Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Cobalt separation from water and food samples based
on penicillamine ionic liquid and dispersive liquid-
liquid microextraction before determination by AT-FAAS
Yaghoub Pourshojaei
a,*
and Alireza Nasiri
b
a
Department of Medicinal Chemistry, Faculty of Pharmacy, Kerman University of Medical Sciences, Kerman, Iran.
b
Environmental Health Engineering Research Center, Kerman University of Medical Sciences, Postal code:7619813159, Kerman, Iran
ABSTRACT
The cobalt compounds have adverse health effect on human and
caused to damage of the DNA cells, neurological and endocrine
systems. Therefore, the separation and determination of cobalt in
water and food samples must be considered. In this research, the
(2S)-2-amino-3-methyl-3-sulfanylbutanoic acid (penicillamine) as a
chelating agent mixed with ionic liquid (OMIM PF
6
) /acetone and
used for extraction of cobalt from 50 mL of water samples by ultra-
assisted dispersive liquid-liquid microextraction (USA-DLLME) at
pH=6. Based on procedure, the samples were shaked for 5 min (25
o
C)
and after complexation of cobalt ions by thiol and amine group of
penicillamine, the ionic liquid phase separated in the bottom of the
conical tube by centrifuging for 3.0 min. The upper liquid phase
was vacuumed by the auto-sampler and the Co
2+
ions back extracted
from the ionic liquid/ penicillamine in acidic pH. Finally, the cobalt
atomic absorption spectrometry (AT-FAAS). The main parameters
such as the sample volume, the penicillamine amount, the ionic liquid
amount and the shaking time were optimized. The linear range, the
L
-1
-1
and 98.5, respectively (r = 0.9995, RSD%=2.2). The
procedure was validated by ET-AAS analysis.
Keywords:
Cobalt,
Water and food,
Penicillamine,
Ionic liquid,
Ultra-assisted dispersive liquid-
liquid microextraction,
spectrometry
ARTICLE INFO:
Received 11 Jun 2021
Revised form 8 Aug 2021
Accepted 30 Aug 2021
Available online 28 Sep 2021
*Corresponding Author: Yaghoub Pourshojaei
Email: pourshojaei@yahoo.com
https://doi.org/10.24200/amecj.v4.i03.148
------------------------
1. Introduction
Cobalt compounds exist in two valence forms include
cobalt (Co II, cobaltous, Co
2+
and Co III, cobaltic,
Co
3+
), the other forms have not environmentally
available. Also, the other cobalt compounds have
toxic effect in the environment and the human body
by extra exposure [1]. The people is exposed to cobalt
through inhalation of air and food and drinking water.
Cobalt ions enter to environment from numerous
industrial factories such as heavy metals activity
process, the grinding, the mining and paint [2].
Furthermore, it can be used for a medical process for
the medicine Company. The cobalt compounds are
widely dispersed in air with a low concentration less
than 2.0 ng m
-3
[3, 4]. Cobalt has a low concentration
-1
in drinking water. The
cobalt concentration in river, the groundwater, the
-1
[5].
Feng et al reported the concentrations of cobalt in
the groundwater had lower than 0.01 mg L
-1
which is
lower than other heavy metals [6]. Lim et al showed
an applied model for the heavy metals such cobalt in
22
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
[7]. United
States Environmental Protection Agency (EPA)
reported that the cobalt levels in sediment and surface
-1
-1
, , respectively
[2]. Food analysis in dietary cobalt intake such as
to control cobalt toxicity in human body which is
[8]. Besides, the
skin contact is a main way that cobalt was entered to
human body. Cobalt as an essential metal exists in the
human body and the maximum amount of it generally
concentrated in the liver. Cobalt in eggs has biological
role in vitamin B12 and named cyanocobalamin [9].
