Octanoic acid

Abstract

Essential oil composition of Helichrysum arenarium (L.) Moench. of natural populations from eastern Lithuania has been studied. Samples of leaves and inflorescences of different colors [yellow and orange (f. aurantiacum (Pers.) Bleck.)] were collected from the same growing localities at flowering stage. The oils were prepared by hydrodistillation and analyzed by GC and GC/MS. The 68 constituents identified comprised 73.8-90.7% of the total oil content. It was found that the principal constituents were: β-caryophyllene (in three inflorescence and one leaf oil), δ-cadinene (in two leaf oils), octadecane (in one leaf oil) and heneicosane (in one inflorescence sample). Monoterpenes and oxygenated monoterpenes made up 4.0-13.9%, aliphatic hydrocarbons 0.4-35.3%, and sesquiterpenes 24.7-71.2% of the oils.

Key Word Index

Helichrysum arenarium, Asteraceae, essential oil composition, β-caryophyllene, δ-cadinene, octadecane, heneicosane.

Plant name

Helichrysum arenarium (L.) Moench.

Source

The plant material was collected in eastern Lithuania (July-August, 2002). Voucher specimens were deposited in the Herbarium of the Institute of Botany (BILAS), Vilnius, Lithuania. Numbers of growing localities of H. arenarium with yellow (Y) and orange (O) flowers were as follows: Svencionys district (Zalavas) - AY-65223, AO-65222 and Ukmerge district (Sventupe) - BY-65219, BO-65220.

Introduction

The genus Helichrysum belonging to the family Asteraceae (1) consists of about 500 species and are mostly spread in the Eastern hemisphere, especially many in Africa and Madagascar where many species grow.

Helichrysum arenarium (L.) Moench. is the only species of the genus that grows wild in Lithuania. The plant is spread over the entire country, but is most common in the southeastern part of Lithuania. The preferred growing habitats are dry and sandy soil in forest or meadow. Helichrysum arenarium is a perennial herb that reaches up to 50 cm in height, with grayish leaves and steins that are covered with white down. The phenotypic study on H. arenarium from natural habitats indicated that color of flowers varies from yellow to orange (2). The majority of inflorescences are of various shades of yellow color, and only few plants (just about 7% of all plants) have orange or even brown racemes (2). The plants with orange inflorescences are treated as morphological form - f. aurantiacum (Pres.) Bleck. (1).

Most of the Helichrysum species have been studied for their essential oils or extracts (3-20), which possess potent pharmacological properties (13-20). The inflorescence of H. arenarium (Helichrysiflos) has long been know in European herbal medicine for its choleretic, diuretic, anti-inflammatory, hepatoprotective, detoxifying and antiradical activities (21-25), bioactivity in many cases influenced by flavonoids, polyphenols, phenolic acids. Three subspecies of H. arenarium growing in Turkey were examined in regard to their flavonoids (26). In Lithuanian folk medicine the H. arenarium has been used internally as a remedy for digestive problems as well as in external medicine. Dried plants are used as a repellent against brown house moths.

Volatile chemistry of different Helichrysum genus was intensively investigated by many researches (3-20), but the number of investigations on the oil of H. arenarium plants is very limited. The oil of H. arenarium plants collected in the Caucasus region has recently been analyzed (27). The inflorescence oil was formed mainly by aliphatic acids (34.6%), their esters (28.5%) and further aromatic compounds (10.2%), in addition to other volatile components typical for Helichrysum genus. The characteristic constituents of the oils were linalool (1.7%), anethole (3.2%), carvacrol (3.6%) andcc-muurolol (1.3%). The major components of the everlasting oils of Polish and Hungarian mercantile samples were methyl palmitate (28.5% and 21.7%, respectively) and caprinic acid (19.8%) of cultivated plants in another study (28).

The aim of the present study was the investigation of chemical composition of the oils of wild H. arenarium plants with yellow and orange [f. aurantiacum (Pers.) Bleck.] flowers collected from the same natural habitats in eastern Lithuania.

Experimental

Helichrysum arenarium plants sampled from two growing localities were dried at room temperature (20°-25°C); flowers were separated from the stems and leaves before drying. The oils were separately isolated from air-dried inflorescences and leaves by hydrodistillation for 2 h using a mixture of hexane and diethyl ether as a collecting organic solvent.

A HP 5890(II) chromatograph equipped with a flame ionization detector (FID) and HP-FFAP capillary column (30 m x 0.25 mm, film thickness 0.3 µm) was used for quantitative analysis. The oven temperature was the following: set at 70°C and isothermal for 10 min, then programmed from 70°-210°C at a rate of 3°C/min and then increased to 250°C at the rate of 5°C/min. The injector and detector temperatures were 200°C and 250°C, respectively. Carrier gas was He with a flow rate of 0.7 mL/min.

