Chemical Compositions of the Leaf Essential Oils of <i>Aralia spinosa</i> from Three Habitats in Northern Alabama

doi:10.4236/ajps.2011.23059

Paper Menu >>

Journal Menu >>

American Journal of Plant Sciences, 2011, 2, 507-510

doi:10.4236/ajps.2011.23059 Published Online September 2011 (http://www.SciRP.org/journal/ajps)

507

Chemical Compositions of the Leaf Essential Oils

of Aralia spinosa from Three Habitats in Northern

Alabama

Purva C. Davé, Bernhard Vogler, William N. Setzer

Department of Chemistry, University of Alabama in Huntsville, Huntsville, USA.

Email: [email protected]

Received May 7th, 2011; revised June 10th, 2011; accepted July 10th, 2011.

ABSTRACT

Aralia spinosa leaves were collected from three different habitats in north Alabama. The leaf essential oils were col-

lected by hydrodistillation and analyzed by gas chromatography/mass spectrometry (GC-MS). The most abundant

components of A. spinosa essential oils were the sesquiterpenes germacrene D (28.0% - 37.3%), (E)-caryophyllene

(8.2% - 15.7%), and α-humulene (1.9% - 4.9%); the monoterpene myrcene (up to 15.1%), and the fatty-acid-derivative

(2E)-hexenal (trace to 28.9%). Fatty-acid derivatives and monoterpene hydrocarbons were more abundant in samples

from suburban Huntsville than those from “natural” habitats (Monte Sano Mountain, Wheeler National Wildlife Ref-

uge), while sesquiterpene hydrocarbons were more abundant in the natural/wild samples.

Keywords: Aralia Spinosa, Araliaceae, Leaf Essential Oil, Chemical Composition, Germacrene D, Myrcene,

(E)-Caryophyllene, (2E)-Hexenal

1. Introduction

Aralia spinosa L. (Araliaceae), “devil’s walking stick”, is

a large shrub/medium-sized (up to 10 m tall) tree native

to the southeastern United States. The leaves are very

large (up to 1.5 m long, 1 m wide), bipinnate with ovate

leaflets, 2 cm - 10 cm long. The plant produces numerous

tiny white flowers in umbels (July-September) and bluish

drupes [1]. To our knowledge, the leaf essential oil of A.

spinosa has not been previously examined. In this work,

we present and compare the chemical compositions of

the leaf essential oils of A. spinosa from three habitats in

north Alabama.

2. Materials and Methods

2.1. Plant Material

Leaves of A. spinosa were collected (July, 2010) from

four mature trees growing in north Alabama: two trees

from suburban Huntsville city (34˚38"77'N, 86˚33"45'W,

187 m elevation), one tree from Monte Sano Mountain

(34˚44"85′N, 86˚31"77'W, 427 m elevation), and one tree

from Wheeler National Wildlife Refuge (34˚37"40'N,

86˚57"08'W, 122 m elevation). The plants were identi-

fied and collected by P. Davé, and a voucher specimen

has been deposited in the University of Alabama in

Huntsville herbarium. The freshly chopped leaves from

each plant were hydrodistilled using a Likens-Nickerson

apparatus. Continuous extraction of the distillates with

CH2Cl2 for three hours gave clear colorless essential oils

(Huntsville #1, 9.52%; Huntsville #2, 6.18%; Monte

Sano, 1.05%; Wheeler NWR, 1.07%).

2.2. Gas Chromatography―Mass Spectrometry

The leaf essential oils of A. spinosa were subjected to gas

chromatographic-mass spectral analysis on an Agilent

system consisting of a Model 6890 gas chromatograph, a

Model 5973 mass selective detector [MSD, operated in

the EI mode (electron energy = 70 eV), scan range = 45

amu - 400 amu, and scan rate = 3.99 scans/sec], and an

Agilent ChemStation data system. The GC column was an

HP-5ms fused silica capillary with a (5% phenyl)-poly-

methylsiloxane stationary phase, film thickness of 0.25

μm, a length of 30 m, and an internal diameter of 0.25

mm. The carrier gas was helium with a column head

pressure of 48.7 kPa and a flow rate of 1.0 mL/min. Inlet

temperature was 200˚C and interface temperature was

280˚C. The GC oven temperature program was used as

follows: 40˚C initial temperature, hold for 10 mins; in-

Chemical Compositions of the Leaf Essential Oils of Aralia spinosa from Three Habitats in Northern Alabama

