Separation and Purification Technology 124 (2014) 141–147

Contents lists available at ScienceDirect

Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

The kinetics of extraction of the medicinal ginger bioactive compounds

using hot compressed water
Mohd Sharizan Md Sarip a,b, Noor Azian Morad a,b,⇑, Nor Azah Mohamad Ali c, Yasmin Anum Mohd Yusof d,
Mohd Azizi Che Yunus e
a
Centre of Lipid Engineering Applied Research (CLEAR), Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur, Malaysia
b
Malaysia – Japan International Institute of Technology (MJIIT), Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur, Malaysia
c
Forest Research Institute of Malaysia (FRIM), Kepong, 52109 Selangor, Malaysia
d
Department of Biochemistry, Faculty of Medicine, Universiti Kebangsaan Malaysia, 54100 Kuala Lumpur, Malaysia
e
Centre of Lipid Engineering Applied Research (CLEAR), Universiti Teknologi Malaysia, 81310 Johor Bahru, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Zingiber officinale or ginger known for its high medicinal compounds is extracted using hot compressed
Received 2 August 2013 water (HCW). The two most important bioactive compounds namely 6-gingerol and 6-shogaol in the gin-
Received in revised form 9 December 2013 ger extracts are analyzed using HPLC. The effects of temperature and time of extraction on 6-gingerol and
Accepted 1 January 2014
6-shogaol are studied using HCW extraction. It is found that HCW extraction can extract these two bio-
Available online 19 January 2014
active compounds; 6-gingerol at 130 °C and 30 min whilst 6-shogaol at 170 °C and 20 min. This finding
shows that HCW extraction is potentially used in selective extraction of bioactive compounds at different
Keywords:
conditions of HCW. The kinetics of extraction for both bioactive compounds is studied from the optimum
Hot compressed water
6-Gingerol
temperatures obtained. The overall mass transfer coefficient which represents the extraction efficiency is
6-Shogaol calculated using mass transfer model. The optimum values of the overall mass transfer coefficient (k) for
Kinetics 6-gingerol is 8  107 m/s at 130 °C whilst for 6-shogaol, is 18  107 m/s at 170 °C using HCW extrac-
Mass transfer model tion. The relationship between the overall mass transfer coefficient and the dielectric constant of various
solvents for 6-gingerol is identified. Similar relationship is identified for 6-shogaol using HCW as solvent.
The dielectric constant does not contribute to the extraction efficiency of 6-gingerol and 6-shogaol.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction
Ginger or zingiber officinale is known to be anticancer [1,2], anti-
oxidants [2] and anticarcinogenic [3]. The main bioactive com-
pounds that exhibit these medicinal properties are the series of
gingerols, shogaol and paradol. The most important medicinal
compounds identified are 6-gingerol, 10-gingerol and 6-shogaol.
6-Gingerol, the most abundant compound in ginger rhizome has
been proven to give positive response in mediating cardiac con-
tractile, act as antioxidant [4], antiproliferative and also apoptosis
[2]. 10-Gingerol has significant medicinal effect such as antibacte-
rial [5] and antimicrobial activities [6]. 6-Shogaol is another pre-
dominant pungent constituent in ginger is proven to reduce cell
death and restores motor function in rat spinal cord injury [7]
and lessen the human oral cancer [8]. Furthermore, pharmacoki-
netics study of 6-gingerol, 10-gingerol, and 6-shogaol shows that
⇑ Corresponding author at: Centre of Lipid Engineering Applied Research (CLEAR),
Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur, Malaysia. Tel.:
+60 326154317.
E-mail address: azian.morad@gmail.com (N.A. Morad).
all these compounds are absorbed quickly in the serum with
majority detected as glucuronide metabolites [9].
The proven medicinal roles of each ginger compound have pro-
moted the search for selective extraction to give an added value to
the ginger oleoresin. Ginger in its fresh form is made up of isolated
cells containing oleoresins comprising of gingerols and shogaols
[10]. In dried ginger, the oleoresin cell wall is ruptured and ex-
posed. This can facilitate the extraction of ginger bioactive
compounds.
The use of water in subcritical region as a ’green’ solvent has at-
tracted the interest of numerous researchers from all over the
world. Thermodynamically, water in its liquid state below the crit-
ical point of 374 °C and 22 MPa is referred to as subcritical water.
Meanwhile, hot compressed water (HCW) specifically refers to
subcritical water above the normal boiling point of 100 °C [11].
HCW extraction has been successfully utilized for herbal extraction
as demonstrated in the extraction of cumin [12], zataria multiflora
[13], centella asiatica [14], thymbra spicata [15], bitter melon [16]
and oregano [17].
HCW does not only act as a ‘green’ solvent but it also has the po-
tential use for selective extraction [18]. Wiboonsirikul and Adachi
have reported that the main parameters that affect the extraction

