Chinese Journal of Chemistry, 2007, 25, 346350

Full Paper

Non-polar Solvent Microwave-Assisted Extraction of Volatile

Constituents from Dried Zingiber Officinale Rosc.
YU, Yong()
LI, Tie-Chun()

WANG, Zi-Ming()
WANG, Yu-Tang()
CHENG, Jian-Hua()
LIU, Zhong-Ying()
ZHANG, Han-Qi*()

College of Chemistry, Jilin University, Changchun, Jilin 130012, China

A new method, non-polar solvent microwave-assisted extraction (NPSMAE), was applied to the extraction of
essential oil from Zingiber officinale Rosc. in closed-vessel system. By adding microwave absorption mediumcarbonyl iron powders (CIP) into extraction system, the essential oil was extracted by the non-polar solvent (ether)
which can be heated by CIP. The constituents of essential oil obtained by NPSMAE were comparable with those
obtained by hydrodistillation (HD) by GC-MS analysis, which indicates that NPSMAE is a feasible way to extract
essential oil from dried plant materials. The NPSMAE took much less extraction time (5 min) than HD (180 min),
and its extraction efficiency was much higher than that of conventional polar solvent microwave-assisted extraction
(PSMAE) and mixed solvent microwave-assisted extraction (MSMAE). It can be a good alternative for the extraction of volatile constituents from dried plant samples.
Keywords
powder

non-polar solvent microwave-assisted extraction, Zingiber officinale Rosc., essential oil, carbonyl iron

Introduction
In recent years, microwave-assisted extraction
(MAE) has been widely used for extraction of active
constituents in plant samples under an open or
closed-vessel system.1-4 The major advantage of MAE is
the inherent ability to heat the sample solvent mixture
rapidly. The effect of microwave energy chiefly dependents on the nature of both the solvent and the solid
matrix, thus a wide range of polar and mixed solvents
were used as extraction solvents.5-7 One of the most
commonly used mixtures is hexane-acetone (11, V
V). 95 semi-volatile organics listed in environmental
protection agency (EPA), and some environmental contaminants, were extracted with hexane-acetone (11,
VV) as the promising extractant.8-10 However, the
non-polar extractants, such as ether, which were often
used in Likens-Nickerson apparatus for the extraction of
volatile constituents,11,12 are difficult to be heated directly by microwave irradiation. Therefore, an improved
solvent mixture system is needed. Par et al.13,14 patented the MAE of volatiles from biological material by
using the non-polar solvent as microwave transparent
solvent, which could induce a sudden temperature increase inside cellular structure, resulting in an eventual
rupturing of the cell walls and the rapid release of their
constituents into the surrounding media. Usually, the in
situ water plays quite important role in this process.
However, the most plant materials obtained are not

fresh and there are little water or other microwave-absorbing components in them, and the essential
oil can not be evaporated efficiently by microwave irradiation.
Zingiber officinale Rosc. has been used traditionally
as a spice for its flavor. The essential oil in the dried
spice was used as cooking seasoning and the pharmaceutical products.15,16 In the previous reports,17,18 a kind
of stable and microwave absorption solid medium, carbonyl iron powders (CIP), was used and an improved
solvent-free microwave extraction (ISFME) of essential
oil from dried plant materials was developed. The CIP
can elevate the temperatures and pressures rapidly in the
closed-vessel system and improve drastically the extraction speed and efficiency.19,20
In this work, the non-polar solvent (ether) mixed
with CIP was used as the extraction of essential oil from
the dried Zingiber officinale Rosc. The improved
NPSMAE method presented smaller quantity of sample
(3 g) and less extraction time (5 min) than hydrodistillation, PSMAE, MSMAE and ISFME.

