alexa Composition of Essential Oils from Five Endemic Hypericum Species of Turkey

ISSN: 2161-0401

Organic Chemistry: Current Research

  • Research Article   
  • Organic Chem Current Res 2013, Vol 2(1): 113

Composition of Essential Oils from Five Endemic Hypericum Species of Turkey

Moussa Ahmed1*, Noureddine Djebli2, Saad Aissat1, Baghdad Khiati1, Salima Douichene2, Abdelmalek Meslem1 and Abdelkader Berrani1
1Institute of Veterinary Sciences University Ibn-Khaldoun, Tiaret, Algeria
2Departments of Biology, Faculty of Sciences, Mostaganem University, Algeria
*Corresponding Author: Moussa Ahmed, Institute of Veterinary Sciences University Ibn-Khaldoun, Tiaret, Algeria, Tel: +213 65234059, Fax: +213 65234059, Email: [email protected]

Received Date: Dec 05, 2012 / Accepted Date: Dec 26, 2012 / Published Date: Dec 30, 2012

Abstract

Nearly 350 Hypericum species exist on the earth, widely spreading in Europe, Asia and North Africa. 32 of 80 species growing in Turkey are endemic. The chemical composition of the essential oils obtained from the aerial parts of the H. uniglandulosum Hausskn. ex Bornm., H. scabroides Robson and Poulter, H. kotschyanum Boiss., H. salsugineum Robson and Hub.-Mor. and H. thymopsis Boiss. By using the hydro-distillation method is identified by GC and GC/ MS. Finally the results are compared with each other. The differences between the results of the H. thymopsis and H. scabroides obtained in this study and the previous studies show that the chemical compositions of the essential oils are different for the same species obtained at different locations. The essential oil compositions of these species, except for the H. thymopsis and H. scabroides are identified for the first time.

Keywords: Hypericum species; Essential oil composition; Turkey

Introduction

The genus Hypericum (Hypericaceae) is represented by nearly 100 taxa grouped under 19 sections in Turkey. Among them, 45 taxa are endemic. In the traditional medicine of Turkey, the genus is known as “sarı kantaron, kantaron, binbirdelik otu, mayasıl otu” and most of them, especially H. perforatum, have been used for the treatment of burns, wounds, haemorroids, diarrhorea and ulcers [1-5]. Moreover, aqueous extracts prepared from the flowering aerial parts of the Hypericum species are being used in the treatment of psychological diseases such as neuralgia, anxiety, neurosis and depression [6]. The preparative forms of the Hypericum perforatum (St. John’s Wort) are sold for the treatment of mild to moderate depression in the USA and Europe.

The chemical composition of the Hypericum species is composed of naphthodianthrones (especially hypericin and pseudohypericin), acylphloroglucinol derivatives (especially hyperforin and adhyperforin), flavonoids (especially quercetin, quercitrin, hyperoside and biapigenin), tannins, n-alkanes, xanthones and essential oils [7-9].

The essential oil compositions of about 50 different Hypericum species have so far been identified [10-13]. In this study, the oils of 5 endemic Hypericum species were obtained by hydro-distillation method. The oil compositions were identified by GC and GC/MS. Except for the H. thymopsis and H. scabroides the essential oil of which were obtained by hydro-distillation and the oils composition of which were reported previously [13,14], the species investigated in this study were studied for the first time to the knowledge of the authors. In this study, a comparison between the volatile oil compositions of H. thymopsis and H. scabroides species obtained from different locations were performed.