508

creased at 3˚C/min to 200˚C; increased at 2˚C/min to

220˚C. A 1% w/v solution of the sample in CH2Cl2 was

prepared and 1 μL was injected using a splitless injection

technique. Identification of the oil components was based

on their retention indices determined by reference to a

homologous series of n-alkanes, and by comparison of

their mass spectral fragmentation patterns with those

reported in the literature [2] and stored on the MS library

[NIST database (G1036A, revision D.01.00)/ChemSta-

tion data system (G1701CA, version C.00.01.080)]. The

percentages of each component are reported as raw per-

centages based on total ion current without standardiza-

tion. The leaf essential oil compositions of A. spinosa are

summarized in Table 1.

Table 1. Chemical compositions of Aralia spinosa leaf essential oils.

Percent Composition

Suburban Huntsville Monte Sano Wheeler

RI Compound

#1 #2 Mountain NWR

760 (2E)-Pentenal 0.1 0.4 0.2 ---

773 (2Z)-Pentenol 1.7 2.0 0.8 ---

795 (3Z)-Hexenal ---a 8.3 --- ---

800 Hexanal 2.8 --- 1.6 trb

833 Furfural --- --- 0.2 ---

845 Unidentified hexenal --- --- 0.5 ---

854 (2E)-Hexenal 24.7 28.9 13.8 tr

911 (2E,4E)-Hexadienal 0.2 0.6 tr ---

934 α-Thujene --- --- tr ---

935 α-Pinene tr 0.6 1.4 ---

953 Camphene --- --- 0.1 ---

978 β-Pinene --- 0.1 0.3 ---

992 Myrcene 13.9 15.1 tr ---

1004 α-Phellandrene --- --- tr ---

1010 δ-3-Carene --- --- 0.3 ---

1027 Limonene --- 0.2 --- tr

1031 Benzyl alcohol 0.3 tr --- tr

1043 Phenylacetaldehyde --- --- --- tr

1087 Terpinolene tr 0.2 1.1 ---

1097 Linalool 0.5 --- 0.2 tr

1184 p-Cymen-8-ol --- --- --- tr

1189 α-Terpineol --- --- --- tr

1374 α-Copaene tr --- tr tr

1383 β-Bourbonene 0.1

--- 0.8 0.6

1391 β-Elemene 0.7 --- 5.1 3.9

1419 (E)-Caryophyllene 10.7 8.2 15.7 12.5

1428 β-Copaene 0.2 --- 0.2 0.2

1453 α-Humulene 2.7 1.9 4.9 4.7

1458 (E)-β-Farnesene --- --- 0.8 0.7

1478 γ-Muurolene 0.2 tr 0.5 0.4

1482 Germacrene D 37.3 28.6 30.2 28.0

1487 (E)-β-Ionone 0.2 tr 0.3 0.4

1494 cis-β-Guaiene --- --- 0.7 1.1

1497 Bicyclogermacrene 0.9 0.4 1.4 1.4

1501 α-Muurolene --- --- 0.2 0.3

1505 Germacrene A --- --- 2.0 3.6

1510 (E,E)-α-Farnesene 0.6 0.3 1.1 1.1

1514 γ-Cadinene --- --- 0.6 0.9

Chemical Compositions of the Leaf Essential Oils of Aralia spinosa from Three Habitats in Northern Alabama509