It uses in structure of vitamin B
12
and produce the red
[9]. Cobalt toxicity cause several health problems
such as cardiomyopathy, nerve/thyroid problems,
hearing and visual impairment, neuropathy,
tinnitus
and glomerulonephritis [10, 11]. Therefore, the
accurate results for determination of cobalt must
be considered by a new technology. The normal
concentration of cobalt is equal to 1.0 ng mL
-1
for
environmental or occupational exposure and more
than this value cause to toxicity. The sources
of cobalt can be entering to human body from
occupational/environmental/food exposures. The
blood Co concentration is 100 µgL
-1
and more than
300 µgL
-1
cause toxicity in human [12, 13]. The
penicillamine a chelating agent, is a trifunctional
compound, containing of a thioalcohol, a carboxylic
acid, and an amine that was used for the treatment
of Wilson’s disease, kidney stones , rheumatoid
arthritis, and removal of heavy metal. Based on
disorder of copper metabolism, copper accumulated
in human body and the penicillamine extracted
extra copper from body but, it can be removed the
other essential metals from body [14, 15]. Many
analytical methods such as electrothermal atomic
absorption spectrometry (ET-AAS) [16],
atomic absorption spectrometry (F-AAS) [17] and
the inductively coupled plasma optical emission/
mass spectrometry (ICP-OES, ICP-MS) [18] have
previously used for the determination of cobalt in
various water and food samples. Moreover, analytical
techniques based on the above instruments cannot
For this purpose, the procedures must be developed
for the separation and preconcentration of cobalt
from samples. There are many methodologies for
matrixes including,
the magnetic solid phase extraction (MSPE) [19],
dispersive micro-solid phase extraction (D-
[20], the liquid-liquid extraction (LLE), the dispersive
liquid-liquid microextraction (DLLME) [21], the
electrochemistry methods (ECM) [22], the cloud
point extraction (CPE) [23] and the precipitation
[24]. Recently, the ultra-assisted dispersive liquid-
liquid microextraction (USA-DLLME) [25] has
been used as one of the most practical methods for
the separation of metal ions. The main advantages
of USA-DLLME to other techniques are simple
separation, high preconcentration, fast analysis, low
time, high recovery and good enrichment factor (EF).
The ionic liquid as green solvent plays critical role for
collection of ligand and metals from samples into two
phases; a IL/ligand phase and liquid phase of water
samples. Metal ions can be extracted from aqueous
solution into the small-volume IL/ligand phase with
hydrophobicity, the more density than water samples
and low solubility in water. In this study, the mixture
of (2S)-2-amino-3-methyl-3-sulfanylbutanoic acid
(penicillamine)/ (OMIM PF
6
) /acetone have been
used for extraction of cobalt from water samples
by USA-DLLME at pH=6. The thiol and amine
groups of penicillamine play an important role in the
coordination of metals and have a strong complex
with the cobalt ions [26]. In this study, this ligand
was used as an ion carrier and as a chelating agent to
cobalt ions accompanied with ionic liquid
2. Experimental
2.1. Instrumental Analysis
The cobalt (Co) value in water and digested food
samples was determined by AT-FAAS (GBC, Aus).
The air-acetylene was used for cobalt measurement by
AT-FAAS. The atom trap accessory as SQT-AT devices
is placed on the burner. In order to improve sensitivity,
SQT which the source beam was passed. SQT-AT
devices cause to increase the sensitivity of absorption
23
Cobalt extraction by penicillamine and ionic liquid Yaghoub Pourshojaei et al
(ABS) per concentration before analysis. The limits
of detection (LOD) were obtained at 0.05 and 0.13
mg L
-1
for the AT-FAAS and FAAS, respectively. The
HCL was adjusted by screws up to maximum energy.
The AT-FAAS for cobalt determination was tuned by
wavelength of 240.7 nm (7 mA). The aspiration of
samples into FAAS was done by the auto-sampler
(0.5-1 mL). The linear range for AT-FAAS was 0.15-
6.0 mg L
for cobalt analysis. The working range for
the AT-FAAS and F-AAS was obtained at 0.15-15
and 0.4-15 mg L
for cobalt, respectively. Graphite
furnace accessory coupled to an atomic absorption
spectrophotometer (GBC) was used for validation of
cobalt in digested food and water samples. The pH of
the samples was adjusted by favorite buffer solutions
(Sigma, Germany) and determined by the Metrohm
pH meter (Swiss). The phosphate buffers (Na
2
HPO
4
and NaH
2
PO
4
) were used to adjust the pH from 6.0
to 8.0.