1383-5866/$ - see front matter Ó 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2014.01.008
142 M.S. Md Sarip et al. / Separation and Purification Technology 124 (2014) 141–147
efficiency during HCW extraction process are temperature and
time [19]. Meanwhile, pressure is proven to have no significant ef-
fect on the extraction efficiency [17]. The effect of temperature and
time for the extraction of 6-gingerol and 6-shogaol from zingiber
officinale using HCW are explored in this study for the potential
use in selective extraction.
There is no known mass transfer data available for 6-gingerol
and 6-shogaol which is required for design purposes in particular
for the optimization of HCW extraction process. The overall mass
transfer model is applied to 6-gingerol and 6-shagaol extraction
using HCW to determine the overall mass transfer coefficient, k.
The k value represents the extraction efficiency of a process. The
k value is affected by the properties of the solute as well as the sol-
vent. The dielectric constant is a fundamental property of a solvent
and it has been shown that it is affected significantly by tempera-
ture and insignificantly by pressure [20]. Dielectric constant varies
with different types of solvent and generally, organic solvents such
as hexane, acetone and chloroform have lower dielectric constants
which increase the solubility of organic solutes. The relationship
between the dielectric constant of different types of solvent on
extraction efficiency of 6-gingerol is confirmed in a study by Shad-
mani et al. [21]. The effect of the dielectric constant of HCW on the
k value of 6-gingerol and 6-shogaol is investigated in this study.
2. Material and method
2.1. Material
Dried and ground ginger was supplied by a local supplier from
Ranau, Sabah, East Malaysia. The ginger standards of 6-gingerol
(85.8% w/w), 10-gingerol (95.1% w/w) and 6-shogaol (96.4% w/w)
were purchased from ChromoDex Inc., CA, USA. Acetonitrile and
methanol were of High Performance Liquid Chromatography
(HPLC) grade, supplied by MERCK, Germany. Distilled water was
used in the HCW extraction.
2.2. Hot compressed water extraction
HCW extraction was done batch wisely using the fabricated
equipment in this laboratory as shown in Fig. 1. Prior to this, pre-
liminary experiments on temperature effect were done using 32 ml
extraction cell of Accelerated solvent extractor (ASE 200, Dionex,
USA) to verify the result of the fabricated equipment. The solvent
of sample ratio used in this equipment was scaled up from the
ASE as recommended by the manufacturer. The fabricated equip-
ment consisted of two vessels with one liter volume each; the
extraction and the cooling cells connected by a 1=4 in. stainless steel
pipeline. 75 g of ground ginger was weighed and loaded into a cov-
ered stainless steel mesh cylinder before being placed into the
extraction cell. 700 ml of distilled water was added into the cell.
The cell was then securely covered with a stainless steel lid. N2
gas was then passed through the cell for 2 min to purge out air
Fig. 1. Schematic diagram of HCW extraction facility.
and dissolved oxygen. Excess pressure was relieved through the re-
lease valve. The temperature was set according to the required
experiment. The electrically jacketed extraction cell took 3–5 min
to achieve the desired temperature. The extraction time started
once the set temperature was achieved as indicated by the temper-
ature indicator in the extraction cell.
The effect of temperature was studied independently from 100
to 200 °C with 10 °C increment and referred to as the first set of
experiments. The extraction time was kept constantly at 30 min.
For example, at 100 °C, the first experiment in the first set was
run for 30 min, the second experiment was run at 110 °C for
30 min and so on up to 200 °C for 30 min, which the temperature
increased but the time was constant.
The effect of extraction time was studied at 10, 20, 30, 40, 50
and 60 min at the determined optimum temperature from the
temperature effect experiment and referred to as the second set
of experiments. For example, if the optimum temperature for 6-
gingerol was T1, the first experiment in the second set was T1
for 10 min, the second experiment was run at T1 for 20 min and
so on up to 60 min at T1. All experiments were carried out at con-
stant pressure of 3.5 MPa. Once the extraction process was com-
pleted, the extractant was transferred into the cooling cell at
25 °C and 1 MPa within 1 min to ensure rapid cooling.
Ginger extracts were collected and subjected to further analysis
using HPLC. Each experimental condition was run triplicate. The
average absolute deviation, AAD was applied for each set of exper-
iment using Eq. (1).
1 Xn jxi  xj
AAD ¼ ð1Þ
N i¼1 xi
where i, n is the no. of runs for one experimental condition; N the
total no. of runs; xi the data for one experimental condition; x is
the average for one experimental condition.
The percent recovery of each bioactive compound was calcu-
lated using Eq. (2).
ci gldried
g bioactive
ginger
Percent recovery ¼  100 ð2Þ
coi ; gldried
g bioactive
ginger
where ci is the species concentration in the bulk solution; coi is the
species initial concentration obtained using eight hours soxhlet
extraction with ethanol.
2.3. HPLC analysis for ginger bioactive compounds
The analysis were carried out using HPLC (Waters Corp., MA,
USA) equipped with Photodiode Array (PDA) detector and the
Lichrocart 250-4, 6 Purospher Star RP-8E (5 Mym) column (MERCK,
Germany). In this analysis, 10 min run time was used with 8 min as
an injection delay. Two mobile phase solutions were used which
were A; 100% acetonitrile and B; 65% (v/v) methanol in water.
The mobile phase ratio A to B increased gradually during the sep-
aration process from 20:80 to 50:50 (volume of A/volume of B) at
a constant flow rate of 1.20 ml/min. 10 ll of sample extracts were
 M.S. Md Sarip et al. / Separation and Purification Technology 124 (2014) 141–147
filtered using syringe filter (PTFE, 0.45 lm, Whatman, USA) before
injected into the HPLC. The standard curve of 6-gingerol, 6-shogaol
and 10-gingerol were established using 10 ll of standards injected
into the HPLC. The ginger bioactive compound concentration was
established through the calibration of HPLC chromatograms using
the standard curves. The method was adapted from Schwertner
and Rios [22].
2.4. Mass transfer coefficient model
The experimental data on ginger bioactive compounds concen-
tration was used to describe the extraction mechanism through the
mass transfer coefficient model. The overall mass transfer coeffi-
cient, k was calculated based on the mass balance for the process
with the assumption that the amount transferred was proportional
to the concentration difference and the interfacial area [23]. Based
on the mass transfer model used as demonstrated in Sarip and
Morad [24], two different first order expressions of mass transfer
coefficients were used in this work. The assumption on the ginger
particles size and total surface area using this model was explained
in Sarip and Morad [24]. The overall mass transfer coefficient, k and
absolute overall mass transfer coefficient, kabs are shown in Eqs. (3)
and (4) [23,25].
VL c oi
k value is expressed as : ki ¼  ln
At c oi  c i
 
