Industrial Crops and Products 94 (2016) 353–362

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Industrial Crops and Products

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

Supercritical fluid extraction of coriander seeds: Process optimization,

chemical profile and antioxidant activity of lipid extracts
Zoran Zeković, Branimir Pavlić, Aleksandra Cvetanović, Saša Ðurović ∗
University of Novi Sad, Faculty of Technology, Bulevar Cara Lazara 1, 21000 Novi Sad, Serbia

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

Article history: Coriander seeds have been used in traditional medicine for the treatment of various ailments. Taking into
Received 25 May 2016 account that operational conditions may influence the chemical composition optimization of supercritical
Received in revised form 31 August 2016 extraction was performed. Influence of three different extraction parameters (pressure, temperature and
Accepted 2 September 2016
CO2 flow) was explored while optimization of the process was performed by using Box-Behnken exper-
Available online 8 September 2016
imental design (BBD) in combination with response surface methodology (RSM). Experimental results
were fitted to a second-order polynomial model with multiple regression, while analysis of variance
Keywords:
(ANOVA) was employed in order to assess model fitness and determine optimal conditions for extrac-
Supercritical fluid extraction
Coriander seed extracts
tion yield (199.50 bar, 40.15 ◦ C, 0.396 kg/h of CO2 ). Investigation of chemical composition showed that
Process optimization linalool was the most abundant compound in all samples, followed by camphor, methyl chavicol, (+)-
Chemical profile limonene, eucalyptol, eugenol, geraniol, ␥-terpinene and ␣-terpineol. Results showed that 100 bar was
Antioxidant activity the best pressure for isolation of monoterpenes, while temperature and CO2 flow rate values differ with
the structure of desired monoterpene class. Furthermore, antioxidant activity of obtained extracts was
determined using two different assays. Obtained results showed that observed extracts exhibit higher
activity against lipid peroxidation, than against DPPH radical with the lowest inhibitory concentrations
of 0.101 mg/mL and 2.364 mg/mL, respectively.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Coriander (Coriandrum sativum L., Apiaceae) is annual Mediter-
ranean herb (Eikani et al., 2007; Grosso et al., 2008; Pavlić et al.,
2015; Wangensteen et al., 2004) known for its bittersweet taste
and its usage in cooking (Dima et al., 2016), and application in
industries such as food (Aluko et al., 2001; Mhemdi et al., 2011;
Pavlić et al., 2015), pharmaceutical (Jabeen et al., 2009; Mhemdi
et al., 2011) and cosmetic (Eyres et al., 2005; Mhemdi et al., 2011).
Seeds of this plant, which have been marked as the most impor-
tant part of the plant, are held responsible for such exploitation
(Wangensteen et al., 2004). Conducted studies showed diversity of
biological activities of coriander seed extracts, such as antioxidant
(Chen et al., 2009; Madsen and Bertelsen, 1995; Ramadan et al.,
2003; Wangensteen et al., 2004), antimicrobial (Delaquis et al.,
2002; Grosso et al., 2008; Lo Cantore et al., 2004; Wangensteen
∗ Corresponding author at: Department of Biotechnology and Pharmaceutical
Engineering, Faculty of Technology, University of Novi Sad, Bulevar Cara Lazara 1,
21000 Novi Sad, Serbia.
E-mail address: sasatfns@uns.ac.rs (S. Ðurović).
et al., 2004), antidiabetic (Chen et al., 2009; Gallagher et al., 2003),
anti-carcinogenic and anti-mutagenic (Chen et al., 2009; Chithra
and Leelamma, 2000) and for treatment of rheumatism and pain
in the joints (Pavlić et al., 2015; Wangensteen et al., 2004). Such
diversity of activities is the main reason why coriander still attracts
considerable attention of scientific community. One of the most
important constituent of the seed itself is essential oil, which con-
tains linalool as the main compound (>50%) (Eikani et al., 2007;
Grosso et al., 2008; Pavlić et al., 2015; Wangensteen et al., 2004)
followed by limonene, camphor and geraniol (Bajpai et al., 2005;
Pavlić et al., 2015; Zeković et al., 2011).
Supercritical fluid extraction (SFE) represents the so-called
green extraction method. The most common solvent in this extrac-
tion technique is carbon dioxide, which showed some advantages
over the other methods and solvents such as lack of solvent residue
and low operational conditions (Akgun et al., 1999; Sahena et al.,
2009), as well as inexpensiveness, nontoxicity, non-flammability,
chemical inactivity and possesses moderate critical parameters
(pc = 73.8 bar and Tc = 31.1 ◦ C) (Filip et al., 2014; Temelli, 2009).
Usage of this method helps to overcome some problems which
occurred during the exploitation of classical extraction techniques.