2.2. Reagents and Materials
The ultra-pure H
2
SO
4
, HCl, NaOH and HNO
3
solutions for cobalt analysis in food and water
samples were prepared from Sigma Aldrich
(Germany). The calibration solutions of Co(II) were
made by dissolving 1.0 g of cobalt nitrate (Co(NO
3
)
2
)
in 1 L of deionized water (DW) solution (2% HNO
3
).
The linear ranges of cobalt were daily prepared by
standard solutions (1g L
-1
, 1000 mg L
-1
) and diluted
by DW (Millipore, USA). All of the laboratory
glassware was cleaned with nitric acid (5% v/v)
and washed with DW for 10 times. ionic liquid of
(HMIM PF
6
, CAS N: 304680-35-1), 1-Methyl-3-
[PF
6
], CAS N: 304680-36-2), 1-methyl-3-
[PF
6
], [BMIM][PF6], CAS N: 304680-36-2), and
( [EMIM][PF
6
], CAS N: 155371-19-0), acetone
(CAS N: 67-64-1) and the penicillamine (CAS N:
52-66-4) were purchased from Sigma, Germany.
The reagents of Na
2
HPO
4
and NaH
2
PO
4
(CAS N:
7558-79-4, 99.95%; CAS N: 7558-80-7, 99%) were
prepared from the Sigma Aldrich, Germany.
2.3. Preparation of water and food samples
All food samples (Rice, Spinach, Broccoli, and
Onion) were pulverized and then ground/ dried/
homogenized before analysis. Finally, the powder
samples are converted to a uniform size and then
place in the oven at 90
C for 3 h. After adding DW
to food samples, the homogenization of sample
was digested with microwave (Antom Paar, multi-
wave) based on book catalog procedure. The food
samples were digested at optimum conditions
(200
C, 500 ps UV radiation). First, 1.0 g of food
powder samples were placed in PTFE tube with
surrounding ceramic tube of microwave and then, 5
mL of HNO
3
with 1 mL of H
2
O
2
solution were added
to samples. The powder samples were digested for
58 min and diluted with DW up to 50 mL before
determination of cobalt by the USA-DLLME at
pH=6. By microwave, the all cobalt forms in foods
(organic foods) convert to Co(II) by induced oxygen
combustion and total cobalt can be determined in
food samples. All water samples prepared based on
3
(2%) by
the ASTM sampling method for water and storage in
PE tube at -4
0
C.
2.4. Procedure of cobalt extraction
The Co (II) ions were separated and preconcentrated
based on the complexation of cobalt-penicillamine
in water and food samples by the USA-DLLME
procedure (Fig.1). Also, the total cobalt in food
samples was determined based on penicillamine
ligand by the AT-AAS. The penicillamine (0.12 g)
dispersed into 180 mg of hydrophobic ionic liquid
([HMIM][PF
6
] and 0.5 mL acetone and then, the
mixture of ligand/([HMIM][PF
6
] /acetone was
injected into 50 mL of water or standard solution
-1
) by a syringe at pH=6.
After sonication of samples for 5.0 min, the
Co(II) ions were complexed by the thiol group of
(2S)-2-amino-3-methyl-3-sulfanylbutanoic acid].
After the extraction process, the Co-ligand was
trapped in the hydrophobic [HMIM][PF
6
] at the
bottom of a conical PE tube by centrifuging for
5 min (3500 rpm). The upper liquid phase was
24
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
evacuated and the Co ions were back-extracted
from ligand/([HMIM][PF
6
] into an aqueous phase
by 0.25 mL of HNO
3
(0.5M) and diluted with
DW up to 0.5 mL. Finally, the Co concentration
in the remaining solution was determined by the
AT-FAAS. In addition, 1.0 g of food powder was
added to HNO
3
/H
2
O
2
solution (5:1) in the PTFE
vials and samples were digested at 58 min based
on the induced oxygen combustion/UV radiation.
The digested food samples are diluted with DW up
to 50 mL before cobalt analysis by the AT-F-AAS
based on same procedure by ligand/([HMIM]
[PF
6
] /acetone at pH=6.