c oi
kabs value is expressed as : kabsi ¼ ln
c oi  c i
where At is the surface area for particle; coi the species initial con-
centration measured using eight hours soxhlet extraction with eth-
anol at 4:1 (ml:g) solvent to sample ratio, lg bioactive/g dried
sample; ci the species concentration in the bulk solution, lg bioac-
tive/g dried sample; i the species, 6-gingerol and 6-shogaol; VL is
the volume of the solution.
The kabs values of 6-gingerol extracted using various organic
solvents which were benzene, hexane, chloroform, ethanol, meth-
anol, acetone, dichloroethane, acetonitrile, diethyl ether, ethyl ace-
tate, isopropanol and dichloromethane were taken from Shadmani
et al. [21]. The respective dielectric constant values of the organic
solvents were obtained from Timmermans [26]. These kabs values
were compared with the kabs value of 6-gingerol extracted using
HCW. The dielectric constant of water at 3.5 MPa was interpolated
from the experimental data between 2.5 and 5 MPa provided by
Uematsu and Frank [20].
3. Results and discussion
3.1. The effect of temperature using HCW on ginger bioactive
compounds
The effect of the extraction temperature on each ginger bioactive
compound concentration (lg bioactive/g dried ginger) is shown in
Fig. 2. The effect can only be seen for the two main ginger bioactive
compounds which were the 6-gingerol and 6-shogaol. Meanwhile,
10-gingerol was not detected in the HCW extracts under these con-
ditions through HPLC analysis. Therefore, it can be considered that
during the HCW extraction 10-gingerol was not extracted within
the experimental temperature range of 100–200 °C at 3.5 MPa.
Fig. 2 shows that from 100 to 120 °C, the modest increase of the
6-gingerol concentration was observed from 610.31 to
721.98 ± 2.19 lg 6-gingerol/g dried ginger; however, 6-shogaol
was not extracted. HCW extraction at temperatures from 120 to
130 °C indicated a rapid increase of 6-gingerol concentration from
721.98 ± 2.19 lg 6-gingerol/g dried ginger to its maximum
143
concentration peak of 1741.54 ± 2.19 lg 6-gingerol/g dried ginger
at 130 °C. 6-Gingerol with the existence of hydroxide group in
the structure was more polar compared to 6-shogaol. The principle
theory of ‘like dissolve like’ was applied during the extraction pro-
cess. The advantage of using HCW as a solvent was that it had a
wide range of polarity which varied with temperature as indicated
in Fig. 2. From 120 to 130 °C, the dielectric constant (measure of
polarity) of water was about 50 [20] and it was indicated that it
was the most suitable condition for extracting the relatively polar
6-gingerol rather than 6-shogaol.
Fig. 3a shows the HPLC chromatogram, which indicates that at
130 °C, only 6-gingerol has been extracted. Fig. 3b indicates that
both 6-gingerol and 6-shogaol peaks were detected in the ginger
extracts using HCW at 170 °C. It was found that extraction using
HCW at 130–170 °C was not favorable for 6-gingerol as the concen-
tration rapidly decreased from 1741.54 to 340.84 ± 2.19 lg 6-ging-
erol/g dried ginger. However, for 6-shogaol, it can be observed that
the bioactive compound concentration steadily increased from the
extraction temperature of 120–170° using HCW. The optimum
extraction temperature was 170 °C with a maximum concentration
of 541.78 ± 2.95 lg 6-shogaol/g dried ginger. The increasing of 6-
shogaol and the decreasing of 6-gingerol concentrations were re-
lated to the decreasing of the dielectric constants of water from
50 at the temperature of 120 °C to 39 at 170 °C [23]. At 170 °C,
the extraction condition favoured the extraction of 6-shogaol
ð3Þ
which was also less polar than 6-gingerol.
The other contributing factor for the decline of 6-gingerol was
the increase in 6-shogaol due to the degradation of 6-gingerol. b-
ð4Þ
hydroxy keto group in the 6-gingerol molecule dehydrates to form
6-shogaol and water molecules as illustrated in Fig. 4. This was the
key feature that made 6-gingerol thermally labile undergo facile
dehydration at high temperature and acidic condition [27,28]. Even
though it was a reversible reaction, the degradation affects 6-ging-
erol since this bioactive was extracted out in abundance at a lower
temperature where as 6-shogaol was significantly absent at below
150 °C.
It was proven that 6-gingerol decreased when HCW extraction
was conducted from 140 to 200 °C. On the other hand, for the same
HCW extraction conditions, 6-shogaol concentration increased in
the ginger extract as shown in Table 1. The changes in lmol for
6-gingerol and 6-shogaol respectively were calculated starting at
130 °C. Subsequent changes in the lmoles of the bioactives were
calculated at an increment of 10 °C. Since the dehydration of 6-
gingerol to 6-shogaol should be in accordance with the stoichiom-
etry, the obvious reason for further decline in 6-gingerol content at
extraction temperatures above 130 °C was attributed to other
forms of degradation [27]. Apart from the degradation of 6-ginger-
ol to 6-shogaol, the further increase in 6-shogaol can be attributed
to the preference of bioactive compound being extracted from gin-
ger samples at higher temperature as indicated in Table 2.
It can be observed that the concentration of both bioactive com-
pounds declined at 180–200 °C. The decrease was due to both bioac-
tive compounds degradation at these temperatures. Further study
on ginger bioactive stability is required to understand the effects
of HCW extraction at higher temperatures. Thus, two different opti-
mum extraction temperatures were identified for the extraction of
6-gingerol and 6-shogaol which were at 130 °C and 170 °C respec-
tively at 30 min extraction time and 3.5 MPa. Further investigation
on the suitable extraction time was required to verify the appropri-
ate optimum extraction time for both bioactive compounds.
3.2. Effect of the extraction time on the bioactive compounds
concentration in the ginger extract
Another important parameter involved in this HCW extraction
study was the extraction time or treatment time. The effects of
144 M.S. Md Sarip et al. / Separation and Purification Technology 124 (2014) 141–147