http://dx.doi.org/10.1016/j.indcrop.2016.09.008
0926-6690/© 2016 Elsevier B.V. All rights reserved.
354 Z. Zeković et al. / Industrial Crops and Products 94 (2016) 353–362
Some of those problems are: thermal degradation of compounds of
interest, occurrence of hydrolysis and residue of organic solvents
in obtained extracts (Grosso et al., 2008). Desired selectivity of the
SFE process may be achieved using the proper combination of pres-
sure and temperature, which finally affect the yield and chemical
profile of obtained extracts (Filip et al., 2014).
Due to significance of the proper choice of the operational condi-
tions, and their influence on the extraction process itself, response
surface methodology (RSM) has been employed to optimize the
extraction process. It used statistics and other mathematical tech-
niques, thus providing the optimization of the extraction process.
Optimization of the process by RSM includes the optimization of the
desired responses, which are affected by variables (Zeković et al.,
2014), in this case pressure, temperature and CO2 flow rate.
Up-to-date conducted studies examined the influence of param-
eters on yield of SFE process and antioxidant activity of obtained
extracts (Anitescu et al., 1997; Chen et al., 2009; Dima et al., 2016;
Grosso et al., 2008; Mhemdi et al., 2011; Pavlić et al., 2015; Reis
Machado et al., 1993; Yepez et al., 2002; Zeković et al., 2015).
Extraction yield and chemical composition of the extracts were
compared with extracts obtained using other extraction tech-
niques (Anitescu et al., 1997; Mhemdi et al., 2011; Pavlić et al.,
2015; Reis Machado et al., 1993; Zeković et al., 2015). Examined
operational conditions in available literature varied in following
ranges: pressure 50–300 bar, temperature 21–50 ◦ C and CO2 flow
rate 0.194–21.8 kg/h. The next logical step would be optimization
of the SFE process and determination of the relationship between
chemical composition and operational parameters. In order to
accomplish those goals, the influence of three different factors
(temperature, pressure and CO2 flow rate) on yield of SFE process,
antioxidant activity and chemical composition of obtained extracts
were investigated, while the extraction yield was optimized using
RSM. Operational parameter ranges were determined according
the available literature data. Chemical profile of extracted oil was
particularly evaluated in order to establish the above mentioned
relationship.
2. Materials and methods
2.1. Plant material
Coriander seeds (CS) were acquired from the Institute of Field
and Vegetable Crops, Novi Sad, Republic of Serbia (year 2011).
Plant material was air-dried and stored at the room temperature.
Dried seeds were milled in the blender and mean particle size
(0.6216 mm) was determined by sieve set (CISA Cedaceria Indus-
trial, Barcelona, Spain).
2.2. Chemicals
Commercial carbon dioxide (Messer, Novi Sad, Serbia) with
>99.98% (w/w) purity was used for laboratory scale supercritical
fluid extraction. Tween 80 was purchased from J. T. Backer, iron(II)
sulfate heptahydrate from Zorka Šabac (Serbia), l-(+)-ascorbic acid
and trichloroacetic acid (TCA) were purchased from Centrohem
(Stara Pazova, Serbia), perchloric acid was purchased from Merck
(Darmstadt, Germany) and 2-thiobarbituric acid (TBA) from Sigma-
Aldrich (Steinheim, Germany). The standard compounds for GC
analysis: ␣-pinene, ␤-pinene, camphor, methyl chavicol (estragole)
and eucalyptol (1,8-cineole) were purchased from Dr Ehrenstor-
fer (Germany), while ␥-terpinene, (+)-limonene, linalool, geraniol,
carvacrol, eugenol and ␣-terpineol were purchased from Carl Roth
(Germany). All other used chemicals were of analytical reagent
grade.
2.3. Supercritical fluid extraction
SFE was performed on laboratory-scale high pressure extrac-
tion plant (HPEP, NOVA-Swiss, Effretikon, Switzerland) described
elsewhere (Filip et al., 2014). The main parts and properties of this
plant are: gas cylinder with carbon dioxide, diaphragm type com-
pressor (with pressure range up to 1000 bar), extractor vessel (with
internal volume 200 mL, maximum operating pressure of 700 bar)
with heating jacket, separator with internal volume 200 mL and
maximum operating pressure of 250 bar, pressure control valve,
temperature regulation system and regulation valves.
Extraction processes were performed at three different pres-
sures (100, 150 and 200 bar), temperatures (40, 55 and 70 ◦ C) and
CO2 flow rates (0.2, 0.3 and 0.4 kg/h), while extraction time (4 h)
was constant for all experiments. After finishing the extraction
processes, total extraction yields (Y) were measured. Separator
conditions were 15 bar and 23 ◦ C. Obtained extracts were trans-
ferred into the glass bottles, sealed and stored at 4 ◦ C in order
to prevent any possible degradation of extract components until
analysis.
2.4. Chemical analysis
GC–MS and GC-FID analysis were performed on Agilent
GC6890N system according to previously described procedure
(Filip et al., 2016). In the case of GC–MS analysis, gas chromatograph
was coupled with Agilent MS5759 mass spectrometer. The HP-5MS
column (30 m length, 0.25 mm inner diameter with 0.25 ␮m film
thickness) was used. Helium flow rate was 2 mL/min, while temper-
ature was as follows: injector 250 ◦ C, detector 300 ◦ C, initial 60 ◦ C
with linear increase of 4 ◦ C/min to 150 ◦ C. Samples were dissolved
in methylene chloride, while injected volume of those solutions
was 5 ␮L with split ratio of 30:1. Compounds were identified by
comparing obtained spectral data to those one from NIST 05 and
Wiley 7n mass spectral libraries and with spectral data of analytical
standards. GC-FID analysis was employed for quantitative analy-
sis of compounds in analyzed samples. Standard solutions were
prepared dissolving standard compounds in methylene chloride in
concentration range of 1–500 ␮g/mL. Standard solutions were used
to create calibration curve, which described the dependence of peak
area on concentration of standard compounds (R2 > 0.99). Obtained
results were expressed as mg of compound per g of coriander seeds
extract (mg/g).
2.5. Lipid peroxidation
Lipid peroxidation that was induced by extent of Fe2+ /ascorbate
system has been determined by TBA assay according to procedure
described in previous research (Beara et al., 2012). Substrate in
this method are polyunsaturated fatty acids (PUFA) obtained from
linseed by Soxhlet extraction. Those PUFAs were added to phos-
phate buffer pH 7.4 in presence of Tween 80 and sonicated for 1.5 h
to obtain emulsion. This emulsion was mixed with FeSO4 , ascor-
bic acid and extract solutions (concentration ranging of extract
solutions were from 20 to 200 mg/mL, diluted with 80% aqueous
isopropyl alcohol). In control, instead of samples, 80% aqueous iso-
propyl alcohol was added. Phosphate buffer and extract dilution
were added in blank. After incubation at 37 ◦ C for 1 h, EDTA solution
was added to all samples followed by TBA reagent (aqueous mix-
ture of TBA, HClO4 and TCA) and the heating at 100 ◦ C for 15 min.
Cooled mixtures were centrifuged for 15 min and absorbance of the
colored product malondialdehyde (MDA) was measured at 532 nm.
 Z. Zeković et al. / Industrial Crops and Products 94 (2016) 353–362 355

Results were expressed as radical scavenging capacity (%ILP), which Table 1

Natural and coded levels of independent variables used in applied RSM design.
were calculated using the following Eqs. ((1)–(3)):
  A  Variable Coded levels
ILP (%) = 1 − × 100 (1) −1
Acon 0 1

Natural levels
A = Aws − Abp (2)
Pressure (bar) 100 150 200
Acon = Acs − Abp (3) Temperature (◦ C) 40 55 70
CO2 flow rate (kg/h) 0.2 0.3 0.4
where A represents absorbance of probe, Acon is absorbance of con-
trol probe, Abp is absorbance of blank, Aws is absorbance of working
solutions, and Acs is absorbance of control solution. Antioxidant numerical factors on three levels. Experiment consisted of fif-
activity was expressed as the inhibition concentration at ILP value teen randomized runs with three replicates in central point. The
50% (ILP50 ), which represents the concentration of test solution independent variables employed in this design were pressure (X1 ,
required to obtain 50% of radical scavenging capacity expressed 100–200 bar), temperature (X2 , 40–70 ◦ C) and CO2 flow rate (X3 ,
as mg per mL (mg/mL). All experiments were performed in three 0.2–0.4 kg/h). Each of the coded variables was force to range from
replicates and the results were expressed as mean value. −1 to 1 normalizing the parameters, thus affecting the response
more evenly and making the units of the parameters irrelevant in
2.6. DPPH assay the same time (Baş and Boyacı, 2007). Variables were coded using
the following equation:
The free radical scavenging activity of coriander seeds extract Xi − X0
X= (5)
was determined according the previously described method (Espín X
et al., 2000) with slight modification. The reaction mixture was where X represents the coded value, Xi is the corresponding actual
prepared in the following manner: certain volume of obtained CS value, X0 represents actual value in the center of the domain and
extract was dissolved in the ethyl acetate and added in the 90 ␮M X is the increment of Xi corresponding to a variation of 1 unit of
solution of 2,2-diphenyl-1-pycril-hydrazyl (DPPH) radical in 95% X. The natural and coded values of independent variables used in
methanol. Absorbance of such mixture was measured at 515 nm this experimental design are presented in Table 1.
after the incubation period of 60 min at the room temperature. The response variables were fitted into the given second-order
Blank solution was prepared by adding ethyl acetate instead sam- polynomial model, which is presented as competent for describ-
ple. Radical scavenging capacity (%RSC) was calculated by following ing the relationship between the responses and the independent
equation: variable (Bezerra et al., 2008):
 
