DOI 10.1007/s10600-014-1184-5 Chemistry of Natural Compounds, Vol. 50, No. 6, December, 2014 [Russian original No. 6, November–December, 2014]
COMPOSITION AND BIOLOGICAL ACTIVITY OF ESSENTIAL OILS FROM EAST-ASIAN SPECIES Angelica viridiflora, A. cincta, AND Coelopleurum gmelinii
E. M. Suleimen,1* Zh. B. Iskakova,1 R. V. Dudkin,2,3,4 P. G. Gorovoi,2 M. Wang,5 I. Khan,5 S. A. Ross,5 and C. H. G. Martins6
Angelica viridiflora (Turcz.) Benth. ex Maxim. [synonyms Gomphopetalum viridiflorum Turcz. and Ostericum viridiflorum (Turcz.) Kitagawa] is a monocarpic (dying after fruiting) perennial of height 50–160 cm with an unthickened tap root, ribbed stem, and triangular (triangular cross section) leaf petioles. The peripheral umbels overgrow the central one. Flower petals are green (in contrast with other Angelica species). It is distributed in eastern Siberia (Dauriya), Amur Oblast, Primorsky Krai, and northeast China [1–5]. It grows in moist (damp) meadows. Angelica cincta Boissieu (synonyms A. amurensis Schischkin, A. anomala auct. non Kitagawa) is a perennial polycarpic plant of height 80–220 cm with a thick-walled stem and leaves that are blue-gray underneath. The morphological signatures of A. cincta are similar to those of A. sachalinensis Maxim. [6]. It is distributed in Primorye, Priamurye, and northeast China [1–4]. It grows in valley meadows; in thinned valley, oak, and oak-birch forests; and on slopes of peaks and mountain meadows in the Alpine zone [1]. Aerial organs (leaves, stems, flowers, fruit) and roots of A. cincta contain essential oil (0.06% in leaves; 0.02, stems; 0.45, flower umbels; 0.08–0.73, roots; and ~1%, ripe fruit) [7]. A coumarin-type compound was isolated from the roots [8]. The East-Asian species Coelopleurum gmelinii (DC.) Ledeb. [synonyms C. lucidum (L.) Fern. var. gmelinii (DC.) Hara and A. gmelinii (DC.)M. Pimen.] was combined by Hulten [9] with the North American C. lucidum (L.) Fern. (Angelica lucida L.) and considered a trans-specific species growing only on seashores of Eastern Asia (from Chukotka peninsula in the north to Japan and southern Primorsky Krai) [1] in addition to northwestern North America. It is a perennial monocarpic plant of height 130–180 cm that flowers in the first half of summer and grows on sandy, pebbly, and rocky sites on the seashore. Chromones were previously isolated from it [10]. The constituent compositions of essential oils from these plants have not been studied. Therefore, we investigated them using GC-MS. Raw material was collected on Sept. 20, 2011, in a moist meadow on the left bank of the Shkotovki River (Tsimukhe) and in the vicinity of Shkotovo, Shkotovskii District, Primorsky Krai (A. viridiflora); on Sept. 29, 2011, on the edge of an oak forest in the vicinity of Smolyaninovo, Shkotovskii District, Primorsky Krai (A. cincta); and on July 27, 2011, in the vicinity of Zapovednyi, Lazovskii District, Primorsky Krai (C. gmelinii). The herbarium codes are 103590 for A. viridiflora; 103591, A. cincta; and 103592, C. gmelinii. Specimens of the plants are preserved in the herbarium of the Laboratory of Chemotaxonomy, G. B. Elyakov Pacific Institute of Bioorganic Chemistry, FEB, RAS (Vladivostok). 1) Institute of Applied Chemistry, L. N. Gumilev Eurasian National University, Republic of Kazakhstan, Astana, 010008, Ul. K. Munaitpasova, 5, e-mail:
[email protected]; 2) Laboratory of Chemotaxonomy, G. B. Elyakov Pacific Institute of Bioorganic Chemistry, Far-East Branch, Russian Academy of Sciences, Russian Federation, Vladivostok, 690022; 3) Laboratory of Flowering-Decorative Plant Introduction and Selection, Botanical Garden-Institute, Far-East Branch, Russian Academy of Sciences, Russian Federation, Vladivostok, 690024, Makovskogo, 142; 4) Far-East Federal University, Russia, Vladivostok; 5) National Center for Natural Products Research and Department of Pharmacognosy, School of Pharmacy, The University of Mississippi; 6) Universidade de Franca, Av. Dr. Armando Salles de Oliveira, 201 Parque Universitario, Franca-SP, CEP 14404-600, Brazil. Translated from Khimiya Prirodnykh Soedinenii, No. 6, November–December, 2014, pp. 989–991. Original article submitted August 5, 2014. 1136
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©2014
Springer Science+Business Media New York
TABLE 1. Constituent Composition of Essential Oils from A. viridiflora, A. cincta, and C. gmelinii Constituent
D-Pinene Camphene Verbenene Sabinene E-Pinene E-Myrcene p-Mentha-1(7),8-diene p-Cymene E-Thujene 1,8-Cineol Limonene trans-4-Methoxythujane D-Pinene oxide D-Campholenic aldehyde trans-Pinocarveol Verbenol Amylbenzene Cryptone Verbenone 2-Methyl-3-phenylpropane G-3-Carene Phellandral D-Fenchylacetate Bornyl acetate cis-Z-D-Bisabolene oxide Caryophyllene D-Humulene Germacrene D ar-Curcumene D-Guaiene Phenylethylpivalate Isobutyl-2-phenylethyl ester of oxalic acid Cuparene J-Muurolene G-Cadinene (Z)-2-Pentadecen-4-yne 7-epi-trans-Sesquisabinene hydrate Spathulenol Caryophyllene oxide D-Farnesene J-Gurjunene Viridiflorol 2-(1,4,4-Trimethylcyclohex-2-enyl)ethanol 2,4,4-Trimethylpentan-1,3-diylic ester of bis-isobutyric acid 7-epi-cis-Sesquisabinene hydrate Carotol Cyclogreenal 3,4-Dimethyl-3-cyclohexan-1-carboxaldehyde Alloaromadendrene Dillapiole Apiol di-epi-D-Cedrene Isospathulenol 2-Isopropyl-5-methyl-9-methylenebicyclo[4.4.0]dec-1-ene cis-Muurola-3,5-diene Widdrene
RT
A. viridiflora
A. cincta
C. gmelinii
7.113 7.867 8.055 8.830 9.084 9.781 10.257 11.603 11.632 11.738 11.740 15.502 15.69 17.613 18.353 18.776 19.219 21.272 22.685 24.969 26.315 27.099 27.32 27.526 28.738 35.392 37.58 39.185 39.584 39.657 40.003 40.426 40.844 41.195 41.565 43.282 43.935 44.916 45.032 45.152 45.363 45.574 45.719 45.806 45.983 46.296 46.633 46.642 47.330 47.652 47.796 47.998 48.108 48.685 48.806 49.027
1.6 – – 0.7 – – – – – 2.6 – – – – – – – – – – – – – – – 1.0 – – – 2.0 – – – – – 1.3 – – 61.7 – 3.2 – – 4.0 – 1.1 – 5.8 0.8 – 0.8 – – – – –
67.2 4.8 0.2 5.8 4.9 1.9 – 0.3 – – 4.0 0.2 1.2 0.6 0.3 1.3 – – 0.5 – 0.5 – – 3.5 0.4 – – – – – – – – – – – – – – – – 0.9 – – – – – – – – – – – – – –
5.3 0.8 – – 0.4 – 0.2 – 16.1 – – – – 0.7 – – 1.0 2.7 – 1.3 1.0 0.6 0.6 – – – 0.4 0.4 1.7 – 2.6 0.9 2.3 0.6 0.6 – 15.3 26.3 – 0.4 – – 0.9 – 1.7 – 1.3 – – 2.4 – 1.0 0.8 0.3 0.5 0.8
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TABLE 1. (continued) Constituent Widdrol D-Amorphene D-Eudesmol Vulgarol E-Bisabolol Caryophylla-3,8(13)-dien-5E-ol Alloaromadendrene (3S,4R,5S,6R,7S)-Apistol-9-en-3-ol Isobutyl-2-methylpent-3-yl ester of phthalic acid Diisobutylphthalate Dibutylphthalate bis-2-Ethylhexyl ester of 1,2-benzenedicarboxylic acid