Fig. 2. The effect of temperature, °C in the ginger bioactive compounds concentration using HCW at constant time of 30 min and constant pressure of 3.5 MPa.

Fig. 3. HPLC profile for HCW extract. (a) 130 °C and (b) 170 °C: (—) Sample, (- - -) Standard.

observed for 6-gingerol since only traces of 6-shogaol was

Fig. 4. The dehydration of 6-gingerol to 6-shogaol [28].
the extraction time in this study focused on the optimum temper-
atures that were 130 °C and 170 °C for 6-gingerol and 6-shogaol
respectively. At 130 °C, the effect of extraction time can be
extracted from the ginger as shown in Fig. 5. The high rate of the
extraction giving 800.33 ± 2.61 lg 6-gingerol/g dried ginger can
be observed after 10 min. When HCW extraction was conducted
for 20 min, a moderate extraction rate with a concentration of
949.38 ± 2.61 lg 6-gingerol/g dried ginger was noted; an incre-
ment of 149.05 lg 6-gingerol/g dried ginger in 10 min. The highest
rate of extraction giving a maximum concentration of
1741.54 ± 2.61 lg 6-gingerol/g dried ginger was achieved for
30 min of extraction time.
During the first 10 min of extraction time, the mass transfer
within the solid matrix is the dominating factor. The low
 M.S. Md Sarip et al. / Separation and Purification Technology 124 (2014) 141–147 145

Table 1
Degradation of 6-gingerol to 6-shogaol.

Temperature (°C) Decrease of 6-gingerol (lmol)a Increase of 6-shogaol (lmol)a Difference in changes (lmol)a
130–140 0.82 1.11 0.29
140–150 2.20 0.03 2.17
150–160 0.93 0.20 0.73
160–170 0.81 0.62 0.19
a
Basis 1 g of dried ginger.

Table 2
Compound initial concentration, co, optimum HCW extract yield, ci and maximum recovery of bioactive at 3.5 MPa.

