Investigation of essential oils from three natural populations of Lonicera iliensis

Lonicera iliensis Pojark. (Caprifoliaceae) is a rare and almost endemic species placed into the Red Book of Kazakhstan [1]. The constituent compositions and biological activities of essential oils (EO) from L. caprifolium L., L. japonica Thunb., and L. nummulariifolia Jaub. & Spach were reported [2–6]. The goal of the present work was to study the chemical composition and enantiomeric ratios of several constituents of EO obtained from three natural populations of L. iliensis growing in Kazakhstan (Almaty District). This is the first report on the composition of volatile constituents from L. iliensis. EO obtained by steam distillation from various parts of L. iliensis was characteristically light-yellow with a mild specific aroma.

DOI 10.1007/s10600-016-1765-6

Chemistry of Natural Compounds, Vol. 52, No. 4, July, 2016

INVESTIGATION OF ESSENTIAL OILS FROM THREE

NATURAL POPULATIONS OF Lonicera iliensis

S. V. Kushnarenko,^1* L. N. Karasholakova,^1,2

G. Ozek,³ K. T. Abidkulova,² N. M. Mukhitdinov,²

K. H. C. Baser,^3,4,5 and T. Ozek³

Lonicera iliensis Pojark. (Caprifoliaceae) is a rare and almost endemic species placed into the Red Book of Kazakhstan [1]. The constituent compositions and biological activities of essential oils (EO) from L. caprifolium L., L. japonica Thunb., and L. nummulariifolia Jaub. & Spach were reported [2–6].

The goal of the present work was to study the chemical composition and enantiomeric ratios of several constituents of EO obtained from three natural populations of L. iliensis growing in Kazakhstan (Almaty District). This is the first report on the composition of volatile constituents from L. iliensis. EO obtained by steam distillation from various parts of L. iliensis was characteristically light-yellow with a mild specific aroma. The quantitative yield of EO varied from 0.003 to 0.012 wt% and did not differ significantly among the studied populations and samples. GC analysis (GC-FID and GC/MS) on HP-Innowax columns was performed using the previously described conditions [7]. A total of 47 constituents making up 67.4–89.4% of the total EO volume were identified (Table 1). Differences in the EO constituent composition were found between populations and samples. Thus, high alkane contents (17.1–44.5%) were detected in all studied plant parts of the first population from the Ili River bottom. In contrast with the first population, the principal classes of EO chemical compounds from the populations on the Chilik and Charyn Rivers were fatty acids (FA) and their esters (31.2–75.1%).

Flowers of L. iliensis from all three populations typically had significant amounts of the sesquiterpenoid hexahydrofarnesylacetone and FA with hexadecanoic acid as the main representative.

Volatile constituents of leaves during flowering of all three populations had high contents of the diterpene phytol and monoterpenoids. The contents of alkanes and aldehydes differed among the populations.

EO isolated from leaves during fruiting of all three populations were characterized by high contents of FA and their

esters, aldehydes, monoterpenoids, and the diterpene phytol. The populations differed in alkane contents. Thus, EO from the first population (Ili River) was dominated by nonacosane (28.4%) whereas its content was 6.6% in the population from the Charyn River and it was not detected in the Chilik River population. Polycyclic aromatic hydrocarbons (3.8 and 4.7%) and sesquiterpenoids (3.1 and 4.4%) were identified in the second and third populations, in contrast with the first.

FA and their esters with the principal representatives hexadecanoic and (Z)-9-hexadecenoic acids prevailed among

volatile constituents of fruit from all populations. Nonacosane (17.1%) was observed only in plants from the first population.

Chiral separation of several enantiomers using Lipodex G columns showed that linalool in L. iliensis EO was practically a racemic mixture whereas the (–)-enantiomers prevailed for - and -pinenes. Sabinene and limonene were found primarily as the (+)-enantiomers (Table 2).

1) Institute of Plant Biology and Biotechnology, Almaty, 050040, Kazakhstan, fax: +772723947562, e-mail: [email protected]; 2) Al-Farabi Kazakh National University, Almaty, 050040, Kazakhstan; 3) Anadolu University, Faculty of Pharmacy, Department of Pharmacognosy, 26470, Eskisehir, Turkey; 4) King Saud University, Botany and Microbiology Department, College of Science, Riyadh 11451, Saudi Arabia; 5) Near East University, Department of Pharmacognosy, Faculty of Pharmacy, Lefcosa (Nicosia), N. Cyprus. Translated from Khimiya Prirodnykh Soedinenii, No. 4, July–August, 2016, pp. 643–645, original article submitted January 29, 2016.