3. Results and Discussion
By the USA-DLLME procedure, the preconcentration/
separation of Co (II) ions in water samples was
occurred for different cobalt concentrations as a
L
) by the penicillamine ligand. Moreover, the total
cobalt extracted from digested food samples such
rice, spinach, broccoli and onion before determined
by the AT-FAAS. The mechanism of extraction is
based on the interaction of nitrogen(--NH) and thiol
(--SH) groups of the penicillamine with cobalt ions
using dative/covalent bonding (Schema 1). The
ion in water/food samples was performed by the
Fig.1. Cobalt extraction based on the complexation of penicillamine in water and food samples
by the USA-DLLME procedure
Schema 1. The mechanism of extraction between nitrogen and thiol of the penicillamine with cobalt ions
25
Cobalt extraction by penicillamine and ionic liquid Yaghoub Pourshojaei et al
penicillamine ligand under optimized conditions
such as the amount of the penicillamine ligand,
pH, ionic liquids content, sample volume, and
interfering ions
3.1. Amount of ligand
In the presented procedure, the amount of
penicillamine as a ligand was optimized for
separation/extraction of cobalt from the water
and digested food samples. Thus, the amounts of
penicillamine on cobalt extraction were studied in
the range of 0.02-0.3 g in the presence of cobalt
-1
) for 50 mL of liquid
samples. The results showed that the quantitative
extraction was obtained at 0.10 g of penicillamine.
amount of ligand which was added to IL /acetone
as an extraction phase for water and food samples.
Also, the effects of ILs on the extraction of cobalt
were examined without any ligand and the recovery
of ILs for cobalt was achieved less than 5%. Due
to Figure 2,
complexation of penicillamine more than 95%.
3.2. Amount of ionic liquids/acetone
By the USA-DLLME procedure, the effects of
different ionic liquids, [OMIM][PF
6
], [BMIM][PF6]
[HMIM][PF
6
] and [EMIM][PF
6
] were studied as
trapping agents for cobalt extraction. So, the amounts
of the hydrophobic ILs on the cobalt extraction were
evaluated in the range of 20-250 mg of ILs containing
-1
of cobalt for 50 mL of water and digested
food samples at pH=6. The quantitative recovery was
achieved for cobalt with 160 mg [OMIM][PF
6
]. So,
180 mg of [OMIM][PF
6
] was used as an optimal IL
for water and food samples. In addition, the effects
of [OMIM][PF
6
] for cobalt extraction were evaluated
without any ligand and the maximum recovery
was obtained less than 5%. Therefore, the [OMIM]
[PF
6
recovery can be collecting cobalt –ligand from the
liquid phase (Fig. 3).
Fig.2. The effect of amount of penicillamine ligand on cobalt extraction
0.05 0.1 0.15 0.2 0.25 0.3 0.35
26
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
3.3. Sample volume
Sample volume is the main parameters for cobalt
extraction in water and foods samples which must be
optimized. Therefore, the different sample volumes
for cobalt extraction/separation/preconcentration in
water and foods samples between 5-100 mL based
on penicillamine ligand were studied containing
-1
of cobalt. According to Figure 4, the
water and food samples at pH=6. So, 50 mL of water
or digested food samples were selected as an optimal
volume by the USA-DLLME procedure (Fig. 4).
Fig.3. The effect of amount of IL on cobalt extraction by the USA-DLLME procedure
Fig.4. The effect of sample volume on cobalt extraction by the USA-DLLME procedure
20 50 100 120 160 180 200 250
27
Cobalt extraction by penicillamine and ionic liquid Yaghoub Pourshojaei et al
3.4. pH Effect
pH is one of the most important parameters for
cobalt extraction in water and digested food
samples Therefore, the pH ranges from 2 to 10
was prepared and adjusted by buffer solution for
recovery based on penicillamine ligand /IL was
-1
)
at pH of 5.5-6.5 in water samples. So, pH 6.0 was
used for extraction of cobalt in water and digested
food samples by the USA-DLLME procedure
(Fig. 5). The proposed mechanism of cobalt
extraction has been shown in the Schema 1 based
on dative/covalent bond of thiol (HS) and amine
(NH
2
) functional groups of penicillamine with the
positive charge of cobalt (Co
2+
) at pH 6.0. Due
to results, the isoelectric pH of penicillamine is
4.85, it can be concluded that above this pH, the
amine and thiol groups of peniclamine are free
and they have nucleophilic ability to attack to
orbitals of cobalt ion, and they easily participate
in the complex formation process to extract
cobalt ion. So in acidic pH, the (NH
2
) group of
penicillamine ligand has positive charged (NH
3
+
)
and the complexation wasn’t occurred due to
electrostatic repulsion between Co
2+
and NH
3
+
,
if some complexation is formed, it is due to the
participation of the thiol group in this process.