Compound Optimum HCW condition co, (lg/g) HCW extract conc., ci (lg/g) Max recovery of bioactive, %
T (°C) Time (mins)
6-Gingerol 130 30 8406.99 1741.54 20.71
6-Shogaol 170 20 716.76 609.51 85.04
10-Gingerol None None 903.41 None None

933.44 ± 2.61 lg 6-gingerol/g dried ginger due to prolonged heat

Fig. 5. The effect of the extraction time on the ginger bioactive compounds
concentration at a constant temperature of 130 °C and a constant pressure of
3.5 MPa.
concentration of 6-gingerol in the bulk liquid causes the high rate
of mass transfer since the driving force is high with large concen-
tration gradient in accordance with the overall mass transfer mod-
el. For the next 10 min, more 6-gingerol is transferred out into the
bulk liquid but at a much reduced concentration about
149.04 ± 2.61 lg 6-gingerol/g dried since most of it is trapped
within the bulk liquid just outside the solid matrix. This will re-
duce the concentration gradient and consequently reduce mass
transfer process. As the extraction time is prolonged to 30 min,
6-gingerol starts to diffuse further into the bulk liquid and this im-
proves the mass transfer and increase by 792.16 ± 2.61 lg 6-ging-
erol/g dried of 6-gingerol. The dominating effect of diffusion of 6-
gingerol from outer surface of solid matrix into the bulk liquid is
illustrated in this region. From 40 to 60 min of extraction, the con-
centration of 6-gingerol is decreased from 1741.54 to
Fig. 6. The effect of the extraction time on the ginger bioactive compounds
concentration at the temperature of 170 °C at constant pressure of 3.5 MPa.
exposure. 6-Gingerol being thermally labile underwent the dehy-
dration and degradation as discussed earlier. At 130 °C, 6-shogaol
is not significantly extracted as indicated in Fig. 5.
The effect of extraction time on the ginger bioactive compounds
at a constant temperature of 170 °C was observed in Fig. 6. At
170 °C and extraction time of 10 min, both ginger bioactive com-
pounds 6-gingerol and 6-shogaol are in high concentration of
969.91 ± 10.68 lg 6-gingerol/g dried ginger and 427.79 ± 6.92 lg
6-shogaol/g dried ginger respectively. The 6-gingerol concentra-
tion however, decreases steadily for extraction times of 20 min to
the concentration of 227.07 ± 10.68 lg 6-gingerol/g dried ginger
at 60 min.
Meanwhile, 6-shogaol concentration increases for the extrac-
tion time of 20 min at 609.51 ± 6.92 lg 6-shogaol/g dried ginger
and remains almost constant for the extraction times of 30 and
40 min. At the extraction times of 50 and 60 min, the 6-shogaol
indicated the reduction to the concentration of 157.13 ± 6.92 lg
6-shogaol/g dried ginger due to the possible degradation to other
forms.
Therefore, it was found that HCW extraction at a constant
temperature of 130 °C gave the maximum 6-gingerol 1741.54 ±
2.61 lg 6-gingerol/g dried ginger at the extraction time of
30 min. At this temperature, it was obvious that selective extrac-
tion took place in which only 6-gingerol was extracted whilst
6-shogaol was significantly absent in the ginger extract.
Meanwhile, 6-shogaol was at its highest concentration of
609.51 ± 6.92 lg 6-shogaol/g dried ginger at the extraction time
of 20 min compared to 541.78 ± 2.95 lg 6-shogaol/g dried ginger
at 30 min of extraction. This indicates that the optimum condi-
tion for 6-shogaol extraction is at 170 °C with 20 min extraction
time.
The optimum HCW extracts and the initial concentration, co
of 8406.99, 716.76 and 903.41 lg bioactive/g dried ginger for
6-gingerol, 6-shogaol and 10-gingerol is tabulated in Table 2.
The percent recovery of 6-gingerol, 6-shogaol and 10-gingerol
using HCW extraction is 20.71, 85.04 and 0%; respectively based
on the co. The higher recovery for 6-shogaol is due to the addi-
tional degradation of 6-gingerol to 6-shogaol which contribute
to its higher concentration. This consequently reduces the over-
all recovery for 6-gingerol. Further improvement in extraction
method need to be studied to increase the extraction efficiency.
This includes the addition of co-solvent in the HCW, introduc-
tion of turbulent mixing between sample and solvent and inclu-
sion of external factors to improve extraction such as sonic
energy.
146 M.S. Md Sarip et al. / Separation and Purification Technology 124 (2014) 141–147

Table 3
k, kabs and e values of 6-gingerol and 6-shogaol at different temperatures.