Materials and Methods

Plant material

Flowering aerial parts of H. uniglandulosum were collected from east Anatolia, namely, Erzincan: Erzincan-Eski Çayırlı road, 10 km to Eski Çayırlı, 1450 m, 15.07.2006, that of H. scabroides were collected from east Anatolia, namely, Erzincan: Erzincan-Kelkit, 15 km to Kelkit, 1550 m, 14.07.2006, that of H. kotschyanum were collected from south Anatolia, namely, İçel: North-west of Arslanköy, 1840 m, 15.06.2006, that of H. salsugineum were collected from central Anatolia, namely, Konya: around The Salt Lake, on 01.07.2005, that of H. thymopsis were collected from central Anatolia, namely, Sivas: Sivas-Malatya road, Ziyarettepe, 1350 m, 10.07.2005. Specimens were identified and vouchers were deposited in the Herbarium of Istanbul University, Faculty of Pharmacy (Ä°stanbul Üniversitesi Eczacılık Fakültesi Herbaryumu, Ä°stanbul, Turkey) under code numbers of ISTE 85344, ISTE 85343, ISTE 83979, ISTE 85341 and ISTE 85342, respectively.

Isolation of the essential oil by hydro-distillation method

Air dried and powdered plant materials were subjected to hydrodistillation in a Clevenger-type apparatus according to the method recommended in the European Pharmacopoeia [15]. The oils obtained for this study were stored at +4°C by avoiding the daylight contact before the analysis.

Gas chromatography/mass spectrometry (GC/MS)

The GC/MS analysis was carried out with an Agilent 5975 GCMSD system. Innowax FSC column (60 m×0.25 mm, 0.25 μm film thickness) was used with helium as carrier gas (0.8 mL/min). GC oven temperature was kept at 60°C for 10 min and programmed to 220°C at a rate of 4°C/min and kept constant at 220°C for 10 min and then programmed to 240°C at a rate of 1°C/min. Injection volume was 1 μL (10%) in hexane. Split ratio was adjusted at 40:1. The injector temperature was set at 250°C. Mass spectra were recorded at 70 eV. Mass range was from m/z 35 to 450.

Gas chromatography (GC)

The GC analysis was carried out using an Agilent 6890N GC system. FID detector temperature was 300°C. To obtain the same elution order with GC-MS, simultaneous auto-injection was done on a duplicate of the same column applying the same operational conditions. Relative percentage amounts of the separated compounds were calculated from FID chromatograms. The analysis results are given in Table 1.