Percent Composition

Suburban Huntsville Monte Sano Wheeler

RI Compound

#1 #2 Mountain NWR

1516 Cubebol --- --- tr 0.9

1525 δ-Cadinene 0.4 0.2 2.0 2.4

1566 (E)-Nerolidol 1.9 1.2 5.9 10.4

1575 Germacrene D-4-ol --- --- --- 1.0

1578 Spathulenol --- --- --- tr

1581 Caryophyllene oxide --- --- 0.3 1.4

1593 Salvial-4(14)-en-1-one --- --- --- tr

1608 Humulene epoxide II --- --- --- 0.2

1614 1,10-di-epi-Cubenol --- --- --- 0.4

1617 Junenol --- --- --- 0.2

1627 1-epi-Cubenol --- --- --- 0.4

1635 Caryophylla-4(12),8(13)-dien-5-ol --- --- --- tr

1641 τ-Muurolol --- --- 2.0 5.2

1645 α-Muurolol (= Torreyol) --- --- 0.3 1.0

1654 α-Cadinol --- --- 2.5 5.5

1659 Unidentified oxygenated sesquiterpenoid --- --- 0.2 0.7

1664 Unidentified oxygenated sesquiterpenoid --- --- 0.4 1.2

1669 14-Hydroxy-9-epi-(Z)-caryophyllene --- --- --- 0.8

1679 Unidentified oxygenated sesquiterpenoid --- --- --- 0.7

1685 Germacra-4(15),5,10(14)-trien-1α-ol --- --- 0.4 1.8

1689 Shyobunol --- --- 0.5 2.3

1739 Mint sulfide --- --- --- 0.1

1760 Cyclocolorenone --- 2.8 --- 0.4

1798 14-Hydroxy-δ-cadinene --- --- --- 0.1

1953 Palmitic acid --- --- --- 0.2

2900 Nonacosane --- --- --- 1.1

Total Identified 99.8 100.0 98.6 95.6

Fatty-acid-derivatives 29.4 40.2 16.5 1.2

Monoterpene hydrocarbons 13.9 16.2 3.2 0.0

Oxygenated monoterpenoids 0.5 0.0 0.2 0.0

Sesquiterpene hydrocarbons 53.7 39.6 66.3 61.8

Oxygenated sesquiterpenoids 1.9 4.0 12.5 34.7

Others 0.5 0.0 1.0 0.5

a“---” = not detected. b“tr” = trace (< 0.05%).

3. Results and Discussion

A total of 60 compounds were identified in the A. spinosa

leaf oils, representing 95.6% - 100% of the compositions.

A. spinosa leaf oils from suburban Huntsville, Alabama,

were composed largely of sesquiterpene hydrocarbons

(53.7% and 39.6%), dominated by germacrene D (37.3%

and 28.6%), (E)-caryophyllene (10.7% and 8.2%), and

α-humulene (1.9% and 2.7%); fatty-acid derivatives (29.4%

and 40.2%), mostly (2E)-hexenal; and the monoterpene

hydrocarbon myrcene (13.9% and 15.1%). The samples

growing wild in natural habitats had much reduced

monoterpenes but increased concentrations of sesquiter-

penoids. The most abundant leaf oil components in the

Monte Sano sample were germacrene D (30.2%),

(E)-caryophyllene (15.7%), (2E)-hexenal (13.8%), (E)-nero-

lidol (5.9%), and α-humulene (4.9%). The Wheeler NWR

sample of A. spinosa has similar concentrations of ses-

quiterpene hydrocarbons to the Monte Sano sample, but

virtually no monoterpenoids or “green leaf” volatiles. It

was composed, however, of a diverse array of oxygen-

ated sesquiterpenoids including relatively large concen-

trations of (E)-nerolidol (10.4%), α-cadinol (5.5%), τ-

muurolol (5.2%), and shyobunol (2.3%).

Essential oils from other members of the Araliaceae

have been analyzed. Pinenes dominated the essential oils

Chemical Compositions of the Leaf Essential Oils of Aralia spinosa from Three Habitats in Northern Alabama

510

of Acanthopanax trifoliatus [3], Schefflera heptaphylla

[4], and Aralia cachemirica [5], while δ-3-carene was the

most abundant component of Dendropanax capillaris [6].