Temperature, °C kabs, min1(103) k, m/s (107) Dielectric constant of water, e[23]

6-Gingerol 6-Shogaol 6-Gingerol 6-Shogaol
110 6.10 N.A 2.46 N.A 53.00
130 20.10 9.10 8.12 3.68 49.03
150 6.80 10.90 2.75 4.40 39.17
170 2.20 45.50 0.89 18.38 35.00

3.3. Kinetics of the HCW extraction process using mass transfer 150 °C to 170 °C. The decrease of kabs values for 6-gingerol from
coefficient model 150 °C to 170 °C is inconsistent with the decrease of water dielec-
tric constant at the same temperatures as demonstrated in Table 3.
The k and kabs values for 6-gingerol and 6-shogaol at the extrac- The relationship between the dielectric constant and kabs value
tion temperatures of 110 °C, 130 °C, 150 °C and 170 °C at the con- for 6-gingerol in the HCW extraction is shown in Fig. 7 together
stant pressure of 3.5 MPa were calculated and tabulated in Table 3. with the experimental values from Shadmani et al. [21] using var-
The values of dielectric constant, e of water at the respective tem- ious solvents at lower temperatures. Two different linear fits for
peratures are also included in the Table 3. data from Shadmani et al. [21] and the HCW extraction data of this
Generally, the higher k value indicates a higher rate of solute work are presented. The relationship between the dielectric con-
transfer from the solid matrix into a solvent [29]. Thus, k value rep- stant and kabs for HCW extraction process of 6-gingerol gives an
resents the extraction efficiency which is related to the solvent and r2 value of 0.0256 and has a low slope of 0.0001. This indicate poor
solute properties. One of the solvent properties which is widely re- relationship between dielectric constant and kabs since a good lin-
lated to the extraction efficiency is the dielectric constant. In the- ear fit will have r2 value approaching 1. A slope of 0.0001 indicates
ory, the extracting power increases as the dielectric constant almost a nonexistence relationship between dielectric constant
decreases. Therefore, in this study, the relationship between k va- and kabs value. Similar trend is observed for the extraction of 6-
lue and dielectric constant of solvents including HCW was gingerol using various solvents with r2 value of 0.0186 and slope
investigated. of 0.00004 [21]. This suggests that the dielectric constant is not
Comparisons were made between the k values derived for SFE the parameter affecting the extraction efficiency of 6-gingerol.
and HCW extraction processes. For SFE process, the k value derived A more important condition affecting extraction efficiency is
for 6-gingerol is 6  105 m/s [30] which is higher compared to the most likely the solvent–solute interaction which includes the sol-
k value of 8  107 m/s for HCW extraction process in this work. A vent shift and the cavity as reported by Horák and Plíva [31]. More-
possible explanation for this variation in the k values is due to the over, the effect of dielectric constant for different types of solvent
different initial concentrations used for both calculations. In SFE
process, the initial concentration, co was 2.4 wt% (on a dry solids
basis) [30] meanwhile for HCW extraction was 0.8 wt% (on a dry
solid basis). The difference on these initial concentrations was
due to the different sample origins, sample preparations and
extraction methods. The higher co values contribute to the higher
k value in SFE extraction. Furthermore, SFE process operates at a
low temperature of 40 °C thus excluding the dehydration and deg-
radation of 6-gingerol to other products. Supercritical CO2 which is
the common supercritical fluid as a solvent most likely promotes
better mass transfer process for thermal labile compounds such
as 6-gingerol compared to HCW. The comparisons between k val-
ues of SFE and HCW extraction is not completely indicative of a
better process in 6-gingerol extraction using SFE. For best compar-
ison, the co values for both SFE and HCW extraction should be the
same using same samples, similar preparation and similar initial
concentration extraction method. Fig. 7. The relationship between the absolute overall mass transfer coefficient, kabs
For 6-shogaol, it can be observed that the k value increases with and dielectric constant of solvents for 6-gingerol.
temperature to its maximum value of 18.3764  107 m/s at
170 °C since extraction above this temperature indicates degrada-
tion of the bioactive compound. The k value for 6-shogaol is higher
compared to k value of 6-gingerol through HCW extraction
process. Apart from the naturally existing 6-shogaol in the ginger
