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Mircea Vinatoru
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Abstract
This paper presents a review of the ultrasonically assisted extraction of bioactive principles from herbs. Much of the work was
carried out under European community grants under the COPERNICUS programme and in a COST D10 network. Some aspects of
classical and non-conventional extraction procedures are also presented and briey discussed. 2001 Elsevier Science B.V. All
rights reserved.
Keywords: Ultrasonic extraction; Tinctures; Ultrasonic swelling index; Ultrasonic extractive value
1. Introduction
Vegetal materials are invaluable resources, useful in
daily life as food, food additives, avors, fragrances,
pharmaceuticals, colors or directly in medicine. This use
of plants has a long history all over the world and, over
the centuries, humanity has developed better methods
for the preparation of such materials. Nowadays, there
is a renaissance of interest in natural remedies, in part
due to some disillusionment with modern medicine and
drugs that either do not perform entirely to expectation
or are accompanied by unwanted side eects. Natural
remedies have the advantage that they have passed the
proof of time. On the other hand some synthetic drugs
even though they have been used for over 100 years,
may still need more time to be proven to be absolutely
harmless.
Perhaps anyone not familiar with the problems related to medicinal herbs might consider this subject
unimportant, or of only minor importance. Others
may feel that, in a period in which synthetic and highly
ecient drugs are available for treatment of various
diseases, medicinal herbs have become archaic and represent only a centuries-old tradition. Others however
consider them a form of natural remedy to oppose
modern drug consumerism.
1350-4177/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 1 3 5 0 - 4 1 7 7 ( 0 1 ) 0 0 0 7 1 - 2
304
Table 1
Entries on herbal drugs in pharmacopoeias
Country
Number of herbal
drugs monographs
French pharmacopoeia
Switzerland pharmacopoeia
USSR pharmacopoeia
Polish pharmacopoeia
British codex
Belgian pharmacopoeia
Holland pharmacopoeia
Hungarian pharmacopoeia
Romanian pharmacopoeia
Italian pharmacopoeia
German pharmacopoeia
British pharmacopoeia
Scandinavian pharmacopoeia
International pharmacopoeia
190
180
140
125
125
120
120
110
105
105
85
80
80
45
herbalist Culpeper, described in a wonderful book several rules for gathering plant parts for herbal preparations [4]. His rules are still applicable today and readers
will nd them useful in the gathering of leaves, owers,
seeds, roots, barks and other parts.
Actually, when research work for developing new
extraction techniques starts up, the rst thing to be done
is to gather the required herbs. However for chemists
not familiar with botany this could prove to be a very
dicult task. Indeed, the chemical content of herbs
strongly depends on the gathering time. For industrial
processing medicinal and aromatic herbs, the harvesting
time as well as the preserving methods are of crucial
importance and therefore a precise technique must be
setup for this purpose [5].
2. A short history of plants and plant extract uses
The history of vegetal materials use is as old as humanity. The rst use was for nutrition, initially from
natural and later from cultivated ora. Soon, the medicinal properties of herbs were discovered. Several
herbs, such as lavender, hyssop, thyme, etc., were introduced into agriculture for their essential oils or their
medicinal compounds.
Egyptian papyruses describe thousands of recipes
showing that coriander and castor oils were used for
medicinal application, cosmetics and preservatives. Hebrew and Chinese manuscripts describe over 2000 herbs,
with details that are useful today. In the Greek and
Roman empires there was an expanding process for the
therapeutic use of herbs, mainly for their essential oil
content. Galenus described, in the second century, in
around 30 papers and recipes, herbal extracts for medicinal purposes which are still up to date. ``Hungarian
water'', known since 1380 was the rst alcoholic extract
from rosemary, and was, for ve centuries, extensively
used in Europe. Paracelsus, in the 16th century made an
305
Table 2
Comparison between dierent extraction methods of 100 g of dill seeds, using hexane
Method used
CE
US
US
M US
M US
M US R
M US R
Extraction time
240 min
30 min
60 min
7 days M 30 min US
7 days M 60 min US
7 days M 30 min US 240 min R
7 days M 60 min US 240 min R
Components
Limonene %
Carvone %
Heavy comp. %
40.79
49.63
51.22
25.08
20.77
20.72
20.28
47.29
48.15
45.84
66.84
65.40
65.69
65.92
0.09
0.05
0.34
0.10
0.34
306
Table 3
Dry residue (g/100 g extract) obtained by direct sonication
Sonication time (min)
Minta
Camomilea
Sagea
Arnicaa
Gentiana
Marigolda
Marigoldb
15
30
60
90
120
180
18 h maturation
Classical 714 days
0.06
0.07
0.25
0.78
0.82
0.91
1.02
1.10
1.30
1.43
1.56
1.79
1.80
1.91
1.73
0.58
0.80
0.92
0.94
1.13
1.15
1.02
0.36
0.42
0.67
1.06
1.20
1.50
1.75
1.67
2.66
2.71
3.24
4.68
4.75
0.94
0.98
1.14
1.33
1.75
2.20
2.25
1.15
1.74
1.97
2.25
2.25
2.25
a
b
Cleaning bath.
Probe system.