TABLE 1. Chemical Compositions of Essential Oils from Lonicera iliensis

Constituent

RRI

Population I, Ili River

Population II, Chilik River

Population III, Charyn River

Monoterpenes

-Pinene

1032

Tr.

0.1

Tr.

0.1

Tr.

0.1

-Pinene

1118

0.1

Tr.

0.1

Tr.

0.1

Tr.

0.1

Sabinene

1132

Tr.

0.1

Tr.

0.1

Limonene

1203

Tr.

0.1

Tr.

0.1

Tr.

Tr. onoterp

0.2 enoids

Tr.

0.4

Tr.

0.4

Linalool

1553

0.1

2.2

0.1

1.4

0.1

–

2.1

0.1

p-Mentha-1,3-dien-7-al

1811

–

1.1

–

(E)--Damascenone

1838

–

1.2

2.3

–

1.9

–

(E)-Geranylacetone

1868

–

1.1

–

2.1

–

(E)--Ionone

1958

–

3.3

2.0

–

3.2

2.8

–

2.7

4.5

–

3,4-Dimethyl-5-pentylidene-2(5H)- furanone

2179

–

1.7

1.6

–

1.1

–

1.2

2.6

–

0.1 8.4 6.0 1.4 0.1 5.5

Polycyclic aromatic hydrocarbons (PAH)

5.0

2.1

0.1

4.0

11.2

0.1

Naphthalene

1763

–

– –

–

1.1

1.0

1.5

–

1.3

–

1-Methylnaphthalene

1884

–

– –

–

1.5

1.7

2.0

–

2.1

1.3

2-Methylnaphthalene

1894

–

– –

–

1.1

1.6

–

1.3

–

– –

Aldehydes

–

2.6

3.8

5.1

–

4.7

1.3

Hexanal

1093

–

1.5

– –

–

1.2

–

(Z)-3-Hexenal

1225

–

11.3

1.9 –

–

13.2

9.9

–

13.0

–

(E)-2-Decanal

1655

–

– 1.3

–

(E,E)-2,4-Decadienal

1827

1.1

–

– –

–

Tetradecanal

1933

–

– –

–

1.5

–

1.0

–

Pentadecanal

2041

–

3.1

11.3 –

–

3.8

14.6

–

1.8

7.5

–

2,3,4-Trimethylbenzaldehyde

2050

–

– –

–

3.3

–

1.1

15.9 Se

13.2 1.3

squiterpenoids

–

18.2

26.0

3.3

–

1.8

21.5

–

Muurola-4,10(14)-dien-8-ol

1983

–

– –

–

1.1

–

4-(2,6,6-Trimethylcyclohexa-1,3- dienyl)but-3-en-2-one

2001

–

– –

–

1.6

–

Hexahydrofarnesylacetone

2131

21.0

2.5

– –

12.2

1.8

–

12.4

1.3

1.8

–

Farnesylacetone

2309

–

– –

–

1.3

–

2.6

–

21.0

2.5

– –

Alcohols

12.2

1.8

3.1

2.7

12.4

1.3

4.4

–

Octanol

1562

1.5

1.8

–

1.0

–

1.1

–

1.3

–

6,10,14-Trimethylpentadecan-2-ol

2212

1.1

–

2,4-bis(1,1-Dimethylethyl)phenol*

2301

–

1.7

–

1-Hexadecanol

2384

–

1.3

1.7

–

1-Octadecanol

2607

–

3.3

1.3

–

2.2

–

2.3

1.2

2.6

5.1

2.6

Diterpen

1.7

–

2.2

1.0

1.7

1.1

2.3

2.5

1.2

Phytol

2622

2.0

13.5

5.2 –

Alkanes

4.2

9.6

3.8

–

2.4

10.9

4.9

–

Dimethyltetradecane

1445

11.0

–

– –

5.6

–

5.6

–

Tricosane

2300

–

– –

–

1.2

–

Nonacosane

2900

33.5

21.3

28.4 17.1

–

6.6

–

44.5

21.3

28.4 17.1

5.6

–

5.6

1.2

6.6

–

752

TABLE 1. (continued)