sample, the addition of 6-shogaol through dehydration of
6-gingerol contributes to the increased concentration at higher
temperatures. However, the k value for 6-shogaol cannot be com-
pared to other means of extraction since there is no such known
experimental data.
For the purpose of identifying the relationship between extrac-
tion efficiency and dielectric constant, kabs is utilized instead of k
values. This is due to the availability of kabs data for various solvent
extractions to be used for comparison purposes with HCW extrac-
tion in this work. The kabs value of 6-gingerol increases from 110 °C Fig. 8. The relationship between the absolute mass transfer coefficient, kabs and
to the highest value of 0.0201 min1 at 130 °C and decline from dielectric constant of HCW for 6-shogaol.
 M.S. Md Sarip et al. / Separation and Purification Technology 124 (2014) 141–147
on 6-gingerol may have different solute solvent interaction. Thus,
6-gingerol would be effectively extracted out at a certain favorable
dielectric constant suited to the 6-gingerol solvent interaction and
not necessarily affected by lower dielectric constant values. Fur-
thermore, another factor affecting the kabs values of 6-gingerol
was confirmed to be the degradation of 6-gingerol to the other
compounds including the 6-shogaol as discussed earlier.
The relationship between the dielectric constant with the kabs
value for 6-shogaol is shown in Fig. 8. It is observed in 6-shogaol
that the changes of kabs towards the dielectric constant is more sig-
nificant when compared to those of 6-gingerol with the r2 value of
0.5754 and slope of 0.0022. The r2 value suggests that there is
some linear correlation between dielectric constant and kabs, how-
ever dependency of kabs on dielectric constant value is still very
low as indicated by low slope. The higher slope value of 0.0022
in 6-shogaol compare to 6-gingerol at 0.0001 is contributed by
the accumulation of 6-shogaol concentration in the sample extract
due to dehydration process. This shows that similar to the 6-ging-
erol, dielectric constant does not contribute to the extraction effi-
ciency of 6-shogaol.
4. Conclusion
HCW offers an alternative solvent for the extraction of 6-ginger-
ol and 6-shogaol. It was observe that the extraction was selective
with the optimum conditions for 6-gingerol of 130 °C and 30 min
whilst 6-shogaol of 170 °C and 20 min with percent recovery of
20.71% and 85.04% respectively. At higher temperatures from
180 °C, the degradation of both compounds occurred. The dielectric
constant of solvent was not directly affecting the extraction effi-
ciency. The overall mass transfer coefficient, k for 6-gingerol is
8  107 m/s whilst for 6-shogaol is18.3764  107 m/s at the
optimum conditions using HCW extraction. HCW extraction has
the potential to be use as an alternative extraction method pro-
vided further improvements in operating conditions avoiding the
degradation of the bioactive compound is addressed. Further study
of using co-solvent or additives to HCW extraction process may
avoid operating in degradation region and also improve the per-
cent recovery of the bioactive compounds.
Acknowledgements
The research is funded by Malaysian Ministry of Agriculture
(MOA) under Science Fund Grant No. 05-01-06-SF1004. The re-
search infrastructure provide by Universiti Teknologi Malaysia is
greatly appreciated. The assistant of En Radzi Ahmad from FRIM
in using HPLC analysis is greatly acknowledged. Other individuals
who have contributed to this research are also duly acknowledged.
References
[1] S. Abdullah, S.A.Z. Abidin, N.A. Murad, S. Makpol, W.Z.W. Ngah, Y.A.M. Yusof,
Ginger extract (Zingiber officinale) triggers apoptosis and G0/G1 cells arrest in
HCT 116 and HT 29 colon cancer cell lines, Afr. J. Biochem. Res. 4 (2010) 134–
142.
[2] Harliansyah, N.A. Murad, W.Z.W. Ngah, Y.A.M. Yusof, Antiproliferative,
antioxidant and apoptosis effects of Zingiber officinale and 6-gingerol on
HepG2 cells, Asian J. Biochem. 2 (2007) 421–426.
[3] Y. Yusof, N. Ahmad, S. Das, S. Sulaiman, N. Murad, Chemopreventive efficacy of
ginger (Zingiber officinale) in ethionine induced rat hepatocarcinogenesis, Afr. J.
Tradit. Complement. Altern. Med. 26 (2008) 87–93.
147
[4] A.Y. Antipenko, A.I. Spielman, M.A. Kirchberger, Interactions of 6-gingerol and
ellagic acid with the cardiac sarcoplasmic reticulum Ca21-ATPase1, J.
Pharmacol. Exp. Ther. 290 (1999) 227–234.
[5] M. Park, J. Bae, D.-S. Lee, Antibacterial activity of [10]-gingerol and [12]-
gingerol isolated from ginger rhizome against periodontal bacteria, Phytother.