Asample × 100 
3 
3 
3
%RSC = 100 − (4)
Ablank Y = ˇ0 + ˇi Xi + ˇii Xi2 + ˇij Xi Xj (6)
i=1 i=1 i<j=1
where: Asample is the absorbance of sample solution and Ablank is
the absorbance of blank probe. Antioxidant activity was expressed where Y represents the response, ␤0 is constant, ␤j , ␤jj , ␤ij are the
as the inhibition concentration at RSC value 50% (IC50 ), which rep- linear, quadratic and interactive coefficients of the model, respec-
resents the concentration of test solution required to obtain 50% tively, Xi and Xj are the levels of the independent variables. Optimal
of radical scavenging capacity expressed as mg per mL (mg/mL). conditions for SFE extraction process were determined consider-
All experiments were performed in three replicates and the results ing total extraction yield as target response. BBD experimental
were expressed as mean value. design and multiple linear regression analysis were conducted
using Design-Expert v.7 Trial (Stat-Ease, Minneapolis, Minnesota,
2.7. Experimental design USA). Obtained results were statistically tested employing analysis
of variance (ANOVA) with the significance level of 0.05. Compe-
The Box-Behnken experimental design (BBD) of RSM was used tence of model was evaluated according to the obtained coefficient
to evaluate the effect of extraction parameters and to optimize of multiple determination (R2 ), coefficient of variance (CV) and p-
the conditions for target response. Design was applied with three values for each model, as well as lack of fit testing.

Table 2
Experimental conditions applied in Box-Behnken design with natural and coded levels of independent variables and experimentally obtained measured response, Y.

Sample No. Independent variables Measured response

X1 Pressure (bar) X2 Temperature (◦ C) X3 CO2 flow rate (kg/h) Y (g/100 g CS)

1 0 (150) 1 (70) −1 (0.2) 2.05

2 1 (200) −1 (40) 0 (0.3) 5.95
3 −1 (100) 0 (55) 1 (0.4) 1.20
4 0 (150) 1 (70) 1 (0.4) 3.50
5 1 (200) 1 (70) 0 (0.3) 5.36
6 0 (150) −1 (40) −1 (0.2) 4.31
7 1 (200) 0 (55) −1 (0.2) 4.90
8 0 (150) 0 (55) 0 (0.3) 3.77
9 0 (150) −1 (40) 1 (0.4) 5.64
10 0 (150) 0 (55) 0 (0.3) 4.02
11 −1 (100) 0 (55) −1 (0.2) 0.95
12 1 (200) 0 (55) 1 (0.4) 7.00
13 −1 (100) −1 (40) 0 (0.3) 2.69
14 0 (150) 0 (55) 0 (0.3) 4.00
15 −1 (100) 1 (70) 0 (0.3) 0.59
356 Z. Zeković et al. / Industrial Crops and Products 94 (2016) 353–362
Table 3
Estimated regression coefficients of the fitted second-order polynomial model for
investigated response.
Coefficient Response
Y
␤0 3.93
Linear
␤1 2.22*
␤2 −0.89*
0.64*
␤3
Interaction
␤12 0.38
␤13 0.46
␤23 0.032
Quadratic
␤11 −0.32
0.038
␤22
␤33 −0.097
*
Statistically significant at p < 0.05.
3. Results and discussion
3.1. Model fitting
RSM was employed to investigate influence of extraction param-
eters, in this case pressure (100–200 bar), temperature (40–70 ◦ C)
and CO2 flow rate (0.2–0.4 kg/h), on total extraction yield (Y) as
investigated response, and to optimize extraction process. Results
of experimentally obtained results for measured responses in BBD
design are presented in Table 2. ANOVA had been used for deter-
mination of regression coefficients of the linear, quadratic and
interaction terms of desired response. Results of ANOVA analysis
are presented in Table 3. Influence of each term could be statistically
significant (p < 0.05) or insignificant (p > 0.05). Calculated statistical
parameters are presented in Table 4, while coefficients of multiple
regression (R2 ), together with ANOVA results, were used as the first
indicator of the model adequacy.
Value of R2 was particularly high for Y (0.9847). Obtained R2
value indicated that second-order polynomial model represented
a good approximation of experimental results. Detailed informa-
tion on statistical significance of investigated model were provided
by ANOVA. Experimental results of investigated response showed
good fitting with mathematical model, since regression for model
was significant (p < 0.05), while lack of fit was insignificant (p > 0.05)
(Table 4). Therefore, regression equations could be successfully
used as predictors of these responses in investigated experimental
domain.
3.2. Total extraction yield (Y)
Presented data (Table 2) showed that Y varied in range of
0.59–7.00 g/100 g CS. The highest yield was obtained under follow-
ing conditions: 200 bar, 55 ◦ C and 0.4 kg/h of CO2 . However, the
lowest Y was observed under 100 bar, 70 ◦ C and 0.3 kg/h of CO2 .
According to Zeković et al. (2015), Y values were 0.94, 1.42 and
1.44 g/100 g of CS at the following operational conditions 100 bar,
40 ◦ C and CO2 flow rate of 0.194 kg/h, using the plant material with
three different mean particle size (1.368, 0.775 and 0.631 mm).
Results showed that Y increasing with decreasing in mean parti-
cle size. Dima et al. (2016) were conducted two sets of experiments
using following conditions: 99 bar, 31 ◦ C and 21.8 kg/h of CO2 for the
first experimental set and 100 bar, 40 ◦ C and 20.6 kg/h of CO2 for the
second experimental set. Also, CS with three different particle size
were used in those experiments (0.50, 0.63 and 0.71 mm). Obtained
Y under described conditions were 0.51, 0.57 and 0.36 g/100 g CS
for the first experimental set and 0.21, 0.23 and 0.18 g/100 g CS
for the second experimental set. It could be noticed that in this
case, in both experiments, Y increased with the particle size in the
beginning, but then decreased. Under the operation conditions of
115.5–279.2 bar and 47.85–57.85 ◦ C, achieved Y was in the range
of 0.880–1.997 g/100 g CS (Yepez et al., 2002). Those results fit into
the obtained range for Y in this research, however represented a
lower values comparing to maximal achieved Y value. On the other
hand, Y values of 1.52 and 8.88 g/100 g CS were achieved under
the operational conditions of 100 bar, 40 ◦ C and 0.194 kg CO2 /h and
300 bar, 40 ◦ C and 0.194 kg CO2 /h, respectively (Pavlić et al., 2015).
Applied experimental conditions in that study showed that pres-
sure exhibited the positive influence on Y, obtaining maximal Y of
8.88 g/100 g CS (Pavlić et al., 2015), which was significantly higher
yield than 7.00 g/100 g CS obtained in this study.
Combined effects of SFE parameters on Y were presented in
Fig. 1, while their significance determined by RSM analysis and
regression coefficients calculated using Eq. (6) are presented in
Table 3. According to ANOVA, linear terms of pressure, temperature
and CO2 flow rate exhibited significant influence on Y (p < 0.05).
Linear terms of pressure and CO2 flow rate were positive, while
linear term of temperature was negative. On the other hand,
quadratic terms of pressure and CO2 flow rate exhibited negative
influence, while quadratic term of temperature was positive. This
suggested that Y would increase with pressure and CO2 flow rate,
although the influence of pressure would be stronger than influ-
ence of temperature. Actually, linear term of pressure exhibited
the strongest influence according the regression coefficients pre-
sented in Table 3. Positive effect of pressure on extraction yield was
rather expected since the elevation of this parameter results in an
increase in CO2 density, which further results in higher solubility
of the compounds (Paixao Coelho and Figueiredo Palavra, 2015;
Pourmortazavi and Hajimirsadeghi, 2007). Positive effect of CO2
flow rate was the result of the reduced thickness of the film layer
around the solid particles thus decreasing the mass transfer resis-
tance surrounding the particles (Döker et al., 2004). On the other
hand, negative linear term of temperature suggested that Y would
decrease with increasing in temperature. Influence of this factor is
rather complex comparing to the influence of pressure. This is due
to combination of two variables, density and vapor pressure. Vapor
pressure increases with temperature causing the increasing in sol-
ubility, while density decreases with temperature which results
in decreased solubility (Jesus and Meireles, 2014; Paixao Coelho
and Figueiredo Palavra, 2015). In this particular case, decreasing in
density with temperature increasing would be the dominant and,
therefore, there was decrease in Y with temperature elevation. Pre-
dicted second-order polynomial model for Y was given by following
equation:
Y = 3.93 + 2.22X1 − 0.89X2 + 0.64X3 + 0.38X1 X2
+0.46X1 X3 + 0.032X2 X3 − 0.32X12 + 0.038X22 − 0.097X32 (7)
3.3. Optimization of supercritical fluid extraction
In order to accomplish maximal Y, desired response was opti-
mized. Optimization process itself was based on the obtained
results from previously obtained extractions and conducted sta-
tistical analysis. As the final result of performed optimization,
predicted maximal values of investigated responses and estimated
optimal conditions of SFE process was obtained (Table 5).
From the data presented in Table 5 it could be noticed that
estimated values for pressure and CO2 flow rate was near maxi-
mal value. On the other hand, estimated temperature was almost
equal to minimal investigated temperature. Under these estimated
conditions, predicted value of Y was 7.30 g/100 g CS.
 Z. Zeković et al. / Industrial Crops and Products 94 (2016) 353–362 357