RT
A. viridiflora
A. cincta
C. gmelinii
49.219 49.416 49.55 50.315 50.383 51.012 51.315 51.330 59.801 59.811 62.599 72.335
0.6 – – 4.0 – – – 1.5 5.5 – 0.6 1.2
– – 0.5 – – – – – – – – –
– 1.6 – – 2.2 0.8 1.1 – – 0.3 – –
Essential oil was obtained from dried and ground aerial plant parts by steam distillation in a Clevenger apparatus for 2 h [11]. The yields for all samples averaged 0.2%. GC-MS of the essential oils was carried out under analogous conditions [12]. The main constituents in the volatiles from A. viridiflora were caryophyllene oxide (61.7%); 3,4-dimethyl-3-cyclohexan1-carboxaldehdye (5.8); and isobutyl-2-methylpent-3-yl ester of phthalic acid (~5.5). The main constituents in essential oil from A. cincta were D-pinene (67.2%), sabinene (5.8), and E-pinene (4.9). The main constituents in essential oil from C. gmelinii were spathulenol (26.3%); E-thujene (16.1); 7-epi-transsesquisabinene hydrate (15.3), and D-pinene (5.3) (Table 1). We also studied the antimicrobial and antimalarial activity of essential oils from A. viridiflora, A. cincta, and C. gmelinii using the literature methods [12, 13]. The experiments showed that the essential oils had very low antimicrobial activity even at concentrations of 50 mg/mL and low antimalarial activity. Essential oil/reference drug
P. falciparum D6, % Inh.
Essential oil/reference drug
P. falciparum D6, % Inh.
Chloroquine A. viridiflora
94 30
A. cincta C. gmelinii
25 10.
Essential oil of A. cincta was tested for cytotoxic activity against brine shrimp Artemia salina using the literature method [14]. According to the results, essential oil of A. cincta at all tested concentrations (10, 5, and 1 mg/mL) exhibited acute lethal toxicity, i.e., all larvae died. Essential oil of A. cincta was tested for antileishmaniasis activity, which was determined from the ability to inhibit Leishmania donovani, a sand-fly protozoa that causes visceral leischmaniasis. The investigations showed that essential oil of A. cincta did not exhibit antileishmaniasis activity. The same oil was tested for activity against aerobic microorganisms, mycobacteria, and yeasts using the literature methods [15-18] and was inactive against them.
ACKNOWLEDGMENTS We thank Dr. M. Jacob (The University of Mississippi, USA) for assistance with the antimicrobial investigation; Dr. Sh. Khan for assistance with the antimalarial investigation; Dr. B. Tekwani, for help with the antileishmaniasis study (Grant No. AI 27094 NIH, NIAID, Division of AIDS, Grant No. 58-6408-1-603 USDA Agricultural Research Service Specific Cooperative Agreement); and T. da Silva Moraes and B. C. Melo de Campos for assistance with the antimicrobial and antituberculosis studies. The work was performed under the auspices of grants from the Ministry of Education and Science, Republic of Kazakhstan for budgetary program 055 “Basic and Applied Scientific Research” on topics “Phytochemical Study of Plants of Kazakhstan and Siberia. Creation of Modified Derivatives of Mono- and Sesquiterpenoids, Flavonoids, and Their Bioscreening” and “Creation of Production Samples of Kazakhstan Steppe Aromas” and from the RFBR 12-04-01325.
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