Also, the observed decline in the Figure 5 at pH
above of 6.5 may be due to the competition of
hydroxyl ions with the penicillamine ligand for
complex formation resulting in the formation of
stable cobalt hydroxide. So, the complexation of
penicillamine ligand with Co
2+
ions
decreased at
more than pH=6.5 as participated cobalt ions by
hydroxide form (Co(OH)
2
).
Fig.5. The effect of pH on cobalt extraction at LLOQ (Blue) and ULOQ (green)
by the USA-DLLME procedure
2 3 4 5 5.5 6 6.5 7 8 9 10
28
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
3.5. Effect of interference of ions
The effect of interference ions on cobalt
extraction based on penicillamine ligand in
water/food samples was evaluated by the USA-
DLLME procedure. So, the main concomitant
ions were studied in water and food samples
with different concentrations between 0.5-
3 mgL
-1
for 50 mL of samples at pH=6. The
results showed that the interfering ions had not
affected for the cobalt extraction in water/food
samples by the proposed procedure (Table 1).
Also, the concentration ratio of interfering ions/
cobalt ions (C
M
/C
Co
) for water ranged between
100-1800. The mean ratios for mercury, nickel
and lead were seen at about 100-200, 700-850,
600-800 in water and digested food samples,
respectively. So, the penicillamine ligand/ionic
liquid phase can be extracted cobalt ions in the
presence of the main interfering ions.
3.6. Eluent concentration and volume
The various eluents such as HNO
3
, HCl and H
2
SO
4
were used for back extraction of cobalt ions from the
penicillamine ligand/IL/acetone. At acidic pH, the
complexation of Co…SH-P was broken down and
cobalt ions released into acid solution. Therefore, the
various acid solutions based on different volumes and
concentrations (0.2-1 mol L
-1
, 0.1-1 mL were used
for cobalt back extraction from IL phase. The Co(II)
ions were quantitatively back-extracted from the
penicillamine ligand/IL by HNO
3
with concentration
more than 0.4 M. So, the 0.5 mol L
-1
of HNO
3
solution
was selected as an eluent. Moreover, the various
volumes of eluents between 0.1-1 mL were used for
back-extraction of cobalt ions in water/food samples.
Due to Figure 6, the 0.25 mL of HNO
3
(0.5 M) had the
Finally, the remained solution was diluted with DW
up to 0.5 mL before determining by AT-FAAS.
Table 1. The effect of interfering ions on extraction of Co(II) in water and digested food samples
by the USA-DLLME procedure
Interfering Ions in blood (M)
Mean ratio
(C
M
/C
Co(II)
)
Recovery (%)
Co(II) Co(II)
Cr
3+
, Al
3+
, Fe
3+
750 97.0
Mn
2+
, Cd
2+
, Mo
2+
800 96.6
Pb
2+
700 99.4
Zn
2+
, Cu
2+
600 97.8
I
-
, Br
-
, F
-
, Cl
-
1200 97.4
Na
+
, K
+
, Ca
2+
, Mg
2+
1400 98.1
CO
3
2-
, PO
4
3-
, HCO3
-
, SO
4
2-
1000 99.2
Ni
2+
800 97.9
NH
4
+
, SCN
-
, NO
3
-
900 98.3
Hg
2+
150 97.2
29
Cobalt extraction by penicillamine and ionic liquid Yaghoub Pourshojaei et al
3.7. Real sample analysis
The extraction of cobalt (II) ions with the
penicillamine ligand in water/food samples were
developed by the USA-DLLME procedure at pH 6.
Also, the total Co(II) in rice, spinach, broccoli and
onion was determined after the digestion process by
proposed procedure. The total Co(II) determined
in digested foods samples after extraction by the
penicillamine ligand/[OMIM][PF
6
] at pH 6.0.
Moreover, the real water and food samples were
validated by spiking of standard solutions of cobalt
in optimized conditions (Table 2). Therefore, the
various concentrations of Co(II) were spiked to
real samples. The results showed us that the high
recovery for Co(II) ions in water/food samples was
created by 1.2 g of the penicillamine ligand and
150 mg of [OMIM][PF
6
].