Fig. 1. Response surface plots showing combined effects of SFE parameters on total extraction yield.
358 Z. Zeković et al. / Industrial Crops and Products 94 (2016) 353–362
Table 4
Analysis of variance (ANOVA) of the fitted second-order polynomial models.
Source Sum of squares
Total extraction yield (Y)
Model 51.00
Residual 0.79
Lack of fit 0.76
Pure error 0.038
Total 51.80
R2 = 0.9847
Table 5
Predicted maximal values of investigated response and estimated optimal condi-
tions for the process.
Optimal conditions Investigated response
Y (g/100 g CS)
Predicted value 7.30
Pressure (bar) 199.50
Temperature (◦ C) 40.15
CO2 flow rate (kg/h) 0.396
3.4. Chemical analysis of extracts
Chemical profile of extract samples obtained by GC–MS and
GC-FID analysis is presented in Table 6, operational conditions of
extraction processes in Table 2, while GC chromatogram of samples
3, 13 and 15 are presented in Fig. 2. From the data in Table 6, it could
be seen that the main compound in the essential oil of coriander
was linalool, which confirmed results obtained in previous stud-
ies (Grosso et al., 2008; Mhemdi et al., 2011; Pavlić et al., 2015;
Zeković et al., 2015), followed by camphor. Those two compounds
were detected and quantified in all fifteen samples and could be
considered as main compounds of CS extracts.
Comparing obtained results (Table 6) with the previously
obtained, domination of linalool was confirmed (Anitescu et al.,
1997; Grosso et al., 2008; Mhemdi et al., 2011; Pavlić et al.,
2015; Zeković et al., 2015). Pavlić et al. (2015) obtained linalool in
amounts of 90 and 64.7 mg/g E using following experimental condi-
tions 100 bar, 40 ◦ C, 0.194 kg/h of CO2 and 300 bar, 40 ◦ C, 0.194 kg/h
of CO2 , respectively. These results showed that linalool was more
soluble in supercritical CO2 under the lower value of pressure. On
the other hand, Zeković et al. (2015) reported linalool contents
of 532.0, 596.1 and 502.1 mg/g of extract at 100 bar, 40 ◦ C and
0.194 kg/h of CO2 using CS with following values of mean parti-
cle size 1.368, 0.775 and 0.631 mm, respectively. Study conducted
by Pavlić et al. (2015) and Zeković et al. (2015) demonstrated lower
results regarding the linalool content in obtained CS extracts com-
paring with the maximal yield of this compound achieved in this
study (717 mg/g). Beside the linalool, camphor (21.0 mg/g), eugenol
(20.7 mg/g), methyl chavicol (18.2 mg/g) and geraniol (10.0 mg/g)
were presented in higher amount. Previous conducted studies con-
firmed the presence of camphor and geraniol in higher content,
while methyl chavicol and eugenol were detected at trace levels
(Pavlić et al., 2015; Zeković et al., 2015).
Obtained chemical profile of CS extracts suggested that chem-
ical compositions of extracts varied depending on the applied
conditions. Thus, obtained data showed that (+)-limonene and
-terpinene were only two quantified monoterpenes. ␣- and ␤-
pinene were detected at trace levels, while p-cymene was detected
in all samples except in sample 5. The highest amount of (+)-
limonene (4.1 mg/g) was achieved in sample 15 (100 bar, 70 ◦ C
and 0.3 kg CO2 /h), while the highest amount of -terpinene was
achieved in sample 3 (100 bar, 55 ◦ C and 0.4 kg CO2 /h). Result sim-
ilar to the highest one for (+)-limonene (4.0 mg/g) was achieved
in sample 6 (150 bar, 40 ◦ C and 0.2 kg CO2 /h). Linalool and geran-
iol were only two acyclic oxygenated monoterpenes detected and
DF Mean square F-value p-value
9 5.67 35.70 0.0005
5 0.16
3 0.25 13.38 0.0703
2 0.019
14
quantified in CS extracts. The highest yield of linalool (717.0 mg/g)
was achieved in sample 3 (100 bar, 55 ◦ C and 0.4 kg/h of CO2 ). On the
other hand, the highest yield of geraniol (10.7 mg/g) was detected
in the sample 15 obtained under the 100 bar, 70 ◦ C and 0.3 kg/h of
CO2 . Camphor, eucalyptol and ␣-terpineol were quantified in all CS
extracts, while terpinen-4-ol was detected only in samples 1, 3 and
4. The highest amount of camphor (21.0 mg/g) was detected in the
sample 3 (100 bar, 55 ◦ C and 0.4 kg/h of CO2 ), ␣-terpineol (6.1 mg/g)
was detected in the sample 11 (100 bar, 55 ◦ C and 0.2 kg/h of CO2 ),
while maximal yield of eucalyptol (3.2 mg/g) was achieved in sam-
ple 10 (150 bar, 55 ◦ C and CO2 flow rate of 0.3 kg/h). As far as
aromatic oxygenated monoterpenes are concerned, eugenol was
quantified in samples 11, 14 and 15, while methyl chavicol was
quantified in most of the samples. On the other hand, carvacrol was
detected in all fifteen samples in rather trace amounts. The highest
yield of eugenol (20.7 mg/g) was detected in sample 15 (100 bar,
70 ◦ C and 0.3 kg/h of CO2 ), while the highest yield of methyl chavi-
col (18.2 mg/g) was achieved in sample 11 at 100 bar, 55 ◦ C and CO2
flow rate of 0.2 kg/h.
Explanation of such diversity of chemical composition of
obtained CS extracts may be the structural diversity of compounds
which affects their solubility in supercritical CO2 . Thus, limonene
and -terpinene possess the same chemical formula (C10 H16 ), as
well as geraniol and linalool, ␣-terpineol and eucalyptol (C10 H18 0),
but they differ in their structure among themselves. Chemical for-
mulas and structure of quantified compounds in CS extracts are
presented in Table 7.
Presented structures of (+)-limonene and -terpinene indicated
that they differ in position of double bond in the structure. This
difference is the most probable cause of their different solubility
under the following conditions. Solubility of limonene under this
conditions is in an agreement with literature data which indicated
that this compound is highly or completely miscible with super-
critical CO2 under the 100 bar and 50 ◦ C (Di Giacomo et al., 1989;
Matos et al., 1989; Reverchon, 1997). On the other hand, geraniol
and linalool are differing in position of hydroxyl functional group in
their structure. While geraniol is primary alcohol, linalool is tertiary
alcohol. Different position of hydroxyl functional group in those
two oxygenated monoterpenes influence their solubility in super-
critical CO2 . Obtained results (Table 6) showed that geraniol was
better extracted at higher temperature, while linalool was better
extracted at lower temperature. Such behavior of these two com-
pounds could be explained by the occurrence of self-association
of aliphatic alcohols (Tufeu et al., 1993). Relationship between the
structure, association and solubility of alcohols in supercritical CO2
was established showing that with increase of branching associ-
ation decrease, while solubility increase (Friedrich and Schneider,
1989). Consequently, the higher temperature would be required for
extraction of geraniol as a primary alcohol.
Structures in Table 7 showed that ␣-terpineol is tertiary alcohol
with one double bond in the ring. Due to branching, suitable posi-
tion of hydroxyl group and presence of double bond, this alcohol
would exhibit low level of association and consequently extracted
under the low pressure and temperature (Dandge et al., 1985;
Friedrich and Schneider, 1989; Tufeu et al., 1993). Camphor pos-
 Z. Zeković et al. / Industrial Crops and Products 94 (2016) 353–362 359