The sesquiterpene hydrocarbons (E)-caryophyllene, α-

humulene, and germacrene D were the dominant com-

ponents of Schefflera stellata [7], Schefflera rodrigu-

eziana [6], and Oreopanax nubigenus [6]; (E)-nerolidol

was abundant in both Pseudopanax discolor [8] and Op-

lopanax horridus [9]; and (2E)-hexenal was a major com-

ponent of Dendropanax gonatopodus [10]. The essential

oils of Pseudopanax discolor and Pseudopanax lessonii

had notable quantities of τ-muurolol [8], while Dendro-

panax arboreus and Oreopanax xalapensis were rich in

shyobunol [11].

4. Acknowledgements

PCD is thankful for the summer research stipend provided

by the University of Alabama in Huntsville Research and

Creative Experiences for Undergraduates (RCEU) pro-

gram. WNS is grateful to an anonymous private donor

for the generous gift of the GC-MS instrumentation.

REFERENCES

[1] C. L. Brown and L. K. Kirkman, “Trees of Georgia and

Adjacent States,” Timber Press, Portland, 1990, pp.

208-209.

[2] R. P. Adams, “Identification of Essential Oil Components

by Gas Chromatography/Mass Spectrometry,” 4th Edition,

Allured Publishing, Carol Stream, 2007.

[3] A. Muselli, T. M. Hoi, L. D. Cu, L. D. Moi, J. M. Bessière,

A. Bighelli and J. Casanova, “Composition of the Essential

Oil of Acanthopanax trifoliatus (L.) Merr. (Araliaceae)

from Vietnam,” Flavour and Fragrance Journal, Vol. 14,

No. 1, 1999, pp. 41-44.

doi:10.1002/(SICI)1099-1026(199901/02)14:1<41:AID-F

FJ781>3.0.CO;2-B

[4] Y. L. Li, C. M. Yeung, L. C. M. Chiu, Y. Z. Cen and V. E.

C. Ooi, “Chemical Composition and Antiproliferative

Activity of Essential Oil from the Leaves of a Medicinal

Herb, Schefflera heptaphylla,” Phytotherapy Research,

Vol. 23, No. 1, 2009, pp. 140-142. doi:10.1002/ptr.2567

[5] R. S. Verma, R. C. Padalia, A. Yadav and A. Chauhan,

“Essential Oil Composition of Aralia cachemirica from

Uttarakhand, India,” Records of Natural Products, Vol. 4,

No. 3, 2010, pp. 163-166.

[6] J. D. Richmond, B. R. Agius, B. S. Wright, W. A. Haber,

D. M. Moriarity and W. N. Setzer, “Essential Oil Compo-

sitions and Cytotoxic Activities of Dendropanax capil-

laris, Oreopanax nubigenus and Schefflera rodrigueziana

from Monteverde, Costa Rica,” Natural Product Commu-

nications, Vol. 4, No. 2, 2009, pp. 271-274.

[7] B. Sabulal, V. George, S. P. Nediyaparambu and M. Dan,

“Volatile Oils from the Root, Stem and Leaves of Schef-

flera stellata (Gaertn.) Harms (Araliaceae): Chemical

Characterization and Antimicrobial Activity,” Journal of

Essential Oil Research, Vol. 20, No. 1, 2008, pp. 79-82.

[8] R. J. Weston, “Essential Oils from the Leaves of Three

New Zealand Species of Pseudopanax (Araliaceae),”

Zeitschrift für Naturforschung, Vol. 59c, 2004, pp. 39-42.

[9] F. X. Garneau, G. Collin, H. Gagnon, F. I. Jean, H. Strobl

and A. Pichette, “The Essential Oil Composition of

Devil’s Club, Oplopanax horridus J. E. Smith Miq.,”

Flavour and Fragrance Journal, Vol. 21, No. 5, 2006, pp.

792-794. doi:10.1002/ffj.1716

[10] W. N. Setzer, “Essential Oil Composition of Dendro-

panax gonatopodus from Monteverde, Costa Rica. An ab

initio Examination of Aromadendrane Sesquiterpenoids,”

Natural Product Communications, Vol. 3, No. 9, 2008,

pp. 1557-1561.

[11] J. S. Werka, A. K. Boehme and W. N. Setzer, “Biological

Activities of Essential Oils of Monteverde, Costa Rica,”

Natural Product Communications, Vol. 2, No. 12, 2007,

pp. 1215-1219.