Based on Table 2
and the satisfactory results was demonstrated
the penicillamine ligand/[OMIM][PF
6
] can
be obtained the accurate and precision results
for cobalt in liquid samples. Also, the method
validation was achieved based on the ET-AAS and
the ICP –MS analyzer by microwave digestion
process (Table 3).
4. Conclusions
A simple and sensitive method based on
the penicillamine ligand/[OMIM][PF
6
] was
obtained for the Co (II) ions determination in
water and digested food samples at pH=6. The
concentrations of cobalt ions were determined
by the AT-FAAS detection method after sample
preparation by the USA-DLLME procedure.
Recovery was achieved between 95.2–103.6 and
relative standard deviation (RSD%) between 1.9-
4.5 under optimized conditions. In this procedure,
the shaking and centrifuging time were 4.5 and
3.0 minutes, respectively. The working range of
were achieved by the presented
method. Therefore, cobalt ions were extracted
and determined effectively using penicillamine
ligand/[OMIM][PF
6
] in water/food samples with
the USA-DLLME coupled to AT-FAAS.
Fig.6. The effect of eluents on cobalt extraction by the USA-DLLME procedure
0/2 0/3 0/5 0/6 0/8 1
0.2 0.3 0.5 0.6 0.8 1
30
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
Table 2. Validation of methodology for Co(II) determination with penicillamine ligand/[OMIM][PF
6
]
based on spiking standard samples by the USA-DLLME procedure coupled to AT-FAAS
Sample* Added
(μg L
-1
)
*
Found W (μg L
-1
)/F(μg g
-1
) Recovery (%)
Well water A
--- 12.1 ± 0.4 ---
10 21.9 ± 0.9 98.0
Wastewater B
--- 45.6 ± 2.3 ---
50 95.2 ± 4.5 99.2
Wastewater C
--- 34.5 ± 1.7 ---
50 85.2 ± 3.9 101.4
Rice
--- 21.2 ± 0.8 ---
20 40.9 ± 1.6 98.5
Spinach
--- 24.6 ± 1.1 ---
25 49.2 ± 2.3 98.4
--- 30.2 ± 1.2 ---
Broccoli 30 60.8 ± 2.4 102
--- 27.8 ± 1.3 ---
Onion 30 57.3 ± 2.7 98.3
Food samples digested by Microwave and determined by proposed procedure
All food samples prepared from supermarket Tehran
Well water A: 25 mL of water prepared from Shahre Ray, Tehran
Wastewater B: 25 mL of water prepared from petrochemical industry, Tehran, Iran
Wastewater C: 25 mL of water prepared from paint factory, Arak, Iran
-1
-1
-1
)
Table 3. The comparing of USA-DLLME /AT-FAAS method with ET-AAS and ICP –MS
-1
-1
), n=20)
Sample
ψ
ICP-MS ET-AAS
ψ ψ
USA-DLLME r* r֎
Wastewater A 11.9 ± 0.1 12.6 ± 0.3 12.3 ± 0.4 0.77 0.70
Wastewater B 46.1 ± 0.9 44.9 ± 2.3 45.5 ± 2.4 0.81 0.73
Rice 21.6 ± 0.5 20.6 ± 1.0 21.3 ± 0.8 0.65 0.78
Spinach 24.1 ± 0.8 25.3 ± 1.3 24.6 ± 1.1 0.62 0.81
Onion 26.9 ± 0.7 29.1 ± 1.5 27.6 ± 1.3 0.59 0.74
*r: Correlation of ET-AAS with USA-DLLME /AT-FAAS method for cobalt determination (n=20)
֎
r: Correlation of ICP-MS with USA-DLLME /AT-FAAS method for cobalt determination (n=20)
, n=20)
31
Cobalt extraction by penicillamine and ionic liquid Yaghoub Pourshojaei et al
5. Acknowledgments
The authors wish to thank from Department
of Medicinal Chemistry, Faculty of Pharmacy,
Kerman University of Medical Sciences, Kerman,
Iran and Environmental Health Engineering
Research Center, Kerman University of Medical
Sciences, Kerman, Iran.
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