Table 6
Chemical profile of SFE extracts of coriander seeds.

Compound Content in sample (mg/g)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Cyclic monoterpenes
(+)-Limonene 1.0 1.0 2.0 1.0 <0.1 4.0 1.0 <0.1 <0.1 <0.1 1.0 1.0 <0.1 <0.1 4.1
␣-Pinene <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
␤-Pinene <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
-Terpinene <0.1 <0.1 3.0 <0.1 <0.1 1.0 <0.1 <0.1 <0.1 2.2 <0.1 <0.1 <0.1 1.1 2.1
p-Cymene D D D D ND D D D D D D D D D D

Acyclic oxygenated monoterpenes

Geraniol <0.1 <0.1 3.0 <0.1 1.0 <0.1 <0.1 <0.1 <0.1 1.0 5.2 <0.1 <0.1 2.8 10.7
Geranyl acetate ND ND D ND ND ND ND ND ND ND ND ND ND ND ND
Linalool 441.0 291.0 717.0 412.0 322.0 400.0 302.0 322.0 215.0 264.0 642.0 155.0 257.1 269.0 608.2
Nerol ND D D ND ND ND ND ND ND ND ND ND ND ND ND

Cyclic oxygenated monoterpenes

Camphor 9.0 4.1 21.0 1.0 8.0 1.0 6.1 1.2 5.0 9.1 10.9 7.2 3.7 2.3 9.6
Eucalyptol <0.1 <0.1 <0.1 <0.1 <0.1 1.0 <0.1 1.0 1.2 3.2 <0.1 <0.1 <0.1 <0.1 1.2
Terpinen-4-ol D ND D D ND ND ND ND ND ND ND ND ND ND ND
␣-Terpineol 1.0 <0.1 2.0 1.0 1.0 1.0 1.2 <0.1 <0.1 <0.1 6.1 1.1 <0.1 <0.1 4.2

Aromatic oxygenated monoterpenes

Carvacrol <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
Eugenol <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 2.0 <0.1 <0.1 2.9 20.7
Methyl chavicol 1.0 1.0 2.0 <0.1 <0.1 <0.1 <0.1 <0.1 2.1 7.2 18.2 <0.1 7.3 2.9 13.2

Furanoids
cis-Linalool oxide ND D D D D D D D D D D D D D D
trans-Linalool oxide D D D D D D D D D D D D D D D
Acyclic oxygenated monoterpenes 441.0 291.0 720.0 412.0 323.0 400.0 302.0 322.0 215.0 265.0 647.2 155.0 257.1 271.8 618.9
Cyclic oxygenated monoterpenes 10.0 4.1 23.0 2.0 9.0 3.0 7.3 2.2 6.2 12.3 17.0 8.3 3.7 2.3 15.0
Aromatic oxygenated monoterpenes 1.0 1.0 2.0 <0.1 <0.1 <0.1 <0.1 <0.1 2.1 7.2 20.2 <0.1 7.3 5.8 33.9
Oxygenated monoterpenes 452.0 296.1 745.0 414.0 332.0 403.0 309.3 324.2 223.3 284.5 684.4 163.3 268.1 279.9 667.8
Monoterpenes 1.0 1.0 5.0 1.0 <0.1 5.0 1.0 <0.1 <0.1 2.2 1.0 1.0 <0.1 1.1 6.2
Total 453.0 297.1 750.0 415.0 332.0 408.0 310.3 324.2 223.3 286.7 685.4 164.3 268.1 281.0 674.0