Experimental
Reagents and materials
The anhydrous ether and ethanol (AR) were obtained
from Beijing Chemical Factory. The dried Zingiber officinale Rosc. was purchased from a market in Changchun city (China). The material was crushed and passed

* E-mail: analchem@mail.jlu.edu.cn; Tel.: 0086-0431-5168399, Fax: 0086-0431-5112355

Received June 9, 2006; revised July 19, 2006; accepted November 21, 2006.
2007 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Chin. J. Chem., 2007 Vol. 25 No. 3 347

Non-polar solvent microwave-assisted extraction

through a 0.4 mm sieve, and stored in a dark place until

used. The moisture of dried sample was detected by the
moisture determinator (Mois. Dec., MX170, Japan). The
moisture of dried Zingiber officinale Rosc. is 7.257%.
Carbonyl iron powders (average granularity is less than
3.5 m, and the content of Fe is more than 97%) were
purchased from Shanxi Xinghua Chemical Company.

PSMAE and MSMAE procedure

The procedures used in PSMAE and MSMAE were
analogous to those used in NPSMAE. 10 mL of ethanol
and mixed ethanol-ether (11, VV) were used as extractants respectively for PSMAE and MSMAE and no
CIP was added.
HD system and procedure

NPSMAE system and procedure

The NPSMAE was performed in a pressurized microwave extraction system (WR-C, Meicheng Kemao
Group, Beijing, China). Its maximum output power is
800 W with 2450 MHz of microwave irradiation frequency. The structure of extraction vessel is shown in
Figure 1.

50 g of sample and 300 mL of water were put into a

500 mL flask and heated with heating jacket at 100
for 3 h by the hydrodistillation according to the method
given in the Chinese Pharmacopoeia.21 The essential oil
was collected, dried with anhydrous sodium sulphate
and stored at 0 until used.
Gas chromatography-mass spectrometry identification

Figure 1 Schematic diagram of the extraction vessel device

used for NPSMAE.

Blend 3 g of sample and 1 g of CIP in the extraction

vessel. Then, add 10 mL of ether into the vessel. The
vessel was subjected to MAE at 200 kPa for 5 min.
When the extraction was finished, the sample was allowed to cool down to room temperature and centrifuged at 3000 r/min for 5 min. Subsequently, transfer
the dehydrated supernatant solution with anhydrous sodium sulphate into a volumetric flask and dilute to 10
mL with ether.
Table 1
Parameter

The identification of compounds was carried out on

a Hewlett Packard computerized system comprising a
6890 gas chromatograph coupled with a 5973 mass
spectrometer, using an HP-5MS column (30.0 m250
m0.25 m film thickness). The flow-rate of carrier
gas (helium) was about 1 mL/min, the temperature program consisted of an initial temperature of 60 held
for 2 min and then increasing to 220 at a rate of 5
/min, and splitless injection was adopted. The detailed
operating conditions are listed in Table 1.
The percentages of compounds were calculated by
the area normalization method. The compositions were
identified by computer matching of their mass spectral
fragmentation patterns based on NIST98 Library as well
as the data published in the literatures.22,23

Results and discussion

Optimal experimental parameters of NPSMAE
The experimental parameters were optimized in order to maximize the yield of essential oil for quanti-

Optimization of parameters
Range studied

Optimum value

NPSMAE parameters
Mixture ratio of CIP to sample/(ww)

1115

13

Extraction pressure/kPa

100500

200

Solvent volume/mL

515

10

Extraction time/min

110

Gas chromatography-mass spectrometry condition

Carrier gas
1

Helium

Carrier gas flow-rate/(mLmin )

0.51.0

Split ratio/(VV)

1510

10

Injection volume/L

1 (HD extracts were 0.2)

Injection temperature/

230

Oven temperature/
Rate of temperature gradient/(min1)
Electron ionization voltage/eV

From 60 to 220
3.05.0

5.0
70

2007 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

348 Chin. J. Chem., 2007, Vol. 25, No. 3

YU et al.