GC/MS analyses were performed, using a chromatograph interfaced with HP 5971 mass spectrometer (ionization voltage 70 eV) and equipped with capillary column CP-SiI 8 CB (50 m x 0.32 mm, film thickness 0.25 µm). The oven temperature was held at 60°C for 2 min, then programmed from 60°-160°C with the increase rate of 5°C/min, held for 1 min, then programmed from 160°-250°C at a rate of 10°C/min, andisothermal at 250°C for 5 min, using He as the carrier gas (1.0 mL/min). Injector and detector temperatures were 250°C.

Qualitative analysis was based on a comparison of retention times, retention indexes and mass spectra with corresponding data in the literature (29) and computer mass spectra libraries (Wiley and NBS 54K).

Results and Discussion

The GC/MS analyses detected over 80 constituents, 68 of which were identified. The chemical composition of flower and leaf oils of H. arenarium is given in Table I. The comparison of the data with the literature is complicated because of the very limited number of papers on everlasting oils. oils under the study were qualitatively different from the inflorescence oil of H. arenarium endemic to the Caucasus region and oils of mercantile and cultivated samples investigated by Hungarian scientists (27,28). Twenty-four components were identified in the above oil (27) containing methyl palmitate (28.5%), dodecanoic (11.9%) and decanoic acid (9.8%) as first main components and appreciable amounts of nonanoic and octanoic acids, anethole, carvacrol, linalool, terpineol, α-murolol, β-asarone andglobulol. Methylpalmitate was also apredominant constituent in the Hungarian and Polish commercial samples together with significant amounts of other alkyl carbonic acids lauric (11.9% and 14.6%), decanoic (9.8% and 8.5%), nonanoic (6.9% and 5.2%) andoctanoic (6.0% and 0.6%) (28). Decanoic acid (19.8%) was the first major component in the everlasting plants cultivated in Hungary, while methyl palmitate (8.0%) was the second constituent and thymol (7.7%) was the third (28). However, many of the constituents identified in the above oils (27,28) were not even detected in the oil of H. arenarium native to Lithuania.

Sesquiterpenoids (44.1-80.4%) were dominant in the seven out of eight analyzed oils. β-Caryophyllene was determined to be the first major constituent in both yellow inflorescence oils (AYF, BYF) and in orange inflorescence (BOF) as well as in leaf oil (BOL) from locality B. Also, β-caryophyllene was the second main component in two leaf oils (AYL 9.8%; BYL 7.5%) and in one inflorescence oil (AOF 9.0%).

According to the published data, β-caryophyllene was found to be among major constituents in other Helichrysum species: in H. italicum collected along Adriatic Coast in Croatia (11), from Tuscany (Italy) (12) and Spain (16); in H. stoechas of Greek origin (14,18); in H. kraussii from South Africa (20); in H. cordifolium, H.faradifani and H. hypnides from Madagascar (9); in H. heldreichii from Greece (17); and in flower oil of H. litoreum collected in the Aeolian archipelago (10).

Two leaf oils (AYL, BYL) were dominated by another sesquiterpene, δ-cadinene, which was the second (BOF, BOL) or third (AYF, AOF, AOL) constituent in another five samples. Amounts of δ-cadinene varied from 0.7% to 7.9% in the oils of H. arenarium in the previous works (27,28).

Many oils of other Helichrysum species represented in literature are also dominated by a sesquiterpene fraction.

Only one sample (AOF) was characterized by the dominance of linear hydrocarbons. The sum of aliphatic hydrocarbons and oxygenated aliphatics was 37.7%, while percentage of sesquiterpenoids was 25.5%. The orange inflorescence oil (AOF) was dominated by heneicosane (32.1%) with moderate amounts of β-caryophyllene, δ-cadinene and (E)-citronellyl tiglate. Leaf oil (AOL) of the same plants contained 8.9% of octadecane as the first major constituent.

Linear hydrocarbons were found to be between main compounds by Roussis et al. in the oils obtained from H. rupestre collected in Balearic Islands (15). The oils obtained from H. orientale from Greece also notably contained several linear hydrocarbons, with nonacosane as the first predominant (17). Rousssis et al. (17) have suggested that the presence of linear chain hydrocarbons with number of carbon atoms from 25 to 31 might be derived from the leaf waxes.

Other constituents present in appreciable amounts were: selina-3,7(ll)-diene (0-8.6%), OC-copaene (1.5-7.2%) and α-cadinol (0.2-5.8%) in the oils of yellow and orange flowering plants in this study.

Analysis of the oils of H. arenarium yellow and orange inflorescences and corresponding leaf oils showed significant quantitative variability. No correlation between volatile chemistry of the aerial parts of plants and phenotypic differences was found in this study.

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A. Judzentiene* and R. Butkiene

Institute of Chemistry, A. Gostauto 9, LT-01108, Vilnius, Lithuania

* Address for correspondence

Received: October 2004

Revised: January 2005

Accepted: January 2005

Copyright Allured Publishing Corporation Jan/Feb 2006
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