Fig. 2. GC chromatograms of samples 3, 11 and 15.

sesses keto group in the structure, while eucalyptol is saturated
cyclic ether. Aldehydes and ketones are soluble in supercritical
CO2 , while the cyclic structure and absence of double bonds neg-
atively affects the solubility of eucalyptol, although it possesses
side groups and ether functional group (Dandge et al., 1985). As
far as oxygenated monoterpenes are concerned, both compounds,
eugenol and methyl chavicol, possess the propenyl and methoxy
groups attached to phenyl ring, while eugenol possesses additional
hydroxyl group. Generally, the presence of hydrocarbon group
and etherified hydroxyl group increase solubility (Dandge et al.,
1985). In this case, presence of 2-propenyl and methoxy groups
increase the solubility of methyl chavicol in supercritical CO2 , while
presence of free hydroxyl group in eugenol modified its solubility
requiring the higher temperature.
In summary, the highest yields of acyclic oxygenated
monoterpenes (720.0 mg/g) and cyclic oxygenated monoterpenes
360 Z. Zeković et al. / Industrial Crops and Products 94 (2016) 353–362

Table 7 to 11.984 mg/mL. The highest antioxidant activity was achieved

Molecular formulas and structures of quantified compounds in CS extracts.
at the following conditions: 150 bar, 40 ◦ C and 0.2 kg/h of CO2 ,
Compound Molecular formula Structure while the lowest antioxidant activity was detected in the sam-
ple obtained at 100 bar, 55 ◦ C and 0.4 kg/h of CO2 . Comparing
(+)-Limonene C10 H16 obtained results with results of previously conducted studies on
antioxidant activity of CS extracts obtained by SFE technique
revealed the similar activity of SFE extracts. Obtained extracts
-Terpinene C10 H16
(experimental conditions: pressure in range of 115.5–279.5 bar,
temperature in range of 37.85–57.85 ◦ C and CO2 flow rate
Linalool C10 H18 O
of 0.08 kg/h) in concentration of 2.5 mg/mL expressed antiox-
idant activity in the range of 32.0–57.4% of DPPH scavenging
Geraniol C10 H18 O (Yepez et al., 2002). On the other hand, extracts obtained using
ultrasound-assisted (UAE) extraction showed antioxidant activ-
ity in concentration range of 0.02479–0.04183 mg/mL (for 70%
Eucalyptol C10 H18 0
ethanolic extracts), while aqueous extracts obtained by the same
extraction technique exhibited activity in concentration range of
0.07499–0.1007 mg/mL (Zeković et al., 2015). Extracts obtained
␣-Terpineol C10 H18 0
during the optimization of microwave-assisted extraction (MAE)
expressed activity against DPPH radical in concentration range of
0.0302–0.0665 mg/mL (Zeković et al., 2016), while the subcriti-
Camphor C10 H16 0 cal water extracts (SWE) exhibited activity in concentration range
of 0.01706–0.06336 mg/mL (Zeković et al., 2014). Comparing the
activity obtained in this study with activity of CS extracts obtained
Eugenol C10 H12 02 by other extraction techniques, it could be concluded that SFE
extracts exhibited the lowest activity toward DPPH radical. Rea-
son for such difference in activity against DPPH radicals may lie
Methyl chavicol C10 H12 0
in fact that UAE, MAE and SCW techniques provide extracts with
high content of polyphenolic compounds unlike the SFE technique
which mostly isolate volatile oil components and other nonpolar
compounds such are fatty acids.
Table 8 Lipid peroxidation represents a series of chain reactions which
Antioxidant activity of CS extracts. may be initiated by hydroxyl radical, alkoxyl radicals, peroxyl rad-
icals, and peroxynitrite (Dasgupta and Klein, 2014). As a result of
Sample IC50 (mg/mL) ILP50 (mg/mL)
such reactions peroxyl and alkoxyl radical are formed (Li, 2011).
1 5.626 0.352
Both radical species, which represent strong oxidants, are capable
2 2.726 0.408
3 11.984 0.873 to damage cell membrane, oxidize proteins and DNA molecules and
4 5.897 0.264 are responsible for propagation reaction of lipid peroxidation pro-
5 5.643 0.283 cess (Dasgupta and Klein, 2014; Li, 2011). Peroxyl radicals are also
6 2.364 1.546 capable to react among each other producing singlet oxygen which
7 3.132 0.234
is also highly reactive species capable of damaging biomolecules
8 5.032 0.176
9 3.696 0.215 (Miyamoto et al., 2007). For those reasons, it is very important to
10 2.794 0.156 establish the activity of obtained extracts against above described
11 10.697 0.138 reactive species. Activity of CS extracts range from 0.101 mg/mL to
12 7.885 0.340
1.546 mg/mL (Table 8). The highest activity was achieved in extract
13 5.269 0.106
14 3.277 0.150 obtained at 100 bar, 70 ◦ C and 0.3 kg/h of CO2 . On the other hand,
15 7.323 0.101 the lowest activity was achieved at 150 bar, 40 ◦ C and CO2 flow rate
of 0.2 kg/h.
Comparing results of this test with the results obtained from
DPPH assay, it could be noticed that extract samples exhibited
(23.0 mg/g), as well as yield of total oxygenated monoterpenes were higher activity against lipid peroxidation than against DPPH rad-
achieved at 100 bar, 55 ◦ C and 0.4 kg/h of CO2 (sample 3, Fig. 2), ical. Sample obtained at 150 bar, 40 ◦ C and CO2 flow rate of 0.2 kg/h
while the highest yields of aromatic oxygenated monoterpenes exhibited the highest activity against DPPH radical, while in the
(33.9 mg/g) and monoterpenes (6.2 mg/g) were achieved under case of lipid peroxidation showed the lowest activity. Samples
100 bar, 70 ◦ C and 0.3 kg/h of CO2 (sample 15, Fig. 2). Amount of with lowest activities against DPPH radical and lipid peroxida-
750.0 mg/g was the highest total yield of CS extract (100 bar, 55 ◦ C tion were obtained at different operational conditions (100 bar,
and CO2 flow rate of 0.4 kg/h) and was achieved in sample 3 (Fig. 2). 55 ◦ C, 0.4 kg/h of CO2 and 150 bar, 40 ◦ C and CO2 flow rate of
It could be noticed that low pressure value was beneficial for all 0.2 kg/h, respectively). The highest activity against lipid peroxida-
class of monoterpenes, while temperature and CO2 flow rate dif- tion (sample 15) exhibited the sample with the highest content