Compound RRI UN SB KC SG TP
α-Pinene 1032 2.7 3.1 14.4 - 44.0
Camphene 1076 - - 0.5 - 5.2
Hexanal 1093 - - - - -
Undecane 1100 1.9 0.3 0.1 tr -
β- pinene 1118 - - 8.7 - 1.7
Limonene 1203 0.2 1.0 5.1 - 7.6
(Z)-3-hexenal 1225 - - - - -
γ - terpinene 1255 - - 0.7 - -
p- cymene 1280 - 0.3 1.5 - -
Terpinolene 1290 - - - - -
6-methyl-5-hepten-2-one 1348 0.9 - - - -
Hexanol 1360 - - - - -
2,6 Dimethyl-3,5 heptadien-2-one* 1377 40.7 - - - -
Nonanal 1400 0.1 - - - -
trans-linalool oxide (furanoid) 1450 - - - 0.2 -
α,p-dimestyrene 1452 - - - - -
cis-linalool oxide (furanoid) 1478 0.9 - - 0.1 -
Longipinene 1482 - - - - -
Bicycloelemene 1495 - - - 0.7 -
α- copaene 1497 0.1 0.5 0.6 0.3 -
α- campholene aldehyde 1499 0.2 0.2 0.6 - -
β- bourbonene 1535 - - - 0.3 -
Linalool 1553 1.2 - - 0.1 -
Octanol 1562 - - - - -
Pinocarvone 1586 - - 0.3 - -
α -Pinene 1032 2.7 3.1 14.4 - 44.0
Camphene 1076 - - 0.5 - 5.2
Hexanal 1093 - - - - -
Undecane 1100 1.9 0.3 0.1 tr -
β- pinene 1118 - - 8.7 - 1.7
Limonene 1203 0.2 1.0 5.1 - 7.6
(Z)-3-hexenal 1225 - - - - -
γ - terpinene 1255 - - 0.7 - -
p- cymene 1280 - 0.3 1.5 - -
Terpinolene 1290 - - - - -
6-methyl-5-hepten-2-one 1348 0.9 - - - -
Hexanol 1360 - - - - -
2,6 Dimethyl-3,5 heptadien-2-one* 1377 40.7 - - - -
Nonanal 1400 0.1 - - - -
trans-linalool oxide (furanoid) 1450 - - - 0.2 -
α,p-dimestyrene 1452 - - - - -
cis-linalool oxide (furanoid) 1478 0.9 - - 0.1 -
Longipinene 1482 - - - - -
Bicycloelemene 1495 - - - 0.7 -
α- copaene 1497 0.1 0.5 0.6 0.3 -
α- campholene aldehyde 1499 0.2 0.2 0.6 - -
β- bourbonene 1535 - - - 0.3 -
Linalool 1553 1.2 - - 0.1 -
Octanol 1562 - - - - -
Pinocarvone 1586 - - 0.3 - -
Carvone 1751 0.1 - - - -
Bicyclogermacrene 1755 - - - 1.0 -
1-decanol 1766 - - - - -
Decanol 1766 - - 0.3 - -
δ-Cadinene 1773 tr 1.6 0.6 0.4 tr
γ -Cadinene 1776 0.4 2.2 0.6 0.3 tr
p-methyl acetophenone 1797 - - - - -
Myrtenol 1804 0.2 - 0.4 - -
α-cadinene 1807 - - - - -
Methyl dodecanoate 1815 - - - 0.2 -
trans -carveol 1845 0.3 0.9 0.3 - -
Calamenene 1849 1.0 1.8 0.9 0.3 -
Geraniol 1857 1.0 - - - -
p-simen-8-ol 1864 - - - - -
(E)-Geranylacetone 1868 0.2 - 0.4 0.1 -
α -calacorene 1941 0.1 1.2 0.6 - -
1,5- Epoxysalvial-4(14)-ene 1945 - - 1.0 - -
(E)-β-Ionone 1958 0.1 - - - -
1 -Dodecanol 1973 0.5 - - 1.5 -
Eicosane 2000 0.1 - - - -
Caryophyllene oxide 2008 0.3 1.7 1.3 0.1 -
Methyl eugenol 2030 - - - - -
Salvial -4(14)-en-1-one 2037 0.6 - - tr -
1-Tridecanol 2077 - - - 0.2 -
Octanoic acid 2084 0.1 1.0 - - -
Globulol 2098 0.2 - - - -
Heneicosane 2100 - - - 0.2 -
Viridiflorol 2104 - - - 0.2 -
Salviadienol 2130 - - - - -
Hexahydrofarnesylacetone 2131 0.6 1.4 0.8 1.1 tr
Spathulenol 2144 1.5 5.3 6.3 - 8.0
1-Tetradecanol 2179 0.3 - - 0.5 -
T -cadinol 2187 - tr - - -
Nonanoic acid 2192 0.3 2.2 - - -
Docosane 2200 0.1 - - - -
T- Muurolol 2209 0.2 - - 0.1 -
Methyl hexadecanoate 2226 0.1 - - 0.2 -
Carvacrol 2239 - - 2.4 - -
α-cadinol 2255 0.3 1.8 0.8 0.2 tr
Cadalene 2256 0.4 3.0 0.8 0.2 0.5
Ethyl hexadecanoate 2262 0.2 - - - -
Decanoic acid 2298 0.6 - - - -
Tricosane 2300 0.9 0.6 0.8 0.6 -
Eudesma-4(15),7-dien-1β-ol 2369 - - 0.9 0.7 tr
1-Hexadecanol 2384 - - - 0.1 -
Undecanoic acid 2400 0.2 - - - -
Tetracosane 2400 - - - 0.4 -
Pentacosane 2500 0.2 2.6 3.9 1.9 -
Dodecanoic acid 2503 2.3 4.1 3.0 0.1 tr
Hexacosane 2600 - - - 0.2 -
Phytol 2622 - - tr 0.7 -
Benzyl benzoate 2655 0.1 - 1.8 - -
Baeckeol 2668 0.9 4.1 2.4 6.1 32.9
Tetradecanoic acid 2670 0.8 2.9 2.4 2.5 -
Heptacosane 2700 0.1 1.2 1.0 2.2 -
Octacosane 2800 - - - 1.3 -
Pentadecanoic acid 2822 - - - 1.2 -
Nonacosane 2900 3.2 4.4 11.1 42.7 tr
Hexadecanoic acid 2931 2.7 17.7 9.2 23.2 tr
TOTAL   72.7 75.3 92.4 96.9 99.9