tative and qualitative analyses in the time as short as

possible. The effects of the parameters on the yield of
essential oil were examined, and the optimum values
found are also listed in Table 1.
Preliminary experimental results indicated that extraction time of 5 min was available for the extraction of
the target constituents from 13 CIP/sample mixture at
200 kPa pressure using ether as solvent.
Effect of CIP
In closed-vessel MAE, it took about 1 min to heat 10
mL of ether and 1 g of CIP from 23 to 100 .
However, about 7 min were needed to heat 10 mL of
ether and 10 mL of water. The results indicate that the
microwave absorption performance of CIP is better than
water. The results presented in Table 2 showed that there
was no obvious constituent difference between two
methods, indicating that the CIP may be a strong microwave-absorbing medium during the extraction process.
Chemical compositions in essential oils
The chemical compositions of volatile constituents
obtained from dried Zingiber officinale Rosc. by
NPSMAE and HD are listed in Table 2.

From Table 2, it can be found that the constituents in

essential oil obtained by NPSMAE and HD methods are
rather similar. It is seen that the sesquiterpene
(70.72%73.83%) is shown to be the main group of
constituents in Zingiber officinale Rosc., 1-(1,5-dimethyl-4-hexenyl)-4-methyl-benzene (14.31%16.08%),
5-(1,5-dimethyl-4-hexenyl)-2-methyl-1,3-cyclohexadiene
(24.56%25.81%), 1-methyl-4-(5-methyl-1-methylene4-hexenyl)-cyclohexene (11.75%13.06%) and -sesquiphellandrene (12.85%14.03%) are the major constituents. There is a little difference in their contents in
essential oil and the content of oxycompound extracted
by NPSMAE is less than that obtained by HD. The reason may be that the water in reactive system would
make some compounds be hydrolyzed. The content of
oxycompound is also influenced by the extraction time.
It can be summarized that more water and longer extraction time can result in the easier occurrence of hydrolyzation and oxidation.
The contents of chemical compositions in essential
oil obtained by PSMAE and MSMAE are also listed in
Table 2, and gas chromatograms of the extracts are
shown in Figure 2. From Table 2 and Figure 2, it can be
seen that the constituents in essential oil obtained by

Table 2 Retention time (R.T.), molecular formula (Mol. form.), extraction time, content, the content fractions of monoterpene and sesquiterpene hydrocarbons, content fraction of oxycompound and total content fraction of constituents in essential oil extracted from
Zingiber officinale Rosc. by NPSMAE, HD, PSMAE and MSMAE
No.

R.T./min

Compound

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23

3.56
3.97
4.15
4.42
4.94
5.14
5.44
5.88
6.02
6.36
6.62
7.32
7.57
8.12
8.57
8.70
9.01
9.27
9.54
9.92
10.32
10.81
11.52

2-Heptanol
1,7,7-Trimethyl-tricyclo[2.2.1.02,6]heptane
-Pinene
Camphene
-Pinene
-Myrcene
-Phellandrene
1-Methyl-4-(1-methylethylidene)-benzene
-Phellandrene
3,7-Dimethyl-1,3,7-octatriene
3-Carene
4-Carene
3,7-Dimethyl-1,6-octadien-3-ol
1,3,3-Trimethyl-bicyclo[2.2.1]heptan-2-ol
1-Methyl-4-(1-methylethyl)-2-cyclohexen-1-ol
Camphor
Isoborneol
Borneol
4-Methyl-1-(1-methylethyl)-3-cyclohexen-1-ol
-Terpineol
Decanal
3,7-Dimethyl-2-octen-1-ol
3,7-Dimethyl-2,6-octadien-1-ol

24
25

11.92
12.06

3,7-dimethyl-2,6-octadienal
4-(1-Methylethyl)-1-cyclohexene-1-carboxaldehyde

2007 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Mol. form.