fered. of monoterpenes (6.2 mg/g) and aromatic oxygenated monoter-
penes (33.9 mg/g), while the lowest activity was achieved by the
3.5. Antioxidant activity sample (sample 6) with the low content of aromatic oxygenated
monoterpenes. Sample 11, which possess high content of aro-
Antioxidant activity was determined by DPPH assay and lipid matic oxygenated monoterpenes (20.7 mg/g), also exhibited high
peroxidation test. Lower IC50 and EC50 values indicated higher activity against lipid peroxidation. This might indicate that aro-
antioxidant activity. Obtained results for the assays are pre- matic oxygenated monoterpenes are one of the responsible class of
sented in Table 8. Measured values of IC50 ranged from 2.364 the compounds responsible for activity against lipid peroxidation.
 Z. Zeković et al. / Industrial Crops and Products 94 (2016) 353–362
Compounds presented in tested SFE extracts were proved to be
better scavenger of peroxyl and alkoxyl radicals than DPPH radical.
4. Conclusion
Optimization of extraction process was successfully conducted
using the RSM. Second-order polynomial model was able to
adequately describe extraction process and antioxidant activity.
Obtained results confirmed the influence of all three parameters
on extraction process, while pressure exhibited the strongest influ-
ence. The highest extraction yield was predicted at the almost
highest pressure and CO2 flow rate and at the almost lowest tem-
perature.
Examination of the influence of extraction parameters of SFE
process on yield and chemical composition of CS essential oil
revealed their significant influence on the process itself. Obtained
results showed that combined effect of pressure and temperature
on density of CO2 and vapor pressure directly influence and mod-
ulate the solubility of volatile compound in subcritical CO2 , thus
affecting their yield and efficiency of the extraction process. Chem-
ical profile of obtained samples demonstrated the significance of
parameters. Linalool, the most abundant compound in samples,
achieved its highest yield at the 100 bar, 55 ◦ C and 0.4 kg/h of CO2 .
The highest total yield was achieved at the same conditions. Gener-
ally, lower pressure, temperature and CO2 flow rate were showed
as better condition for acyclic and cyclic oxygenated monoterpenes,
while higher temperature was beneficial for aromatic oxygenated
monoterpenes and monoterpenes yield. Different requirements in
operational conditions is connected with difference in structure
of monoterpene classes. This relationship between structure and
solubility was described in this study.
Acknowledgement
The financial support of the Ministry of Education, Science and
Technological development of the Republic of Serbia is gratefully
acknowledged (Project No. TR31013).
References
Akgun, M., Akgun, N.A., Dincer, S., 1999. Phase behaviour of essential oil
components in supercritical carbon dioxide. J. Supercrit. Fluids 15, 117–125.
Aluko, R.E., McIntosh, T., Reaney, M., 2001. Comparative study of the emulsifying
and foaming properties of defatted coriander (Coriandrum sativum) seed flour
and protein concentrate. Food Res. Int. 34, 733–738.
Anitescu, G., Doneanu, C., Radulescu, V., 1997. Isolation of coriander oil:
comparison between steam distillation and supercritical CO2 extraction.
Flavour Fragr. J. 12, 173–176.
Baş, D., Boyacı, İ.H., 2007. Modeling and optimization I: usability of response
surface methodology. J. Food Eng. 78, 836–845.
Bajpai, M., Mishra, A., Prakash, D., 2005. Antioxidant and free radical scavenging
activities of some leafy vegetables. Int. J. Food Sci. Nutr. 56, 473–481.
Beara, I.N., Lesjak, M.M., Četojević-Simin, D.D., Orčić, D.Z., Janković, T., Anačkov,
G.T., Mimica-Dukić, N.M., 2012. Phenolic profile, antioxidant,
anti-inflammatory and cytotoxic activities of endemic Plantago reniformis G.
Beck. Food Res. Int. 49, 501–507.
Bezerra, M.A., Santelli, R.E., Oliveira, E.P., Villar, L.S., Escaleira, L.A., 2008. Response
surface methodology (RSM) as a tool for optimization in analytical chemistry.
Talanta 76, 965–977.
Chen, Q., Yao, S., Huang, X., Luo, J., Wang, J., Kong, L., 2009. Supercritical fluid
extraction of Coriandrum sativum and subsequent separation of isocoumarins
by high-speed counter-current chromatography. Food Chem. 117, 504–508.
Chithra, V., Leelamma, S., 2000. Coriandrum sativum—effect on lipid metabolism in
1,2-dimethyl hydrazine induced colon cancer. J. Ethnopharmacol. 71, 457–463.
Döker, O., Salgın, U., Şanal, İ., Mehmetoğlu, Ü., Çalımlı, A., 2004. Modeling of
extraction of ˇ-carotene from apricot bagasse using supercritical CO2 in
packed bed extractor. J. Supercrit. Fluids 28, 11–19.
Dandge, D.K., Heller, J.P., Wilson, K.V., 1985. Structure solubility correlations:
organic compounds and dense carbon dioxide binary systems. Ind. Eng. Chem.
Prod. Res. Dev. 24, 162–166.
Dasgupta, A., Klein, K., 2014. Antioxidants in Food, Vitamins and Supplements.
Prevention and Treatment of Disease, 1st ed. Elsevier Inc., London.
361
Delaquis, P.J., Stanich, K., Girard, B., Mazza, G., 2002. Antimicrobial activity of
individual and mixed fractions of dill, cilantro, coriander and eucalyptus
essential oils. Int. J. Food Microbiol. 74, 101–109.
Di Giacomo, G., Brandani, V., Del Re, G., Mucciante, V., 1989. Solubility of essential
oil components in compressed supercritical carbon dioxide. Fluid Phase
Equilib. 52, 405–411.
Dima, C., Ifrim, G.A., Coman, G., Alexe, P., Dima, Ş., 2016. Supercritical CO2
extraction and characterization of Coriandrum sativum L. essential oil. J. Food
Process Eng 39, 204–211.
Eikani, M.H., Golmohammad, F., Rowshanzamir, S., 2007. Subcritical water
extraction of essential oils from coriander seeds (Coriandrum sativum L.). J.
Food Eng. 80, 735–740.
Espín, J.C., Soler-Rivas, C., Wichers, H.J., 2000. Characterization of the total free
radical scavenger capacity of vegetable oils and oil fractions using
2,2-diphenyl-1-picrylhydrazyl radical. J. Agric. Food Chem. 48, 648–656.
Eyres, G., Dufour, J.P., Hallifax, G., Sotheeswaran, S., Marriott, P.J., 2005.