Res. 22 (2008) 1446–1449.
[6] C. Nagoshi, S. Shiota, T. Kuroda, T. Hatano, T. Yoshida, R. Kariyama, T. Tsuchiya,
Synergistic effect of [10]-gingerol and aminoglycosides against Vancomycin-
Resistant Enterococci (VRE), Biol. Pharm. Bull. 29 (2006) 443–447.
[7] K.S. Kyung, J.H. Gon, K.Y. Geun, J.J. Sup, W.J. Suk, K.J. Ho, 6-Shogaol, a natural
product, reduces cell death and restores motor function in rat spinal cord
injury, Eur. J. Neurosci. 24 (2006) 1042–1052.
[8] C.Y. Chen, Y.H. Yang, S.Y. Kuo, Effect of [6]-shogaol on cytosolic Ca2+ levels and
proliferation in human oral cancer cells (OC2), J. Nat. Prod. 73 (2010) 1370–
1374.
[9] S.M. Zick, Z. Djuric, M.T. Ruffin, A.J. Litzinger, D.P. Normolle, S. Alrawi, M.R.
Feng, D.E. Brenner, Pharmacokinetics of 6-gingerol, 8-gingerol, 10-gingerol,
and 6-shogaol and conjugate metabolites in healthy human subjects, Cancer
Epidemiol. Biomar. Prev. 17 (2008) 1930–1936.
[10] M. Noor Azian, A.A. Mustafa Kamal, M. Nurul Azlina, Changes of cell structure
in ginger during processing, J. Food Eng. 62 (2004) 359–364.
[11] N.A. Morad, N. Mulop, A.N. Darus, Introduction to Thermodynamics for
Engineering Students, Pearson Custom Publishing, Kuala Lumpur, Malaysia,
2011.
[12] M.H. Eikani, F. Golmohammad, M. Mirza, S. Rowshanzamir, Extraction of
volatile oil from cumin (Cuminum Cyminum L.) with superheated water, J.
Food Process Eng. 30 (2007) 255–266.
[13] M. Khajenoori, A.H. Asl, F. Hormozi, M.H. Eikani, H.N. Bidgoli, Subcritical water
extraction of essential oils from Zataria multiflora Boiss, J. Food Process Eng. 32
(2009) 804–816.
[14] W.J. Kim, J. Kim, B. Veriansyah, J.D. Kim, Y.W. Lee, S.G. Oh, R.R. Tjandrawinata,
Extraction of bioactive components from Centella Asiatica using subcritical
water, J. Supercrit. Fluids 48 (2009) 211–216.
[15] M.Z. Ozel, F. Gogus, A.C. Lewis, Subcritical water extraction of essential oils
from Thymbra Spicata, Food Chem. 82 (2002) 381–386.
[16] P. Budrat, A. Shotipruk, Enhanced recovery of phenolic compounds from bitter
melon (Momordica charantia) by subcritical water extraction, Sep. Purif.
Technol. 66 (2009) 125–129.
[17] R. Soto Ayala, M.D. Luque de Castro, Continuous subcritical water extraction as
a useful tool for isolation of edible essential oils, Food Chem. 75 (2001) 109–
113.
[18] A.A. Galkin, V.V. Lunin, Subcritical and supercritical water: a universal medium
for chemical reactions, Russ. Chem. Rev. 74 (2005) 21–35.
[19] J. Wiboonsirikul, S. Adachi, Extraction of functional substances from
agricultural products or by-products by subcritical water treatment, Food
Sci. Technol. Res. 14 (2008) 319–328.
[20] M. Uematsu, E.U. Frank, Static dielectric constant of water and steam, J. Phys.
Chem. Ref. Data 9 (1980) 1291–1306.
[21] A. Shadmani, I. Azhar, F. Mazhar, M.M. Hassan, S.W. Ahmed, I. Ahmad, K.
Usmanghani, S. Shamim, Kinetic studies on Zingiber officinale, Pak. J. Pharm.
Sci. 17 (2004) 47–54.
[22] H.A. Schwertner, D.C. Rios, High performance liquid chromatographic analysis
of 6-gingerol, 8-gingerol, 10-gingerol, and 6-shogaol in ginger-containing
dietary supplements, spices, teas, and beverages, J. Chromatogr. B 856 (2007)
41–47.
[23] E.L. Cussler, Diffusion: Mass Transfer in Fluid Systems, Cambridge University
Press, New York, 1984.
[24] M.S.M. Sarip, N.A. Morad, Determination of overall mass transfer coefficient for
6-gingerol and 6-shagoal in subcritical water extraction, Adv. Mater. Res. 550–
553 (2012) 1900–1903.
[25] M. Spiro, D.S. Jago, Kinetics and equilibria of tea infusion. Part 3 – Rotating-disc
experiments interpreted by a steady-state model, J. Chem. Soc., Faraday Trans.
1 (78) (1982) 295–305.
[26] J. Timmermans, Physico-Chemical Constants of Pure Organic Compounds,
Elsevier Publishing Company Inc., Brussel, 1950.
[27] S.D. Jolad, R.C. Lantz, A.M. Solyom, G.J. Chen, R.B. Bates, B.N. Timmermann,
Fresh organically grown ginger (Zingiber officinale): composition and effects on
LPS-induced PGE2 production, Phytochemistry 65 (2004) 1937–1954.
[28] S. Bhattarai, V.H. Tran, C.C. Duke, The stability of gingerol and shogaol in
aqueous solutions, J. Pharm. Sci. 90 (2001) 1658–1664.
[29] S.M. Ghoreishi, R.G. Shahrestani, Subcritical water extraction of mannitol from
olive leaves, J. Food Eng. 93 (2009) 474–481.
[30] Balachandran, S.E. Kentish, R. Mawsonb, The effects of both preparation
method and season on the supercritical extraction of ginger, Sep. Purif.
Technol. 48 (2006) 94–105.
[31] M. Horák, J. Plíva, Studies of solute-solvent interactions—I. General
considerations, Spectrochim. Acta 21 (1965) 911–917.