco [12]Algiers [19]
[13][27]TaDb
Tricyclenetr1.600.04
α-Thujene0.160.10.4
α-Pinene1.2313.418.18.5423.36.6617.56
Camphenetr.0.440.30.090.50.170.33
Sabinene1.231.279.46.133.76.952.59
β-Pinene0.231.132.01.133.12.041.56
Myrcene3.076.6227.912.4816.38.653.22
3-Octanol0.06
α-Phellandrenetr0.050.811.6
Hexyl acetate0.7
δ-3-Carene0.156.871.70.871.880.13
α-Terpinene0.110.300.50.791.30.650.04
p-Cymen1.111.410.70.273.07
Limonenetr5.031.10.981.30.80.14
β-Phllandrene1.01.270.970.66
1,8-Cineole1.671.3
cis-β-Ocimene0.110.07
trans-β-Ocimene0.210.41.772.050.04
γ-Terpinenetr0.420.80.242.41.180.02
cis-Sabinene hydrate0.1
α-Terpinolene0.133.079.910.10.19t
cis-3-Hexene-1-olt0.09
3,5-Dimethyl-styrenett
α-Pinene oxide0.06tt
Linalooltr0.780.30.410.392.01
Fenchol0.11
Camphortrt0.05
Borneol0.130.02
Umbellulone0.1
Terpinen-4-oltr0.73.80.59
p-Cymen-8-oltrt0.14
α-Terpineol0.070.540.20.60.291.48
cis-piperitolt
Methyl chavicol5.06
Decanale0.83
Fenchyl acetate0.28
Nerol0.04
d-Citronellolo1.26
l-Citronellolo0.41
Methyl thymyl ether0.10
Geranioltt
2-Phenyl ethyl acetate2.50.12
Bornyl acatatet0.16
Carvacrol1.72
δ-Elmene0.030.20
α-Terpenyl acetatetr0.01
α-Cubebene0.170.1tt
Citronellyl acetate0.19
Eugenol0.60
Neryl acetate0.36
α-Yalangene0.640.240.21
α-Copaene0.40.5t0.03
Z-3-Hexenyl-isovaleratett
Geranyl acetate0.190.30.865.3t0.29
β-Elemenet0.20
Methyl eugenoltt
(Z)-β-Caryophyllene40.31
(E)-β-Caryophyllene7.072.69
β-Caryophyllenec19.0516.426.3114.2
α-Gurjunene1.18
α-Guaiene0.1
α-Cedrene0.08
Aromadendrene7.1
cis-carane-trans 2-olt0.54
α-Elemenet0.58
α-Humullene7.923.362.93.22.771.38
Allo-aromadendrene0.65
Calarene0.39
Methyl iso-eugenol-20.27t
(E)-β-Farnesene0.2t0.03
9-epi-(E)-Caryophyllene0.1
γ-Muurolene0.060.290.19
Germacrene D0.490.50.10.210.03
δ-Selinenett
Phenyl ethyl-3-methyl butanoate1.2
Epi-Cubebol0.2
Bicyclogermacrenetr
Methyl iso-eugenol-l5.060.17t
α-Muurolene0.530.40.50.290.19
Bicycloelemenett
β-Bisabolenetr
trans-γ-Cadinene0.3
Calamenenet0.18
δ-Cadinene0.130.550.31.00.870.47
β-Sesquiphellandrene0.53
Levomenolt0.03
Ethyl lauratett
Terpenyl-n-butyratet1.48
β-Phenyl ethyl-isobutyratett
Phenyl ethyl 2-methyl-butyrate0.9710.29
Phenyl ethyl-isovalerate7.378.38
Elemol0.680.36t
Nerolidol0.07t
Caryophyllene oxide0.11.2
Globulol0.01
Phenyl ethyl-tiglate (E)tt
Guaiol1.050.30.200.17
Phenyl ethyl n-hexanoatett
Humulene epoxyde II0.170.17
Cubenolt
β-Eudesmolt
α-Eudesmol0.410.1
Cadinol1.1t0.17
α-Cadinol0.180.15
δ- Cadinol0.23
trans-Cadinolt0.17
γ-Eudesmol0.08
Phenyl ethyl-tiglate (Z)tt
Torreyoltt
Aristolene1.09
  • Butanoic acid, 3-methyl,
  • 2-phenyl ethyl ester
6.57
Kaureuoltt
Diethyl-phatalate0.08
Cembrene7.62
(11E,13Z) Labdadien-8-ol0.30
Neocembrene
Manoyle oxidetrt

a T: Tissemsilt.

b D: Djelfa.

c Correct isomer not identified.

Our results differ from those obtained by Hmamouchi et al. [12] who studied the oil composition of needles of the same specie sample in Morocco, in which α-pinene (23.3%) was revealed to be dominant and β-caryophylene (14.2%) present. Several reports on the composition of the needle oils of other Pinus species revealed that monoterpene hydrocarbons were the major constituents in the most of the oil, they often constituted 50% or more of the oil [4,12,13].

The comparison of our result with literature (Table 2) shows some qualitative and quantitative differences in compositions of P. halepensis oils. The variability in oil composition is present even in P. halepensis and these variations, sufficient to allow the distinction of different chemotypes, are the results of an adaptative process to particular ecologic conditions.

Acknowledgements

We are very grateful to P. Roland-Gosselin Thermo-Finnigan, France for her technical assistance.


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