Identification of character-impact odorants in coriander and wild coriander
leaves using gas chromatography-olfactometry (GCO) and comprehensive
two-dimensional gas chromatography-time-of-flight mass spectometry
(GC × GC-TOFMS). J. Sep. Sci. 28, 1061–1074.
Filip, S., Vidović, S., Adamović, D., Zeković, Z., 2014. Fractionation of non-polar
compounds of basil (Ocimum basilicum L.) by supercritical fluid extraction
(SFE). J. Supercrit. Fluids 86, 85–90.
Filip, S., Vidović, S., Vladić, J., Pavlić, B., Adamović, D., Zeković, Z., 2016. Chemical
composition and antioxidant properties of Ocimum basilicum L. extracts
obtained by supercritical carbon dioxide extraction: drug exhausting method.
J. Supercrit. Fluids 109, 20–25.
Friedrich, J., Schneider, G.M., 1989. Near-infrared spectroscopic investigations on
phase behaviour and association of 1-octadecanol, 3-hexanol, and
3-methyl-3-pentanol in carbon dioxide and chlorotrifluoromethane. J. Chem.
Thermodyn. 21, 307–319.
Gallagher, A.M., Flatt, P.R., Duffy, G., Abdel-Wahab, Y.H.A., 2003. The effects of
traditional antidiabetic plants on in vitro glucose diffusion. Nutr. Res. 23,
413–424.
Grosso, C., Ferraro, V., Figueiredo, A.C., Barroso, J.G., Coelho, J.A., Palavra, A.M.,
2008. Supercritical carbon dioxide extraction of volatile oil from Italian
coriander seeds. Food Chem. 111, 197–203.
Jabeen, Q., Bashir, S., Lyoussi, B., Gilani, A.H., 2009. Coriander fruit exhibits gut
modulatory, blood pressure lowering and diuretic activities. J.
Ethnopharmacol. 122, 123–130.
Jesus, S.P., Meireles, M.A.M., 2014. Supercritical fluid extraction: a global
perspective of the fundamental concepts of this eco-friendly extraction
technique. In: Chemat, F., Vian, M.A. (Eds.), Alternative Solvents for Natural
Products Extraction. Springer-Verlag, Berlin, pp. 39–72.
Li, Y., 2011. Antioxidants in Biology and Medicine: Essentials, Advances, and
Clinical Applications, 1st ed. Nova Science Publishers Inc., New York.
Lo Cantore, P., Iacobellis, N.S., De Marco, A., Capasso, F., Senatore, F., 2004.
Antibacterial activity of Coriandrum sativum L. and Foeniculum vulgare Miller
Var. vulgare (Miller) essential oils. J. Agric. Food Chem 52, 7862–7866.
Madsen, L., Bertelsen, G., 1995. Spices as antioxidants. Trends Food Sci. Technol. 6,
271–277.
Matos, H.A., De Azevedo, E.G., Simoes, P.C., Carrondo, M.T., Da Ponte, M.N., 1989.
Phase equilibria of natural flavours and supercritical solvents. Fluid Phase
Equilib. 52, 357–364.
Mhemdi, H., Rodier, E., Kechaou, N., Fages, J., 2011. A supercritical tuneable process
for the selective extraction of fats and essential oil from coriander seeds. J.
Food Eng. 105, 609–616.
Miyamoto, S., Ronsein, G.E., Prado, F.M., Uemi, M., Corrêa, T.C., Toma, I.N.,
Bertolucci, A., Oliveira, M.C.B., Motta, F.D., Medeiros, M.H.G., Di Mascio, P.,
2007. Biological hydroperoxides and singlet molecular oxygen generation.
IUBMB Life 59, 322–331.
Paixao Coelho, J.A., Figueiredo Palavra, A.M., 2015. Supercritical fluid extraction of
compounds from spices and herbs. In: Fornari, T., Stateva, R.P. (Eds.), High
Pressure Fluid Technology for Green Food Processing. Springer, New York, pp.
357–396.
Pavlić, B., Vidović, S., Vladić, J., Radosavljević, R., Zeković, Z., 2015. Isolation of
coriander (Coriandrum sativum L.) essential oil by green extractions versus
traditional techniques. J. Supercrit. Fluids 99, 23–28.
Pourmortazavi, S.M., Hajimirsadeghi, S.S., 2007. Supercritical fluid extraction in
plant essential and volatile oil analysis. J. Chromatogr. A 1163, 2–24.
Ramadan, M.F., Kroh, L.W., Mörsel, J.-T., 2003. Radical scavenging activity of black
cumin (Nigella sativa L.) coriander (Coriandrum sativum L.), and niger (Guizotia
abyssinica Cass.) crude seed oils and oil fractions. J. Agric. Food Chem. 51,
6961–6969.
Reis Machado, A.S., de Azevedo, E.G., da Ponte, M.N., Sardinha, R.M.A., 1993. High
pressure carbon dioxide cxtraction from coriander plants. Headspace analysis.
J. Essent. Oil Res. 5, 645–649.
Reverchon, E., 1997. Supercritical fluid extraction and fractionation of essential oils
and related products. J. Supercrit. Fluids 10, 1–37.
Sahena, F., Zaidul, I.S.M., Jinap, S., Karim, A.A., Abbas, K.A., Norulaini, N.A.N., Omar,
A.K.M., 2009. Application of supercritical CO2 in lipid extraction—a review. J.
Food Eng. 95, 240–253.
Temelli, F., 2009. Perspectives on supercritical fluid processing of fats and oils. J.
Supercrit. Fluids 47, 583–590.
362 Z. Zeković et al. / Industrial Crops and Products 94 (2016) 353–362
Tufeu, R., Subra, P., Plateaux, C., 1993. Contribution to the experimental
determination of the phase diagrams of some (carbon dioxide + a terpene)
mixtures. J. Chem. Thermodyn. 25, 1219–1228.
Wangensteen, H., Samuelsen, A.B., Malterud, K.E., 2004. Antioxidant activity in
extracts from coriander. Food Chem. 88, 293–297.
Yepez, B., Espinosa, M., López, S., Bolaños, G., 2002. Producing antioxidant fractions
from herbaceous matrices by supercritical fluid extraction. Fluid Phase Equilib.
194–197, 879–884.
Zeković, Z., Adamović, D., Ćetković, G., Radojković, M., Vidović, S., 2011. Essential
oil and extract of coriander (Coriandrum sativum L.). Acta Period. Technol. 288,
281–288.
Zeković, Z., Vidović, S., Vladić, J., Radosavljević, R., Cvejin, A., Elgndi, M.A., Pavlić, B.,
2014. Optimization of subcritical water extraction of antioxidants from
Coriandrum sativum seeds by response surface methodology. J. Supercrit.
Fluids 95, 560–566.
Zeković, Z., Bušić, A., Komes, D., Vladić, J., Adamović, D., Pavlić, B., 2015. Coriander
seeds processing: sequential extraction of non-polar and polar fractions using
supercritical carbon dioxide extraction and ultrasound-assisted extraction.
Food Bioprod. Process. 95, 218–227.
Zeković, Z., Vladić, J., Vidović, S., Adamović, D., Pavlić, B., 2016. Optimization of
microwave-assisted extraction (MAE) of coriander phenolic antioxidants –
response surface methodology approach. J. Sci. Food Agric., http://dx.doi.org/
10.1002/jsfa.7679 (Article in press).