UN: H. uniglandulosum, SB: H. scabroides, KC: H. kotschyanum, SG: H. salsugineum
TP: H. thymopsis
RRI Relative retention indices calculated against n-alkanes
% calculated from FID data
tr Trace (<0.1%)
*Tentative identification

Table 1: Percentage of volatiles of 5 endemic Hypericum species.

Identification of components

Identification of the essential oil components were carried out by comparison of their relative retention times with those of authentic samples or by comparison of their relative retention index (RRI) to series of n-alkanes. Computer matching against commercial (Wiley GC/MS Library, Adams Library, MassFinder 3 Library) [16,17], and inhouse “Başer Library of Essential Oil Constituents” built up by genuine compounds and components of known oils, as well as MS literature data [18,19], was also used for the identification.

Results and Discussion

By hydro-distillation, volatile oils were obtained from the aerial parts of the H. uniglandulosum, H. scabroides, H. kotschyanum, H. salsugineum and H. thymopsis with yields of 0.67% (v/w), trace (in hexane), 0.67% (v/w), trace (in hexane), 0.67% (v/w), respectively. The analyses were performed by using GC and GC/MS. The list of the essential oil components where the oils were obtained by hydrodistillation, are given in Table 1. Fifty-eight constituents corresponding to the 72.7% of the oil (UN) from the H. uniglandulosum, thirtytwo constituents corresponding to the 75.3% of the oil (SB) from H. scabroides, forty-five constituents corresponding to the 92.4% of the oil (KC) from the H. kotschyanum, fifty-four constituents corresponding to the 96.9% of the oil from the H. salsugineum, seventeen constituents corresponding to the 99.9% of the oil (TP) from the H. thymopsis were identified. 2,6-Dimethyl-3,5-heptadien-2-one (40.7%), nonacosane (3.2%), hexadecanoic acid (2.7%) and α-pinene (2.7%) were characterized as the main components of the H. uniglandulosum (UN).

Hexadecanoic acid (17.7%), spathulenol (5.3%), nonacosane (4.4%), dodecanoic acid (4.1%), baeckeol (4.1%) and γ-muurolene (3.9%) were characterized as the main components of the H. scabroides (SB). α-pinene (14.4%), nonacosane (11.1%), hexadecanoic acid (9.2%), β-pinene (8.7%), spathulenol (6.3%) and limonene (5.1%) were characterized as the main components of the H. kotschyanum (KC). Nonacosane (42.7%), hexadecanoic acid (23.2%) and baeckeol (6.1%) were characterized as the main components of the H. salsugineum (SG). α-pinene (44.0%), baeckeol (32.9%), spathulenol (8.0%), limonene (7.6%) and camphene (5.2%) were characterized as the main components of the H. thymopsis (TP). The chemical class distribution of the volatile oils of 5 different species obtained by hydro-distillation is given in Table 2.

Chemical Class UN (#/%) SB (#/%) KC (#/%) SG (#/%) TP (#/%)
Monoterpene Hydrocarbons 2 / 2.9 3 / 4.4 6 / 30.9 - 4 / 58.5
Oxygenated Monoterpenes 12 / 4.3 4 / 5.0 11 / 7.5 6 / 0.7 2 / Tr
Sesquiterpene Hydrocarbons 11 / 3.5 9 / 16.2 9 / 7.1 17 / 7.3 4 / 0.5
Oxygenated Sesquiterpenes 6 / 3.0 4 / 7.2 5 / 10.1 5 / 1.1 2 / 8.0
Alkanes + Alkenes 7 / 6.5 5 / 9.1 5 / 16.9 9 / 49.5 1 / Tr
Fatty acids 8 / 7.9 5 / 27.9 3 / 14.6 6 / 27.3 2 / Tr
Others 12 / 44.6 2 / 5.5 5 / 5.3 11 / 11.0 2 / 32.9
TOTAL 58 / 72.7 32 / 75.3 45 / 92.4 54 / 96.9 17 / 99.9

#: number of compound, % relative percentage

Table 2: The chemical class distribution of the oil components of 5 endemic Hypericum species.