Table 4
Comparison of dierent ultrasonic extraction procedures for sage
Extraction procedure
Thujone
Borneol
Probe (2 h)
Cleaning batha
Cleaning bath stirrera
Silent control experimentb
24.3
16.5
22.7
14.0
167.2
118.1
141.9
176.6
5.8
3.6
6.3
6.5
a
b
Table 5
Supercritical extraction (selected examples)
Herb, air dried
Main constituents
Molecular
weight
Extractable
at (bar)
Caraway seeds
Limonene
Carvone
Triglycerides
Menthol
Menthone
Cannabidiol
Cannabinol
Tetrahydrocannabinol
136
160
>600
158
156
314
310
315
70
70
90
70
70
85
90
90
Peppermint
leaves
Cannabis
307
suggested for the rst time by Issaev and Mitev [14] and
performed by the same authors [15] for Cytisus laburnum
(broom). This extraction technique is represented in
Scheme 3. The alkaloid yield during the extraction of
Rauwola by electrical discharge was increased by 25%,
according to Boiko and Mizineko [16]. All authors
working with this type of apparatus noted that during
electrical discharges, cavitation bubbles are produced
and that this technique therefore has similarities to ultrasonic extraction.
3.4. Ultrasonic extraction
obvious that using a high speed stirrer, the contact between vegetal material and solvent is improved and
therefore the diusion process through the cell walls is
increased. Moreover, during vortical extraction hydrodynamic cavitation bubbles are produced and their
collapse acts in a similar way to the eect of ultrasonic
devices. If the vegetal material is well milled, the dierences between classical and vortical extraction diminish.
Electrical discharges within the extraction mixture
were also claimed to increase the extraction yield, as
Table 6
Eect of milling degree and type of extraction on the dry residue and
tannins content of tincture of tormentil
Extraction method
Milling degree
Dry residue
(%)
Tannins
(g)
Maceration
Vortical extraction
Maceration
Vortical extraction
Maceration
Vortical extraction
25 mm
''
Up to 1 mm
''
0.10.5 mm
''
4.40
4.72
4.75
5.00
5.05
5.12
2.15
2.35
2.28
2.45
2.45
2.60
4. Extraction mechanisms
Vegetal tissue consists of cells surrounded by walls
(Fig. 1). The extraction mechanism involves two types of
physical phenomena: diusion through the cell walls and
washing out (rinsing) the cell contents once the walls are
broken. Both phenomena are signicantly eected by
ultrasonic irradiation. Some cells exist in the form of
glands (external or internal) that are lled with essential
308
Table 7
Examples of ultrasonically assisted extraction
Ultrasonic frequency (kHz)
Extracted drugs
Remarks
References
2400
400
500
Cinchona bark
Peanuts (oil)
Belladonna leaves
[19]
[20]
[21]
25
2040
20
Rauwola roots
Datura stramonium (thorn apple)
Cinchona bark
1000
800
Digitalis leaves
20
Berberine
1000
800
Urtica dioica
Inula helenium and Telekia speciosa
Amarantus retroexus
1000
a
[22]
[23]
[24]
[25,26]
[27]
[28]
[29]
[30]
[31]
Extraction
technique
Milling degree
Eugenol extracted
(g/100g)
30
30
30
30
Silent
Silent
US
US
not milled
0.10.5 mm
not milled
0.10.5 mm
4.10
25.20
4.22
32.66
a
Extraction solvent ethyl alcohol 96%, cleaning bath with stirring.
Silent method involve only stirring.
309
Fig. 2. The enhancement of vegetal material swelling induced by ultrasonic treatment [29].
Table 9
Comparison of extractive value of sonicated and silent methods for some vegetal species [29]
Vegetal species
Method
ETH
ETHW
WATER
GLYW
EETH
Classic
1/2 h US
1 h US
Classic
1/2 h US
1 h US
Classic
1/2 h US
1 h US
Classic
1/2 h US
1 h US
Classic
1/2 h US
1 h US
10.2
13.7
14.3
20.4
22.8
27.0
16.0
16.5
18.0
16.2
17.3
19.0
8.5
9.3
9.7
7.4
7.3
7.5
27.0
31.0
32.0
20.0
22.0
23.0
16.2
17.0
18.6
21.3
26.3
27.2
8.2
11.0
15.6
24.0
28.3
29.5
30.0
30.5
31.4
21.4
22.0
22.0
26.4
26.5
26.8
13.4
13.4
15.2
22.5
28.0
31.0
22.5
27.8
28.0
24.6
25.2
26.7
12.2
16.0
19.3
4.5
6.3
7.2
9.2
9.5
9.7
14.8
15.6
16.8
3.2
3.6
4.2
ETH: ethanolwater (94 v/v), ETHW: ethanolwater (70 v/v), WATER: water, GLYW: glycerolwater (3.5 v/v) and ETEH: ethyl ether.
310
Fig. 5. Pot marigold petal sonicated at 500 kHz. Only top of excretion
hairs are destroyed.
311
312
Fig. 12. Inhibitory eect of winter savory essential oil on wheat seedlings.
7. Conclusions
Two main conclusions can be drawn from the information presented in this paper:
1. Ultrasound has been proven to assist solvent extraction and should prove to be a powerful tool for the
phytopharmaceutical extraction industry.
2. Ultrasonically assisted extraction is a versatile technique that can be used both on a small and large
scale.
Acknowledgements
Thanks are due to EU for nancial support (COPERNICUS research program ERB-CIPA-CT94-02271995 and SAFE COST D10/0016/99) of the research
work included in this paper and to the Romanian
Academy for partial nancial support.
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