Content/%
NPSMAE

HD

PSMAE MSMAE

C7H16O
C10H16
C10H16
C10H16
C10H16
C10H16
C10H16
C10H16
C10H16
C10H16
C10H16
C10H16
C10H18O
C10H18O
C10H18O
C10H16O
C10H18O
C10H18O
C10H18O
C10H18O
C10H20O
C10H20O
C10H18O

0.12
2.19
3.74
0.31
1.98
2.13
0.35
4.27
0.17
0.31
0.92
1.21

0.11
0.24
0.40
0.89
0.14
0.82
0.42
0.13
0.26

0.12
0.09
1.35
3.26
0.15
0.68
0.71
0.28
10.24
0.08
0.15
0.65
0.71
0.10
0.16
0.17
0.14
1.79
0.38
0.95
0.11
0.28
0.43

1.43

2.17

1.09

C10H16O
C10H16O

0.27
0.12

0.33
0.09

Chin. J. Chem., 2007 Vol. 25 No. 3 349

Non-polar solvent microwave-assisted extraction

Continued
No.R.T./min Compound

Mol. form.

26
27
28
29
30
31
32
33
34
35
36
37

12.37
12.50
13.94
14.01
14.37
14.63
14.79
15.03
15.35
15.72
16.09
16.67

1-Methoxy-4-(1-propenyl)-benzene
2-Undecanone
-Cubebene
cis-2,6-Dimethyl-2,6-octadiene
Isoledene
Copaene
3,7-Dimethyl-acetate-2,6-octadien-1-ol
1-Ethenyl-1-methyl-2,4-bis(1-methylethenyl)-cyclohexane
5-(1,5-Dimethyl-4-hexenyl)-2-methyl-1,3-cyclohexadiene
Caryophyllene
2,6-Dimethyl-6-(4-methyl-3-pentenyl)-bicyclo[3.1.1]hept-2-ene
Decahydro-1,1,7-trimethyl-4-methylene-1H-cycloprop[e]azulene
1,2,3,4,4a,5,6,8a-Octahydro-7-methyl-4-methylene-1-(1-methylethyl)38 16.98
naphthalene
39 17.20 Germacrene D
40 17.35 1-(1,5-Dimethyl-4-hexenyl)-4-methyl-benzene
41 17.68 5-(1,5-Dimethyl-4-hexenyl)-2-methyl-1,3-cyclohexadiene
42 17.99 1-Methyl-4-(5-methyl-1-methylene-4-hexenyl)-cyclohexene
43 18.37 -Sesquiphellandrene
44 18.62 -Panasinsene
45 19.07 Germacrene B
46 19.17 3,7,11-Trimethyl-1,6,10-dodecatrien
Content fraction of monoterpene hydrocarbon/%
Content fraction of sesquiterpene hydrocarbon/%
Content fraction of oxycompound/%
Total content fraction of determined compound/%
Extraction time/min

PSMAE and MSMAE are much fewer than these obtained by NPSMAE. The experiment results indicate
obviously that the extraction yields obtained by PSMAE
and MSMAE are lower than that obtained by NPSMAE.

Content/%
NPSMAE

HD

PSMAE MSMAE

C10H12O
C11H22O
C12H20O2
C10H18
C15H24
C15H24
C15H24
C15H24
C15H24
C15H24
C15H24
C15H24

0.87
1.21

0.32
0.23
0.44
1.12
0.23
0.39
0.43
0.22
0.37

2.91
0.56
0.04
0.26
0.58
1.09
0.99
0.55
0.40
0.38
0.30
0.51

0.91
0.84

1.02

C15H24

0.75

1.54

2.13

C15H24
C15H22
C15H24
C15H24
C15H24
C15H24
C15H24
C15H26O

0.31
16.08
25.81
13.06
14.03
0.12
0.24
0.35
16.81
73.83
7.44
98.08
5

0.10
14.31
24.56
11.75
12.85
0.65
0.16
1.02
17.90
70.72
10.29
98.91
180

21.31
35.21
18.95
20.12

1.43
95.59

97.02
5

19.26
30.12
17.79
19.97

1.09

3.26
93.13

96.39
5

GC/MS. CIP has better microwave absorption capacity

and higher calefaction speed than polar solvents, such as
water. The non-polar solvents have better extraction
capacity for essential oil than polar solvent. Thus, the
NPSMAE takes advantage over the traditional HD in
extraction time and sample consumption. The NPSMAE
has much higher extraction efficiency than PSMAE and
MSMAE. Furthermore, it seems possible to extend this
method to the extraction of the other non microwaveabsorbing samples by changing the extraction conditions.