Constituent			RRI	Population I, Ili River				Population II, Chilik River					Population III, Charyn River
				1	2	3	4	1	2		3	4	1		2	3	4
				Fatty acids, fatty-acid esters (FA, FAE)
(Z)-3-Hexen-1-ylbenzoate			2148	–	–	–	–	–	–		1.2	–	–		–	–	–
Ethyl hexadecanoate (=Ethyl palmitate)			2262	–	–	–	–	–	–		–	1.7	–		–	–	–
Decanoic acid			2290	–	–	–	–	–	–		–	1.9	–		–	–	–
Methyl palmitoleate			2299	–	–	–	–	–	–		–	4.2	–		–	–	–
9,12-Hexadecadienoic acid methyl ester			2313	–	–	–	–	–	–		1.3	–	–		–	–	–
(Z)-9-Methyl octadecanoate (=Methyl oleate)			2456	–	–	–	–	–	–		–	1.6	–		–	–	–
Dodecanoic acid (=Lauric acid)			2503	2.1	1.0	4.0	3.7	1.1	6.2		10.1	6.7	1.4		3.6	8.9	4.0
Ethyl octadecadienoate (=Ethyl linoleate)			2538	–	–	–	–	–	–		–	1.3	–		–	2.4	–
Methyl linolenate			2583	–	–	–	–	1.1	–		–	–	–		–	–	–
Tetradecanoic acid (=Myristic acid)			2670	2.6	1.8	5.6	5.0	3.4	6.8		7.1	6.1	3.8		5.8	8.1	6.9
Hexadecanoic acid (=Palmitic acid)			2931	6.0	2.5	6.8	16.0	61.6	25.3		15.0	22.8	59.6		56.4	11.8	40.2
(Z)-9-Hexadecenoic acid (=Palmitoleic acid)			2948	–	–	–	18.5	–	–		–	18.6	–		–	–	24.0
				10.7	5.3	16.4 Othe	43.2 rs	67.2	38.3		34.7	64.9	64.8		65.8	31.2	75.1
1,3,5-Tri-tert-butylbenzene*			2432	1.1	2.6	1.7 2.5		–	–		1.9	4.7	–		–	2.4	–
1,2,4,5-tetrakis(1-Methylethyl)benzene*			2434	–	–	– –		–	2.3		–	–	–		–	–	1.5
Total				83.2	74.6	73.5 67.4		89.3	80.5		79.3	84.9	86.4		87.3	89.4	79.6
______ 1, flowers; 2, leaves during flowering; 3, leaves during fruiting; 4, fruit. by Wiley Library; Tr, trace amount. TABLE 2. Ratio of Enantiomers in Lonicera iliensis Essential Oils								RRI, relative retenti				on index. *Tentative identification
Enantiomer		Population I, Ili River					Population II, Chilik River					Population III, Charyn River
	1	2		3	4		1	2		4		1		2		3	4
(1R)-(+)--Pinene	–	–		–	38.9		–	–		36.8		–		–		–	41.8
(1S)-(–)--Pinene	–	–		–	61.1		–	–		63.2		–		–		–	58.2
(1R)-(+)--Pinene	28.0	–		–	20.8		–	–		24.2		–		–		–	27.9
(1S)-(–)--Pinene	72.0	–		–	79.2		–	–		75.8		–		–		–	72.1
(1R,5R)-(+)-Sabinene	–	–		–	–		–	–		61.6		–		–		–	64.6
(1S,5S)-(–)-Sabinene	–	–		–	–		–	–		38.4		–		–		–	35.4
(4R)-(+)-Limonene	–	–		–	–		–	–		84.3		–		–		–	83.4
(4S)-(–)-Limonene	–	–		–	–		–	–		15.7		–		–		–	16.6
(3S)-(+)-Linalool	47.1	47.8		55.1	49.9		42.8	44.3		44.6		38.7		45.1		51.0	43.7
(3R)-(–)-Linalool	52.9	52.2		44.9	50.1		57.2	55.7		55.4		61.3		54.9		49.0	56.3

______

1, flowers; 2, leaves during flowering; 3, leaves during fruiting; 4, fruit.

REFERENCES

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753

DOI 10.1007/s10600-016-1765-6

Springer Science+Business Media

Dimethyltetradecane 1445 11

S )-(–)-Limonene – – – – – – 15

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