It has been observed that, the UN oil was rich in terms of carbonylic compounds and fatty acids. The oil of SB was rich in terms of sesquiterpene hydrocarbons and fatty acids. The KC oil, on the other hand, was dominated by monoterpene hydrocarbons, alkanes, oxygenated sesquiterpene hydrocarbons and fatty acids. The SG oil contained alkanes and fatty acids. The TP oil was found to be rich in monoterpene hydrocarbons and a phenolic-compound. As a result of this research α-pinene, 2,6 dimethyl-3,5-heptadien-2-one, baeckeol, nonacosane and hexadecanoic acid were identified as major volatile constituents (>10%) in Hypericum species.

Comparing the main constituent of the H. uniglandulosum oil to the other studies, the followings are observed; 2,6 Dimethyl-3,5- heptadien-2-one was found to be the major component only in H. tetrapterum from Serbia [20].

Hexadecanoic acid and spathulenol were detected in high amount in H. scabroides in this study, however, the δ-3-carene and sabinene were reported as the main constituents of the H. scabroides collected from different locations [21]. Nonacosane was found to be the major component only in two species, namely H. salsugineum and H. davisii [14].

It was observed that α-pinene was found to be the main component in H. kotschyanum and H. thymopsis. Among the previous studies about Hypericum essential oils from Turkey, many taxa were characterized by the high amount of α-pinene [11,18,22-29], namely H. calycinum, H. cerastoides, H. montbretii, H. scabrum, H. perforatum [30,31], H. hyssophyfolium subsp. elongatum var. elongatum [32], H. capitatum var. capitatum, H. aviculariifolium subsp. depilatum var. depilatum [32], H. apricum [19], α-pinene, baeckeol, limonene and spathulenol were identified as major components in H. thymopsis, although baeckeol and limonene were not determined in a previous study. α-pinene, germacrene D, δ-cadinene, γ-cadinene, spathulenol, α-cadinol, eudesma-4(15),7-dien-1β-ol, nonacosane and hexadecanoic acid were identified both in this study and the previous one [13]. Essential oil compositions of species show difference in the sense of collecting regions and dates. Chemical profiling using volatiles may be useful in taxonomical classifications.

Acknowledgements

The authors would like to thank Tuba KIYAN for her assistance.

References

Citation: Ahmed M, Djebli N, Aissat S, Khiati B, Douichene S, et al. (2013) Composition of Essential Oils from Five Endemic Hypericum Species of Turkey. Organic Chem Curr Res 2: 113.

Copyright: ©2013 Ahmed M, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

Select your language of interest to view the total content in your interested language

Post Your Comment Citation
Share This Article
Relevant Topics
Recommended Conferences
  • International Conference on Organic and Inorganic Chemistry

    July 12-13, 2018 Paris, France

  • 5th International Conference on Organic and Inorganic Chemistry

    July 12-13, 2018 Paris, France

  • International Conference on Organic & Inorganic Chemistry

    July 18-19 , 2018 Atlanta, USA

  • International conference on Organic Farming & Biological Treatment

    September 19-20, 2018 Dallas, USA

  • 10th Europian Organic Chemistry Congress

    March 21-22, 2019 Rome, Italy

Viewmore
Article Usage
  • Total views: 11879
  • [From(publication date): 3-2013 - May 24, 2018]
  • Breakdown by view type
  • HTML page views: 8093
  • PDF downloads: 3786

Post your comment

captcha   Reload  Can't read the image? click here to refresh
Leave Your Message 24x7