References
1
2
3
Figure 2 Gas chromatograms of essential oil extracted from
Zingiber officinale Rosc. by PSMAE, MSMAE and NPSMAE.

Conclusion

The proposed extraction method, NPSMAE, offers a

rapid and efficient sample preparation for the determination of volatile constituents in dried plant materials by

6
7

Pan, X. J.; Niu, G. G.; Liu, H. Z. J. Chromatogr., A 2001,

922, 371.
Ganzler, K.; Szinai, I. J. Chromatogr., A 1990, 520, 257.
Mattina, M. J. I.; Berger, W. A. I.; Denson, C. L. J. Agric.
Food Chem. 1997, 45, 4691.
Eskilsson, C. S.; Bjrklund, E. J. Chromatogr., A 2000, 902,
227.
Xiong, G.; Liang, J.; Zou, S.; Zhang, Z. Anal. Chim. Acta
1998, 371, 97.
Ackley, K. L.; Hymer, C. B.; Sutton, K. L.; Caruso, J. A. J.
Anal. Atom. Spectrom. 1999, 14, 577.
Pastor, A.; Vzquez, E.; Ciscar, R.; Guardia, M. Anal. Chim.

2007 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

350 Chin. J. Chem., 2007, Vol. 25, No. 3

8
9
10
11
12
13
14
15
16

Acta 1997, 344, 241.

Lopez-Avila, V.; Young, R.; Benedicto, J.; Ho, P.; Kim, R.;
Beckert, W. F. Anal. Chem. 1995, 67, 2096.
Chee, K. K.; Wong, M. K.; Lee, H. K. J. Chromatogr., A
1996, 723, 259.
Egizabal, A.; Zuloaga,O.; Etxebarria, N.; Fernndez, L. A.;
Madariaga, J. M. Analyst 1998, 123, 1679.
Singute, S.; Gramshaw, J. W. Food Chem. 1998, 62, 483.
Igor, J.; Josip, M. J. Phytochemistry 2003, 63, 109.
Par, J. R. J. US 5002784, 1991 [Chem. Abstr. 1991, 7,
519558].
Par, J. R. J. US 5338557, 1994 [Chem. Abstr. 1994, 11,
529358].
Vaiyapuri, M.; Namasivayam, N. J. Clin. Chim. Acta 2005,
125, 60.
Javidnia, K.; Dastgheib, L.; Nasiri, A. Phytomedicine 2003,
10, 455.

YU et al.
17

18
19
20
21

22
23

Wang, Z. M.; Ding, L; Li, T. C.; Zhou, X.; Wang, L.; Zhang,
H. Q.; Liu, L.; Li, Y.; Liu, Z. H. J. Chromatogr., A 2006,
1102, 11.
Wang, Z. M.; Ding, L.; Wang, L.; Feng J.; Li, T. C.; Zhou,
X.; Zhang, H. Q. Chin. J. Chem. 2006, 24, 649.
Ruan, S. P.; Xu, B. K.; Suo, H.; Wu, F. Q.; Xiang, S. Q.;
Zhao, M. Y. J. Magn. Magn. Mater. 2000, 212, 175.
How, H.; Vittoria, C. J. Appl. Phys. 1991, 69, 5183.
Editorial Committee of Pharmacopoeia of the Peoples Republic of China, Pharmacopoeia of the Peoples Republic of
China, Chemical Industry Press, Beijing, 2005, p. 132 (in
Chinese).
Shao, Y. J.; Marriott, P.; Shellie, R. J. Flavour Fragr. 2003,
18, 5.
Mimica-Duki, N.; Kujund, S.; Sokovi, M.; Counladis,
M. Phytother. Res. 2003, 17, 368.

(E0606096

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LI, W. H.)